Note: Descriptions are shown in the official language in which they were submitted.
CA 02227752 1998-O1-23
WO 97/04067 PCT/US96/11898
1
DINGY FABRIC CLEAN-UP WITH AMYLASE
ENZYME IN DETERGENT COMPOSITIONS
TECHNICAL FIELD
The present invention relates to granule, liquid, or bar detergent
compositions
comprising certain levels of specially selective amylase enzymes which boost
fabric
laundry performance especially on dingy stains and soil. The detergent
compositions
preferably further comprise other enzymes and surfactants.
BACKGROUND OF THE INVENTION
It has been found that amylase enzymes in detergent compositions provide
surprisingly effective cleaning. These amylase enzymes show new and unexpeced
dingy cleaning benefits and whiteness maintenance.
Amylase enzymes have long been recognized in dishwashing compositions to
provide the removal of starchy food residues or starchy films from dishware,
flatware, and glasses. A typical amyolytic enzyme for use in dishwash is
TEPSvIfAMYLR available from Novo Nordisk S/A. Therefore, while amylase is
known to act on starch stains, there remains a substantial technical challenge
in
formulating laundry components comprising amylase and surfactants in such a
manner as to meet the consumer's need for superior cleaning performance on
starchy
soils as well as other soils typically encountered in laundry applications.
Moreover,
such detergent compositions must provide an excellent value and a safe,
environmentally acceptable product which leaves laundered fabrics, especially
those
particularly prone to dingy soiling, in dingy-free and undamaged condition. A
need
therefore exists for the development of detergent compositions comprising
amylase
enzymes designed to be especially effective at dingy clean up.
It is an object of the instant invention to provide improved laundry
compositions containing amyolytic enzymes which provide effective dingy stain
removal and overall cleaning benefits. It is a further object to provide a
means for
maintaining whiteness of fabrics using laundry compositions containing amylase
enzyme and surfactant. In another aspect of the invention, it is an object
herein to
provide fully-formulated laundry compositions wherein the amylases are
combined
with additional selected ingredients so as to deliver superior cleaning
results. These
and other objects are secured herein, as will be seen from the following
disclosures.
BACKGROUND ART
WO/94/02597, Novo Nordisk A/S, published Feb. 3, 1994, describes cleaning
CA 02227752 2001-10-03
2
compositions which incorporate mutant amylases. See also WO 94/18314 A,
Genecor, published August 18, 1994, and WO 95/10603, Novo Nordisk A/S,
published April 20, 1995.
Suitable amylases for use in the compositions of this invention include both
ac
and B amylases. oc-amylases are known in the art and include those disclosed
in U.S.
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).
SCTMMARY OF TH1; INVENTION
It has now surprisingly been discovered that amylase enzymes, particularly
those recently developed by conventional genetic engineering techniques,
provide
unexpected, superior dingy clean up, whiteness maintenance, and overall
cleaning
performance. Such performance is illustrated by, but not limited to, excellent
soil
removal on pillow cases, T-shirts and sock bottoms.
This invention relates to liquid, granule, or bar detergent compositions which
provide especially effective surface cleaning of textiles. This invention also
relates to
methods for cleaning fabrics using such detergent compositions.
A laundry detergent composition for cleaning and whitening dingy fabrics
laundered therewith, which composition comprises:
A. a detergent surfactant which is selected from the group consisting of
anionic,
nonionic, cationic, ampholytic and zwitterionic surfactants and combinations
thereof
and which is present at a level of from about 1% to about 40% by weight of the
composition thereof; and
B. one or more amylase enzymes which are present in
an amount of 0.001% to 0.1% by weight of active enzyme
and that is effective to increase the whiteness of dingy fabrics laundered
with laundry
solutions formed from said detergent compositions in comparison with similar
compositions which contain no amylase.
The present invention also relates to methods for laundering fabrics to
maintain
or increase whiteness and provide dingy cleanup, said method comprising
contacting
fabrics in need of whiteness and dingy clean-up with an aqueous solution
formed
from a detergent composition comprising surfactant and amylase enzyme at a
concentration such that the whitening performance of said composition is
increased
in comparison with similar compositions which contain no amylase.
The present invention also relates to a method for laundering fabrics to
reduce
the odors associated with soils and stains, said method comprising contacting
stained
and soiled fabrics in need of odor control with an aqueous solution formed
from a
detergent composition comprising surfactant and amylase enzyme, said detergent
CA 02227752 2001-10-03
_ 3
composition is present at a concentration such that the reduction in odor
associated
with said soils and stains is increased as compared to the reduction in odor
associated
with soiled fabrics washed with similar compositions which contain no amylase.
Finally, the present invention relates to methods for laundering fabrics to
maintain or increase whiteness and provide dingy cleanup, said method
comprising
contacting fabrics in need of whiteness and dingy clean-up with an aqueous
solution
formed from a detergent composition comprising surfactant and amylase enzyme
in
multiple wash cycles or for a sufficient period of time such that the fabrics
appear
whitened and less dingy.
All parts, percentages and ratios used herein are expressed as percent weight
unless otherwise specified.
DETAILED DESCRIPTION OF THE 1T1VENTION
The detergent compositions herein are preferably nonphosphate laundry
detergents which contain amylase enzyme and surfactants for good cleaning of
soiled
laundry. For purposes of this invention, the term "liquid" refers to detergent
compositions in any suitable liquid form, e.g., structured liquids, isotropic
liquids,
gels, etc.
The laundry detergent compositions herein provide effective and e~cient
surface cleaning of textiles, particularly on dingy stains over a wide range
of laundry
washing temperatures. Examples of dingy stains are those typically found on
pillow
cases, T-shirts, and sock bottoms. Laundry wash solutions are preferably at
temperatures between about SoC and about 95oC, preferably between about lOoC
and about 60oC, for this cleaning benefit.
Without limitation by theory, it is believed that dingy soils and stains are
the
result of combinations of fatty soils and particulate soils. Fatty soils
comprise lipids,
proteins, and pigments that are deposited on fabrics from contact with human
or
animal skin. The majority of lipids are secreted from the sebecous gland as
sebum.
Proteins and pigments from skin fragments are liberated by the breakdown of
skin
cells. Particulate soils comprise mostly airborne soil and ffoor/ground dust.
