Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT COMPOSITIONS COMPRISING STABILISED
POLYAMINO ACID COMPOUNDS
Fi~ld of the invention
The present invention relates to the use of polyamino acid
containing compounds and salts thereof in detergent
compositions. More particularly, it relates to the use of a
polyamino acid, including polyaspartic acid, wherein said
polyamino acid is in close physical proximity with a protein so as
to protect it from degradation.
Background of the invention
Polyamino acid agents can be used in detergent compositions
as builders or dispersing agents. Such disclosure is given in EP
454126 which described polyamino acids, including
polyaspartic acid, as biodegradable builders/co-builders in the
formulation of detergents. The said polymers, especially those
derived from aspartic acid, glutamic acid and mixtures thereof,
are described as resistant to heat, stable to pH, non toxic, non
irritant and entirely biodegradable. However, a problem
encountered by such use is the degradability of those
polymers under storage and over a period of time.
PCT/US93/12090 discloses the use of polyamino acid
protected from contact with a level of alkalinity as would
cause degradation thereof. The said polyamino acid is provided
with a coating, encapsulated or mixed in the form of an
agglomerate or granulate with at least one other material
which is preferably an alkaline or alkaline reacting compound.
However, research by the present Applicant has revealed that
this kind of protection will also degrade under storage. This
being 'partially' due to the enzymatic action and alkaline
hydrolysis.
It has now been found that a detergent composition containing
a detersive surfactant, at least one polyamino acid compound
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and at least one protein wherein said polyamino acid compound and
said protein are in close physical proximity shows enhanced storage
stability.
A further advantage to the close physical proximity of said
polyamino acid compound and said protein is the enhanced stability
and protection against bleaches.
It is a further object of the present invention to provide a detergent
composition with effective stain and soil removal performance.
Summary of the invention
In accordance with one aspect of the present invention there is
provided a process for producing a detergent composition
containing a detersive surfactant, at least one polyamino acid
compound selected from the group consisting of homopolymers,
copolymers of two or more aminoacids, and mixtures thereof and at
least one protein selected from the group consisting of micro-
organisms and proteins extracted therefrom, animal proteins and
vegetable proteins; and which comprises the steps of: a-contacting
said protein with said polyamino acid compound in the presence of
water, b-agitating the resulting mixture so as to obtain a solid brittle
agglomerate, c-grinding said agglomerate so as to obtain a particle
size of from about 250Nm to about 800~m, d-incorporating the
agglomerate in the detergent composition.
In accordance with another aspect of the present invention there is
provided a detergent composition containing a detersive surfactant,
a polyamino acid compound/protein agglomerate comprising at least
one polyamino acid compound and at least one protein, and one or
more detergent components selected from the group consisting of
bleaching agents, dye transfer inhibiting agents, fabric softening
agents, suds suppressors, enzymes, chelants, builders, soil release
polymers, brighteners and mixtures thereof.
In accordance with yet another aspect of the present invention there
is provided a detergent composition containing a detersive
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surfactant, a polyamino acid compound/protein particle comprising
at least one protein coated with at least one polyamino acid
compound, and one or more detergent components selected from
the group consisting of bleaching agents, dye transfer inhibiting
agents, fabric softening agents, suds suppressors, enzymes,
chelants, builders, soil release polymers, brighteners and mixtures
thereof.
The present invention relates to a detergent composition containing
a detersive surfactant, at least one polyamino acid compound and at
least one protein wherein said polyamino acid compound and said
protein are in close physical proximity.
For the purpose of the present invention, the term close physical
proximity means one of the following:
i) an agglomerate or extrudate in which said polyamino acid
compound and said protein are in intimate admixture;
ii) a polyamino acid particulate coated with one or more layers
wherein at least one layer contains the protein;
iii) a protein coated with one or more layers wherein at least one
layer contains the polyamino acid compound.
It has to be understood by close physical proximity that the
polyamino acid compound and the protein are not two separate
discrete particles in the detergent composition.
The polyamino acid compound and the protein mixture may be
present within the detergent composition in a form selected from an
agglomerate, a granulate, a tablet and mixture thereof.
Also provided herein is a process for producing such mixture in a
form of an agglomerate within a detergent composition.
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Technical field of the invention
The present invention contemplates dispersant containing-
detergent compositions having an excellent storage stability
° against enzymes as well as against bleaches. More
particularly, it relates to a detergent composition containing a
' detersive surfactant, at least one polyamino acid compound
and at least one protein wherein said polyamino acid
compound and said protein are in close physical proximity.
An essential component for the purpose of the invention is a
polyamino acid compound.
The expression 'polyamino acid compound' includes herein not
only a polyamino acid as such but also a derivative thereof,
such as an amide, an ester or a salt. The polyamino acid may
be a homopolymer or may be a copolymer of two or more
amino acids. The amino acid may be a D-amino acid, a~ L-
amino acid or a mixture, e.g. a racemic mixture, thereof. The
amino acids include, for instance, alanine, glycine, tyrosine,
serine and lysine, although glutamic, carboxyglutamic and
aspartic acids are preferred. Of these, aspartic acid is
particularly preferred.
Normally, for the purpose of formulating a detergent
composition, in particular a laundry detergent composition, the
polyamino acid will be used in the form of a salt thereof,
preferably an alkali metal salt and more preferably the sodium
salt.
It will be understood that the polyamino acid compound may
be constituted by a mixture of two or more compounds of the
appropriate description.
The molecular weight of the polyamino acid compound may
be varied within wide limits. Preferably, the molecular weight
is from 500 to 200,000, more preferably 2000 to 20,000.
The polyamino acid described herein before will comprise from
°~ to 90 %, preferably from 10 % to 40 °~ and more
preferably from 10% to 20% by weight of the polyamino acid-
protein mixture.
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The other essential component useful for the purpose of the
invention is a protein which is in intimate contact with the
polyamino acid so as to protect it from attack by enzymes and
further by bleaches.
By protein, it is meant any of a class of high molecular-weight
polymer compounds composed of a variety of a-amino acids
joined by peptide linkages, excluding those from a group of
catalytic proteins that are produced by living cells and that
mediate and promote the chemical processes of life without
themselves being altered or destroyed.
Suitable proteins for the purpose of the invention are micro-
organisms (yeast, bacteria, mould, etc.) and those proteins
extracted therefrom, animal proteins (collagen, gelatin, glue,
keratin, casein, egg albumin, etc.) and vegetable proteins
(soybean protein, wheat gluten, etc.).
A preferred protein is white egg albumin.
The protein described herein before will comprise from 10°~ to
90%, preferably from 10°~ to 40% and more preferably from
10% to 20°~ by weight of the polyamino acid-protein mixture.
