Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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DETERGENT COMPOSITIONS COMPRISING ALKALINE
POLYGALACTURONASE
FIELD OF THE INVENTION
This invention relates to detergent compositions,
including household cleaning, dishwashing and laundry
compositions, comprising an alkaline polygalacturanase
enzyme substantially free of other pectic enzymes.
BACKGROUND OF THE INVENTION
The overall performance of a detergent product, for
use in washing or cleaning method, such as a laundry or
dishwashing method, is judged by a number of factors,
including the ability to remove soils, and the ability to
prevent the redeposition of the soils, or the breakdown
products of the soils on the articles in the wash.
Removal of stains stemming from plants, wood, mould-
clay based soil and fruits is one of today~s toughest
cleaning task; in particular with the trends to move to low
wash temperatures. These stains typically contain complex
mixtures of fibrous material based mainly on carbohydrates
and their derivatives : fibres and cell wall components.
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Plant based soils are additionally accompanied with
amylose, sugars and their derivatives.
Food soils are often difficult to remove effectively
from a soiled substrate. Highly coloured or 'dried-on'
soils derived from fruit and/or vegetable juices are
particularly challenging soils to remove. Specific examples
of such soils would include orange juice, tomato juice,
banana, mango or broccoli soils. The substrates can be
fabrics, dishware or hard surfaces.
Pectic substances are found in, for example, fruit
juices. The pectic substances act to hold dispersed
particulates in suspension in such fruit juices, which will
tend to be viscous and opaque in nature. Pectic enzymes are
commonly used in the fruit/vegetable juice processing
industry in the clarification of juices by breakdown of the
pectic substances therein (depectinization).
German Patent Specification 3,635,427, published April
23, 1985 by Lion Corporation, is directed to phosphate-free
detergents for cleaning clothes containing enzymes with
pectinase activity, which is said to include such enzymes
as polygalacturonase, pectin lyase, and/or pectinesterase.
However, aside from the general teachings therein relating
to mixtures of these pectinase enzymes for the removal of
inorganic soiling from clothes, the only specific teaching
regarding an individual pectinase enzyme is found in
Example 3, where the enzyme (designated "Enzyme D") is
characterized as containing a large quantity of pectin
lyase. Table III provides the results of the evaluation of
this Enzyme D in a detergent formulation, indicating that
this high pectin lyase mixture has the highest ~ pectinase
activity (lO~) and one of the higher detergency values
(83~) in combination with water-soluble high molecular
compounds by comparison to the other enzyme compositions
reported.
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Benefits for the specific use of polygalacturanase
enzymes which is substantially free from other pectic
enzymes in detergent formulations, particularly those
designed for use in laundry, dishwashing and household
cleaning operations have been recognized in the copending
US patent application US08/529816.
It is an object of the present invention to provide
laundry, dishwashing or household detergent compositions
which provide improved soil / stain removal benefits when
used in washing and cleaning operations.
According to the present invention, it has now been
surprisingly found that the polygalacturonase enzyme having
at least 10%, preferably 25~, more preferably 40~ of its
optimum activity, at a pH ranging from 7 to ll and in
particular with an optimum activity at a pH ranging from 7-
ll improves significally the removal of a broad range of
plant and fruit based stains and enhances the realistic
item cleaning profile of the detergent compositions.
Indeed, the inclusion of alkaline polygalacturonase
enzyme provides in particular improved removal of dried-on
fruit and vegetables juice soils/stains.
In addition, it has been found that the alkaline
polygalacturonase enzyme substantially free of other pectic
enzymes presents improved compatibility and enhanced
activity in the wash solution thereby providing improved
removal of body, dried-on fruit and vegetables juice
soils/stains, especially when stemming from heavy duty
laundry or dishwashing compositions. It has also been found
that the alkaline polygalacturonase enzyme substantially
free of other pectic enzymes demonstrates a better
compatibility with detergent matrix, e.g. during product
process and shelf life.
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Furthermore, it has also been surprisingly been found
that the inclusion of dispersants, particularly organic
polymer dispersants, is of great value in detergent
compositions containing alkaline polygalacturonase enzymes.
The dispersants aid dispersion of the breakdown products of
the enzymatic soil degradation, thus preventing their
redeposition on articles on the wash.
Improved cleaning performance has been also observed
when the alkaline polygalacturonase enzymes are combined
with other detergent enzymes. Enzymatic bleaching system or
conventional activated bleach system together with alkaline
polygalacturonase enzymes provides enhanced performance
benefits on a wider range of stains.
Furthermore, polymers providing dye transfer
inhibition combined with alkaline polygalacturonase enzymes
results in improved whiteness maintenance and /or soil
release properties.
SUMMARY OF THE INVENTION
The present invention relates to detergent
compositions, including dishwashing, hard surface cleaning
and laundry compositions comprising an alkaline
polygalacturonase enzyme substantially free of other pectic
enzymes for improved overall cleaning performance and
enhanced stain / soil removal benefits and in particular
improved removal of plant, dried-on fruit and vegetables
juice soils/stains.
DETAILED DESCRIPTION OF THE INVENTION
Alakaline Polygalacturanase enzymes
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An essential component of the detergent compositions
of the invention is an alkaline polygalacturanase enzyme.
The term "alkaline" is intended to cover polygalacturonase
enzyme having an enzymatic activity of at least 10~,
preferably 25~, more preferably 40~ of its optimum
activity, at a pH ranging from 7 to 11 and to cover
polygalacturonase enzyme having an optimum activity at a pH
ranging from 7 to 11. The enzymatic activity can be
measured according to the "Assay of APGase" described by K.
Horikoshi in Agr. Biol. Chem, Vol 36(2), 286.
As used herein, "substantially free of other pectic
enzymes" means polygalacturanase enzyme-containing
compositions which contain less than 50% of pectic enzymes
which are not alkaline polygalacturanase enzymes,
preferably less than about 25~, more preferably less than
about 10~, and most preferably less than about 5~. Such
pectic enzymes include, for example, the pectin
methylesterases which hydrolyse the pectin methyl ester
linkages, and the pectin transeliminases or lyases which
act on the pectic acids to bring about non-hydrolytic
cleavage of alpha-1-4 glycosidic linkages to form
unsaturated derivatives of galacturonic acid.
The alkaline polygalacturanase enzyme is preferably
incorporated into the compositions in accordance with the
invention at a level of from 0.0001~ to 2%, preferably from
0.0005~ to 0.5~, more preferably from 0.001~ to 0.1~ pure
enzyme by weight of the total composition.
By alkaline polygalacturanase enzyme it is meant
herein any enzyme which acts to break down pectic
substances by cleaving the glycosidic bonds between
galacturonic acid molecules. Pectic substances may be
found in plant tissues, and are common constituents of
fruit juices such as orange, tomato and grape juices.
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Pectic substances contain galacturonic acids and/or their
derivatives.
Pectic substances include pectins and pectic acids.
Pectins are, in general, polymers made up of chains of
galacturonic acids joined by alpha-1-4 glycosidic linkages.
Typically, in natural pectins approximately two-thirds of
the carboxylic acid groups are esterified with methanol.
Partial hydrolysis of these methyl esters gives low
methoxyl pectins, which tend to form gels with calcium
ions. Complete methyl ester hydrolysis gives pectic acids.
Alkaline polygalacturanase enzymes herein include
naturally derived alkaline polygalacturanase enzymes and
any variants obtained by, for example, genetic engineering
techniques.
Alkaline polygalacturonase enzymes are produced by
alkalophilic microorganisms e.g. bacterial, fungal and
yeast microorganisms such as Bacillus species. Preferred
microorganisms are Bacillus firmus, bacillus circulans and
bacillus subtilis as described in JP 56131376 and JP
56068393. Said enzymes can also be produced by the Erwinia
species. Preferred are E. chrysanthemi, E. carotovora, E.
amylovora, E. herbicola, E. dissolvens as described in JP
59066588, JP 63042988 and in World J. Microbiol.
Microbiotechnol. ~8, 2, 115-120) 1992. Said alkaline
degrading pectin enzymes can also be produced by Bacillus
species as disclosed in JP 73006557 and Agr. Biol. Chem.
(1972), 36(2) 285-93.
Pectin degrading enzymes are produced by alkalophilic
microorganisms e.g. bacterial, fungal and yeast
microorganisms such as Bacillus species. Preferred
microorganisms are Bacillus firmus, Bacillus circulans and
Bacillus subtilis as described in JP 56131376 and JP
56068393. Pectin decomposing enzymes include galacturan-
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1/4-~-galacturonase (EC 3.2.1.67), poly-galacturonase
activities (EC3.2.1.15, pectin esterase (EC 3.1.1.11),
pectate lyase (EC 4.2.2.2) and their iso enzymes and they
can be produced by the Erwinia species. Preferred are E.
chrysanthemi, E. carotovora, E. amylovora, E. herbicola, E.
dissolvens as described in JP 59066588, JP 63042988 and in
World J. Microbiol. Microbiotechnol. (8, 2, 115-120) 1992.
Said pectin enzymes can also be produced by Bacillus
species as disclosed in JP 73006557 and Agr. Biol. Chem.
(1972), 36(2) 285-93. Such enzymes may be used following
purification to isolate polygalacturanase enzymes
substantially free of other pectic enzyme. Preferred are
pectic enzyme compositions consisting essentially of
polygalacturanase enzymes.
Nowadays, it is common practice to modify wild-type
enzymes via protein / genetic engineering techniques in
order to optimise their performance efficiency in the
cleaning compositions of the invention. For example, the
variants may be designed such that the compatibility of the
enzyme to commonly encountered ingredients of such
compositions is increased. Alternatively, the variant may
be designed such that the optimal pH, bleach stability,
catalytic activity and the like, of the enzyme variant is
tailored to suit the particular cleaning application.
In particular, attention should be focused on amino acids
sensitive to oxidation in the case of bleach stability and
on surface charges for the surfactant compatibility. The
isoelectric point of such enzymes may be modified by the
substitution of some charged amino acids, e.g. an increase
in isoelectric point may help to improve compatibility with
anionic surfactants. The stability of the enzymes may be
further enhanced by the creation of e.g. additional salt
bridges and enforcing calcium binding sites to increase
chelant stability.
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Dispersants
It has also been surprisingly been found that the
inclusion of dispersants, particularly organic polymer
dispersants, is of great value in detergent compositions
containing alkaline polygalacturonase enzymes. The
dispersants aid dispersion of the breakdown products of the
enzymatic soil degradation, thus preventing their
redeposition on articles on the wash.
Suitable water-soluble organic salts are the homo- or
co-polymeric acids or their salts, in which the
polycarboxylic acid comprises at least two carboxyl
radicals separated from each other by not more than two
carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756.
Examples of such salts are polyacrylates of MW 2000-5000
and their copolymers with maleic anhydride, such copolymers
having a molecular weight of from 1,000 to 100,000.
Especially, copolymer of acrylate and methylacrylate
such as the 480N having a molecular weight of 4000, at a
level from 0.5-20~ by weight of composition can be added in
the cleaning compositions of the present invention.
The compositions of the invention may contain a lime
soap peptiser compound, which has a lime soap dispersing
power (LSDP), as defined hereinafter of no more than 8,
preferably no more than 7, most preferably no more than 6.
The lime soap peptiser compound is preferably present at a
level from 0~ to 20~ by weight.
A numerical measure of the effectiveness of a lime soap
peptiser is given by the lime soap dispersant power (LSDP)
which is determined using the lime soap dispersant test as
described in an article by H.C. Borghetty and C.A. Bergman,
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J. Am. Oil. Chem. Soc., volume 27, pages 88-90, (1950).
This lime soap dispersion test method is widely used by
practitioners in this art field being referred to, for
example, in the following review articles; W.N. Linfield,
Surfactant science Series, Volume 7, page 3; W.N. Linfield,
Tenside surf. det., volume 27, pages 159-163, (1990); and
M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries,
volume 104, pages 71-73, (1989). The LSDP is the ~ weight
ratio of dispersing agent to sodium oleate required to
disperse the lime soap deposits formed by 0.025g of sodium
oleate in 30ml of water of 333ppm CaCo3 (Ca:Mg=3:2)
equivalent hardness.
Surfactants having good lime soap peptiser capability
will include certain amine oxides, betaines, sulfobetaines,
alkyl ethoxysulfates and ethoxylated alcohols.
Exemplary surfactants having a LSDP of no more than 8
for use in accord with the present invention include C16-
C1g dimethyl amine oxide, C12~Clg alkyl ethoxysulfates with
an average degree of ethoxylation of from 1-5, particularly
C12-Cls alkyl ethoxysulfate surfactant with a degree of
ethoxylation of amount 3 (LSDP=4), and the C14-C15
ethoxylated alcohols with an average degree of ethoxylation
of either 12 (LSDP=6) or 30, sold under the tradenames
Lutensol A012 and Lutensol A030 respectively, by BASF GmbH.
Polymeric lime soap peptisers suitable for use herein
are described in the article by M.K. Nagarajan, W.F.
Masler, to be found in Cosmetics and Toiletries, volume
104, pages 71-73, (1989).
Hydrophobic bleaches such as 4-[N-octanoyl-6-
aminohexanoyl]benzene sulfonate, 4-[N-nonanoyl-6-
aminohexanoyl]benzene sulfonate, 4-[N-decanoyl-6-
aminohexanoyl]benzene sulfonate and mixtures thereof; and
nonanoyloxy benzene sulfonate together with hydrophilic /
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hydrophobic bleach formulations can also be used as lime
soap peptisers compounds.
Detergent enzymes
Improved removal of a broad range of plant and fruit
based stains is achieved with a combination of alkaline
polygalacturonase enzymes with other detergent enzyme.
Synergistic effects are observed from detergent
compositions comprising an alkaline polygalacturonase
enzyme and a cellulase, xylanase and/or protease.