It is
believed that sebum is the major soil present on laundry, and its removal is
important
because unremoved fat acts as a matrix to hold particulate soils. Further it
is
believed that compounds present in the sebum oxidize to contribute to
yellowing of
fabrics. Particulate soils include topsoil and products produced during the
incomplete combustion of petroleum products. "Dingy clean-up", as used herein,
means the ability of a detergent composition to remove such dingy soil build-
up, over
one or more washes, resulting in a measurable improvement in fabric
appearance.
CA 02227752 1998-O1-23
WO 97/04067 PCT/US96/11898
4
Whiteness maintenance is the monitoring of the whiteness of wash & wear
fabrics over a number of washing cycles. A good performing detergent has a
good
whiteness maintenance profile, i.e. it ensures that the whiteness of washed
fabrics is
maintained at a high level during the complete life cycle of wearing &
washing.
"Whitening performance", as used herein, means the relative ability of laundry
detergent compositions comprising certain selected amylase to produce dingy
clean-
up and/or whiteness maintenance results.
The performance on dingy clean-up can be measured in teams of the Hunter
Whiteness Values (V~, which is calculated according to the following equation:
W=(7L2-40Lb)/700
wherein L,a,b are determined from a tristimulus meter reading and represent a
three
axis opponent color scale system based on the theory that color is perceived
by
black-white (L), red-green (a), and yellow-blue (b) sensations. The higher the
value
for W, the better the whiteness performance and dingy clean-up. See R. S.
Hunter
and R. W. Harold, The Measurement of Anpearance~ Second Ed., John Whey &
Sons, New York, 1987 and ASTM Standards on Color and Appearance
measurement. Third Ed., ASTM, Philadelphia, PA, 1991.
Amylase Enzymes - The detergent compositions of the present invention
comprise from about 0.001 mg to about 2 mg, preferably from about 0.01 to
about 1
mg, of active amylase enzyme per gram of composition. Stated otherwise, the
compositions herein will typically comprise from about 0.0001% to about 0.2%,
preferably 0.001%-0.1%, by weight of active enzyme. In yet another aspect of
the
invention herein the detergent composition comprises from about 0.15% to about
0.2% of active enzyme.
Suitable amylases for use in the compositions of this invention include both
cc
and B amylases. a-amylases are known in the art and include those disclosed in
U.S.
Pat. no. 5,003,257; EP 252,666; WO 91/00353; WO 96/05295; FR 2,676,456; EP
285,123; EP 525,610; and EP 368,341. Preferred amylases include TermamylR
(Novo Nordisk) and BANR (Novo Nordisk). TermamylR is described in British
Patent Specification No. 1,296,839 (Novo).
Highly preferred amylases of this invention include those amylases having
improved stability in detergents, especially improved oxidative stability. In
general,
the stability-enhanced amylases can be obtained from Novo Nordisk A/S , or
from
Genencor International.
Preferred amylases herein have the commonality of being derived using site-
directed mutagenesis from one or more of the Baccillus amylases, especialy the
Bacillus alpha-amylases, regardless of whether one, two or multiple amylase
strains
CA 02227752 2001-10-03
are the immediate precursors. Methionine (Met) was identifed as the most
likely
residue to be modified and substitued with any of the naturally occuring L-
amino
acids.
As noted, "oxidative stability-enhanced" amylases are preferred for use
herein. Such amylases are non-limitingly illustrated by the following:
(a) An amylase according to the hereinbefore referenced WO/94/02597, Novo
Nordisk A/S, published Feb. 3, 1994, as further illustrated by a mutant in
which
substitution is made, using alanine or threonine (preferably threonine), of
the
methionine residue located in position 197 of the B.licheniformis alpha-
amylase,
known as TERMAMYL~), or the homologous position variation of a similar parent
amylase, such as B. amylolique,~'aciens, B.subtilis, or B.stearothermophilus;
(b) Stability-enhanced amylases, including Purafact Ox AmR, as described by
Genencor International in a paper entitled "Oxidatively Resistant alpha-
Amylases"
presented at the 207th American Chemical Society National Meeting, March 13-17
1994, by C. Mitchinson and in WO 94/18314A, published August 18, 1994. Therein
it was noted that improved oxidative stability amylases have been made by
Genencor
from B.licheniformis NCIB8061. Methionine (Met) was identified as the most
likely
residue to be modified. Met was substituted, one at a time, in positions 8,
15, 197,
256, 304, 366, and 438 leading to specific mutants, particularly important
being .
M197L and M197T with the M197T variant being the most stable expressed
variant;
See also WO 96/05295 from Genencor International which discloses amylases
having
M197T, M15T and W138Y variants;
(c) Particularly preferred herein are amylase variants having additional
modification
in the immediate parent available from Novo Nordisk A/S. These amylases,
disclosed in WO 9510603, published April 1995, are known by the trademark
Duramyl~) and are those referred to by the supplier as QL37+M197T.
Any other oxidatively stable amylase can be used, for example as derived by
site-directed mutagenesis from known chimeric, hybrid or simple mutant parent
forms of available amylases.
Detergent Surfacta~ - The compositions of this invention also include from
about 1 to about 40 weight % of water-soluble detergent surfactant selected
from the
group consisting of avionics, nonionics, cationic, zwitterionics, ampholytics,
and
mixtures thereof. From about 2 to about 25 weight % of detergent surfactant is
preferred and from about 5 to about I S weight % is most preferred. Example of
preferred surfactants include amine surfactants, salts of C11-13 linear' alkyl
benzene
sulfonate, C12-16 alkyl sulfate and/or methyl ester sulfonates. In one
embodiment,
the preferred surfactant is an amine.
CA 02227752 2001-10-03
6
Detergent surfactants useful herein are listed in U.S. Patents 3,664,961,
Norris,
issued May 23, 1972, and 3,919,678, Laughlin et al, issued December 30, 1975.
The
following are representative examples of detergent surfactants useful in the
present
compositions.
One class of preferred surfactants for use herein includes primary amines
according to the formula R1R2R3N wherein R1 and R2 are both H, R3 is a C4-Clg
preferably C6-C12 alkyl chain, R3 alkyl chains may be straight or branched and
may
be interrupted with up to 12 ethylene oxide moieties, most preferably
interrupted with
up to 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
1-
hexylamine, 1-octylamine, laurylamine, palmitylamine, stearylamine,
oleylamine,
coconutalkylamine, tallowalkyl-amine.