According to the present invention, a polyamino acid
compound is stabilised against degradation sufficiently to
render it acceptably storage-stable. This is effected, in
particular, by protecting the said compound from contact with
enzymes, bleaches and high alkalinity. Said stabilisation may
be obtained by admixing to said polyaspartate a protein such
as described herein before wherein said polyamino acid
compound and said protein are in close physical proximity (e.g.
the protein is admixed to the polyamino acid in a such intimate
contact that the enzymes, source of damage for said
polyamino acid, will preferentially and selectively attack the
protein instead of the polyamino acid compound).
Another advantage to said mixture is the further protection of
said polyamino acid against bleaches and high alkalinity which
have also been shown as being detrimental to the stability of
said polyamino acid upon storage.
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The stabilisation or protection should be such that the amount
of degradation of the polyamino acid compound in the
detergent composition is less than 50 % over a 4 week storage
period under stressed conditions (90°F (32.2°C) and 80%
relative humidity) and preferably less than 30%.
a
Further components may be admixed to said mixture. Suitable
components are those having no deleterious effect on the
mixture properties so that the amount of degradation of the
polyamino acid remains as specified herein before.
Suitable components which may be admixed to said mixture
are carbonates (including bicarbonates), sulphates and
aluminosilicates.
Another preferred embodiment suitable for the purpose of the
invention comprises agglomerates formed from the polyamino
acid and the protein mixture and contained in such detergent
composition to enhance stabilisation. Other components may,
of course, be included in such agglomerates. The
agglomeration of the polyamino acid compound and the
protein may be carried out using any suitable agglomeration
technique and apparatus, if appropriate with compatible
agglomeration auxiliaries. Such techniques, apparatus and
auxiliaries are well-known in the detergent formulating art.
Once the agglomerates are formed, they may be dried, if
required, by conventional means.
A suitable process for producing a detergent composition,
containing said polyamino acid-protein mixture in the form of
an agglomerate, comprises the steps of:
a-contacting said protein with said polyamino acid in the
. presence of water,
b-agitating the resulting mixture so as to obtain a solid brittle
. agglomerate,
c-grinding said agglomerate so as to obtain a size of from 250
~m to 800pm,
d-incorporating the agglomerate in the detergent composition.
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A typical agglomerate formulation comprises:
Polyamino acid compound 10 to 90%
Protein 10 to 40%
The molten materials, viz the polyamino acid compound and
the protein agglomerating agent are fed to the agglomerator at
a temperature between 35°C and 40°C: The resulting mass is
then mixed for a further 3 hours until a yellow/browned colour
paste is formed. The mixing is then stopped and the paste is
left in an oven at 35°C for 24 hours. The resulting solid is
crushed in a mortar and pestle to a fine powder. The product
is then sieved and materials that are greater than 800
micrometers and smaller than 250 micrometers are removed.
The stabilised polyamino acid (e.g. the polyamino acid-protein
mixture) according to the present invention is used as a
dispersing agent (which term includes a clay-soil-suspending
agent and/or an anti-redeposition agent) in solid (e.g. granular
or other particulate) detergent compositions and will generally
be employed therein at a level of from 0.1 % to 50%, usually
at least 0.4%, preferably 1 to 15%, more preferably 1 % to
% and most preferably 2.5 % to 5.5 % by weight of the
detergent composition.
The polyamino acid-protein mixture will usually have a ratio of
said polyamino acid to said protein of from 9:1 to 1:9,
preferably from 4:1 to 1:4 and more preferably from 2:1 to
1:2.
Although the polyamino acid-protein mixture may be included
in a wide variety of cleaning compositions, for example hard-
surface and other household cleaners and dishwashing
compositions, they are particularly suitable for use in laundry
detergent compositions, e.g. general-purpose or heavy-duty
laundry detergent compositions. These will contain not only
the stabilised polyamino acid compound-protein mixture and
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detersive surfactant but also, optionally, one or more further
components conventional in the art; these may be selected
from, for example, a detergent builder, a bleach (in particular a
' source of hydrogen peroxide, e.g. sodium perborate or sodium
percarbonate), a bleach activator, an enzyme, a polymeric soil-
release agent, a chelating agent, a conventional dispersing
agent, a brightener, a suds suppressor, a pH-buffering agent, a
dye, a dye transfer inhibition agent or a pigment. It will be
understood that any of the above-mentioned components,
whether essential or optional, may be constituted, if desired,
by a mixture of two or more compounds of the appropriate
description.
Detersive Surfactants
The total amount of surfactants will be generally up to 70%,
typically 1 to 55 %, preferably 1 to ~30%, more preferably 5 to
25°~ and especially 10 to 20% by weight of the total
composition.
Nonlimiting examples of surfactants useful herein include the
conventional C 1 1-C 1 g alkyl benzene sulfonates ("LAS") and
primary, branched-chain and random C10-C20 alkyl sulfates
("AS"), the C1 p-C1 g secondary (2,3) alkyl sulfates of the
formula CH3(CH2)x(CHOS03-M + ) CH3 and CH3
(CH2)y(CHOS03-M + ) CH2CH3 where x and (y + 1 ) are
integers of at least 7, preferably at least 9, and M is a
water-solubilizing cation, especially sodium, unsaturated
sulfates such as oleyl sulfate, the C10-C1 g alkyl alkoxy
sulfates ("AEXS"; especially EO 1-7 ethoxy sulfates), C 10-C 18
alkyl alkoxy carboxylates (especially the EO 1-5
ethoxycarboxylates), the C 10-18 glycerol ethers, the C 1 p-C 18
alkyl polyglycosides and their corresponding sulfated
- polyglycosides, and C 12-C 1 g alpha-sulfonated fatty acid
esters. If desired, the conventional nonionic and amphoteric
surfactants such as the C 12-C 1 g alkyl ethoxylates (°'AE"),
including the so-called narrow peaked alkyl ethoxylates and
Cg-C12 alkyl phenol alkoxylates (especially ethoxylates and
mixed ethoxy/propoxy), C12-C1 g betaines and sulfobetaines
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g
("sultaines"), C10-C1 g amine oxides, and the like, can also be
included in the overall compositions. The C 10-C 1 g N-alkyl
polyhydroxy fatty acid amides can also be used. Typical
examples include the C 12-C 1 g N-methyiglucamides. See WO
9,206,154. Other sugar-derived surfactants include the N-
alkoxy polyhydroxy fatty acid amides, such as C10-C1 g N-(3-
methoxypropyl) glucamide. The N-propyl through N-hexyl
C 12-C 1 g glucamides can be used for low sudsing. C 10-C20
conventional soaps may also be used. If high sudsing is
desired, the branched-chain C10-C16 soaps may be used.