The cellulases 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, Barbesgoard et al,
which discloses fungal cellulase produced from Humicola
insolens. Suitable cellulases are also disclosed in GB-A-
2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by
a strain of Humicola insolens (Humicola grisea var.
thermoidea), particularly the Humicola strain DSM 1800.
Other suitable cellulases are cellulases originated from
Humicola insolens having a molecular weight of about 50KDa,
an isoelectric point of 5.5 and containing 415 amino acids.
Especially suitable cellulases are the cellulases having
color care benefits. Examples of such cellulases are
cellulases described in European patent application No.
91202879.2, filed November 6, 1991 (Novo). Carezyme and
Celluzyme (Novo Nordisk A/S) are especially useful. See
also WO91/17243.
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Suitable xylanases include the commercail available
xylanases like Pulpzyme HB and SP431 (Novo Nordisk),
Lyxasan (Gist-Brocades), Optipulp and Xylanase (Solvay).
Suitable proteases are the subtilisins which are
obtained from particular strains of B. subtilis and B.
licheniformis (subtilisin BPN and BPN'). One suitable
protease is obtained from a strain of Bacillus, having
maximum activity throughout the pH range of 8-12, developed
and sold as ESPERASE by Novo Industries A/S of Denmark,
hereinafter "Novo". The preparation of this enzyme and
analogous enzymes is described in GB 1,243,784 to Novo.
Other suitable proteases include ALCALASE~, DURAZYM~ and
SAVINASE~ from Novo and MAXATASE , MAXACAL~, PROPERASE~
and MAXAPEM~ (protein engineered Maxacal) from
International Bio-Synthetics, Inc., The Netherlands; as
well as Protease A as disclosed in EP 130,756 A, January 9,
1985 and Protease B as disclosed in EP 303,761 A, April 28,
1987 and EP 130,756 A, January 9, 1985. See also a high pH
protease from Bacillus sp. NCIMB 40338 described in WO
93/18140 A to Novo. Enzymatic detergents comprising
protease, one or more other enzymes, and a reversible
protease inhibitor are described in WO 92/03529 A to Novo.
Other preferred proteases include those of WO 95/10591 A to
Procter & Gamble. When desired, a protease having decreased
adsorption and increased hydrolysis is available as
described in WO 95/07791 to Procter & ~amble. A
recombinant trypsin-like protease for detergents suitable
herein is described in WO 94/25583 to Novo.
In more detail, protease referred to as "Protease D" is
a carbonyl hydrolase variant having an amino acid sequence
not found in nature, which is derived from a precursor
carbonyl hydrolase by substituting a different amino acid
for a plurality of amino acid residues at a position in
said carbonyl hydrolase equivalent to position +76,
preferably also in combination with one or more amino acid
residue positions equivalent to those selected from the
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group consisting of +99, +101, +103, +104, +107, +123, +27,
+105, +109, +126, +128, +135, +156, +166, +195, +197, +204,
+206, +210, +216, +217, +218, +222, +260, +265, and/or +274
according to the numbering of Bacillus amyloliquefaciens
subtilisin, as described in W095/10591 and in the patent
application of C. Ghosh, et al, "Bleaching Compositions
Comprising Protease Enzymes" having US Serial No.
08/322,677, filed October 13, 1994. Also suitable for the
present invention are proteases described in patent
applications EP 251 446 and WO91/06637 and the protease
BLAP2 described in WO91/02792.
Improved plant and fruit stains / soils removal is
observed with detergent compositions of the present
invention further comprising starch-, sugar- and their
derivatives-degrading enzymes such as amylase, gluco
amylase, dextranase, pullulanase, invertase, laccase
insulinase.
Suitable amylases (a and/or ~) to be included in the
- detergent compositions of the present invention are
W094~02597, Novo Nordisk A/S published February 03, 1994,
describes cleaning compositions which incorporate mutant
amylases. See also W094/18314, Genencor, published August
18, 1994; WO95/10603, Novo Nordisk A/S, published April 20,
1995 and W096/05295, genencor, published February 22, 1996.
Other amylases known for use in cleaning compositions
include both a- and ~-amylases. a-Amylases are known in
the art and include those disclosed in US Pat. no.
5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP
285,123; EP 525,610; EP 368,341; and British Patent
specification no. 1,296,839 (Novo). Other suitable amylase
are stability-enhanced amylases including Purafact Ox AmR
described in WO 94/18314, published August 18, 1994 and
amylase variants having additional modification in the
immediate parent available from Novo Nordisk A/S, disclosed
in WO 95/10603, published April 95. Examples of
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commercial a-amylases products are Termamyl~, Ban~
,Fungamyl~ and Duramyl , all available from Novo Nordisk
A/S Denmark. W095/26397 describes other suitable amylases :
a-amylases characterised by having a specific activity at
least 25~ higher than the specific activity of Termamyl~ at
a temperature range of 25~C to 55~C and at a pH value in
the range of 8 to 10, measured by the Phadebas~ a-amylase
activity assay. Other amylolytic enzymes with improved
properties with respect to the activity level and the
combination of thermostability and a higher activity level
are described in W095/35382.
Other carbohydrases combined with alkaline
polygalacturonase enzymes show synergistic performance
benefits, such as ~-glucanase (lichenase, laminarase) and
exo-glucanase (lignase, tannase, pentosanase, malanase and
hemi-cellulase)
Finally, combinations of enzymes hydrolysing fat and
waxes such as lipases, cutinases and wax esterases and
alkaline polygalacturonase enzymes provide synergistic
improved plant and fruit stains / soils removal
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
- British Patent 1,372,034. Suitable lipases include those
which show a positive immunological cross-reaction with the
antibody of the lipase, produced by the microorganism
Pseudomonas fluorescent IAM 1057. This lipase is available
from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under
the trade name Lipase P "Amano," hereinafter referred to as
"Amano-P". Other suitable commercial lipases include Amano-
CES, lipases ex Chromobacter viscosum, e.g. Chromobacter
viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co.,
Tagata, Japan; Chromobacter viscosum lipases from U.S.
Biochemical Corp., U.S.A. and Disoynth Co., The
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Netherlands, and lipases ex Pseudomonas gladioli.
Especially suitable lipases are lipases such as M1 LipaseR
and LipomaxR (Gist-Brocades) and LipolaseR and Lipolase
UltraR(Novo) which have found to be very effective when
used in combination with the compositions of the present
invention.
Also suitable are cutinases [EC 3.1.1.50] which can be
considered as a special kind of lipase, namely lipases
which do not require interfacial activation. Addition of
cutinases to detergent compositions have been described in
e.g. WO-A-88/09367 (Genencor).
The lipases and/or cutinases are normally incorporated in
the detergent composition at levels from 0.0001~ to 2~ of
active enzyme by weight of the detergent composition.
The above-mentioned enzymes may be of any suitable
origin, such as vegetable, animal, bacterial, fungal and
yeast origin. Said enzymes are normally incorporated in the
detergent composition at levels from 0.0001~ to 2~ of
active enzyme by weight of the detergent composition. The
enzymes can be added as separate single ingredients
(prills, granulates, stabilized liquids, etc... containing
one enzyme ) or as mixtures of two or more enzymes ( e.g.
cogranulates ).
Other suitable detergent ingredients that can be added
are enzyme oxidation scavengers which are described in
Copending European Patent application 92870018.6 filed on
January 31, 1992. Examples of such enzyme oxidation
scavengers are ethoxylated tetraethylene polyamines.
A range of enzyme materials and means for their
incorporation into synthetic detergent compositions is also
disclosed in WO 9307263 A and WO 9307260 A to Genencor
International, WO 8908694 A to Novo, and U.S. 3,553,139,
January 5, 1971 to McCarty et al. Enzymes are further
disclosed in U.S. 4,101,457, Place et al, July 18, 1978,
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and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme
materials useful for liquid detergent formulations, and
their incorporation into such formulations, are disclosed
in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for
use in detergents can be stabilised by various techniques.
Enzyme stabilisation techniques are disclosed and
exemplified in U.S. 3,600,319, August 17, 1971, Gedge et
al, EP 199,405 and EP 200,586, October 29, 1986, Venegas.
Enzyme stabilisation systems are also described, for
example, in U.S. 3,519,570. A useful Bacillus, sp. AC13
giving proteases, xylanases and cellulases, is described in
WO 9401532 A to Novo.
Bleaching agent
It has been found that a wider range of plant and/or
fruit based stains / soils removal is achieved with
detergent compositions comprising an enzymatic bleaching
system or conventional activated bleach system in addition
to the alkaline polygalacturonase enzyme.
Bleaching agents such as Hydrogen peroxide, PB1, PB4
and percarbonate with a particle size of 400-800 microns.
These bleaching agent components can include one or more
oxygen bleaching agents and, depending upon the bleaching
agent chosen, one or more bleach activators. When present
oxygen bleaching compounds will typically be present at
levels of from about 1~ to about 25~.
The bleaching agent component for use herein can be
any of the bleaching agents useful for cleaning
compositions including oxygen bleaches as well as others
known in the art. The bleaching agent suitable for the
present invention can be an activated or non-activated
bleaching agent.
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One category of oxygen bleaching agent that can be used
encompasses percarboxylic acid bleaching agents and salts
thereof. Suitable examples of this class of agents include
magnesium monoperoxyphthalate hexahydrate, the magnesium
salt of meta-chloro 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 Application 740,446, European Patent
Application 0,133,354 and U.S. Patent 4,412,934. Highly
preferred bleaching agents also include 6-nonylamino-6-
oxoperoxycaproic acid as described in U.S. Patent
4,634,551.
Another category of bleaching agents that can be used
encompasses the halogen bleaching agents. Examples of
hypohalite bleaching agents, for example, include trichloro
isocyanuric acid and the sodium and potassium
dichloroisocyanurates and N-chloro and N-bromo alkane
sulphonamides. Such materials are normally added at 0.5-10~
by weight of the finished product, preferably 1-5~ by
weight.
The hydrogen peroxide releasing agents can be used in
combination with bleach activators such as
tetraacetylethylenediamine (TAED), nonanoyloxybenzene-
sulfonate (NOBS, described in US 4,412,934), 3,5,-
trimethylhexanoloxybenzenesulfonate (ISONOBS, described in
EP 120,591) or pentaacetylglucose (PAG)or Phenolsulfonate
ester of N-nonanoyl-6-aminocaproic acid (NACA-OBS,
described in WO94/28106), which are perhydrolyzed to form a
peracid as the active blèaching species, leading to
improved bleaching effect. Also suitable activators are
acylated citrate esters such as disclosed in Copending
European Patent Application No. 91870207.7.
Useful bleaching agents, including peroxyacids and
bleaching systems comprising bleach activators and
peroxygen bleaching compounds for use in detergent
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compositions according to the invention are described in
our co-pending applications USSN 08/136,626,
PCT/US95/07823, W095/27772, W095/27773, W095/27774 and
W095/27775.
The hydrogen peroxide may also be present by adding an
enzymatic system (i.e. an enzyme and a substrate therefore)
which is capable of generating hydrogen peroxide at the
beginning or during the washing and/or rinsing process.
Such enzymatic systems are disclosed in EP Patent
Application 91202655.6 filed October 9, 1991.
Peroxidase enzymes are used in combination with oxygen
sources, e.g. percarbonate, perborate, persulfate, hydrogen
peroxide, etc. They are used for "stain and 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, WO89/09813 and in
European Patent application EP No. 91202882.6, filed on
November 6, 1991 and EP No. 96870013.8, filed February 20,
1996. Also suitable is the laccase enzyme.
Preferred enhancers are substitued phenothiazine and
phenoxasine 10-Phenothiazinepropionicacid (PPT), 10-
ethylphenothiazine-4-carboxylic acid (EPC), 10-
phenoxazinepropionic acid (POP) and 10-methylphenoxazine
(described in WO 94/12621) and substitued syringates (C3-C5
substitued alkyl syringates) and phenols. Sodium
percarbonate or perborate are preferred sources of hydrogen
peroxide.
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Said peroxidases are normally incorporated in the
detergent composition at levels from 0.0001g6 to 2~ of
active enzyme by weight of the detergent composition.
Metal-containing catalysts for use in bleach
compositions, include cobalt-containing catalysts such as
Pentaamine acetate cobalt(III) salts and manganese-
containing catalysts such as those described in EPA 549
271; EPA 549 272; EPA 458 397; US 5,246,621; EPA 458 398;
US 5,194,416 and US 5,114,611. Bleaching composition
comprising a peroxy compound, a manganese-containing bleach
catalyst and a chelating agent is described in the patent
application No 94870206.3.
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. These
materials can be deposited upon the substrate during the
washing process. Upon irradiation with light, in the
presence of oxygen, such as by hanging clothes out to dry
in the daylight, the sulfonated zinc phthalocyanine is
activated and, consequently, the substrate is bleached.
Preferred zinc phthalocyanine and a photoactivated
bleaching process are described in U.S. Patent 4,033, 718.
Typically, detergent compositions will contain about 0. 025~
to about 1.25~, by weight, of sulfonated zinc
phthalocyanine.
Dye transfer inhibition
Enhanced whiteness maintenance and/or soil release
properties have been observed when the detergent
compositions of the present invention include compounds for
inhibiting dye transfer from one fabric to another of
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W O 98/06809 19 PCTrUS96/12963
solubilized and suspended dyes encountered during fabric
laundering operations involving colored fabrics.
Polymeric dye transfer inhibiting agents
The detergent compositions according to the present
.
invention also comprise from 0.001~ to 10 ~, preferably
from 0.01~ to 2~, more preferably from 0.05~ to 1~ by
weight of polymeric dye transfer inhibiting agents. Said
polymeric dye transfer inhibiting agents are normally
incorporated into cleaning compositions in order to inhibit
the transfer of dyes from colored fabrics onto fabrics
washed therewith. These polymers have the ability to
complex or adsorb the fugitive dyes washed out of dyed
fabrics before the dyes have the opportunity to become
attached to other articles in the wash.