Other suitable primary amines include amines according to the formula
R1R2R3N wherein R1 and R2 are both H ; R3 is R4X(CH2)n, X is -O-; C(O)NH- or
-NH-~ R4 is a C4-Clg~ preferably C6-C12 alkyl chain and R4 may be branched or
straight, n is between 1 to 5. Preferred amines according to the formula
herein above
3-isopropoxypropylanune, 3-(2-methoxyethoxy)-propylamine and 2-(2-
aminoethoxy)-ethanol, Cg-Clp octyl oxy propylamine, 2-
ethylhexyloxypropylamine,
lauryl amido propylamine and coco amido propylamine.
Suitable tertiary amines for use herein include tertiary amines having the
formula R1R2R3N wherein neither R1 nor R2 is H; R1 and R2 are C1-Cg
alkylchains
or
Rs
-C CHI-CH-O~H
whereby x is between 1 to 6; R3 is either a C4-C 1 g,
preferably C6-C 12 alkyl chain, or R3 is R4X(CH2)n, whereby X is -O-, -C(O)NH-
or
-NH-, R4 is a C4-Clg, n is between 1 to 5, and RS is H or C1-C2 alkyl. R3, R4
are
preferably C6-C 12 alkyl chains and may be straight or branched ; R3 alkyl
chains may
be interrupted with up to 12 ethylene oxide moieties, most preferably
interrupted with
up to 5 ethylene oxide moieties.
Suitable tertiary amines for use herein include coconutalkyldimethylamine,
dimethyloleylamine, hexa-decyltris (ethyleneoxy)dimethylamine,tallowalkylbis(2-
hydroxyethyl)amine, stearoylbis(2-hydroxyethyl)amine and oleoylbis(2-
hydroxyethyl)amine.
Of all of the foregoing amines the preferred materials are the trialkyl amines
marketed under the trademark ADOGEN, the long chain alkyldimethyl amines
marketed under the trademark ARNIEEN and the ethoxylated amines marketed under
CA 02227752 2001-10-03
7
the trademark ETHOMEEN. The most preferred amines for use in the compositions
herein are I-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine.
Especially
desirable for odor characteristics are n-dodecyl-dimethylamine (ARMEEN DM12D)
and bishydroxyethyl-coconutalkylamine (ETHOMEEN C/12, BEROL 307)and
oleylamine 7 times ethoxylated(BEROL 28), lauryl amido propylamine and corn
amido propylamine.
Other suitable amines include tertiary amines having the formula
O
Ri -~-NH-( CHy ~ N-( R2 2
wherein R1 is C4-C10, preferably Cg-C10 alkyl; n is 2-4,
preferably n is 3; R2 is C1-C4 or
R3
I
(CH2-CH-O)xH, whereby x is I-5, R3 is H or C1-C2 alkyl.
Ampholytic surfactants include derivatives of aliphatic or aliphatic
derivatives
of heterocyclic secondary and tertiary amines in which the aliphatic moiety
can be
straight chain or branched and wherein one of the aliphatic substituents
contains from
about 8 to 18 carbon atoms and at least one aliphatic substituent contains an
anionic
water-solubilizing group.
Water-soluble salts of the higher fatty acids, i.e., "soaps", are useful
anionic
surfactants in the compositions herein. This includes alkali metal soaps such
as the
sodium, potassium, ammonium, and alkylammonium salts of higher fatty acids
containing from about 8 to about 24 carbon atoms, and preferably from about 12
to
about 18 carbon atoms. Soaps can be made by direct saponification of fats and
oils
or by the neutralization of free fatty acids. Particularly useful are the
sodium and
potassium salts of the mixtures of fatty acids derived from coconut oil aad
tallow,
i.e., sodium or potassium tallow and coconut soap.
Useful anionic surfactants also include the water-soluble salts, preferably
the
alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction
products having in their molecular structure an alkyl group containing from
about 10
to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
(Included
in the term "alkyl" is the alkyl portion of aryl groups.) Examples of this
group of
synthetic surfactants are the sodium and potassium alkyl sulfates, especially
those
obtained by sulfating the higher alcohols (Cg-C 1 g carbon atoms) such as
those
produced by reducing the glycerides of tallow or coconut oil; and the sodium
and
CA 02227752 1998-O1-23
WO 97/04067 PCT/LTS96/11898
8
potassium alkylbenzene sulfonates in which the alkyl group contains from about
9 to
about 15 carbon atoms, in straight chain or branched chain configuration,
e.g., those
of the type described in U.S. Patents 2,220,099 and 2,477,383. Especially
valuable
are linear straight chain alkylbenzene sulfonates in which the average number
of
carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C 11-
13LAS.
Other anionic surfactants herein are the sodium alkyl glyceryl ether
sulfonates,
especially those ethers of higher alcohols derived from tallow and coconut
oil;
sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or
potassium salts of alkyl phenol ethylene oxide ether sulfates containing from
about 1
to about 10 units of ethylene oxide per molecule and wherein the alkyl groups
contain from about 8 to about 12 carbon atoms; and sodium or potassium salts
of
alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of
ethylene
oxide per molecule and wherein the alkyl group contains from about 10 to about
20
carbon atoms.
Other useful anionic surfactants herein include the water-soluble salts of
esters
of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in
the
fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-
soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from about 2 to 9
carbon
atoms in the acyl group and from about 9 to about 23 carbon atoms in the
allcane
moiety; water-soluble salts of olefin and paraffin sulfonates containing from
about 12
to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about
1 to 3
carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the
alkane
moiety.
Water-soluble nonionic surfactants are also useful in the compositions of the
invention. Such nonionic materials include compounds produced by the
condensation of alkylene oxide groups (hydrophilic in nature) with an organic
hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The
length of the polyoxyalkylene group which is condensed with any particular
hydrophobic group can be readily adjusted to yield a water-soluble compound
having
the desired degree of balance between hydrophilic and hydrophobic elements.
Suitable nonionic surfactants include the polyethylene oxide condensates of
alkyl phenols, e.g., the condensation products of alkyl phenols having an
alkyl group
containing from about 6 to 1 S carbon atoms, in either a straight chain or
branched
configuration, with from 3 to 12 moles of ethylene oxide per mole of alkyl
phenol.
Preferred nonionics are the water-soluble and water-dispersible condensation
products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either
straight
chain or branched configuration, with from 3 to 12 moles of ethylene oxide per
mole
CA 02227752 1998-O1-23
WO 97/04067 PCT/LTS96/11898
9
of alcohol. Particularly preferred are the condensation products of alcohols
having
an alkyl group containing from about 9 to 15 carbon atoms with from about 4 to
8
moles of ethylene oxide per mole of alcohol.
Highly preferred nonionic surfactants are polyhydroxy fatty acid amide
- surfactants of the formula.