Other suitable surfactants suitable for the purpose of the invention are
the anionic alkali metal sarcosinates of formula:
R-CON(R1)CH2COOM
wherein R is a C9-C1~ linear or branched alkyl or alkenyl group, R1
is a C 1-C4 alkyl group and M is an alkali metal ion. Preferred
examples are the lauroyl, cocoyl (C 12-C 14), myristyl and oleyl methyl
sarcosinates in the form of their sodium salts.
Mixtures of anionic and nonionic surfactants are especially
useful. Other conventional useful surfactants are listed in
standard texts.
Add na c~ Ingredients
The compositions herein can optionally include one or
more other detergent adjunct materials or other materials for
assisting or enhancing cleaning performance, treatment of the
substrate to be cleaned, or to modify the aesthetics of the
detergent composition (e.g., perfumes, colorants, dyes, etc.).
The following are illustrative examples of such adjunct
materials.
uil rs - Detergent builders can optionally be included in
the compositions herein to assist in controlling mineral -
hardness. Inorganic as well as organic builders can be used.
Builders are typically used in fabric laundering compositions to
assist in the removal of particulate soils.
The level of builder can vary widely depending upon the
end use of the composition and its desired physical form.
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Granular formulations typically comprise from 10% to 80%,
more typically from 15 % to 50 % by weight, of the detergent
builder. Lower or higher levels of builder, however, are not
' meant to be excluded.
Inorganic or phosphate-containing detergent builders
include, but are not limited to, the alkali metal, ammonium and
alkanolammonium salts of polyphosphates (exemplified by the
tripolyphosphates, pyrophosphates, and glassy polymeric
meta-phosphates).
Non-phosphate builders may also be used. These can include,
but are not restricted to phytic acid, silicates, alkali metal
carbonates (including bicarbonates and sesquicarbonates),
sulphates, aluminosilicates, monomeric polycarboxylates,
homo or copolymeric polycarboxylic acids or their salts in
which the polycarboxylic acid comprises at least two
carboxylic radicals separated from each other by not more
than two carbon atoms, organic phosphonates and
aminoalkylene poly (alkylene phosphonates). The compositions
herein also function well in the presence of the so-called
"weak" builders (as compared with phosphates) such as
citrate, or in the so-called "underbuilt" situation that may
occur with zeolite or layered silicate builders.
Examples of silicate builders are the so called
'amorphous' alkali metal silicates, particularly those having a
Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and crystalline
layered silicates, such as the layered sodium silicates
described in U.S. Patent 4,664,839. NaSKS-6 is the
trademark for a crystalline layered silicate marketed by
Hoechst (commonly abbreviated herein as "SKS-6"). Unlike
zeolite builders, the Na SKS-6 silicate builder does not contain
aluminum. NaSKS-6 has the delta-Na2Si205 morphology
form of layered silicate. It can be prepared by methods such
as those described in German DE-A-3,417,649 and DE-A-
3,742,043. SKS-6 is a highly preferred layered silicate for use
herein, but other such layered silicates, such as those having
the general formula NaMSix02x+1'yH2~ wherein M is
sodium or hydrogen, x is a number from 1.9 to 4, preferably 2,
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and y is a number from 0 to 20, preferably 0 can be used
herein. Various other layered silicates from Hoechst include
NaSKS-5, NaSKS-7 and NaSKS-1 1, as the alpha, beta and
gamma forms. As noted above, the delta-Na2Si205 (NaSKS- '
6 form) is most preferred for use herein. Other silicates may
also be useful such as for example magnesium silicate, which '
can serve as a crispening agent in granular formulations, as a
stabilizing agent for oxygen bleaches, and as a component of
suds control systems.
Examples of carbonate builders are the alkaline earth and
alkali metal carbonates as disclosed in German Patent
Application No. 2,321,001 published on November 15, 1973.
Aluminosilicate builders are useful in the present
invention. Aluminosilicate builders are of great importance in
most currently marketed heavy duty granular detergent
compositions, and can also be a significant builder ingredient
in liquid detergent formulations. Aluminosilicate builders
include those having the empirical formula:
Nazf(A102)z(Si02)yl~xH20
wherein z and y are integers of at least 6, the molar ratio of z
to y is in the range from 1.0 to 0.5, and x is an integer from
to 264.
Useful aluminosilicate ion exchange materials are
commercially available. These aluminosilicates can be
crystalline or amorphous in structure and can be naturally-
occurring aluminosilicates or synthetically derived. A method
for producing aluminosilicate ion exchange materials is
disclosed in U.S. Patent 3,985,669. Preferred synthetic
crystalline aluminosilicate ion exchange materials useful herein
are available under the designations Zeolite A, Zeolite P (B),
Zeolite MAP and Zeolite X. In an especially preferred
embodiment, the crystalline aluminosilicate ion exchange
material has the formula:
Nal2((A102)12(Si02)121~xH20
wherein x is from 20 to 30, especially 27. This material is
known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may
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also be used herein. Preferably, the aluminosilicate has a
particle size of 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of
the present invention include, but are not restricted to, a wide
variety of polycarboxylate compounds. As used herein, "poly-
' carboxylate" refers to compounds having a plurality of
carboxylate groups, preferably at least 3 carboxylates.
Polycarboxylate builder can generally be added to the
composition in acid form, but can also be added in the form of
a neutralized salt. When utilized in salt form, alkali metals,
such as sodium, potassium, and lithium, or alkanolammonium
salts are preferred.
Included among the polycarboxylate builders are a variety
of categories of useful materials. One important category of
polycarboxylate builders encompasses the ether polycarboxy-
lates, including oxydisuccinate, as disclosed in U.S. Patent
3,128,287 and U.S. Patent 3,635,830. See also "TMS/TDS"
builders of U.S. Patent 4,663,071. Suitable ether
polycarboxylates also include cyclic compounds, particularly
alicyclic compounds, such as those described in U.S. Patents
3,923,679; 3,835,163; 4,158,635; 4,120,874 and
4,102,903.
Other useful detergency builders include the ether
hydroxypolycarboxylates, copolymers of malefic anhydride with
ethylene or vinyl methyl ether or acrylic acid, 1, 3, 5-
trihydroxy benzene-2, 4, 6-trisulphonic acid, and
carboxymethyloxysuccinic acid, the various alkali metal,
ammonium and substituted ammonium salts of polyacetic
acids such as ethylenediamine tetraacetic acid and
nitrilotriacetic acid, as well as polycarboxylates such as
mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid,
benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic
acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof
tparticularly sodium salt), are polycarboxylate builders of
particular importance for heavy duty liquid detergent
formulations due to their availability from renewable resources
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and their biodegradability. Citrates can also be used in
granular compositions, especially in combination with zeolite
and/or layered silicate builders. Oxydisuccinates are also
especially useful in such compositions and combinations.
Also suitable in the detergent compositions of the
present invention are the 3,3-dicarboxy-4-oxa-1,6-
hexanedioates and the related compounds disclosed in U.S.