Especially suitable polymeric dye transfer inhibiting
agents are polyamine N-oxide polymers, copolymers of N-
vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone
polymers, polyvinyloxazolidones and polyvinylimidazoles or
mixtures thereof.
Addition of such polymers also enhances the performance of
the enzymes according the invention.
a) Polyamine N-oxide polymers
The polyamine N-oxide polymers suitable for use
contain units having the following structure formula :
p
I
(I) AX
I
R
wherein P is a polymerisable unit, whereto the R-N-O group
can be attached to or wherein the R-N-O group forms
part of the polymerisable unit or a combination of
both.
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O O O
Il 11 11
A is NC, CO, C, -O-,-S-, -N- ; x is O or l;
R are aliphatic, ethoxylated aliphatics, aromatic,
heterocyclic or alicyclic groups or any
combination thereof whereto the nitrogen of the N-O
group can be attached or wherein the nitrogen of
the N-O group is part of these groups.
The N-O group can be represented by the following general
structures :
O O
(Rl)x -N- (R2~y =N- (Rl)x
I
(R3)z
wherein Rl, R2, and R3 are aliphatic groups, aromatic,
heterocyclic or alicyclic groups or combinations
thereof, x or/and y or/and z is 0 or 1 and wherein
the nitrogen of the N-O group can be attached or
wherein the nitrogen of the N-O group forms part of
these groups.
The N-O group can be part of the polymerisable unit
(P) or can be attached to the polymeric backbone or a
combination of both.
Suitable polyamine N-oxides wherein the N-O group forms
part of the polymerisable unit comprise polyamine N-oxides
wherein R is selected from aliphatic, aromatic, alicyclic
or heterocyclic groups.
One class of said polyamine N-oxides comprises the group of
polyamine N-oxides wherein the nitrogen of the N-O group
forms part of the R-group. Preferred polyamine N-oxides
are those wherein R is a heterocyclic group such as
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pyrridine, pyrrole, imidazole, pyrrolidine, piperidine,
quinoline, acridine and derivatives thereof.
Another class of said polyamine N-oxides comprises the
group of polyamine N-oxides wherein the nitrogen of the N-O
group is attached to the R-group.
Other suitable polyamine N-oxides are the polyamine
oxides whereto the N-O group is attached to the
polymerisable unit.
Preferred class of these polyamine N-oxides are the
polyamine N-oxides having the general formula (I) wherein R
is an aromatic, heterocyclic or alicyclic groups wherein
the nitrogen of the N-0 functional group is part of said R
group.
Examples of these classes are polyamine oxides wherein R is
a heterocyclic compound such as pyrridine, pyrrole,
imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the
polyamine oxides having the general formula (I) wherein R
are aromatic, heterocyclic or alicyclic groups wherein the
nitrogen of the N-0 functional group is attached to said R
groups.
Examples of these classes are polyamine oxides wherein
R groups can be aromatic such as phenyl.
Any polymer backbone can be used as long as the amine
oxide polymer formed is water-soluble and has dye transfer
inhibiting properties. Examples of suitable polymeric
backbones are polyvinyls, polyalkylenes, polyesters,
polyethers, polyamide, polyimides, polyacrylates and
mixtures thereof.
The amine N-oxide polymers of the present invention
typically have a ratio of amine to the amine N-oxide of
10:1 to 1:1000000. However the amount of amine oxide groups
present in the polyamine oxide polymer can be varied by
appropriate copolymerization or by appropriate degree of N-
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oxidation. Preferably, the ratio of amine to amine N-oxide
is from 2:3 to 1:1000000. More preferably from 1:4 to
1:1000000, most preferably from 1:7 to 1:1000000. The
polymers of the present invention actually encompass random
or block copolymers where one monomer type is an amine N-
oxide and the other monomer type is either an amine N-oxide
or not. The amine oxide unit of the polyamine N-oxides has
a PKa < 10, preferably PKa ~ 7, more preferred PKa ~ 6.
The polyamine oxides can be obtained in almost any degree
of polymerisation. The degree of polymerisation is not
critical provided the material has the desired water-
solubility and dye-suspending power.
Typically, the average molecular weight is within the
range of 500 to 1000,000; preferably from 1,000 to 50,000,
more preferably from 2,000 to 30,000, most preferably from
3,000 to 20,000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
The N-vinylimidazole N-vinylpyrrolidone polymers used
in the present invention have an average molecular weight
range from 5,000-1,000,000, preferably from 5,000-200,000.
Highly preferred polymers for use in detergent
compositions according to the present invention comprise a
polymer selected from N-vinylimidazole N-vinylpyrrolidone
copolymers wherein said polymer has an average molecular
weight range from 5,000 to 50,000 more preferably from
8,000 to 30,000, most preferably from 10,000 to 20,000.
The average molecular weight range was determined by light
scattering as described in Barth H.G. and Mays J.W.
Chemical Analysis Vol 113,"Modern Methods of Polymer
Characterization".
Highly preferred N-vinylimidazole N-vinylpyrrolidone
copolymers have an average molecular weight range from
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W098/06809 23 PCT~S96tl2963
5,000 to 50,000; more preferably from 8,000 to 30,000; most
~ preferably from 10,000 to 20,000.
The N-vinylimidazole N-vinylpyrrolidone copolymers
characterized by having said average molecular weight range
provide excellent dye transfer inhibiting properties while
not adversely affecting the cleaning performance of
detergent compositions formulated therewith.
The N-vinylimidazole N-vinylpyrrolidone copolymer of the
present invention has a molar ratio of N-vinylimidazole to
N-vinylpyrrolidone from 1 to 0. 2, more preferably from 0.8
to 0. 3, most preferably from 0. 6 to 0.4 .
c) Polyvinylpyrrolidone
The detergent compositions of the present invention
may also utilize polyvinylpyrrolidone ("PVP'~) having an
average molecular weight of from about 2,500 to about
400,000, preferably from about 5,000 to about 200,000, more
preferably from about 5,000 to about 50,000, and most
preferably from about 5,000 to about 15,000. Suitable
polyvinylpyrrolidones are commercially vailable from ISP
Corporation, New York, NY and Montreal, Canada under the
product names PVP K- 15 (viscosity molecular weight of
10,000), PVP K-30 (average molecular weight of 40,000), PVP
K-60 (average molecular weight of 160,000), and PVP K-90
(average molecular weight of 360,000) . Other suitable
polyvinylpyrrolidones which are commercially available from
BASF Cooperation include Sokalan HP 165 and Sokalan HP 12;
polyvinylpyrrolidones known to persons skilled in the
detergent field (see for example EP-A-262, 897 and EP-A-
256,696) .
d) Polyvinyloxazolidone :
The detergent compositions of the present invention
may also utilize polyvinyloxazolidone as a polymeric dye
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098/0680g 24 PCT~S96/12963
transfer inhibiting agent. Said polyvinyloxazolidones have
an average molecular weight of from about 2,500 to about
400,000, preferably from about 5,000 to about 200,000, more
preferably from about 5,000 to about 50,000, and most
preferably from about 5,000 to about 15,000.
e) Polyvinylimidazole :
The detergent compositions of the present invention
may also utilize polyvinylimidazole as polymeric dye
transfer inhibiting agent. Said polyvinylimidazoles have an
average
about 2,500 to about 400,000, preferably from about 5,000
to about 200,000, more preferably from about 5,000 to about
50,000, and most preferably from about 5,000 to about
15,000.
f) Cross-linked polymers :
Cross-linked polymers are polymers whose backbone are
interconnected to a certain degree; these links can be of
chemical or physical nature, possibly with active groups n
the backbone or on branches; cross-linked polymers have
been described in the Journal of Polymer Science, volume
22, pages 1035-1039.
In one embodiment, the cross-linked polymers are made in
such a way that they form a three-dimensional rigid
structure, which can entrap dyes in the pores formed by the
three-dimensional structure. In another embodiment, the
cross-linked polymers entrap the dyes by swelling.
Such cross-linked polymers are described in the co-
pending patent application 94870213.9
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W098/06809 25 PCT~S96/12963
Deterqent components
The cleaning compositions of the invention may also
contain additional detergent components. The precise
nature of these additional components, and levels of
incorporation thereof will depend on the physical form of
the composition, and the nature of the cleaning operation
for which it is to be used.
The cleaning compositions according to the invention
can be liquid, paste, gels, bars, tablets, powder or
granular forms. Granular compositions can also be in
"compact" form, the liquid compositions can also be in a
"concentrated" form.
The compositions of the invention may for example, be
formulated as hand and machine dishwashing compositions,
hand and machine laundry detergent compositions including
laundry additive compositions and compositions suitable for
use in the soaking and/or pretreatment of stained fabrics,
rinse added fabric softener compositions, and compositions
for use in general household hard surface cleaning
operations.
Such compositions containing alkaline
polygalacturonase enzyme can provide fabric cleaning, stain
removal, whiteness maintenance, softening, color appearance
and dye transfer inhibition when formulated as laundry
detergent compositions.
When formulated as compositions for use in manual
dishwashing methods the compositions of the invention
preferably contain a surfactant and preferably other
detergent compounds selected from organic polymeric
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W098/06809 26 PCT~S96/12963
compounds, suds enhancing agents, group II metal ions,
solvents, hydrotropes and additional enzymes.
When formulated as compositions suitable for use in a
laundry machine washing method, the compositions of the
invention preferably contain both a surfactant and a
builder compound and additionally one or more detergent
components preferably selected from organic polymeric
compounds, bleaching agents, additional enzymes, suds
suppressors, dispersants, lime-soap dispersants, soil
suspension and anti-redeposition agents and corrosion
inhibitors. Laundry compositions can also contain
softening agents, as additional detergent components.
The compositions of the invention can also be used as
detergent additive products. Such additive products are
intended to supplement or boost the performance of
conventional detergent compositions.
If needed the density of the laundry detergent
compositions herein ranges from 400 to 1200 g/litre,
preferably 600 to 950 g/litre of composition measured at
20~C.
The "compact" form of the compositions herein is best
reflected by density and, in terms of composition, by the
amount of inorganic filler salt; inorganic filler salts are
conventional ingredients of detergent compositions in
powder form; in conventional detergent compositions, the
filler salts are present in substantial amounts, typically
17-35~ by weight of the total composition.
In the compact compositions, the filler salt is
present in amounts not exceeding 15~ of the total
composition, preferably not exceeding lO~, most preferably
not exceeding 5~ by weight of the composition.
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The inorganic filler salts, such as meant in the
present compositions are selected from the alkali and
alkaline-earth-metal salts of sulphates and chlorides.
A preferred filler salt is sodium sulphate.
Liquid detergent compositions according to the present
invention can also be in a "concentrated form", in such
case, the liquid detergent compositions according the
present invention will contain a lower amount of water,
compared to conventional liquid detergents.
Typically the water content of the concentrated liquid
detergent is preferably less than 40~, more preferably less
than 30~, most preferably less than 20~ by weight of the
detergent composition.
Surfactant system
The cleaning compositions according to the present
invention comprise a surfactant system wherein the
surfactant can be selected from nonionic and/or anionic
and/or cationic and/or ampholytic and/or zwitterionic
and/or semi-polar surfactants.
The surfactant is typically present at a level of from
O.l~ to 60~ by weight. More preferred levels of
incorporation are l~ to 35~ by weight, most preferably from
l~ to 30~ by weight of cleaning compositions in accord with
the invention.
The surfactant is preferably formulated to be compatible
with enzyme components present in the composition. In
liquid or gel compositions the surfactant is most
preferably formulated such that it promotes, or at least
does not degrade, the stability of any enzyme in these
compositions.
.. ~ .. . .. .
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WO 98/06809 28 PCTrUS96/12963
Preferred surfactant systems to be used according to the
present invention comprise as a surfactant one or more of
the nonionic and/or anionic surfactants described herein.
Polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols are suitable for use as the
nonionic surfactant of the surfactant systems of the
present invention, with the polyethylene oxide condensates
being preferred. These compounds include the condensation
products of alkyl phenols having an alkyl group containing
from about 6 to about 14 carbon atoms, preferably from
about 8 to about 14 carbon atoms, in either a straight-
chain or branched-chain configuration with the alkylene
oxide. In a preferred embodiment, the ethylene oxide is
present in an amount equal to from about 2 to about 25
moles, more preferably from about 3 to about 15 moles, of
ethylene oxide per mole of alkyl phenol. Commercially
available nonionic surfactants of this type include
IgepalTM C0-630, marketed by the GAF Corporation; and
TritonTM X-45, X-114, X-100 and X-102, all marketed by the
Rohm & Haas Company. These surfactants are commonly
referred to as alkylphenol alkoxylates (e.g., alkyl phenol
ethoxylates).
The condensation products of primary and secondary
aliphatic alcohols with from about 1 to about 25 moles of
ethylene oxide are suitable for use as the nonionic
surfactant of the nonionic surfactant systems of the
present invention. The alkyl chain of the aliphatic alcohol
can either be straight or branched, primary or secondary,
and generally contains from about 8 to about 22 carbon
atoms. Preferred are the condensation products of alcohols
having an alkyl group containing from about 8 to about 20
carbon atoms, more preferably from about 10 to about 18
carbon atoms, with from about 2 to about lO moles of
ethylene oxide per mole of alcohol. About 2 to about 7
moles of ethylene oxide and most preferably from 2 to 5
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WO 98/06809 29 PCTrUS96/12963
moles of ethylene oxide per mole of alcohol are present in
said condensation products. Examples of commercially
available nonionic surfactants of this type include
TergitolTM 15-S-9 (the condensation product of C11-C15
linear alcohol with 9 moles ethylene oxide), TergitolTM 24-
L-6 NMW (the condensation product of C12-C14 primary
alcohol with 6 moles ethylene oxide with a narrow molecular
weight distribution), both marketed by Union Carbide
Corporationi NeodolTM 45-9 ~the condensation product of
C14-C1s linear alcohol with 9 moles of ethylene oxide),
NeodolTM 23-3 (the condensation product of C12-C13 linear
alcohol with 3.0 moles of ethylene oxide), NeodolTM 45-7
(the condensation product of C14-C1s linear alcohol with 7
moles of ethylene oxide), NeodolTM 45-5 (the condensation
product of C14-C1s linear alcohol with 5 moles of ethylene
oxide) marketed by Shell Chemical Company, KyroTM EOB (the
condensation product of C13-C1s alcohol with 9 moles
ethylene oxide), marketed by The Procter & Gamble Company,
and Genapol LA 030 or 050 (the condensation product of C12-
C14 alcohol with 3 or 5 moles of ethylene oxide) marketed
by Hoechst. Preferred range of HLB in these products is
from 8-11 and most preferred from 8-10.