R2 - C - N - Z,
II I
O R1
wherein R1 is H, or R1 is C1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl
or a
mixture thereof, R2 is CS-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, RZ is a straight
C11-15
alkyl or C16-18 ~k3'1 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.
Semi-polar nonionic surfactants include water-soluble amine oxides containing
one alkyl moiety of from about 10 to 18 carbon atoms and two moieties selected
from the group of alkyl and hydroxyalkyl moieties of from about 1 to about 3
carbon
atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10
to 18
carbon atoms and two moieties selected from the group consisting of alkyl
groups
and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-
soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon
atoms
and a moiety selected from the group consisting of alkyl and hydroxyalkyl
moieties of
from about 1 to 3 carbon atoms.
Zwitterionic surfactants include derivatives of aliphatic, quaternary,
ammonium,
phosphonium, and sulfonium compounds in which one of the aliphatic
substituents
contains from about 8 to 18 carbon atoms.
Cationic detersive surfactants suitable for use in the laundry detergent
compositions of the present invention are those having one long-chain
hydrocarbyl
group. Examples of such cationic surfactants include the ammonium surfactants
such
as alkyltrirnethylammonium halogenides, and those surfactants having the
formula
CR2(OR3)yjtR4(OR3)yl2R5N+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(CH20H)-, -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-
CHOHCOR~CHOHCH20H wherein R6 is any hexose or hexose polymer having a
CA 02227752 1998-O1-23
WO 97/04067 PCT/US96/11898
molecular weight less than about 1000, and hydrogen when y is not 0; RS is the
same
as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus
RS 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.
Highly preferred Cat10111c SuffaCtBIlts are the watr~r-enl»i,lA .".~fa.-..~.-.
ammonium compounds useful in the present composition having the formula
R1R2R3R4~_ (i)
wherein R1 is Cg-C 16 alkyl, each of R2, R3 and R4 is independently C 1-C4
alkyl,
C 1-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 R 1 is C 12-C 15 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. Prefers-ed
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;
C 12-1 S 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 offonnula (i) wherein R1 is
CH2-CH2-O-C(O)-C12-14 amyl ~d R2R3R4 are methyl);
di-alkyl imidazolines [compounds of fonnula (i)J.
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.
When included therein, the laundry detergent compositions of the present
invention typically comprise from 0.2% to about 25%, preferably from about 1%
to
about 10% by weight of such cationic surfactants.
A~ij~unct Ingredients - The compositions herein can optionally include one or
more other detergent adjunct materials or other materials for assisting or
enhancing
CA 02227752 2001-10-03
11
cleaning performance, treatment of the substrate to be cleaned, or to modify
the
aesthetics of the detergent composition (e.g., perfumes, colorants, dyes,
etc.). The
following are illustrative examples of such adjunct materials.
Optional Deter ency Builder . From 1 to about 80, preferably about 20 to
about 70, weight % of detergency builder can optionally be, and preferably is,
included herein. Inorganic as well as organic builders can be used. Preferred
builders include those selected from fatty acids, citrates, carbonates,
silicates,
' sulfates, phosphates, aluminosilicates, and combinations thereof.
Inorganic detergency builders include, but are not limited to, the alkali
metal,
ammonium and alkanolammonium salts of polyphosphates (exemplified by the
tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates),
phosphonates, phytic acid, silicates, carbonates (including bicarbonates and
sesquicarbonates), sulphates, and aluminosilicates. Borate builders, as well
as
builders containing borate-forming materials that can produce borate under
detergent
storage or wash conditions (hereinafter, collectively "borate builders"), can
also be
used. Preferably, non-borate builders are used in the compositions of the
invention
intended for use at wash conditions Less than about SOoC, especially less than
about
40oC.
Examples of silicate builders are the alkali metal silicates, particularly
those
having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates,
such as
the layered sodium silicates described in U.S. Patent 4,664,839, issued May
12, 1987
to H. P. Rieck. However, other silicates may also be useful.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates, including sodium carbonate and sesquicarbonate and mixtures
thereof
with ultra-fine calcium carbonate as disclosed in German Patent Application
No.
2,321,001 published on November 15, 1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate
builders include those having the empirical formula:
Mz(zA102Si02)
wherein M is sodium, potassium, ammonium or substituted ammonium, z is from
about 0.5 to about 2; and y is 1; this material having a magnesium ion
exchange
capacity of at least about 50 milligram equivalents of CaC03 hardness per gram
of
anhydrous aluminosilicate. Preferred aluminosilicates are zeolite builders
which have
the formula:
Naz[(AIO~z (Si02h,].xH20
CA 02227752 2001-10-03
1Z
wherein z and y are integers of at least 6, the molar ratio of z to y is in
the range from
1.0 to about 0.5, and x is an integer from about 15 to about 264. Preferred
synthetic
crystalline aluminosilicate ion exchange materials useful herein are available
under the
designations Zeolite A, Zeolite P (B), and Zeolite X.
Specific examples of polyphosphates are the alkali metal tripolyphosphates,
sodium, potassium and ammonium pyrophosphate, sodium and potassium and
ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta
phosphate in which the degree of polymerization ranges from about 6 to about
21,
and salts of physic acid.
Organic detergent builders preferred for the purposes of the present invention
include polycarboxylate compounds which have a plurality of carboxylate
groups,
preferably at least 3 carboxylates.
Polycarboxylate builder can generally be added to the composition in acid
form, but can also be added in the form of a neutralized salt. When utilized
in salt
form, alkali metals, such as sodium, potassium, and lithium, or
alkanolammonium
salts are preferred.
One important category of polycarboxylate builders encompasses the ether
polycarboxylates. Examples of useful ether poiycarboxylates include
oxydisuccinate,
as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and
Lamberti et
al., U.S. Patent 3,635,830, issued January 18, 1972.
A specific type of ether polycarboxylates useful as builders in the present
invention also include those having the general formula:
CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B)
wherein A is H or OH; B is H or -O-CH(COOX)-CH2(COOX); and X is H or a salt-
forming cation. Suitable examples of these builders are disclosed in U.S.
Patent
4,663,071, issued to Bush et al., on May 5, 1987.
Suitable ether polycarboxylates also include cyclic compounds, particularly
alicyclic compounds, such as those described in U.S. Patents 3,923,679;
3,835,163;
4,158,635; 4,120,874 and 4,102,903 .
Other useful detergency builders include the ether hydroxypolycarboxylates and
the copolymers of malefic anhydride with ethylene or vinyl methyl ether, 1, 3,
5-
trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic
acid.