Patent 4,566,984. Useful succinic acid builders include the
C5-C20 alkyl and alkenyl succinic acids and salts thereof. A
particularly preferred compound of this type is do-
decenylsuccinic acid. Specific examples of succinate builders
include: laurylsuccinate, myristylsuccinate, palmitylsuccinate,
2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate,
and the like. Laurylsuccinates are the preferred builders of this
group, and are described in EP 0,200,263.
Other suitable polycarboxylates are disclosed in U.S.
Patent 4,144,226 and in U.S. Patent 3,308,067. See also
U.S. Patent 3,723,322.
Fatty acids, e.g., C12-C1 g monocarboxylic acids, can
also be incorporated into the compositions alone, or in
combination with the aforesaid builders, especially citrate
and/or the succinate builders, to provide additional builder
activity. Such use of fatty acids will generally result in a
diminution of sudsing, which should be taken into account by
the formulator.
In situations where phosphorus-based builders can be
used, and especially in the formulation of bars used for hand-
laundering operations, the various alkali metal phosphates such
as the well-known sodium tripolyphosphates, sodium
pyrophosphate and sodium orthophosphate can be used.
Phosphonate builders such as ethane-1-hydroxy-1,1-
diphosphonate and other known phosphonates tsee, for
example, U.S. Patents 3,159,581; 3,213,030; 3,422,021;
3,400,148 and 3,422,137) can also be used.
Bleaching Compounds - Bleachin4 Agents and Bleach
Activators - The detergent compositions herein may optionally
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contain bleaching agents or bleaching compositions containing
a bleaching agent and one or more bleach activators. When
present, bleaching agents will typically be at levels of from
0.1 % to 60%, more typically from 1 % to 30% and more
preferably from 5% to 20% by weight, of.the detergent
' composition, especially for fabric laundering.
The bleaching agents used herein can be any of the
bleaching agents useful for detergent compositions in textile
cleaning, hard surface cleaning, or other cleaning purposes
that are now known or become known. The bleaching agent,
source of alkaline hydrogen peroxide in the wash liquor, is an
inorganic perhydrate bleach normally in the form of the sodium
or magnesium salt.
The perhydrate may be any of the alkali inorganic salts such as
perborate monohydrate or tetrahydrate, percarbonate,
perphosphate and persilicate salts, but is conventionally an
alkali metal perborate or percarbonate.
Sodium percarbonate, which is the preferred perhydrate, is an
addition compound having a formula corresponding to
2Na2C03.3H202, and is available commercially as a
crystalline solid. Most commercially available material includes
a low level of a heavy metal sequestrant such as EDTA, 1-
hydroxyethylene 1,1-diphosphonic acid (HEDP) or an
aminophosphonate, that is incorporated during the
manufacture process. For the purposes of the detergent
composition aspect of the invention, the percarbonate can be
incorporated into detergent compositions without additional
protection, but preferred executions of such compositions
utilise a coated form of the material. A variety of coatings can
be used including borosilicate borate, boric acid and citrate or
sodium silicate of Si02:Na20 ratio from 1.6:1 to 3.4:1,
preferably 2.8:1, applied as an aqueous solution to give a level
of from 2°~ to 10%, (normally from 3°~ to 5°~) of
silicate
solids by weight of the percarbonate. However the most
preferred coating is a mixture of sodium carbonate and
sulphate or sodium chloride.
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The particle size range of the crystalline percarbonate is from
350 micrometers to 1500 micrometers with a mean of
approximately 500-1000 micrometers.
Another category of bleaching agent that can be used in
place of or in combination with the mixture of an inorganic
perhydrate and a bleach activator encompasses the preformed
peracid bleaching agents and salts thereof. Suitable examples
of this class of agents include (6-octylamino)-6-oxo-caproic
acid, (6-nonylamino)-6-oxo-caproic acid, (6-decylamino)-6-oxo-
caproic acid, magnesium monoperoxyphthalate hexahydrate,
the magnesium salt of metachloro perbenzoic acid, 4-
nonylamino-4-oxoperoxybutyric acid and
diperoxydodecanedioic acid. Such bleaching agents are
disclosed in U.S. Patent 4,483,781, U.S. Patent 4,634551,
EP 0,133,354, U.S. Patent 4,412,934 and EP 0,170,386.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the
percarbonates, etc., are preferably combined with bleach
activators, which lead to the in situ production in aqueous
solution (i.e., during the washing process) of the peroxy acid
corresponding to the bleach activator. The amount of bleach
activators will typically be from 0.1 % to 60%, more typically
from 0.5 °~ to 40 °~ by weight of the detergent composition.
Various nonlimiting examples of activators are disclosed in
U.S. Patent 4,915,854 and U.S. Patent 4,412,934. The
nonanoyloxybenzene sulfonate (NOBS),
isononanoyloxybenzene sulfonate (IS~NOBS) and tetraacetyl
ethylene diamine (TAED) activators are typical, and mixtures
thereof can also be used.
Highly preferred amido-derived bleach activators are
those of the formulae:
R1 N(R5)C(O)R2C(O)L or R1 C(O)N(R5)R2C(O)L ,
wherein R1 is an alkyl group containing from 6 to 12 carbon
atoms, R2 is an alkylene containing from 1 to 6 carbon atoms, .
R5 is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon
atoms, and L is any suitable leaving group. A leaving group is
any group that is displaced from the bleach activator as a
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consequence of the nucleophilic attack on the bleach activator
by the perhydrolysis anion. A preferred leaving group is phenyl
sulfonate.
Preferred examples of bleach activators of the above
formulae include (6-octanamido-caproyl)oxybenzenesulfonate,
- (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-
caproyl)oxybenzenesulfonate, and mixtures thereof as
described in U.S. Patent 4,634,551.
Another class of bleach activators comprises the
benzoxazin-type activators disclosed in U.S. Patent
4,966,723. A highly preferred activator of the benzoxazin-
type is:
0
II
CEO
O C
N
Still another class of preferred bleach activators includes
the acyl lactam activators, especially acyl caprolactams and
acyl valerolactams of the formulae:
O
II
O C-C H2-C H2
R6-C-N~ \C H2
C H2-C H2
O
II
Rs-O N-C H2- ~ H2
~C H2-C H2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group
containing from 1 to 12 carbon atoms. Highly preferred
lactam activators include benzoyl caprolactam, octanoyl
caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl
caprolactam, decanoyl caprolactam, undecenoyl caprolactam,
benzoyl valerolactam, octanoyl valerolactam, decanoyl
valerolactam, undecenoyl valerolactam, nonanoyl
valerolactam, 3,5,5-trimethylhexanoyl valerolactam and
mixtures thereof. See also U.S. Patent 4,545,784 which
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WO 96/22352 PCT/US96I00522
16
discloses acyl caprolactams, including benzoyl caprolactam,
adsorbed into sodium perborate.