Also useful as the nonionic surfactant of the surfactant
systems of the present invention are the
alkylpolysaccharides disclosed in U.S. Patent 4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic
group containing from about 6 to about 30 carbon atoms,
preferably from about 10 to about 16 carbon atoms and a
polysaccharide, e.g. a polyglycoside, hydrophilic group
containing from about 1.3 to about 10, preferably from
about 1.3 to about 3, most preferably from about 1.3 to
about 2.7 saccharide units. Any reducing saccharide
containing 5 or 6 carbon atoms can be used, e.g., glucose,
galactose and galactosyl moieties can be substituted for
the glucosyl moieties (optionally the hydrophobic group is
attached at the 2-, 3-, 4-, etc. positions thus giving a
CA 02262790 1999-02-08
~098/06~9 30 PCT~S96/12963
glucose or galactose as opposed to a glucoside or
galactoside). The intersaccharide bonds can be, e.g.,
between the one position of the additional saccharide units
and the 2-, 3-, 4-, and/or 6- positions on the preceding
saccharide units.
The preferred alkylpolyglycosides have the formula
R20(CnH2nO)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl,
alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures
thereof in which the alkyl groups contain from about 10 to
about 18, preferably from about 12 to about 14, carbon
atoms; n is 2 or 3, preferably 2; t is from 0 to about 10,
preferably 0; and x is from about 1.3 to about 10,
preferably from about 1.3 to about 3, most preferably from
about 1.3 to about 2.7. The glycosyl is preferably derived
from glucose. To prepare these compounds, the alcohol or
alkylpolyethoxy alcohol is formed first and then reacted
with glucose, or a source of glucose, to form the glucoside
(attachment at the l-position). The additional glycosyl
units can then be attached between their l-position and the
preceding glycosyl units 2-, 3-, 4- and/or 6-position,
preferably predominately the 2-position.
The condensation products of ethylene oxide with a
hydrophobic base formed by the condensation of propylene
oxide with propylene glycol are also suitable for use as
the additional nonionic surfactant systems of the present
invention. The hydrophobic portion of these compounds will
preferably have a molecular weight of from about 1500 to
about 1800 and will exhibit water insolubility. The
addition of polyoxyethylene moieties to this hydrophobic
portion tends to increase the water solubility of the
molecule as a whole, and the liquid character of the
product is retained up to the point where the
polyoxyethylene content is about 50~ of the total weight of
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W098/0~09 31 PCT~S96/12963
the condensation product, which corresponds to condensation
with up to about 40 moles of ethylene oxide. Examples of
compounds of this type include certain of the commercially-
available PlurafacTM LF404 and PluronicTM surfactants,
marketed by BASF.
Also suitable for use as the nonionic surfactant of the
nonionic surfactant system of the present invention, are
the condensation products of ethylene oxide with the
product resulting from the reaction of propylene oxide and
ethylenediamine. The hydrophobic moiety of these products
consists of the reaction product of ethylenediamine and
excess propylene oxide, and generally has a molecular
weight of from about 2500 to about 3000. This hydrophobic
moiety is condensed with ethylene oxide to the extent that
the condensation product contains from about 40~ to about
80~ by weight of polyoxyethylene and has a molecular weight
of from about 5,000 to about 11,000. Examples of this type
of nonionic surfactant include certain of the commercially
available TetronicTM compounds, marketed by BASF.
Preferred for use as the nonionic surfactant of the
surfactant systems of the present invention are
polyethylene oxide condensates of alkyl phenols,
condensation products of primary and secondary aliphatic
alcohols with from about 1 to about 25 moles of ethylene
oxide, alkylpolysaccharides, and mixtures thereof. Most
preferred are Cg-C14 alkyl phenol ethoxylates having from 3
to 15 ethoxy groups and Cg-C1g alcohol ethoxylates
(preferably C1o avg.) having from 2 to 10 ethoxy groups,
and mixtures thereof.
Highly preferred nonionic surfactants are polyhydroxy
fatty acid amide surfactants of the formula.
R2 - C - N - z
Il I
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W098/06809 32 PCT~S96/12963
O Rl _
wherein R1 is H, or R1 is C1_4 hydrocarbyl, 2-hydroxy
ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5_31
hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a
linear hydrocarbyl chain with at least 3 hydroxyls directly
connected to the chain, or an alkoxylated derivative
thereof. Preferably, R1 is methyl, R2 is a straight C11_15
alkyl or C16_1g alkyl or alkenyl chain such as coconut
alkyl or mixtures thereof, and Z is derived from a reducing
sugar such as glucose, fructose, maltose, lactose, in a
reductive amination reaction.
Suitable anionic surfactants to be used are linear alkyl
benzene sulfonate, alkyl ester sulfonate surfactants
including linear esters of Cg-C20 carboxylic acids (i.e.,
fatty acids) which are sulfonated with gaseous SO3
according to "The Journal of the American Oil Chemists
Society", 52 (1975), pp. 323-329. Suitable starting
materials would include natural fatty substances as derived
from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially
for laundry applications, comprise alkyl ester sulfonate
surfactants of the structural formula :
o
I I .
R3 - CH - C - oR4
I
SO3M
wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or
combination thereof, R4 is a C1-C6 hydrocarbyl, preferably
an alkyl, or combination thereof, and M is a cation which
forms a water soluble salt with the alkyl ester sulfonate.
Suitable salt-forming cations include metals such as
sodium, potassium, and lithium, and substituted or
unsubstituted ammonium cations, such as monoethanolamine,
diethanolamine, and triethanolamine. Preferably, R3 is
CA 02262790 1999-02-08
W0981068U9 33 PCT~S96/12963
Clo-C16 alkyl, and R4 is methyl, ethyl or isopropyl.
Especially preferred are the methyl ester sulfonates
wherein R3 is C1o-C16 alkyl.
Other suitable anionic surfactants include the alkyl
sulfate surfactants which are water soluble salts or acids
of the formula ROS03M wherein R preferably is a C1o-C24
hydrocarbyl, preferably an alkyl or hydroxyalkyl having a
C1o-C20 alkyl component, more preferably a C12-C1g alkyl or
hydroxyalkyl, and M is H or a cation, e.g., an alkali metal
cation (e.g. sodium, potassium, lithium), or ammonium or
substituted ammonium (e.g. methyl-, dimethyl-, and
trimethyl ammonium cations and quaternary ammonium cations
such as tetramethyl-ammonium and dimethyl piperdinium
cations and quaternary ammonium cations derived from
alkylamines such as ethylamine, diethylamine,
triethylamine, and mixtures thereof, and the like).
Typically, alkyl chains of C12-C16 are preferred for lower
wash temperatures (e.g. below about 50~C) and C16_18 alkyl
chains are preferred for higher wash temperatures (e.g.
above about 50~C).
Other anionic surfactants useful for detersive purposes
can also be included in the cleaning compositions of the
present invention. These can include salts (including, for
example, sodium, potassium, ammonium, and substituted
ammonium salts such as mono-, di- and triethanolamine
salts) of soap, Cg-C22 primary of secondary
alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated
polycarboxylic acids prepared by sulfonation of the
pyrolyzed product of alkaline earth metal citrates, e.g.,
as described in British patent specification No. 1,082,179,
Cg-C24 alkylpolyglycolethersulfates (containing up to 10
moles of ethylene oxide); alkyl glycerol sulfonates, fatty
acyl glycerol sulfonates, fatty oleyl glycerol sulfates,
alkyl phenol ethylene oxide ether sulfates, paraffin
sulfonates, alkyl phosphates, isethionates such as the acyl
isethionates, N-acyl taurates, alkyl succinamates and
... .
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sulfosuccinates, monoesters of sulfosuccinates (especially
saturated and unsaturated Cl2-Clg monoesters) and diesters
of sulfosuccinates (especially saturated and unsaturated
C6-Cl2 diesters), acyl sarcosinates, sulfates of
alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds
being described below), branched primary alkyl sulfates,
and alkyl polyethoxy carboxylates such as those of the
formula RO(CH2CH20)k-CH2COO-M+ wherein R is a Cg-C22 alkyl,
k is an integer from l to lO, and M is a soluble salt-
forming cation. Resin acids and hydrogenated resin acids
are also suitable, such as rosin, hydrogenated rosin, and
resin acids and hydrogenated resin acids present in or
derived from tall oil.
Further examples are described in "Surface Active Agents
and Detergents" (Vol. I and II by Schwartz, Perry and
Berch). A variety of such surfactants are also generally
disclosed in U.S. Patent 3,929,678, issued December 30,
1975 to Laughlin, et al. at Column 23, line 58 through
Column 29, line 23 (herein incorporated by reference).
When included therein, the laundry detergent compositions
of the present invention typically comprise from about l~
to about 40~, preferably from about 3% to about 20~ by
weight of such anionic surfactants.
Highly preferred anionic surfactants include alkyl
alkoxylated sulfate surfactants hereof are water soluble
salts or acids of the formula RO(A)mS03M wherein R is an
unsubstituted Clo-C24 alkyl or hydroxyalkyl group having a
ClO-C24 alkyl component, preferably a Cl2-C20 alkyl or
hydroxyalkyl, more preferably Cl2-Cl8 alkyl or
hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater
than zero, typically between about 0.5 and about 6, more
preferably between about 0.5 and about 3, and M is H or a
cation which can be, for example, a metal cation (e.g.,
sodium, potassium, lithium, calcium, magnesium, etc.),
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ammonium or substituted-ammonium cation. Alkyl ethoxylated
sulfates as well as alkyl propoxylated sulfates are
contemplated herein. Specific examples of substituted
ammonium cations include methyl-, dimethyl, trimethyl-
ammonium cations and ~uaternary ammonium cations such as
tetramethyl-ammonium and dimethyl piperdinium cations and
those derived from alkylamines such as ethylamine,
diethylamine, triethylamine, mixtures thereof, and the
like. Exemplary surfactants are C12-C18 alkyl
polyethoxylate (1.0) sulfate (C12-ClgE(l.0)M)~ C12-C18
alkyl polyethoxylate (2 .25) sulfate (C12-C1gE(2 .25)M), C12-
C1g alkyl polyethoxylate (3.0) sulfate (C12-ClgE(3.0)M),
and C12-C1g alkyl polyethoxylate (4.0) sulfate (C12-
C1gE(4.0)M), wherein M is conveniently selected from sodium
and potassium.
The cleaning compositions of the present invention may
also contain cationic, ampholytic, zwitterionic, and semi-
polar surfactants, as well as the nonionic and/or anionic
surfactants other than those already described herein.
Cationic detersive surfactants suitable for use in the
cleaning compositions of the present invention are those
having one long-chain hydrocarbyl group. Examples of such
cationic surfactants include the ammonium surfactants such
as alkyltrimethylammonium halogenides, and those
surfactants having the formula :
[R2(oR3)y]~R4(0R3)y]2R5N+X~
wherein R2 is an alkyl or alkyl benzyl group having from
about 8 to about 18 carbon atoms in the alkyl chain, each
R3 is selected from the group consisting of -CH2CH2-,
CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2-, and mixtures
thereof; each R4 is selected from the group consisting of
C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures
formed by joining the two R4 groups, -CH2CHOH-
CHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose
.__._ . .. .
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polymer having a molecular weight less than about 1000, and
hydrogen when y is not 0; R5 is the same as R4 or is an
alkyl chain wherein the total number of carbon atoms of R2
plus R5 is not more than about 18; each y is from 0 to
about 10 and the sum of the y values is from 0 to about 15;
and X is any compatible anion.
Quaternary ammonium surfactant suitable for the
present invention has the formula (I):
R2 R3
~o ~ ~Rs X-
Formula I
whereby Rl is a short chainlength alkyl (C6-C10) or
alkylamidoalkyl of the formula (II) :
o
Formula II
y is 2-4, preferably 3.
whereby R2 is H or a Cl-C3 alkyl,
whereby x is 0-4, preferably 0-2, most preferably 0,
whereby R3, R4 and R5 are either the same or different and
can be either a short chain alkyl (Cl-C3) or alkoxylated
alkyl of the formula III,
whereby X~ is a counterion, preferably a halide, e.g.
chloride or methylsulfate.
7R8
H
Formula III
R6 is Cl-C4 and z is 1 or 2.
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Preferred quat ammonium surfactants are those as
defined in formula I whereby
Rl is C8, Clo or mixtures thereof, x=o,
R3, R4 = CH3 and Rs = CH2CH20H.
Highly preferred cationic surfactants are the water-
soluble quaternary ammonium compounds useful in the
present composition having the formula :
RlR2R3R4N X ( i )
wherein Rl is Cg-C16 alkyl, each of R2, R3 and R4 is
independently Cl-C4 alkyl, Cl-C4 hydroxy alkyl, benzyl, and
-(C2H40)XH where x has a value from 2 to 5, and X is an
anion. Not more than one of R2, R3 or R4 should be benzyl.
The preferred alkyl chain length for Rl is C12-C15
particularly where the alkyl group is a mixture of chain
lengths derived from coconut or palm kernel fat or is
derived synthetically by olefin build up or OXO alcohols
synthesis. Preferred groups for R2R3 and R4 are methyl and
hydroxyethyl groups and the anion X may be selected from
halide, methosulphate, acetate and phosphate ions.