Still other useful detergency builders include tartrate mono succinate or
tartrate
disuccinate.
Organic polycarboxylate builders also include the various alkali metal,
CA 02227752 2001-10-03
_ 13
ammonium and substituted ammonium salts of polyacetic acids. Examples include
the sodium, potassium, lithium, ammonium and substituted ammonium salts of
ethylenediamine tetraacetic acid, and nitrilotriacetic acid.
Also included are polycarboxylates such as mellitic acid, succinic acid,
oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, and
carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium
salt), are polycarboxyIate builders which can also be used in the compositions
herein.
Other carboxylate builders include the carboxylated carbohydrates disclosed in
U.S. Patent 3,723,322, Diehl, issued March 28, 1973.
Also suitable in the detergent compositions of the present invention are the
3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in
U.S.
Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic
acid builders include the Cs-C~ alkyl succinic acids and salts
thereof. The succinate builders are preferably used in the form of their water-
soluble
salts, including the sodium, potassium, ammonium and alkanolammonium salts.
Examples of useful builders also include sodium and potassium
carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexane- .
hexacarboxylate, cis-cyclopentane-tetracarboxylate, water-soluble
polyacrylates, and
the copolymers of malefic anhydride with vinyl methyl ether or ethylene.
Other suitable polycarboxylates are the polyaceta) carboxylates disclosed in
U.S. Patent 4,144,226, Crutchfield et al., issued March 13, 1979.
Polycarboxylate builders are also disclosed in U.S. Patent 3,308,067, Diehl,
issued March 7, 1967. Such materials include the water-soluble salts
of homo- and copolymers of aliphatic carboxylic acids such as
malefic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid,
citraconic acid
and methylenemalonic acid.
Other organic builders known in the art can also be used. For example, fatty
acids, also known as monocarboxylic acids, and soluble salts thereof, having
long
chain hydrocarbyls can be utilized. These would include materials generally
referred
to as "soaps." Chain lengths of C10-C20 are typically utilized. The
hydrocarbyls can
be saturated or unsaturated.
Preferably the detergency builder herein is selected from the group consisting
of the salts, preferably the sodium salt, of carbonate, silicate, sulfate,
phosphate,
aluminosilicate, and citric acid and mixtures thereof.
CA 02227752 2001-10-03
14
Second Enzyme - Optional, and preferred, ingredients include second enzymes.
Said second enzymes include enzymes selected from proteasees, lipases,
cellulases,
hemicellulases, peroxidases, gluco-amylases, cutinases, pectinases, xylanases,
reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases,
tannases, pentosanases, malanases, f3-glucanases, arabinosidases or mixtures
thereof.
Highly preferred are protease, lipase, peroxidase, cellulase, and mixtures
thereof. By
"second enzyme" is meant one or more enzymes in addition to amylase which are
also added to the composition.
The amount of second enzyme used in the composition varies according to the
type of enzyme and the use intended. In general, from about 0.0001 to about
1.0,
more preferably about Ø001 to about 0.5, weight % of the composition on an
active
basis of these second enzymes are preferably used.
Purified or nonpurified forms of these enzymes may be used. Enzymes
produced by chemically or genetically modified mutants are included by
definition, as
are close structural enzyme variants.
Lipase Enzymes - Lipase enzymes which optionally may be considered for
inclusion in the detergent compositions of the present invention include those
produced by microorganisms of the Pseudomonas group, such as Pseudomonas
stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Lipases
include
those which show a positive immunological cross-reaction with the antibody of
the
lipase, produced by the microorganism Pseudomonas fluorescens IAM 1057. This
lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under
the
trade marks Lipase P "Amano," hereinafter referred to as "Amaao-P". Lipases
include Ml LipaseR and LipomaxR (Gist-Brocades) and LipolaseR (Novo).
The lipases are normally incorporated in the detergent composition at levels
from 0.0001% to 2% of active enryme by weight of the detergent composition.
A preferred component of the detergent composition according to the invention
is the D96L lipolytic enzyme variant of the native lipase derived from
Humicola
lanuginosa. Preferably the Humicola lanuginosa strain DSM 4106 is used. This
enzyme is preferably incorporated into the composition in accordance with the
invention at a level of from about 50 LU to about 8500 LU per liter wash
solution.
More preferably the variant D96L is present at a level of from about 100 LU to
about
7500 LU per liter of wash solution, and most preferably at a level of from
about 150
LU to about 5000 LU per liter of wash solution.
By D96L lipolytic enzyme variant is meant the lipase variant as described in
patent application WO 92/05249 viz. wherein the native lipase ex Humicola
lanuginosa aspartic acid (D) residue at position 96 is changed to Leucine (L).
CA 02227752 2001-10-03
is
According to this nomenclature said substitution of aspartic acid to Leucine
in
position 96 is shown as : D96L.
To determine the activity of the enzyme D96L the standard LU assay was used
(Analytical method, internal Novo Nordisk number AF 95/6-GB 1991.02.07). A
substrate for D96L was prepared by emulsifying glycerine tributyrat (Merck)
using
gum-arabic as emulsifier. Lipase activity was assayed at pH 7 using pH stet.
method.
One unit of lipase activity (LU/mg) is defined as the amount needed to
liberate one
micromole fatty acid per minute.
The D96L variant of the native Humicola lanuginosa lipase has the additional
advantage of delivering a significant benefit in whiteness maintenance when
compared to the wildtype lipase.
Protease Enz r~ nes - Protease enzymes are optionally present at levels
sufl'rcient to provide from 0.001 to 0.1 Anson units (AU) of activity per gram
of
composition. The protealytic enzyme can be of animal, vegetable or
microorganism
(preferred) origin. More preferred is serine protealytic enzyme of bacterial
origin.
Purified or nonpurified forms of enzyme may be used. Protealytic enzymes
produced
by chemically or genetically modified mutants are included by definition, as
are close
structural enzyme variants. Particularly preferred by way of protealytic
enzyme is
bacterial serine protealytic enzyme obtained from Bacillus, Bacillus subtilis
and/or
Bacillus licheniformis. Suitable commercial protealytic enzymes which rnay be
considered for inclusion in the present invention compositions include
Alcalase~,
Biosam~, EsperaseC~?, Durazym~, Savinase~, Maxatase0, Maxacal~, and
Maxapem~ 15 (protein engineered Maxacal); Purafect~ and subtilisin BPN and
BPN.