Another class of preferred bleach activators include the
cationic bleach activators, derived from the valerolactam and
acyl caprolactam compounds, of formula:
R"
R
\ N~ ~
II
CH~ ~ C - (CH2)x - C ~ 2
''
/ CH2
CH2 - CH2
wherein x is 0 or 1, substituents R, R' and R" are each C1-
C10 alkyl or C2-C4 hydroxy alkyl groups, or [(CyH2y)O]n-R'°'
wherein y = 2-4, n = 1-20 and R"' is a C 1-C4 alkyl group or
hydrogen and X is an anion.
Bleaching agents other than oxygen bleaching agents are also
known in the art and can be utilized herein. One type of non-
oxygen bleaching agent of particular interest includes
photoactivated bleaching agents such as the sulfonated zinc
and/or aluminum phthalocyanines. See U.S. Patent
4,033,718. If used, detergent compositions will typically
contain from 0.025 % to 1.25 %, by weight, of such bleaches,
especially sulfonate zinc phthalocyanine.
If desired, the bleaching compounds can be catalyzed by
means of a manganese compound. Such compounds are well
known in the art and include, for example, the manganese-
based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat.
5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,1 14,606; and
EP 549,271 A1, 549,272A1, 544,440A2, and 544,490A1;
Preferred examples of these catalysts include MnIV2(u-
O)3( 1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2,
Mnlll2(u-O) 1 (u-OAc)2( 1,4,7-trimethyl-1,4,7-triazacyclono-
nane)2_(C104)2, MnlV4(u-O)6( 1,4,7-
triazacyclononane)4(C104)4, MnllIMnlV4(u-O)1 (u-OAc)2_
( 1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)3, MnIV-
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WO 96/22352 PCT/US96/00522
17
( 1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH3)3(PF6), and
mixtures thereof. Other metal-based bleach catalysts include
those disclosed in U.S. Pat. 4,430,243 and U.S. Pat.
5,1 14,61 1. The use of manganese with various complex
ligands to enhance bleaching is also reported in the following
- United States Patents: 4,728,455; 5,284,944; 5,246,612;
5,256,779; 5,280,1 17; 5,274,147; 5,153,161; 5,227,084;
As a practical matter, and not by way of limitation, the
compositions and processes herein can be adjusted to provide
on the order of at least one part per ten million of the active
bleach catalyst species in the aqueous washing liquor, and will
preferably provide from 0.1 ppm to 700 ppm, more preferably
from 1 ppm to 500 ppm, of the catalyst species in the laundry
liquor.
~helatino ACIBnt~-TI'te dPtPrgent rnmnncitinne herein mw
r - -err- -~ r..vvmmw mv1Va11 111pr
also optionally contain one or more iron and/or manganese
chelating agents. Such chelating agents can be selected from
the group consisting of amino carboxylates, amino
phosphonates, polyfunctionally-substituted aromatic chelating
agents and mixtures therein, all as hereinafter defined.
Without intending to be bound by theory, it is believed that the
benefit of these materials is due in part to their exceptional
ability to remove iron and manganese ions from washing
solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents
include ethylenediaminetetracetates, N-
hydroxyethylethylenediaminetriacetates, nitrilotriacetates,
ethylenediamine tetraproprionates, triethylenetetraamine-
hexacetates, diethylenetriaminepentaacetates, and ethanoldi-
glycines, alkali metal, ammonium, and substituted ammonium
salts therein and mixtures therein.
Preferred biodegradable non-phosphorus chelants for use
. herein are ethylenediamine disuccinate ("EDDS"), especially
the [S,S] isomer as described in U.S. Patent 4,704,233,
ethylenediamine-N,N'-diglutamate (EDDG) and 2-
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WO 96/22352 PC~YLTS96100522
18
hydroxypropylene-diamine-N,N'-disuccinate tHPDDS)
compounds.
Amino phosphonates are also suitable for use as
chelating agents in the compositions of the invention when at
least low levels of total phosphorus are permitted in detergent
compositions, and include ethylenediaminetetrakis
(methylenephosphonates) available under the trademark
DEQUEST from Monsanto. Preferably, these amino
phosphonates do not contain alkyl or alkenyl groups with more
than 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents
are also useful in the compositions herein. See U.S. Patent
3,812,044. Preferred compounds of this type in acid form are
dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-
disulfobenzene.
If utilized, these chelating agents will generally comprise
from 0.1 °~ to 10% by weight of the detergent compositions
herein. More preferably, if utilized, the chelating agents will
comprise from 0.1 % to 3.0% by weight of such compositions.
n m - Enzymes can be included in the formulations herein
for a wide variety of fabric laundering purposes, including
removal of protein-based, carbohydrate-based, or triglyceride-
based stains, for example, for the prevention of fugitive dye
transfer, and for fabric restoration. The enzymes to be
incorporated include proteases, amylases, lipases, cellulases,
and peroxidases, as well as mixtures thereof. Other types of
enzymes may also be included. They may be of any suitable
origin, such as vegetable, animal, bacterial, fungal and yeast
origin. However, their choice is governed by several factors
such as pH-activity and/or stability optima, thermostability and
stability versus active detergents and builders. In this respect
bacterial or fungal enzymes are preferred, such as bacterial
amylases and proteases, and fungal cellulases.
Enzymes are normally incorporated at levels sufficient to
provide up to 5 mg by weight, more typically 0.01 mg to 3
mg, of active enzyme per gram of the composition. Stated
CA 02208701 2000-07-17
19
otherwise, the compositions herein will typically comprise
from 0.001 °~ to 596, preferably 0.0196-1 °r6 by weight of a
commercial enzyme preparation.
Suitable examples of proteases are the subtilisins which
are obtained from particular strains of B. subtilis and B.
licheniforms. Another suitable protease is obtained from a
strain of Bacillus, having maximum activity throughout the pH
range of 8-12, developed and sold by Novo Industries A/S
under the registered trade mark ESPERASE. The preparation
of this enzyme and analogous enzymes is described in GB
1,243,784 of Novo. Proteolytic enzymes suitable for
removing protein-based stains that are commercially available
include those sold under the trademarks ALCALASE and
SAVINASE by Novo Industries A/S f Denmark) and MAXATASE
by International Bio-Synthetics, Inc. (The Netherlands). Other
proteases include Protease A (see EP 130,756 ) and Protease
B (see EP 257,189).
Amylases include, for example, a-amylases described in
GB1,296,839 fNovo), RAPIDASE;""International Bio-Synthetics,
Inc. and TERMAMYL;MNovo Industries. 1=UNGAMYLM(Novo) is
especially useful.