Examples of suitable quaternary ammonium compounds of
formulae (i) for use herein are :
coconut trimethyl ammonium chloride or bromide;
coconut methyl dihydroxyethyl ammonium chloride or
bromide;
decyl triethyl ammonium chloride;
decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C12_15 dimethyl hydroxyethyl ammonium chloride or
bromide;
coconut dimethyl hydroxyethyl ammonium chloride or
bromide;
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein Rl is
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CH2-CH2-O-C-C12_14 alkyl and R2R3R4 are methyl).
o
di-alkyl imidazolines [compounds of formula (i)].
Other cationic surfactants useful herein are also
described in U.S. Patent 4,228,044, Cambre, issued October
14, 1980 and in European Patent Application EP 000,224.
Typical cationic fabric softening components include
the water-insoluble quaternary-ammonium fabric softening
actives, the most commonly used having been di-long alkyl
chain ammonium chloride or methyl sulfate.
Preferred cationic softeners among these include the
following:
1) ditallow dimethylammonium chloride (DTDMAC);
2) dihydrogenated tallow dimethylammonium chloride;
3) dihydrogenated tallow dimethylammonium
methylsulfate;
4) distearyl dimethylammonium chloride;
5) dioleyl dimethylammonium chloride;
6) dipalmityl hydroxyethyl methylammonium chloride;
7) stearyl benzyl dimethylammonium chloride;
8) tallow trimethylammonium chloride;
9) hydrogenated tallow trimethylammonium chloride;
10) C12-14 alkyl hydroxyethyl dimethylammonium
chloride;
11) Cl2-l8 alkyl dihydroxyethyl methylammonium
chloride;
12) di(stearoyloxyethyl) dimethylammonium chloride
(DSOEDMAC)i
13) di(tallowoyloxyethyl) dimethylammonium chloride;
14) ditallow imidazolinium methylsulfate;
15) 1-(2-tallowylamidoethyl)-2-tallowyl imidazolinium
methylsulfate.
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Biodegradable quaternary ammonium compounds have been
presented as alternatives to the traditionally used di-long
alkyl chain ammonium chlorides and methyl sulfates. Such
quaternary ammonium compounds contain long chain alk(en)yl
groups interrupted by functional groups such as carboxy
groups. Said materials and fabric softening compositions
containing them are disclosed in numerous publications such
as EP-A-0,040,562, and EP-A-0,239,910.
The quaternary ammonium compounds and amine precursors
herein have the formula (I) or (II), below :
R3\ R3
\/ 1 + N -(cH2)n-clH-cH2 X~
+ N-(CHk~-Q--T X R3 Q
Rl Tl T2
or
(I) (II)
wherein Q is selected from -O-C(O)-, -C(O)-O-, -O-C(O)-O-,
-NR4-C(o)-, -C(o)-NR4-;
R1 is (CH2)n-Q-T2 or T3;
R2 is (CH2)m-Q-T4 or T5 or R3;
R3 is Cl-C4 alkyl or C1-C4 hydroxyalkyl or Hi
R4 is H or Cl-C4 alkyl or Cl-C4 hydroxyalkyl;
Tl, T2, T3, T4, T5 are independently Cll-C22 alkyl or
alkenyl;
n and m are integers from 1 to 4; and
X~ is a softener-compatible anion.
Non-limiting examples of softener-compatible anions include
chloride or methyl sulfate.
The alkyl, or alkenyl, chain T1, T2, T3, T4, T5 must
contain at least 11 carbon atoms, preferably at least 16
carbon atoms. The chain may be straight or branched.
.. _....
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Tallow ls a convenient and inexpensive source of long
chain alkyl and alkenyl material. The compounds wherein
T1, T2, T3, T4, T5 represents the mixture of long chain
materials typical for tallow are particularly preferred.
Specific examples of quaternary ammonium compounds
suitable for use in the aqueous fabric softening
compositions herein include :
1) N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium
chloride;
2) N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl)
ammonium methyl sulfate;
3) N,N-di(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl ammonium
chloride;
4) N,N-di(2-tallowyl-oxy-ethylcarbonyl-oxy-ethyl)-N,N-
dimethyl ammonium chloride;
5) N-(2-tallowyl-oxy-2-ethyl)-N-(2-tallowyl-oxy-2-oxo-
ethyl)-N,N-dimethyl ammonium
chloride;
6) N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium
chloride;
7) N-(2-tallowyl-oxy-2-oxo-ethyl)-N-(tallowyl-N,N-dimethyl-
ammonium chloride; and
8) 1,2-ditallowyl-oxy-3-trimethylammoniopropane chloride;
and mixtures of any of the above materials.
When included therein, the cleaning compositions of the
present invention typically comprise from 0.2~ to about
25~, preferably from about 1~ to about 8~ by weight of such
cationic surfactants.
Ampholytic surfactants are also suitable for use in the
cleaning compositions of the present invention. These
surfactants can be broadly described as aliphatic
derivatives of secondary or tertiary amines, or aliphatic
derivatives of heterocyclic secondary and tertiary amines
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in which the aliphatic radical can be straight- or
branched-chain. One of the aliphatic substituents contains
at least about 8 carbon atoms, typically from about 8 to
about 18 carbon atoms, and at least one contains an anionic
water-solubilizing group, e.g. carboxy, sulfonate, sulfate.
See U.S. Patent No. 3,929,678 to Laughlin et al., issued
December 30, 1975 at column 19, lines 18-35, for examples
of ampholytic surfactants.
When included therein, the cleaning compositions of the
present invention typically comprise from 0.2~ to about
15~, preferably from about 1~ to about 10~ by weight of
such ampholytic surfactants.
Zwitterionic surfactants are also suitable for use in
cleaning compositions. These surfactants can be broadly
described as derivatives of secondary and tertiary amines,
derivatives of heterocyclic secondary and tertiary amines,
or derivatives of quaternary ammonium, quaternary
phosphonium or tertiary sulfonium compounds. See U.S.
Patent No. 3,929,678 to Laughlin et al., issued December
30, 1975 at column 19, line 38 through column 22, line 48,
for examples of zwitterionic surfactants.
When included therein, the cleaning compositions of the
present invention typically comprise from 0.2~ to about
15~, preferably from about 1% to about 10~ by weight of
such zwitterionic surfactants.
Semi-polar nonionic surfactants are a special category of
nonionic surfactants which include water-soluble amine
oxides containing one alkyl moiety of from about 10 to
about 18 carbon atoms and 2 moieties selected from the
group consisting of alkyl groups and hydroxyalkyl groups
containing from about 1 to about 3 carbon atoms; water-
soluble phosphine oxides containing one alkyl moiety of
from about 10 to about 18 carbon atoms and 2 moieties
_ _, .. . . . . .. . .
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selected from the group consisting of alkyl groups and
hydroxyalkyl groups containing from about 1 to about 3
carbon atomsi and water-soluble sulfoxides containing one
alkyl moiety of from about 10 to about 18 carbon atoms and
a moiety selected from the group consisting of alkyl and
hydroxyalkyl moieties of from about 1 to about 3 carbon
atoms.
Semi-polar nonionic detergent surfactants include the amine
oxide surfactants having the formula
o
R3(oR4)xN(R5) 2
wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group
or mixtures therof containing from about 8 to about 22
carbon atoms; R4 is an alkylene or hydroxyalkylene group
containing from about 2 to about 3 carbon atoms or mixtures
thereof; x is from O to about 3; and each R5 is an alkyl or
hydroxyalkyl group containing from about 1 to about 3
carbon atoms or a polyethylene oxide group containing from
about 1 to about 3 ethylene oxide groups. The R5 groups can
be attached to each other, e.g., through an oxygen or
nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include Clo-
C18 alkyl dimethyl amine oxides and Cg-C12 alkoxy ethyl
dihydroxy ethyl amine oxides.
When included therein, the cleaning compositions of the
present invention typically comprise from 0. 2~ to about
15~, preferably from about 1~ to about 10~ by weight of
such semi-polar nonionic surfactants.
The cleaning composition of the present invention
may further comprise a cosurfactant selected from the group
of primary or tertiary amines.
Suitable primary amines for use herein include amines
according to the formula RlN~2 wherein R1 is a C6-C12
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preferably C6-C10 alkyl chain or R4X(CH2)n, X is -O-,-
C(O)NH- or -NH-, R4 is a C6-C12 alkyl chain n is between 1
to 5, preferably 3 . R1 alkyl chains may be straight or
branched and may be interrupted with up to 12, preferably
less than 5 ethylene oxide moieties.
Preferred amines according to the formula herein above are
n-alkyl amines. Suitable amines for use herein may be
selected from l-hexylamine, 1-octylamine, 1-decylamine and
laurylamine. Other preferred primary amines include C8-C10
oxypropylamine, octyloxypropylamine, 2 -ethylhexyl-
oxypropylamine, lauryl amido propylamine and amido
propylamine.
Suitable tertiary amines for use herein include
tertiary amines having the formula R1R2R3N wherein Rl and
R2 are C1-C8 alkylchains or
R5
- (C112-CH - O ~H
R3 is either a C6-C12, preferably C6-C1o alkyl chain, or R3
is R4X (CH2)n, whereby X is -O-, -C(O) NH- or -NH- R4 is a
C4 -C12, n is between 1 to 5, preferably 2-3. R5 is H or C1-
C2 alkyl and x is between 1 to 6 .
R3 and R4 may be linear or branched ; R3 alkyl chains may
be interrupted with up to 12, preferably less than 5,
ethylene oxide moieties.
Preferred tertiary amines are R1R2R3N where Rl is a
C6-C12 alkyl chain, R2 and R3 are Cl-C3 alkyl or
Rl 5
- (CH2-CH - O ~H
where R5 is H or CH3 and x = 1- 2.
Also preferred are the amidoamines of the formula:
Rl - C-NH -(CH2n- N -(R2)2
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wherein R1 is C6-C12 alkyl; n is 2 -4,
preferably n is 3; R2 and R3 is C1-C4
Most preferred amines of the present invention include
l-octylamine, 1-hexylamine, l-decylamine, 1-
dodecylamine,C8-lOoxypropylamine, N coco 1-3diaminopropane,
coconutalkyldimethylamine, lauryldimethylamine, lauryl
bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl
amine 2 moles propoxylated, octyl amine 2 moles
propoxylated, lauryl amidopropyldimethylamine, C8-10
amidopropyldimethylamine and C10 amidopropyldimethylamine.
The most preferred amines for use in the compositions
herein are 1-hexylamine, 1-octylamine, 1-decylamine, 1-
dodecylamine. Especially desirable are n-
dodecyldimethylamine and bishydroxyethylcoconutalkylamine
and oleylamine 7 times ethoxylated, lauryl amido
propylamine and cocoamido propylamine.
Color care benefits
Technologies which provide a type of color care benefit
can also be included. Examples of these technologies are
metallo catalysts for color maintenance. Such metallo
catalysts are described in copending European Patent
Application No. 92870181.2.
Builder system
The compositions according to the present invention may
further comprise a builder system. Any conventional
builder system is suitable for use herein including
aluminosilicate materials, silicates, polycarboxylates,
alkyl- or alkenyl-succinic acid and fatty acids, materials
such as ethylenediamine tetraacetate, diethylene triamine
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pentamethyleneacetate, metal ion sequestrants such as
aminopolyphosphonates, particularly ethylenediamine
tetramethylene phosphonic acid and diethylene triamine
pentamethylenephosphonic acid. Phosphate builders can also
be used herein.
Suitable builders can be an inorganic ion exchange
material, commonly an inorganic hydrated aluminosilicate
material, more particularly a hydrated synthetic zeolite
such as hydrated zeolite A, X, B, HS or MAP.
Another suitable inorganic builder material is layered
silicate, e.g. SKS-6 ~Hoechst). SKS-6 is a crystalline
layered silicate consisting of sodium silicate (Na2Si2O5).
Suitable polycarboxylates containing one carboxy group
include lactic acid, glycolic acid and ether derivatives
thereof as disclosed in Belgian Patent Nos. 831,368,
821,369 and 821,370. Polycarboxylates containing two
carboxy groups include the water-soluble salts of succinic
acid, malonic acid, (ethylenedioxy) diacetic acid, maleic
acid, diglycollic acid, tartaric acid, tartronic acid and
fumaric acid, as well as the ether carboxylates described
in German Offenlegenschrift 2,446,686, and 2,446,687 and
U.S. Patent No. 3,935,257 and the sulfinyl carboxylates
described in Belgian Patent No. 840,623. Polycarboxylates
containing three carboxy groups include, in particular,
water-soluble citrates, aconitrates and citraconates as
well as succinate derivatives such as the
carboxymethyloxysuccinates described in British Patent No.
1,379,241, lactoxysuccinates described in Netherlands
Application 7205873, and the oxypolycarboxylate materials
such as 2-oxa-1,1,3-propane tricarboxylates described in
British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups
include oxydisuccinates disclosed in British Patent No.
1,261,829, 1~l~2~2-ethane tetracarboxylates, 1,1,3,3-
propane tetracarboxylates and 1,1,2,3-propane
.
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tetracarboxylates. Polycarboxylates containing sulfo
substituents include the sulfosuccinate derivatives
disclosed in British Patent Nos. 1,398,421 and 1,398,422
and in U.S. Patent No. 3,936,448, and the sulfonated
pyrolysed citrates described in British Patent No.
1,082,179, while polycarboxylates containing phosphone
substituents are disclosed in British Patent No. 1,439,000.
Alicyclic and heterocyclic polycarboxylates include
cyclopentane-cis,cis,cis-tetracarboxylates,
cyclopentadienide pentacarboxylates, 2,3,4, 5-tetrahydro-
furan - cis, cis, cis-tetracarboxylates, 2, 5-tetrahydro-
furan -cis - dicarboxylates, 2,2,5, 5-tetrahydrofuran
tetracarboxylates, 1,2, 3,4, 5,6-hexane -hexacar-boxylates
and and carboxymethyl derivatives of polyhydric alcohols
such as sorbitol, mannitol and xylitol. Aromatic poly-
carboxylates include mellitic acid, pyromellitic acid and
the phthalic acid derivatives disclosed in British Patent
No. 1, 425,343.