Protealytic enzymes also encompass modified bacterial serine professes, such
as
those described in European Patent Application 251,446, published
January 7, 1988 (particularly pages 17, 24 and 98), and which is called herein
"Protease B", and in European Patent Application 199,404, Venegas, published
October 29, 1986, which refers to a modified bacterial serine protealytic
enzyme
which is called "Protease A" herein. More preferred is what is called herein
"Protease C", which is a variant of an alkaline serine protease from acillus
in which
lysine replaced arginine at position 27, tyrosine replaced valise at position
104, serine
replaced asparagine at position 123, and alanine replaced threonine at
position 274.
Protease C is described in EP 451,244, corresponding to WO 91/06637,
published May 16, 1991. Genetically modified variants, particularly of
Protease C, are
also included herein.
Preferred protealytic enzymes are selected from the group consisting of
CA 02227752 2001-10-03
16
Savinase~, Esperase~, MaxacalO, Purafect~, BPN, Protease A and Protease B,
and mixtures thereof. Bacterial serine protease enzymes obtained from Bacillus
subtilis and/or Bacillus licheniformis are preferred.
An especially preferred protease herein 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 the amino acid residue 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 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 amyloliquefacierrs subtiIisin, as described in the
concurrently filed patent application of A. Baeck et al. entitled "Protease-
Containing
Cleaning Compositions" having U.S. Patent No. 5,679,630, issued October 21,
1997.
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
ceIlulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which
discloses
fungal cellulase produced from Humicola insolens. Suitable cetlulases 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 SOICDa, 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 United
States
Patent No. 5,520,838, issued May 28, 1996.
Peroxidase enzymes are used in combination with oxygen sources, e.g.
percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for
"solution bleaching", i.e. to prevent transfer of dyes or pigments removed
from
substrates during wash operations to other substrates in the wash solution.
Peroxidase enrymes 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 and in CA 2,122,987.
CA 02227752 1998-O1-23
WO 97/04067 PCT/US96/11898
_ 17
Said cellulases and/or peroxidases are normally incorporated in the detergent
composition at levels from 0.0001% to 2% of active enzyme by weight of the
detergent composition.
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 cutinases are normally incorporated in the detergent
composition at
levels from 0.0001 % to 2% of active enzyme by weight of the detergent
composition.
l~~r zyme Stabilizers - The enzymes employed herein are stabilized by the
presence of water-soluble sources of calcium and/or magnesium ions in the
finished
compositions which provide such ions to the enzymes. (Calcium ions are
generally
somewhat more effective than magnesium ions and are preferred herein if only
one
type of cation is being used.) Alternatively, stability can be provided by the
presence
of various other art-disclosed stabilizers, especially borate species: see
Severson,
U.S. 4,537,706. Typical detergents, especially liquids, will comprise from
about 1 to
about 30, preferably from about 2 to about 20, more preferably from about 5 to
about 1 S, and most preferably from about 8 to about 12, millimoles of calcium
ion
per liter of finished composition. This can vary somewhat, depending on the
amount
of enzyme present and its response to the calcium or magnesium ions. The level
of
calcium or magnesium ions should be selected so that there is always some
minimum
level available for the enzyme, after allowing for complexation with builders,
fatty
acids, etc., in the composition. Any water-soluble calcium or magnesium salt
can be
used as the source of calcium or magnesium ions, including, but not limited
to,
calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium
hydroxide, calcium formate, and calcium acetate, and the corresponding
magnesium
salts. A small amount of calcium ion, generally from about O.OS to about 0.4
millimoles per liter, is often also present in the composition due to calcium
in the
enzyme slurry and formula water. In solid detergent compositions the
formulation
may include a sufficient quantity of a water-soluble calcium ion source to
provide
such amounts in the laundry liquor. In the alternative, natural water hardness
may
suffice.
' It is to be understood that the foregoing levels of calcium and/or magnesium
ions are sufficient to provide enzyme stability. More calcium and/or magnesium
ions
can be added to the compositions to provide an additional measure of grease
removal
performance. Accordingly, as a general proposition the compositions herein
will
typically comprise from about O.OS% to about 2% by weight of a water-soluble
source of calcium or magnesium ions, or both. The amount can vary, of course,
with
CA 02227752 1998-O1-23
WO 97/04067 PCT/US96/11898
18
the amount and type of enzyme employed in the composition.
The compositions herein may also optionally, but preferably, contain various
additional stabilizers, especially borate-type stabilizers. Typically, such
stabilizers
will be used at levels in the compositions from about 0.25% to about 10%,
preferably
from about 0.5% to about 5%, more preferably from about 0.75% to about 3%, by
weight of boric acid or other borate compound capable of forming boric acid in
the
composition (calculated on the basis of boric acid). Boric acid is preferred,
although
other compounds such as boric oxide, borax and other alkali metal borates
(e.g.,
sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable.
Substituted boric acids (e.g., phenylboronic acid, butane boronic acid, and p-
bromo
phenylboronic acid) can also be used in place of boric acid.
Other Ingredients - Other ingredients suitable for use in the present
compositions, such as water, perfume, carriers, hydrotropes, processing aids,
brightener, conditioners such as fumed silica, polyethylene glycol, dyes and
colorants,
and peroxyacids, can be included. Preferred ingredients are from about 0.5 to
about
wt.% of the composition of polyethylene glycol (preferably with molecular
weight
between 5,000 and 10,000, most preferably 8,000), from about 0.01 to about 0.7
wt.% of fluorescent whitening and/or brightening agents, and from about 0.01
to
about 1.0 wt.% of perfume. If high sudsing is desired, suds boosters such as
the
C10-C16 alkanolamides can be incorporated into the compositions, typically at
1%-
10% levels. The C 10-C 14 monoethanol and diethanol amides illustrate a
typical class
of such suds boosters. Use of such suds boosters with high sudsing adjunct
surfactants such as the amine oxides, betaines and sultaines noted above is
also
advantageous. If desired, soluble magnesium salts such as MgCl2, MgS04, and
the
like, can be added at levels of, typically, 0.1%-2%, to provide additional
suds and to
enhance grease removal performance.
Various detersive ingredients employed in the present compositions optionally
can be further stabilized by absorbing said ingredients onto a porous
hydrophobic
substrate, then coating said substrate with a hydrophobic coating. Preferably,
the
detersive ingredient is admixed with a surfactant before being absorbed into
the
porous substrate. In use, the detersive ingredient is released from the
substrate into
the aqueous washing liquor, where it performs its intended detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica
(trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme -
solution containing 3%-5% of C13-15 ethoxylated alcohol (E0 7) nonionic
surfactant. Typically, the enzyme/surfactant solution is 2.5 X the weight of
silica.