The cellulase usable in the present invention include both
bacterial or fungal cellulase. Preferably, they will have a pH
optimum of between 5 and 9.5. Suitable cellulases are
disclosed in U.S. Patent 4,435,307, which discloses fungal
ceilulase produced from Humicola insolens and Humicola strain
DSM 1800 or a cellulase 212-producing fungus belonging to
the genus Aeromonas, and cellulase extracted from the
hepatopancreas of a marine mollusk (Dolabella Auricula
Solander). suitable cellulases are also disclosed in GB-A-
2.075.028; GB-M -2.095.275 and DE-OS-2.247.832. ENDO
A, CAREZYME both from Novo Industries A/S are especially
useful.
Suitable lipase enzymes for detergent usage include
those produced by microorganisms of the Pseudomonas group,
such as Pseudomonas stutzeri ATCC 19.154, as disclosed in
GB 1,372,034. See also lipases in Japanese Patent
CA 02208701 2000-07-17
20
Application 53,20487, laid open to public inspection on
February 24, 1978. This lipase is available from Amano
Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade mark
Upase P "Amano," hereinafter referred to as "Amano-P."
Other commercial fipases include Amano-CES, lipases ex
Chromobacter viscosum, e.g. Chromobacter viscosum var.
lipolyticum NRRLB 3673, commercially available from Toyo
Jozo Co., Tagata, Japan; and further Chromobacter viscosum
lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co.,
The Netherlands, and lipases ex Pseudomonas gladioli. The
LIPOLASETenzyrne derived from Humicola lanuginosa and
commercially available from Novo (see also EP 0,341,947 is a
preferred lipase for use herein.
Peroxidase enzymes are used in combination with
oxygen sources, e.g., percarbonate, perborate, persulfate,
hydrogen peroxide, etc. They are used for "solution
bleaching," i.e. to prevent transfer of dyes or pigments
removed from substrates during wash operations to other
substrates in the wash solution. Peroxidase enzymes are
known in the art, and include, for example, horseradish
peroxidase, ligninase, and haloperoxidase such as chloro- and
bromo-peroxidase. Peroxidase-containing detergent
compositions are disclosed, for example, in PCT International
Application WO 89/099813 assigned to Novo Industries AIS.
A wide range of enzyme materials and means for their
incorporation into synthetic detergent compositions are also
disclosed in U.S. Patent 3,553,139. Enzymes are further
disclosed in U.S. Patent 4,101,457 and in U.S. Patent
4,507,219. Enzyme materials useful for liquid detergent
formulations, and their incorporation into such formulations,
are disclosed in U.S. Patent 4,261,868. Enzymes for use in
detergents can be stabilized by various techniques. Enzyme
stabilization techniques are disclosed and exemplified in U.S.
Patent 3,600,319 and EP 0 199 405. Enzyme stabilization
systems are also described, for example, in U.S. Patent
3,519,570.
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WO 96/22352 PCTIUS96100522
21
enzyme Stabilizers - The enzymes employed herein are
stabilized by the presence of water-soluble sources of calcium
and/or magnesium ions in the finished compositions which
provide such ions to the enzymes. (Calcium ions are generally
somewhat more effective than magnesium ions and are
preferred herein if only one type of cation is being used.)
Additional stability can be provided by the presence of various
other art-disclosed stabilizers, especially borate species: see
Severson, U.S. 4,537,706. The level of calcium or
magnesium ions should be selected so that there is always
some minimum level available for the enzyme, after allowing
for complexation with builders, fatty acids, etc., in the
composition. Any water-soluble calcium or magnesium salt
can be used as the source of calcium or magnesium ions,
including, but not limited to, calcium chloride, calcium sulfate,
calcium malate, calcium maleate, calcium hydroxide, calcium
formate, and calcium acetate, and the corresponding
magnesium salts. A small amount of calcium ion, generally
from 0.05 to 0.4 millimoles per liter, is often also present in
the composition due to calcium in the enzyme slurry and
formula water. In solid detergent compositions the
formulation may include a sufficient quantity of a water-
soluble calcium ion source to provide such amounts in the
laundry liquor. In the alternative, natural water hardness may
suffice.
It is to be understood that the foregoing levels of calcium
and/or magnesium ions are sufficient to provide enzyme
stability. More calcium and/or magnesium ions can be added
to the compositions to provide an additional measure of grease
removal performance. Accordingly, as a general proposition
the compositions herein will typically comprise from 0.05 % to
2% by weight of a water-soluble source of calcium or
magnesium ions, or both. The amount can vary, of course,
with the amount and type of enzyme employed in the
composition.
The compositions herein may also optionally, but
preferably, contain various additional stabilizers, especially
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WO 96/22352 PCT/US96/00522
22
borate-type stabilizers. Typically, such stabilizers will be used
at levels in the compositions from 0.25 % to 10 %, preferably
from 0.5 % to 5 %, more preferably from 0.75 % to 3 %, by
weight of boric acid or other borate compound capable of
forming boric acid in the composition (calculated on the basis
of boric acid). Boric acid is preferred, although other
compounds such as boric oxide, borax and other alkali metal
borates (e.g., sodium ortho-, meta- and pyroborate, and '
sodium pentaborate) are suitable. Substituted boric acids -
(e.g., phenylboronic acid, butane boronic acid, and p-bromo
phenylboronic acid) can also be used in place of boric acid.
Other Ingredients
A wide variety of other functional ingredients commonly used
in detergent compositions can be included in the compositions
of the present invention. These include additional clay soil
removal/anti-redeposition agents, polymeric soil release
agents, dye transfer inhibiting agents, brighteners, suds
suppressors and fabric softeners. Suitable additional clay soil
removal/anti-redeposition agents may include acrylic/maleic
based copolymers, polyethylene glycol (PEG), water-soluble
ethoxylated amines and carboxy methyl cellulose (CMC).
Other ingredients useful in detergent compositions can be
included in the compositions herein, including other active
ingredients, carriers, hydrotropes, processing aids, dyes or
pigments, solvents for liquid formulations, solid fillers for bar
compositions, etc. If high sudsing is desired, suds boosters
such as the C10-C1 g alkanolamides can be incorporated into
the compositions, typically at 1 %-10% levels. The C10-C14
monoethanol and diethanol amides illustrate a typical class of
such suds boosters. Use of such suds boosters with high
sudsing adjunct surfactants such as the amine oxides,
betaines and sultaines noted above is also advantageous. If
desired, soluble magnesium salts such as MgCl2, MgSOq., and -
the like, can be added at levels of, typically, 0.1 °~-2%, to
provide additional suds and to enhance grease removal
performance.