Of the above, the preferred polycarboxylates are
hydroxycarboxylates containing up to three carboxy groups
per molecule, more particularly citrates.
Preferred builder systems for use in the present
compositions include a mixture of a water-insoluble
aluminosilicate builder such as zeolite A or of a layered
silicate (SKS-6), and a water-soluble carboxylate chelating
agent such as citric acid. preferred builder system for
liquid detergent compositions of the present invention are
soaps and polycarboxylates.
A suitable chelant for inclusion in the detergent
compositions in accordance with the invention is
ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali
metal, alkaline earth metal, ammonium, or substituted
ammonium salts thereof, or mixtures thereof. Preferred EDDS
compounds are the free acid form and the sodium or
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magnesium salt thereof. Examples of such preferred sodium
salts of EDDS include Na2EDDS and Na4EDDS. Examples of such
preferred magnesium salts of EDDS include MgEDDS and
Mg2EDDS. The magnesium salts are the most preferred for
inclusion in compositions in accordance with the invention.
.
Preferred builder systems include a mixture of a
water-insoluble aluminosilicate builder such as zeolite A,
and a watersoluble carboxylate chelating agent such as
citric acid. Preferred builder systems for use in liquid
detergent compositions of the present invention are soaps
and polycarboxylates.
Other builder materials that can form part of the
builder system for use in granular compositions include
inorganic materials such as alkali metal carbonates,
bicarbonates, silicates, and organic materials such as the
organic phosphonates, amino polyalkylene phosphonates and
amino polycarboxylates.
Other suitable water-soluble organic salts are the
homo- or co-polymeric acids or their salts, in which the
polycarboxylic acid comprises at least two carboxyl
radicals separated from each other by not more than two
carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756.
Examples of such salts are polyacrylates of MW 2000-5000
and their copolymers with maleic anhydride, such copolymers
having a molecular weight of from 20,000 to 70,000,
especially about 40,000.
Detergency builder salts are normally included in
amounts of from 5~ to 80~ by weight of the composition
preferably from 10~ to 70% and most usually from 30~ to 60
by weight.
Suds suppressor
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Another optional ingredient is a suds suppressor,
exemplified by silicones, and silica-silicone mixtures.
Silicones can be generally represented by alkylated
polysiloxane materials while silica is normally used in
finely divided forms exemplified by silica aerogels and
xerogels and hydrophobic silicas of various types. These
materials can be incorporated as particulates in which the
suds suppressor is advantageously releasably incorporated
in a water-soluble or water-dispersible, substantially non-
surface-active detergent impermeable carrier. Alternatively
the suds suppressor can be dissolved or dispersed in a
liquid carrier and applied by spraying on to one or more of
the other components.
A preferred silicone suds controlling agent is
disclosed in Bartollota et al. U.S. Patent 3 933 672. Other
particularly useful suds suppressors are the self-
emulsifying silicone suds suppressors, described in German
Patent Application DTOS 2 646 126 published April 28, 1977.
An example of such a compound is DC-544, commercially
available from Dow Corning, which is a siloxane-glycol
copolymer. Especially preferred suds controlling agent are
the suds suppressor system comprising a mixture of silicone
oils and 2- alkyl-alcanols. Suitable 2- alkyl-alkanols are 2-
butyl-octanol which are commercially available under the
trade name Isofol 12 R.
Such suds suppressor system are described in Copending
European Patent application N 92870174.7 filed 10
November, 199 2.
Especially preferred silicone suds controlling agents
are described in Copending European Patent application
N~92201649. 8. Said compositions can comprise a
silicone/silica mixture in combination with fumed nonporous
silica such as AerosilR.
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The suds suppressors described above are normally
employed at levels of from 0.001% to 2% by weight of the
composition, preferably from 0.01% to 1% by weight.
Others
Other components used in cleaning compositions may be
employed, such as soil-suspending agents, soil-release
agents, optical brighteners, abrasives, bactericides,
tarnish inhibitors, coloring agents, and/or encapsulated or
non-encapsulated perfumes.
Especially suitable encapsulating materials are water
soluble capsules which consist of a matrix of
polysaccharide and polyhydroxy compounds such as described
in GB 1,464,616.
Other suitable water soluble encapsulating materials
comprise dextrins derived from ungelatinized starch acid-
esters of substituted dicarboxylic acids such as described
in US 3,455,838. These acid-ester dextrins are,preferably,
prepared from such starches as waxy maize, waxy sorghum,
sago, tapioca and potato. Suitable examples of said
encapsulating materials include N-Lok manufactured by
National Starch. The N-Lok encapsulating material consists
of a modified maize starch and glucose. The starch is
modified by adding monofunctional substituted groups such
as octenyl succinic acid anhydride.
Antiredeposition and soil suspension agents suitable
herein include cellulose derivatives such as
methylcellulose, carboxymethylcellulose and
hydroxyethylcellulose, and homo- or co-polymeric
polycarboxylic acids or their salts. Polymers of this type
include the polyacrylates and maleic anhydride-acrylic acid
copolymers previously mentioned as builders, as well as
copolymers of maleic anhydride with ethylene, methylvinyl
~.
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W O 98/0680g 50 PCTAUS96/12963
ether or methacrylic acid, the maleic anhydride
constituting at least 20 mole percent of the copolymer.
These materials are normally used at levels of from 0.5~ to
10~ by weight, more preferably from 0.75~ to 8%, most
preferably from 1~ to 6~ by weight of the composition.
Preferred optical brighteners are anionic in
character, examples of which are disodium 4,4'-bis-~2-
diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-
2:2' disulphonate, disodium 4, - 4'-bis-(2-morpholino-4-
anilino-s-triazin-6-ylamino-stilbene-2:2' - disulphonate,
disodium 4,4' - bis-~2,4-dianilino-s-triazin-6-
ylamino)stilbene-2:2' - disulphonate, monosodium 4',4''
bis-(2,4-dianilino-s-tri-azin-6 ylamino)stilbene-2-
sulphonate, disodium 4,4' -bis-(2-anilino-4-(N-methyl-N-2-
hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2'
disulphonate, di-sodium 4,4' -bis-(4-phenyl-2,1,3-triazol-
2-yl)-stilbene-2,2' disulphonate, di-so-dium 4,4'bis(2-
anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-
ylami-no)stilbene-2,2'disulphonate, sodium 2(stilbyl-4''-
(naphtho-1',2':4,5)-1,2,3 - triazole-2''-sulphonate and
4,4'-bis(2-sulphostyryl)biphenyl. Highly preferred
brighteners are the specific brighteners of copending
European Patent application No. 95201943.8.
Other useful polymeric materials are the polyethylene
glycols, particularly those of molecular weight 1000-10000,
more particularly 2000 to 8000 and most preferably about
4000. These are used at levels of from 0.20~ to 5~ more
preferably from 0.25~ to 2.5~ by weight. These polymers and
the previously mentioned homo- or co-polymeric
polycarboxylate salts are valuable for improving whiteness
maintenance, fabric ash deposition, and cleaning
performance on clay, proteinaceous and oxidizable soils in
the presence of transition metal impurities.
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Soil release agents useful in compositions of the
present invention are conventionally copolymers or
terpolymers of terephthalic acid with ethylene glycol
and/or propylene glycol units in various arrangements.
Examples of such polymers are disclosed in the commonly
assigned US Patent Nos. 4116885 and 4711730 and European
Published Patent Application No. 0 272 033. A particular
preferred polymer in accordance with EP-A-O 272 033 has the
formula
(CH3(PEG)43)0.75(poH)o.25[T-po)2.8(T-pEG)o.4]T(
H)0.25((pEG)43cH3)o.75
where PEG is -(OC2H4)O-,po is (OC3H60) and T is
( pcOC6H4 CO ) .
Also very useful are modified polyesters as random
copolymers of dimethyl terephthalate, dimethyl
sulfoisophthalate, ethylene glycol and 1-2 propane diol,
the end groups consisting primarily of sulphobenzoate and
secondarily of mono esters of ethylene glycol and/or
propane-diol. The target is to obtain a polymer capped at
both end by sulphobenzoate groups, "primarily", in the
present context most of said copolymers herein will be end-
capped by sulphobenzoate groups. However, some copolymers
will be less than fully capped, and therefore their end
groups may consist of monoester of ethylene glycol and/or
propane 1-2 diol, thereof consist "secondarily" of such
species.
The selected polyesters herein contain about 46~ by
weight of dimethyl terephthalic acid, about 1696 by weight
of propane -1.2 diol, about 10~ by weight ethylene glycol
about 13~ by weight of dimethyl sulfobenzoic acid and about
15~ by weight of sulfoisophthalic acid, and have a
molecular weight of about 3.000. The polyesters and their
... . . . ..... , . ,,, ............. ~
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method of preparation are described in detail in EPA 311
342.
Is is well known in the art that free chlorine in tap
water rapidly deactivates the enzymes comprised in
detergent compositions. Therefore, using chlorine scavenger
such as perborate, ammonium sulfate, sodium sulphite or
polyethyleneimine at a level above 0.1~ by weight of total
composition, in the formulas will provide improved through
the wash stability of the pectin enzyme. Compositions
comprising chlorine scavenger are described in the European
patent application 92870018.6 filed January 31, 1992.
Alkoxylated polycarboxylates such as those prepared
from polyacrylates are useful herein to provide additional
grease removal performance. Such materials are described
in WO 91/08281 and PCT 90/01815 at p. 4 et seq.,
incorporated herein by reference. Chemically, these
materials comprise polyacrylates having one ethoxy side-
chain per every 7-8 acrylate units. The side-chains are of
the formula ~(CH2CH2O)m(CH2)nCH3 wherein m is 2-3 and n is
6-12. The side-chains are ester-linked to the polyacrylate
"backbone" to provide a "comb" polymer type structure. The
molecular weight can vary, but is typically in the range of
about 2000 to about 50,000. Such alkoxylated
polycarboxylates can comprise from about 0. 05~ to about
10~, by weight, of the compositions herein.
Softening agent~
Fabric softening agents can also be incorporated into
laundry detergent compositions in accordance with the
present invention. These agents may be inorganic or organic
in type. Inorganic softening agents are exemplified by the
smectite clays disclosed in GB-A-l 400 898 and in USP
5,019,292. Organic fabric softening agents include the
water insoluble tertiary amines as disclosed in GB-Al 514
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276 and EP-B0 011 340 and their combination with mono C12-
C14 quaternary ammonium salts are disclosed in EP-B-0 026
527 and EP-B-0 026 528 and di-long-chain amides as
disclosed in EP-B-0 242 919. Other useful organic
ingredients of fabric softening systems include high
molecular weight polyethylene oxide materials as disclosed
in EP-A-0 299 575 and 0 313 146.
Levels of smectite clay are normally in the range from
2g~ to 20~, more preferably from 5~6 to 15~ by weight, with
the material being added as a dry mixed component to the
remainder of the formulation. Organic fabric softening
agents such as the water-insoluble tertiary amines or
dilong chain amide materials are incorporated at levels of
from 0.5~ to 5g6 by weight, normally from 1~ to 3g6 by weight
whilst the high molecular weight polyethylene oxide
materials and the water soluble cationic materials are
added at levels of from 0.1~ to 29~, normally from 0.15~ to
1.5~ by weight. These materials are normally added to the
spray dried portion of the composition, although in some
instances it may be more convenient to add them as a dry
mixed particulate, or spray them as molten liquid on to
other solid components of the composition.
Method of washinq
The compositions of the invention may be used in
essentially any washing or cleaning methods, including
soaking methods, pretreatment methods and methods with
rinsing steps for which a separate rinse aid composition
may be added.
The process described herein comprises contacting
fabrics with a laundering solution in the usual manner and
exemplified hereunder.
. _ ...... . . .
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The process of the inventlon is conveniently carried
out in the course of the cleaning process. The method of
cleaning is preferably carried out at 5~C to 95~C,
especially between 10~C and 60~C. The pH of the treatment
solution is preferably from 7 to ll.
A preferred machine dishwashing method comprises
treating soiled articles with an aqueous liquid having
dissolved or dispensed therein an effective amount of the
machine diswashing or rinsing composition. A conventional
effective amount of the machine dishwashing composition
means from 8-60 g of product dissolved or dispersed in a
wash volume from 3-lO litres.
According to a manual dishwashing method, soiled dishes are
contacted with an effective amount of the diswashing
composition, typically from 0.5-20g (per 25 dishes being
treated). Preferred manual dishwashing methods include the
application of a concentrated solution to the surfaces of
the dishes or the soaking in large volume of dilute
solution of the detergent composition.
The following examples are meant to exemplify
compositions of the present invention, but are not
necessarily meant to limit or otherwise define the scope of
the invention.
In the detergent compositions, the enzymes levels are
expressed by pure enzyme by weight of the total composition
and unless otherwise specified, the detergent ingredients
are expressed by weight of the total compositions. The
abbreviated component identifications therein have the
following meanings:
LAS : Sodium linear C12 alkyl benzene
sulphonate
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TAS : Sodium tallow alkyl sulphate
CXYAS : Sodium C1x - C1y alkyl sulfate
25EY : A C12_C1s predominantly linear primary
alcohol condensed with an average of Y
moles of ethylene oxide
CXYEZ : A ClX - Cly predominantly linear primary
alcohol condensed with an average of Z
moles of ethylene oxide
XYEZS : ClX - Cly sodium alkyl sulfate condensed
with an average of Z moles of ethylene
oxide per mole
QAS R2.N+(CH3)2 ~C2H40H) with R2 = C12-C14
Soap : Sodium linear alkyl carboxylate derived
from a 80/20 mixture of tallow and
coconut oils.