The resulting powder is dispersed with stirring in silicone oil (various
silicone oil
CA 02227752 2001-10-03
19
viscosities in the range of 500-12,500 can be used). The resulting silicone
oil
dispersion is emulsified or otherwise added to the final detergent matrix. By
this
means, ingredients such as the aforementioned enzymes, bleaches, bleach
activators,
bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and
hydrolyzable surfactants can be "protected" for use in detergents, including
liquid
laundry detergent compositions.
Liquid detergent compositions can contain water and other solvents as
carriers.
Low molecular weight primary or secondary alcohols exemplified by methanol,
ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are
preferred
for solubilizing surfactant, but polyols such as those containing from 2 to
about 6
carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol,
ethylene
glycol, glycerine, and 1,2-propanediol) can also be used. The compositions may
contain from 5% to 90%, typically 10% to 50% of such carriers.
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 mark Isofol 12R.
Such suds suppressor system are described in CA 2,146,636.
Especially preferred silicone suds controlling agents are described in
European
Patent Application 573,699, published June 6, 1992. Said compositions can
comprise a
silicone/silica mixture in combination with fumed nonporous silica such as
AerosilR.
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
CA 02227752 1998-O1-23
WO 97/04067 PCT/US96/11898
weight.
Other components used in detergent 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 malefic anhydride-acrylic
acid
copolymers previously mentioned as builders, as well as copolymers of malefic
anhydride with ethylene, methylvinyl ether or methacrylic acid, the malefic
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-y1)-stilbene-2,2' disulphonate, di-sodium
4,4'bis(2-
anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylami-no)stilbene-
2,2'disul- -
phonate, sodium 2(stilbyl-4"-(naphtho-1',2':4,5)-1,2,3 - triazole-2"-
sulphonate and
4,4'-bis(2-sulphostyryl)biphenyl.
Other useful polymeric materials are the polyethylene glycols, particularly
those
CA 02227752 1998-O1-23
WO 97/04067 PCT/US96/11898
21
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.
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. 4I 16885 and 4711730 and
European Published Patent Application No. 0 272 033. A particular preferred
polymer in accordance with EP-A-0 272 033 has the formula
(CH3 (PEG)43 )0.75 ~0~0.25 ~T-PO)2. 8(T-PEG)0.41T~0_
~0.25(~EG)43CH3)0.75
where PEG is -(OC2H4)O-,PO is (OC3H60) and T is (pcOC6H4C0).
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 16% 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 method of preparation are described in detail in EPA 311
342.
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-1 400 898 and in USP 5,019,292. Organic
fabric
softening agents include the water insoluble tertiary amines as disclosed in
GB-Al
514 276 and EP-BO 011 340 and their combination with mono C12-C14 quaternary
CA 02227752 1998-O1-23
WO 97/04067 PCT/US96/11898
22
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 5% to 15%, more
preferably from 8% to 12% 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 5% by weight, normally from I% to 3% 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 2%, 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.
The present invention also relates to a process for inhibiting dye transfer
from
one fabric to another of solubilized and suspended dyes encountered during
fabric
laundering operations involving colored fabrics.
The detergent compositions according to the present invention may 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 detergent 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.
The polyamine N-oxide polymers suitable for use contain units having the
following structure formula
P
CI) Ax
R
CA 02227752 1998-O1-23
WO 97/04067 PCT/US96/11898
23
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; A is NC(O), C02, C(O), -O-, -S-, -N- ; x is O or 1; 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 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
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
CA 02227752 2001-10-03
_ 24
copolymerization or by appropriate degree of N-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.
The N-vinylimidazole N-vinylpynrolidone polymers which may be used in the
present invention have an average molecular weight range from 5,000-1,000,000,
preferably from 20,000-200,000.
I~ghly 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 known light scattering
methods.
Highly prefenred N-vinylimidazole N-vinylpyrrolidone copolymers have 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 N-vinylimidazole N-vinylpynrolidone 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-vinylpyrroGdone from 1 to 0.2, more
preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4 .
The detergent compositions of the present invention may also utilize
polyvinylpyrrolidone ("PVP") having an average molecillar weight of from about
2,500 to about 400,000, preferably from about 5,000 to about 200,000, more
CA 02227752 2001-10-03
Zs
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).
The detergent compositions of the present invention may also utilize
polyvinyloxazolidone as a polymeric dye 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.
The detergent compositions of the present invention may also utilize
polyvinylimidazole as polymeric dye transfer inlu'biting 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.
The detergent compositions herein will preferably'be formulated such that,
during use in aqueous cleaning operations, the wash water will have a pH of
between
about 6.5 and about 11, preferably between about 7.5 and 11. Techniques for
controlling pH at recommended usage levels include the use of buffers,
alkalis, acids,
etc., and are well known to those skilled in the art.
The liquid detergent composition is added to the wash, usually at levels of
0.06L
to 0.24E.
This invention further provides a method for cleaning fabrics in the wash by
contacting the fabrics with a wash solution which contains an effective amount
of the
detergent compositions hereinbefore described. Agitation is preferably
provided in
the washing machine for good cleaning. Washing is preferably followed by
drying
the wet fabric in a conventional clothes dryer. An effective amount of the
liquid
detergent composition in the washing machine is preferably from about 500 to
about
7000 ppm, more preferably from about 1000 to about 3000 ppm.
The following examples illustrate the 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 abbreviated component identifications
have the following meanings:
CA 02227752 2001-10-03
26
Amine . Selected from coconutalkyldimethylamine, dimethyloleylamine,
hexa-
Surfactantsdecyltris (ethyleneoxy)dimethylamine,tallowalkyJbis(2-hydroxyethylj-
amine, stearoylbis(2-hydroxyethyl)amine and olooylbis(2-hydroxy-
ethyl)amine, and mixtures thereof
LAS . Sodium linear C12 alkyl benzene sulphonate
TAS . Sodium tallow alkyl sulphate
AS . Sodium Cg - Clg alkyl sulfate
SAS . C12C14 ~n~Y (2,3) alkyl sulfate in the form of
the sodium salt.
APG . Alkyl polyglycoside surfactant of formula Cl2 -
(glycosyl)x,
when x is 1.3
AEC . Alkyl ethoxycarboxylate surfactant of formula C12
ethoxy
(2) carboxylate.