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WO 96/22352 PCT/US96/00522
23
Various detersive ingredients employed in the present
compositions optionally can be further stabilized by absorbing
said ingredients onto a porous hydrophobic substrate, then
coating said substrate with a hydrophobic coating. Preferably,
the detersive ingredient is admixed with a surfactant before
being absorbed into the porous substrate. In use, the
detersive ingredient is released from the substrate into the
aqueous washing liquor, where it performs its intended
detersive function.
To illustrate this technique in more detail, a porous
hydrophobic silica (trademark SIPERNAT D10, DeGussa) is
admixed with a proteolytic enzyme solution containing 3%-5%
of C13-15 ethoxylated alcohol (EO 7) nonionic surfactant.
Typically, the enzyme/surfactant solution is 2.5 X the weight
of silica. The resulting powder is dispersed with stirring in
silicone oil (various silicone oil viscosities in the range of 500-
12,500 can be used). The resulting silicone oil dispersion is
emulsified or otherwise added to the final detergent matrix.
By this means, ingredients such as the aforementioned
photoactivators, dyes, fluorescers, fabric conditioners and
hydrolyzable surfactants can be "protected" for use in
detergents, including liquid laundry detergent compositions.
Liquid detergent compositions can contain water and
other solvents as carriers. Low molecular weight primary or
secondary alcohols exemplified by methanol, ethanol,
propanol, and isopropanol are suitable. Monohydric alcohols
are preferred for solubilizing surfactant, but polyols such as
those containing from 2 to 6 carbon atoms and from 2 to 6
hydroxy groups (e.g., 1,3-propanediol, ethylene glycol,
glycerine, and 1,2-propanediol) can also be used. The
compositions may contain from 5% to 90%, typically 10% to
50% of such carriers.
The detergent compositions herein will preferably be
. formulated such that, during use in aqueous cleaning
operations, the wash water will have a pH of between 6.5 and
11, preferably between 7.5 and 10.5. Liquid dishwashing
product formulations preferably have a pH between 6.8 and
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WO 96!22352 PCTJLTS96/00522
24
9Ø Laundry products are typically at pH 9-1 1 . Techniques
for controlling pH at recommended usage levels include the
use of buffers, alkalis, acids, etc., and are well known to those
skilled in the art.
The bulk density of granular detergent compositions is
typically at least 450 g/litre, more usually at least 600 gllitre
and more preferably from 650 g/litre to 1000 g/litre.
The invention is illustrated in the following non limiting
examples, in which all percentages are on a weight basis
unless otherwise stated.
In the detergent compositions, the abbreviated component
identifications have the following meanings:
LAS . Sodium linear C 12 alkyl benzene
sulphonate
TAS . Sodium tallow alkyl sulphate
XYAS . Sodium C1X - Cly alkyl sulphate
C24EY . A C 12-14 Predominantly linear primary
alcohol condensed with an average of Y
moles of ethylene oxide
C25EY . A C 12-15 Predominantly linear primary
alcohol condensed with an average of Y
moles of ethylene oxide
C45EY . A C 14 - C 15 Predominantly linear primary
alcohol condensed with an average of Y
moles of ethylene oxide
CXYEZS . C1X - C1Y sodium alkyl sulphate
r
condensed with an average of Z moles of
ethylene oxide per mole
polyhydroxy fatty. N-Lauroyl N-Methyl Glucamine
acid amide
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NaSKS-6 . Crystalline layered silicate of formula
8-Na2Si205
PAS . Polyaspartic acid of molecular weight in
the range of 500 to 200,000
Carbonate . Anhydrous sodium carbonate
Silicate . Amorphous sodium silicate (Si02:Na2O
ratio normally follows)
MA/AA . Copolymer of 1:4 maleic/acrylic acid,
average molecular weight about 70,000
Zeolite A . Hydrated Sodium Aluminosilicate of
formula Nal2[(A102)(Si02)]12~ 2~H20
- having a primary particle size in the range
from 1 to 10 micrometers
Photobleach . Tetra sulphonated zinc phthalocyanine
Citrate . Tri-sodium citrate dihydrate
Citric acid . Anhydrous Citric Acid
PB1 . Sodium perborate monohydrate bleach of
nominal formula NaB02.H202
PB4 . Sodium perborate tetrahydrate bleach of
nominal formula NaB02.H202.3H20
Percarbonate . Anhydrous sodium percarbonate bleach of
empirical formula 2Na2C03.3H202 coated
with a mixed salt of formula
Na2S04.n.Na2C03 where n is 0.29 and
where the weight ratio of percarbonate to
mixed salt is 39:1
TAED . Tetraacetyl ethylene diamine
Savinase . Proteolytic enzyme activity 4 KNPU/g
CA 02208701 2000-07-17
26
Alcalase . Proteolytic enzyme activity 3.3AU/g
Lipolase . Lipolytic enzyme activity 100 KLU/g
Cellulase . Cellulytic enzyme activity 1000 SCEYU/g
Endo A . Cellulytic enzyme activity 5000 SCEVU/g
all sold by NOVO Industries A/S
PVNO . Polyvinyl pyridine N-oxide polymer of
molecular weight 10,000
PVPVI . Polyvinyl (pyrrolidone-co-imidazole)
polymer of molecular weight in the range
of 100 to 1000000
MgS04 . Anhydrous Magnesium Sulphate
SRP . modified anionic polyester Soil Release
Polymer
CMC . Sodium carboxymethyl cellulose
EDDS . Ethylenediamine -N, N'- disuccinic
acid, 1S,SI isomer in the form of the
sodium salt.
Brightener . Disodium 4,4'-bis-(2-sulphostyryl)-
biphenyl.
DETPMP . Diethylenetriamine yenta (Methylene
phosphonic acid) marketed by
Monsanto under the Trade mark
bequest 2060.
Mixed Suds . 25% paraffin wax Mpt 50°C, 1796
suppressor hydrophobic silica, 5896 paraffin oil.
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WO 96/22352 PCT/US96/00522
27
Preparation of the polyamino acid-protein agglomerate
contained in a detergent composition
1 OOg of a polyaspartic acid solution (25 % active) was mixed
with 20g of albumin ( 100 % active) in a round bottom flask.
The resulting mixture was then stirred for a further 3 hours at
' a temperature between 35°C and 40°C at a paddle speed of
150 r.p.m, until a yellow/browned coloured paste formed. The
mixing was then stopped and the paste was left in an oven at
35°C for a further 24 hours. The resulting soliri wac rri ichprl
using a mortar and pestle into a fine powder (yellow/brown in
colour). The product was then sieved and materials that were
greater than 800 microns and smaller than 250 microns were
removed. The remaining material was used in the testing.