Nonionic : C13-C1s mixed ethoxylated/propoxylated
fatty alcohol with an average degree of
ethoxylation of 3.8 and an average
degree of propoxylation of 4.5 sold
under the tradename Plurafac LF404 by
BASF Gmbh.
CFAA : C12-C14 alkyl N-methyl glucamide
TFAA : C16-C1g alkyl N-methyl glucamide.
TPKFA : C12-C14 topped whole cut fatty acids.
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DEQA : Di-(tallow-oxy-ethyl) dimethyl ammonium
chloride.
SDASA : 1:2 ratio of stearyldimethyl
amine:triple-pressed stearic acid.
Neodol 45-13 : C14-C15 linear primary alcohol
ethoxylate, sold by Shell Chemical CO.
Silicate : Amorphous Sodium Silicate (SiO2:Na2O
ratio = 2.0)
NaSKS-6 : Crystalline layered silicate of formula
â-Na2si2o5 .
Carbonate : Anhydrous sodium carbonate with a
particle size between 200 ~m and 900~m.
Bicarbonate : Anhydrous sodium bicarbonate with a
particle size between 400 ~m and 1200~m.
STPP : Anhydrous sodium tripolyphosphate
MA/AA : Copolymer of 1:4 maleic/acrylic acid,
average molecular weight about 80,000
PA30 : Polyacrylic acid of average molecular
weight of approximately 8,000.
Terpolymer : Terpolymer of average molecular weight
approx. 7,000, comprising
acrylic:maleic:ethylacrylic acid monomer
units at a weight ratio of 60:20:20
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480N : Random copolymer of 3:7
acrylic/methacrylic acid, average
molecular weight about 3,500.
Polyacrylate : Polyacrylate homopolymer with an average
molecular weight of 8,000 sold under the
tradename PA30 by BASF GmbH
Zeolite A : Hydrated Sodium Aluminosilicate of
formula Nal2(AlO2SiO2)12. 27H20 having a
primary particle size in the range from
0.1 to 10 micrometers
Citrate : Tri-sodium citrate dihydrate of activity
86,4~ with a particle size distribution
between 425 ~m and 850 ~m.
Citric : Anhydrous citric acid
PB1 : Anhydrous sodium perborate monohydrate
bleach, empirical formula NaBO2.H2O2
PB4 : Anhydrous sodium perborate tetrahydrate
Percarbonate : Anhydrous sodium percarbonate bleach of
empirical formula 2Na2CO3.3H2O2
TAED : Tetraacetyl ethylene diamine.
NOBS : Nonanoyloxybenzene sulfonate in the form
of the sodium salt.
Photoactivated : Sulfonated zinc phtlocyanine
Bleach encapsulated in dextrin soluble polymer.
PAAC : Pentaamine acetate cobalt(III) salt.
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Paraffin : Paraffin oil sold under the tradename
Winog 70 by Wintershall.
BzP : Benzoyl Peroxide.
Poly : Alkaline polygalacturonase as described
galacturonase in Agr. Biol. Chem. (1972) 36(2) 285-93.
Protease : Proteolytic enzyme sold under the
tradename Savinase, Alcalase, Durazym by
Novo Nordisk A/S, Maxacal, Maxapem sold
by Gist-Brocades and proteases described
in patents WO91/06637 and/or WO95/10591
and/or EP 251 446.
Amylase : Amylolytic enzyme sold under the
tradename Purafact Ox Am~ described in
WO 94/18314, sold by Genencor; Termamyl~
, Fungamyl~ and Duramyl , all available
from Novo Nordisk A/S and those
described in W095/26397.
Lipase : Lipolytic enzyme sold under the
tradename Lipolase, Lipolase Ultra by
Novo Nordisk A/S
Cellulase : Cellulytic enzyme sold under the
tradename Carezyme, Celluzyme and/or
Endolase by Novo Nordisk A/S.
CMC : Sodium carboxymethyl cellulose.
HEDP : l,l-hydroxyethane diphosphonic acid.
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DETPMP Diethylene triamine penta (methylene
phosphonic acid), marketed by Monsanto
under the Trade name Dequest 2060.
PVNO : Poly(4-vinylpyridine)-N-Oxide.
PVPVI : Poly (4-vinylpyridine)-N-oxide/copolymer
of vinyl-imidazole and vinyl-
pyrrolidone.
Brightener 1 : Disodium 4,4'-bis(2-
sulphostyryl)biphenyl.
Brightener 2 : Disodium 4,4'-bis(4-anilino-6-
morpholino-1.3.5-triazin-2-yl) stilbene-
2:2'-disulfonate.
Silicone : Polydimethylsiloxane foam controller
antifoam with siloxane-oxyalkylene copolymer as
dispersing agent with a ratio of said
foam controller to said dispersing agent
of 10:1 to 100:1.
Granular Suds : 12~ Silicone/silica, 18~ stearyl
Suppressor alcohol,70~ starch in granular form
SRP 1 : Sulfobenzoyl end capped esters with
oxyethylene oxy and terephtaloyl
backbone.
SRP 2 : Diethoxylated poly (1,2 propylene
terephtalate) short block polymer.
Sulphate : Anhydrous sodium sulphate.
HMWPEO : High molecular weight polyethylene oxide
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PEG : Polyethylene glycol.
BTA : Benzotriazole
Bismuth nitrate : Bismuth nitrate salt
NaDCC : Sodium dichloroisocyanurate
Encapsulated : Insoluble fragrance delivery technology
perfume utilising zeolite 13x, perfume and a
particles dextrose/glycerin agglomerating binder.
KOH : 100~ Active solution of Potassium
Hydroxide
pH : Measured as a 1~ solution in distilled
water at 20~C.
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Example 1
The following laundry detergent compositions were prepared
in accord with the invention:
I II III IV V VI
LAS 8.0 8.0 8.0 8.0 8.0 8.0
C25E3 3.4 3.4 3.4 3.4 3.4 3 4
QAS - 0.8 0.8 - 0.8 0.8
Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1
Carbonate 13.0 13.0 13.0 27.0 27.0 27.0
Silicate 1.4 1.4 1.4 3.0 3.0 3.0
Sulfate 26.1 26.1 26.1 26.1 26.1 26.1
PB4 9.0 9.0 9.0 9.0 9.0 9.0
TAED 1.5 1.5. 1.5 1.5 1.5 1.5
DETPMP 0.25 0.25 0.25 0.25 0.25 0.25
HEDP 0.3 0.3 0.3 0.3 0.3 0.3
Poly 0.005 0.01 0.05 0.01 0.02 0.08
galacturonase
Protease 0.0026 0.0026 0.0026 0.0026 0.0026 0.0026
Amylase 0.0009 0.0009 0.0009 0.0009 0.0009 0.0009
MA/AA 0.3 0.3 0.3 0.3 0.3 0.3
CMC 0.2 0.2 0.2 0.2 0.2 0.2
Photoactivated 15 15 15 15 15 15
bleach (ppm)
Brightener 10.09 0.09 0.09 0.09 0.09 0.09
Perfume 0.3 0.3 0.3 0.3 0.3 0.3
Silicone 0.5 0.5 0.5 0.5 0.5 0.5
antifoam
Misc/minors to 100%
Density in 850 850 850 850 850 850
g/litre
_ .. . . , .. . , .. , . ,, . .. .. _ .,
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Example 2
The following granular laundry detergent compositions of
bulk density 750 g/litre were prepared in accord with the
invention:
I II III
LAS 5.25 5.61 4.76
TAS 1.25 1.86 1.57
C45AS - 2.24 3.89
C25AE3S - 0.76 1.18
C45E7 3.25 - 5.0
C25E3 - 5.5
QAS 0.8 2.0 2.0
STPP 19.7
Zeolite A - 19.5 19.5
NaSKS-6/citric acid - 10.6 10.6
(79:21)
Carbonate 6.1 21.4 21.4
Bicarbonate - 2.0 2.0
Silicate 6.8
Sodium sulfate 39.8 - 14.3
PB4 5.0 12.7
TAED 0.5 3.1
DETPMP 0.25 0.2 0.2
HEDP - 0.3 0.3
Poly galacturonase 0.001 0.02 0.005
Protease 0.0026 0.0085 0.045
Lipase 0.003 0.003 0.003
Cellulase 0.0006 0.0006 0.0006
Amylase 0.0009 0.0009 0.0009
MA/AA 0.8 1.6 1.6
CMC 0.2 0.4 0.4
Photoactivated 15 ppm 27 ppm 27 ppm
bleach (ppm)
Brightener 1 0.08 0.19 0.19
Brightener 2 - 0.04 0.04
Encapsulated perfume0.3 0.3 0.3
particles
Silicone antifoam 0.5 2.4 2.4
Minors/misc to 100~
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Example 3
The following detergent formulations, according to the
present invention were prepared, where I is a phosphorus-
containing detergent composition, II is a zeolite-
containing detergent composition and III is a compact
detergent composition:
I II III
Blown Powder
STPP 24.0 - 24.0
Zeolite A - 24.0
C45AS 9.0 6.0 13.0
MA/AA 2.0 4.0 2.0
LAS 6.0 8.0 11.0
TAS 2.0
Silicate 7.0 3.0 3.0
CMC 1.0 1.0 0.5
Brightener 2 0.2 0.2 0.2
Soap 1.0 1.0 1.0
DETPMP 0.4 0.4 0.2
Spray On
C45E7 2.5 2.5 2.0
C25E3 2.5 2.5 2.0
Silicone antifoam 0.3 0.3 0.3
Perfume 0.3 0.3 0.3
Dry additives
Carbonate 6.0 13.0 15.0
PB4 18.0 18.0 10.0
PB1 4.0 4.0 0
TAED 3.0 3.0 1.0
Photoactivated 0.02 0.02 0.02
bleach
Poly galacturonase 0.05 0.05 0.01
Protease 0.01 0.01 0.01
Lipase 0.009 0.009 0.009
Amylase 0.002 0.003 0.001
Dry mixed sodium 3.0 3.0 5.0
sulfate
Balance (Moisture &100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 630 670 670
. _ , ,, , _, ... . . .
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ExamPle 4
The following nil bleach-containing detergent formulations
of particular use in the washing of colored clothing,
according to the present invention were prepared:
I II III
Blown Powder
Zeolite A 15.0 15.0
Sodium sulfate 0.0 5.0
LAS 3.0 3.0
DETPMP 0.4 0.5
CMC 0.4 0.4
MA/AA 4.0 4.0
Agglomera tes
C45AS - - 11. 0
LAS 6.0 5.0
TAS 3.0 2.0
Silicate 4.0 4.0
Zeolite A 10.0 15.0 13.0
CMC - - 0 5
MA/AA - - 2.0
Carbonate 9.0 7.0 7.0
Spray On
~Perfume 0.3 0.3 0.5
C45E7 4.0 4.0 4.0
C25E3 2.0 2.0 2.0
Dry additives
MA/AA - - 3.0
NaSKS-6 - - 12.0
Citrate 10.0 - 8.0
Bicarbonate 7.0 3.0 5.0
Carbonate 8.0 5.0 7.0
PVPVI/PVNO 0.5 0.5 0.5
Poly galacturonase 0.05 0.005 0.02
Protease 0.026 0.016 0.047
Lipase 0.009 0.009 0.009
Amylase 0.005 0.005 0.005
Cellulase 0.006 0.006 0.006
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 9.0 0.0
Balance tMoisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 700 700 700
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Example 5
The following detergent formulations, according to the
present invention were prepared:
II III IV
LAS 20.0 14.0 24.0 22.0
QAS 0.7 1.0 - 0.7
TFAA - 1.0 - -
C25E5/C45E7 - 2.0 - 0.5
C45E3S - 2.5
STPP 30.0 18.0 30.0 22.0
Silicate 9.0 5.0 10.0 8.0
Carbonate 13.0 7.5 - 5.0
Bicarbonate - 7.5
DETPMP 0.7 1.0
SRP 1 0.3 0.2 - 0.1
MA/AA 2.0 1.5 2.0 1.0
CMC 0.8 0.4 0.4 0.2
Poly 0.08 0.04 0.05 0.01
galacturonase
Protease 0.008 0.01 0.026 0.026
Amylase 0.007 0.004 - 0.002
Lipase 0.004 0.002 0.004 0.002
Cellulase 0.0015 0.0005
Photoactivated 7Oppm 45ppm - lOppm
bleach (ppm)
Brightener 1 0.2 0.2 0.08 0.2
PB1 6.0 2.0
NOBS 2.0 1.0
Balance 100 100 100 100
(Moisture and
Miscellaneous)
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Example 6
The following detergent formulations, according to the
present invention were prepared:
I II III IV
Blown Powder
Zeolite A 30.0 22.0 6.0 6.7
Na SkS-6 - - _ 3.3
Polycarboxylate - - - 7.1
Sodium sulfate 19.0 5.0 7.0
MA/AA 3.0 3.0 6.0
LAS 14.0 12.0 22.0 21.5
C45AS 8.0 7.0 7.0 5.5
Cationic - - - 1.0
Silicate - 1.0 5.0 11.4
Soap - - 2.0
Brightener 1 0.2 0.2 0.2
Carbonate 8.0 16.0 20.0 10.0
DETPMP - 0.4 0.4
Spray On
C45E7 1.0 1.0 1.0 3.2
Dry additives
PVPVI/PVNO 0.5 0.5 0.5
Poly galacturonase0.005 0.01 0.01 0.005
Protease 0.052 0.01 0.01 0.01
Lipase 0.009 0.009 0.009 0.009
Amylase 0.001 0.001 0.001 0.001
Cellulase 0.0002 0.0002 0.0002 0.0002
NOBS - 6.1 4.5 3.2
PB1 1.0 5.0 6.0 3.9
Sodium sulfate - 6.0 - to
balance
Balance (Moisture 100 100 100
and Miscellaneous)
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Example 7
The following high density and bleach-containing detergent
formulations, according to the present invention were
prepared:
I II III
- Blown Powder
Zeolite A15.0 15.0 15.0
Sodium sulfate 0.0 5.0 0.0
LAS 3.0 3.0 3 0
QAS - 1.5 1.5
DETPMP 0.4 0.4 0.4
CMC 0.4 0.4 0 4
MA/AA 4.0 2.0 2.0
Agglomerates
LAS 5.0 5.0 5 0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
Spray On
Perfume 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0 - _
Dry additives
Citrate 5.0 - 2.0
Bicarbonate - 3.0
Carbonate 8.0 15.0 10.0
TAED 6.0 2.0 5.0
PB1 14.0 7.0 10.0
Polyethylene oxide of MW - - 0.2
5,000,000
Bentonite clay - - 10.0
Poly galacturonase 0.005 0.01 0.08
Protease 0.01 0.01 0.01
Lipase 0.009 0.009 0.009
Amylase 0.005 0.005 0.005
Cellulase 0.002 0.002 0.002
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 850 850 850
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Exam~le 8
The following high density detergent formulations,
according to the present invention were prepared:
I II
Agglomerate
C45AS 11.0 14.0
Zeolite A 15.0 6.0
Carbonate 4.0 8.0
MA/AA 4.0 2.0
CMC 0.5 o 5
DETPMP 0.4 0.4
Spray On
C25E5 5.0 5.0
Perfume 0.5 0.5
Dry Adds
HEDP 0.5 0.3
SKS 6 13.0 10.0
Citrate 3.0 1.0
TAED 5.0 7.0
Percarbonate 20.0 20.0
SRP 1 0.3 0.8
Poly galacturonase 0.02 0. 05
Protease 0.04 0.04
Lipase 0.009 0.009
Cellulase 0.004 0.004
Amylase 0. 005 0. 005
Silicone antifoam 5.0 5.0
Brightener 1 0.2 0.2
Brightener 2 0.2
Balance (Moisture and 100 100
Miscellaneous)
Density (g/litre) 850 850
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Example 9
The following granular detergent formulations, according to
the present invention were prepared:
I II III IV V
LAS 21.0 25.0 18.0 18.0
Coco C12-14 AS - - - - 21.9
AE3S - - 1.5 1.5 2.3
Decyl dimethyl - 0.4 0.7 0.7 0.8
hydroxyethyl NH4+Cl
Nonionic 1.2 - o g 0 5
Coco C12-14 Fatty - - - - 1.0
Alcohol
STPP 44.0 25.0 22.5 22.5 22.5
Zeolite A 7.0 10.0 - - 8.0
MA/AA - - o.g o.g
SRPl 0.3 0.15 0.2 0.1 0.2
CMC 0.3 2.0 0.75 0.4 1.0
Carbonate 17.5 29.3 5.0 13.0 15.0
Silicate 2.0 - 7.6 7.9
Poly galacturonase0.0050.01 0.007 0.01 0.01
Protease 0.0070.007 0.007 0.007 0.007
Amylase - 0.004 0.004 0.004 0.004
Lipase 0.0030.003 0.003
Cellulase - 0.001 0.001 0.001 0.001
NOBS - - - 1.2 1.0
PB1 - - - 2.4 1.2
Diethylene triamine - - - 0.7 1.0
penta acetic acid
Diethylene triamine - - 0.6
penta methyl
phosphonic acid
Mg Sulfate - - 0.8
Photoactivated bleach 45 50 15 45 42
ppm ppmppm ppm ppm
Brightener 1 0.05 - 0.04 0.04 0.04
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Brightener 2 0.1 0.3 0.05 0.13 0.13
Water and Mlnors up to 100~
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Example 10
The following liquid detergent formulations, according to
the present invention were prepared:
I II III IV V VI VII VIII
LAS 10.0 13.0 9.0 - 25.0 - - -
C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 15.