4.8 % by weight of said polyaspartic acid/albumin agglomerate
was taken and incorporated in a nil dispersant detergent matrix
(100g). The nil dispersant detergent matrix had the following
composition in % by weight:
45AS 6.84
C25E3S 1.71
C24E5 3.37
olyh droxy fatty acid amide 1.45
Zeolite A 10.19
Citric 2.45
SKS-6 9.0
Carbonate 5.38
CMC 0.30
SRP 0.20
PVNO 0.02
Savinase 0.69
Lipolase 0.18
Cellulase 0.20
Endo A 0.25
Termam I 0.6
TAED 3.75
DETPMP 0.6
M S04 0.6
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WO 96/22352 PCTlUS96/00522
28
Percarbonate 16.9
Bri htener 0.22
Photoactivated bleach 0.002
Suds su ressor 2.75
Perfume 0.35
Water minors and miscellaneous
to
balance
Storage stability results of the polyaspartic acid-albumin
agglomerate contained in a detergent composition vs a pure
polyaspartate granule contained in a detergent composition
after a 4 week storage period under stressed conditions (90°F
(32.2°C) and 80% relative humidity).
A comparative composition was prepared containing 4°!° by
weight of the polyaspartic acid granule and incorporated in
100g of the herein before described nil dispersant detergent
matrix.
The storage stability analysis was carried out on the stored
product, after a 4 week storage period under stressed
conditions (90°F (32.2°C) and 80% relative humidity), using
HPLC. The results are as follows:
polyaspartic acid/albumin polyaspartic acid granule
a lomerate
80~ 50%
It can be seen that the polyaspartic acid/albumin agglomerate
contained in the detergent composition shows enhanced
storage stability over the polyaspartic acid granule contained in
the same detergent composition.
Example 2
The following detergent compositions were prepared (parts by
weight). Compositions A, B, C, D, E are in accordance with
the present invention, wherein the polyaspartic acid/albumin
CA 02208701 1997-06-25
WO 96/22352 PCTlUS96100522
29
agglomerate is as defined in Example 1 and composition F ~is a
comparative composition wherein the polyaspartic
acid/albumin agglomerate is replaced with a malefic acid/acrylic
acid copolymer supplied by BASF.
' A B C D E F
~S - - 6.54 6.92 6.9 -
2
TAS - - 2.94 2.05 2.0 -
5
45AS 6.84 6.86 - - - 6.84
C25E3S 1.71 1.71 0.16 0.16 0.1 1.71
6
C45E7 - - 4.0 4.0 5.0 -
C24E5 3.37 - _ - - 3.37
C25E5 - 2.21 - - - -
A B C D E F
C25E3 - 1.16 - - 3.0 -
polyhydroxy fatty 1.45 1.45 - - - 1.45
acid amide
Zeolite A 10.1 10.2 1 R 20.2 26. 10.1
.0 0 9
Citrate - - - 5.5 10. -
4
Citric 2.45 2.3 2.35 - - 2.45
SKS-6 9.0 8.5 8.64 - - 9.0
PAS-albumin 4.8 4.8 4.8 4.8 4.8 -
a lomerate
Carbonate 5.38 9.8 16.0 15.4 11. 5.38
9
Silicate (2.0 - - 0.56 3.0 2.0
ratio)
Bicarbonate - - 4.6 - 6.0 -
Sul hate - 8.0 - - 4.8 -
MA/AA - 3.0 - - 4.6 4.0
CMC 0.30 0.30 0.30 0.30 0.3 0.30
0
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WO 96122352 PCT/US96/00522
SRP 0.20 0.15 0.20 0.30 0.3 0.20
0
PVPVI - - - 0.01 0.0 -
4
PVNO 0.02 - - 0.01 0.0 0.02
4
Savinase 0.69 0.25 0.37 1.4 - 0.69
Alcalase - - - - 0.5 -
5
Lipolase 0.18 0.07 0.22 0.36 0.2 0.18
5
Cellulase 0.20 - - - 0.1 0.20
3
Endo A 0.25 0.12 0.13 0.13 - 0.25
Termam I 0.6 - - - - 0.6
PB4 - - - ~ 11.6 - -
4
PB 1 - _ _ 8 .7 - _
TAED 3.75 1.6 - 5.0 - 3.75
DETPMP 0.6 - 4.8 0.38 0.6 0.6
M S04 0.6 0.38 0.4 0.40 - 0.6
Percarbonate 16.9 10.0 17.5 - - 16.9
EDDS - 0.21 0.21 - - -
Bri htener 0.22 0.18 0.19 0.19 - 0.22
Photoactivated 0.00 0.00 0.00 0.00 - 0.00
bleach 2 2 2 2 2
Suds su ressor 2.75 2.75 0.85 0.85 1.0 2.75
Perfume 0.35 0.4 0.35 0.43 0.3 0.35
5
Water minors and miscellaneous to balance
Compositions A to E were all seen to have a good polyaspartic
acid storage stability.
Test protocol - stain removal
Four white cotton sheets were prewashed in a nil polymer
detergent matrix of density ca 700 mg/litre. 10 stains were
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WO 96/22352 PCTlUS96100522
31
then applied to one sheet, 1 D stains to the second sheet, 10
stains to the third one and 10 to the fourth one. Sets of eight
test swatches of size 1 Ocm x 1 Ocm squared were cut from
each sheet.
The sets of fabric swatches were subjected to one wash cycle
in an automatic washing machine(Miele type short wash
cycle). The swatches were then assessed for removal of the
particulate, greasy, enzymatic and bleachable stains using a
well-established lightness measurement method.
In more detail, a Miele 756 WM automatic washing machine
was employed, and the 90oC short cycle programme selected.
Water of 25o German hardness ( = 3.75 mol Ca2 + /litre) was
used. 100g of detergent, dispensed from a granulette
dispensing device was employed. One swatch of each fabric
type was washed along with a ballast load of 2.6Kg of lightly
soiled sheets.
Stain removal was assessed by making LAB (lightness)
measurements using the X-rite (tradename) colour eye
spectrophotometer. An unstained cotton sheet was used as
the reference. A stain removal index, DR, was calculated as
follows:
OR - f(Lwashed - Lunwashed)/(Lunwashed - Lreference)1 x
100
where differences of 0R below 4% are not significant.
comparative testinq~ - stain removal
The above test protocol was followed in comparing the
efficiency of Compositions A and F in removing different type
of dispersant sensitive stains.
The results obtained were as follows:
CA 02208701 1997-06-25
WO 96/22352 PCT/U596/00522
32
Average OR t%) A F
Avera a particulate 57 61 '
Avera a reasy 63 57
Avera a enz matic 43 45
Avera a bleachable 55 50 a
All results are non significant differences
The stain removal obtained for each of Compositions A and F
is shown to be comparable. Thus the presence of albumin as
co-agglomerating agent of the polyaspartic acid, in
Composition A does not significantly compromise the stain
removal capacity of that Composition versus that of
Composition F.