C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0
C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0
TFAA - - - 4.5 - 6.0 8.0 8.0
QAS - - - - 3.0 1.0
TPKFA 2.0 - 13.0 2.0 - 15.0 7.0 7.0
Rapeseed - - - 5.0 - -4 0 4 0
fatty acids
Citric 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0
Dodecenyl/ 12.0 10.0 - - 15.0
tetradecenyl
succlnlc acld
Oleic acid 4.0 2.0 1.0 - 1.0 - - -
Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0
1,2 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.-
Propanediol
Mono Ethanol - - - 5.0 - - 9.0 9.0
Amine
Tri Ethanol - - 8
Amine
NaOH (pH) 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2
Ethoxylated 0.5 - 0.5 0.2 - - 0.4 0.3
tetraethylene
pentamine
DETPMP 1.0 1.0 0.5 1.0 2.0 1.2 1.0
SRP 2 0.3 - 0.3 0.1 - - 0.2 0.1
PVNO - - - - - -- 0.10
Poly .005 .005 .004 .003 .008 .005.003 .006
galacturonase
Protease .016 .016 .013 .008 .048 .0160.01 .019
Lipase - .002 - .001 - - 003 .00
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Amylase .002 .002.005 .004 .002 .008.005 .005
Cellulase - -- .ooo - - ooo ooo
1 2
Boric acid 0.1 0.2- 2.0 1.0 1.52.5 2.5
Na formate - - 1.0 - - - _ _
Ca chloride - 0.01 - 0.01
Bentonite - - - - 4.0 4 0
clay
Suspending - - - - 0.6 0.3
clay SD3
Balance 100 100 100 100 100 100 100 100
Moisture and
Miscellaneous
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ExamPle 1 1
Granular fabric cleaning compositions which provide
"softening through the wash" capability were prepared in
accord with the present invention :
I II
45AS - 10.0
LAS 7.6
68AS 1.3
45E7 4.0
25E3 - 5 0
Coco-alkyl-dimethyl hydroxy- 1.4 1.0
ethyl ammonium chloride
Citrate 5.0 3.0
Na-SKS-6 - 11.0
Zeolite A 15.0 15.0
MA/AA 4.0 4.0
DETPMP o 4 o 4
P~31 15.0
Percarbonate - 15.0
TAED 5.0 5 0
Smectite clay 10.0 10.0
HMWPEO - 0.1
Poly galacturonase 0.01 0.01
Protease 0.02 0.1
Lipase 0.02 0.01
Amylase 0.03 0.005
Cellulase 0.001
Silicate 3.0 5.0
Carbonate 10.0 10.0
Granular suds suppressor 1.0 4.0
CMC 0.2 0.1
Water/minors Up to 100~
.. _~, .. , . ,. . ~
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Exam~le 12
The following rinse added fabric softener composition
was prepared in accord with the present invention :
Softener active 20.0
Poly galacturonase 0.01
Amylase 0.001
Cellulase 0.001
HCL 0.03
Antifoam agent 0.01
Blue dye 25ppm
CaCl2 0.20
Perfume o.go
Water / minors Up to 100~
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Example 13
The following fabric softener composition was prepared
in accord with the present invention :
I II III
DEQA 2.6 19.0
SDASA _ _ 70 0
Stearic acid of IV=O 0.3 _ _
Neodol 45-13 - - 13.0
Hydrochloride acid 0.02 0.02
Ethanol - - 1.0
PEG - 0.6
Poly galacturonase 0. 005 0.05 0.01
Perfume 1.0 1.0 0.75
Digeranyl Succinate - - 0.38
Silicone antifoam 0.01 0.01
Electrolyte - 60Oppm
Dye lOOppm 50ppm 0.01
Water and minors 100~ 100~
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Example 14
Syndet bar fabric cleaning compositions were prepared
in accord with the present invention :
I II III IV
C26 AS 20.00 20.00 20.00 20.00
CFAA 5 0 5 0 5 o 5 0
~AS (C11-13) 10.0 10.0 10.0 10.0
Sodium carbonate 25.0 25.0 25.0 25.0
Sodium pyrophosphate 7.0 7.0 7.0 7.0
STPP 7. 0 7.0 7.0 7.0
Zeolite A 5.0 5.0 5.0 5.0
CMC 0.2 0.2 0.2 0.2
Polyacrylate (MW 1400) 0.2 0.2 0.2 0.2
Coconut monethanolamide 5.0 5.0 5.0 5.0
Poly galacturonase 0.1 0.1 0.15 0.2
Amylase 0.01 0.02 0.01 0.01
Protease 0.3 - 0.5 0.05
Brightener, perfume 0.2 0.2 0.2 0.2
CaS04 1.0 1.0 1.0 1.0
MgSO4 1.0 1.0 1.0 1.0
Water 4.0 4.0 4.0 4.0
Filler* : balance to 100~
*Can be selected from convenient materials such as CaC03,
talc, clay (Kaolinite, Smectite), silicates, and the li~e.
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ExamPle 15
The following compact high density (0.96Kg/l)
dishwashing detergent compositions I to VI were prepared in
accord with the present invention:
I II III IV V VI
STPP - - 49.0 38.0
Citrate 33.0 17.5 - - 54.0 25.4
Carbonate - 17. 5 _ 20.0 14.0 25.4
Silicate 33.0 14.8 20.4 14.8 14.8
Metasilicate - 2. 5 2.5
PB1 1.9 9.7 7.8 14.3 7.8
PB4 8.6
Percarbonate - - - - - 6.7
Nonionic 1.5 2.0 1.5 1.5 1.5 2.6
TAED 4.8 2.4 2.4 - 2.4 4.0
HEDP 0.8 1.0 0.5
DETPMP 0.6 0.6
PAAC - - - 0.2
BzP - - - 4.4
Paraffin 0.5 0.5 0.5 0.5 0.5 0.2
Poly 0.07 0.05 0.1 0.1 0.08 0.01
galacturonase
Protease 0.075 0.05 0.10 0.10 0.08 0.01
Lipase - 0.001 - 0.005
Amylase 0.01 0.0050.015 0.015 0.010.0025
BTA 0.3 0.3 0.3 0.3 0.8
Bismuth Nitrate - 0.3
PA30 4.0
Terpolymer - - - 4.0
480N - 6.0 2.8
Sulphate 7.1 20.8 8.4 - 0.5 1.0
pH (1~ solution) 10.8 11.0 10.9 10.8 10.9 9.6
~ .. . . .. . .. . .
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ExamPle 16
The following granular dishwashing detergent
compositions examples I to IV of bulk density 1.02Kg/L were
prepared in accord with the present invention :
I II III IV V VI
STPP 30.0 30.0 30.0 27.9 34.5 26.7
Carbonate 30.5 30.5 30 5 23.0 30.5 2.80
Silicate 7.4 7.4 7 4 12.0 8.0 20.3
PBl 4.4 4.4 4.4 - 4 4
NaDCC - - - 2.0 - 1.5
Nonionic 0.75 0.75 0.75 1.9 1.2 0.5
TAED 1.0 1.0 - - 1.0
PAAC - - 0 004
BzP - 1.4
Paraffin 0.25 0.25 0.25
Poly 0.01 0.01 0.01 0.05 0.01 0.05
galacturonase
Protease 0.05 0.05 0.05 - 0.1
Lipase 0.005 - 0.001
Amylase 0.003 0.001 0.01 0.02 0.01 0.015
BTA 0.15 - 0.15
Sulphate 23.9 23.9 23.9 31.4 17.4
pH (1~ solution) 10.8 10.8 10.8 10.7 10.7 12.3
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Example 17
The following detergent composition tablets of 25g
weight were prepared in accord with the present invention
by compression of a granular dishwashing detergent
composition at a pressure of 13KN/cm2 using a standard 12
head rotary press:
I II III
STPP 48.8 47.5
Citrate 26.4 - -
Carbonate - 5.0
Silicate 26.4 14.8 25.0
Poly galacturonase 0.007 0.01 0.05
Protease 0.03 0.075 0.01
Lipase 0.005
Amylase 0.01 0.005 0.001
PBl 1.6 7.8
PB4 6.9 - 11.4
Nonionic 1.2 2.0 1.1
TAED 4.3 2.4 0.8
HEDP 0 7
DETPMP 0.65
Paraffin 0.4 0.5
BTA 0.2 0.3
PA30 3.2
Sulphate 25.0 14.7 3.2
pH (1~ solution) 10.6 10.6 11.0
... ..
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Example l8
The following liquid dishwashing detergent
compositions were prepared in accord with the present
invention I to II, of density 1.40Kg/L :
I II
STPP 33.3 20.0
Carbonate 2.7 2.0
Silicate - 4.4
NaDCC l.l l.15
Nonionic 2.5 l.0
Paraffin 2.2
Poly galacturonase 0.005 0.05
Protease 0.03 0.02
Amylase 0.005 0.0025
480N 0 50 4 00
KOH - 6.00
Sulphate l.6
pH (l~ solution) 9.l l0.0
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Example 19
The following liquid hard surface cleaning
compositions were prepared in accord with the present
invention :
I II III IV V VI
Poly galacturonase 0.005 0.01 0.02 0.02 0.005 0.005
Amylase 0.01 0.002 0.005 0.02 0.001 0.005
Protease 0.05 0.01 0.02 0.03 0.005 0.005
EDTA* - - 2.90 2.90 - -
Citrate - - - - 2.90 2.90
LAS 1.95 - 1.95 - 1.95
C12 AS - 2.20 - 2.20 - 2.20
NaC12(ethoxy) - 2.20 - 2.20 - 2.20
**sulfate
C12 Dimethylamine - 0.50 - 0.50 - 0.50
oxide
SCS 1.30 - 1.30 - 1.30
Hexyl Carbitol**6.306.30 6.30 6.30 6.30 6.30
Water Balance to 100
*Na4 ethylenediamine diacetic acid
**Diethylene glycol monohexyl ether
***All formulas adjusted to pH 7
_. .. . .
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Example 20
The following spray composition for cleaning of hard
surfaces and removing household mildew was prepared in
accord with the present invention :
Poly galacturonase 0.01
Amylase 0.01
Protease 0.01
Sodium octyl sulfate 2.00
Sodium dodecyl sulfate 4.00
Sodium hydroxide 0. 80
Silicate (Na) 0.04
Perfume 0.35
Water/minors up to 100