SS . Secondary soap surfactant of formula 2-butyl octanoic
acid
251r1' . A C12C15 Predominantly linear primary alcohol condensed
with an average of Y moles of ethylene oxide
45EY . A Cl4 - C15 Predominantly linear primary alcohol
condensed with
an average of Y moles of ethylene oxide
XYEZS . ClX - Cly sodium alkyl sulfate condensed with an
average ofZ
moles of ethylene oxide per mole
Nonionic . C13C15 ~x~ 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 trademark Plurafax LF404 by
BASF Gmbh
C12'Cl4 ~yl N-methyl glucamide
TFAA . C16-C18 ~Yl N-methyl glucamide.
S~~te . Amorphous Sodium Silicate (Si02:N20 ratio = 2.0)
NaSKS-6 . Crystalline layered silicate of formula S-Na2Si205
Carbonate . Anhydrous sodium carbonate
Phosphate . Sodium tripolyphosphale
MAIAA . Copolymer of 1:4 maleic/acrylic acid, average molecular
weight
about80,000
Polyacrylate. Polyacrylate homopolymer with an average molecular
weight of
8,000 sold under the trademark PA30 by BASF GmbH
Zeolite A . Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si02)12. 27H20 having a primary particle size
in the range frora 1 to 10 micrometers
CA 02227752 2001-10-03
27
Citrate . Tri-soditun citrate dehydrate
Citric . Citric Acid
Perborate . Anhydrous sodium perborate monohydrate
bleach, empirical formula
NaB02.H202
PB4 , ~Y~o~ sodium perborate teirahydrate
Percarbonate. Anhydrous sodium percarbonate bleach
of empirical formula
2Na2C03.3H202
TAED . Tetraacetyl ethylene diamine
Paraffin . Parailin oil sold under the trademark
Winog 70 by Wintershall.
Xylanase . Xylanolytic enzyme sold under the trademarks
Pulpzyme H8
or SP431 by Novo Nordisk A/S or Lyxasan
(Gist-Brocades)
or Optipulp or Xylanase (Solvay).
Protease . Proteolytic enzyme sold under the h'ademark
Savinase~
by Novo Nordisk A/S.
Protease . Proteolytic enzyme which is a Bacillus
D leatus subtilisin variant
N76D/S103A/V, 104I, according to the numbering
of Bacillus
amyloliqueJaciens subdlisin.
Amylase . Amylolytic enzyme sold under the trademark
Termamyl~
by Novo Nordisk A/S
Lipase . Lipolytic enzyme sold under the trademark
Lipolase~
by Novo Nordisk A/S
D96L Lipase. Variant of the native lipase derived
from Humicola lanugitiasa
Peroxidase. Peroxidase enzyme
Cellulose . Cellulosic enzyme sold under the trademarkCarezyme~
or Celluzyme~ by Novo Nordisk A/S.
CMC . Sodium carboxymethyl cellulose
HEDP . 1,1-hydroxyethane diphosphonic acid
DE'TPMP . Diethylene triamine pants (methylene
phosphoric acid),
marketed by Monsanto under the Trade mark
bequest 2060~
PVP . Polyvinyl pyrrolidone polymer
EDDS . Ethylenediamine -N, N- disuccinic acid,
(S,S] isomer in the
form of the sodium salt.
Suds Suppressor25% paraffin wax Mpt50C, 17% hydrophobic
. silica, 58% paraffin oil
or 12% Siliconelsilica, 18% stearyl alcoho1,70%
starch in granular form
SCS . Sodium camera sulphonate
Sulphate . Anhydrous sodium sulphate.
CA 02227752 2001-10-03
28
HMWPEO . High molecular weight polyethylene oxide
PGMS . Polyglyceroi monostearate having a trademark of Radiasurf 248
TAE 25 . Tallow alcohol ethoxylate (25)
In the following examples all levels of enzyme quoted are expressed as %
active
enzyme by weight of the composition:
EXAMPLE I
The wash performance of amylase enzyme is evaluated in non-phosphate liquid
detergent prepared according to the following composition:
Materi Wt.o/u
C 12-C 14 ~kYl N-methyl glucamide 3.0
NaC25 AE2.5 S 17.0
Neodol 23-9 1.0
Citric Acid builder 2.0
Fatty Acid builder 3.0
Ethane 3.0
Propanedioi 5.0
NaOIi 3.0
Sodium formate 0.05
Borax 2.5
Methylethyleneamine 1.0
Protease 0.2
~yl~* 0.2
Silicone Antifoam 0.1
PEI 189 E15-18
(Ethoxylated tetraethylene pentaimine) 1.0
Water and miscellaneous to 100%
The following amylases are substituted for the amylase enzyme at the levels
listed below: Termamyl~, Genecor's Purafact Ox Am~, and Duramyl~.
To a top-loading automatic washing machines is added 5 lbs. of naturally
soiled fabrics and 64 liters-of 35°C city water having a hardness of
1.58 grams/E. To
each machine is added 0.12 f of liquid detergent with the amylase enzyme.
The washing machines are then allowed to complete their normal washing and
rinsing cycles, and the test fabrics are dryer dried. This procedure is
repeated four
times.
After completion of the four cycles, the fabrics are arranged under suitable
lighting for. comparison of soil and stain removal. The fabrics show improved
whiteness.
CA 02227752 1998-O1-23
WO 97/04067 PCT/LTS96/11898
29
EXAMPLE II
Heavy duty liquid fabric cleaning compositions suitable for use in the
pretreatment of stained fabrics, and for use in a machine laundering method,
in
accord with the invention are prepared as follows:
I II III IV V
Amine 10.0 15.0 5.0 10.0 5.0
24AS 20.0 20.0 20.0 20.0 20.0
SS 5.0 5.0 5.0 5.0 S.0
Citrate 1.0 1.0 1.0 1.0 I.0
12E 13.0 13.0 13.0 13.0 13.0
Monethanolamine 2.5 2.5 2.5 2.5 2.5
Protease 0.005 0.01 0.1 0.0 0.005
Am Iase 0.005 0.05 0.2 0.0004 0.01
Cellulase 0.0 0.04 0.004 0.001 0.0
Water/ ro lene I
col/ethanol 100:1:1
Amylase enzymes include: TermamylU, Genecor's Purafact Ox Am~, and
Duramyl~.
EXAMPLE III
Heavy duty liquid fabric cleaning compositions in accord with the invention
are nrenared ac fnlinwc~
I II III IV
LAS acid form - - 25.0 -
C12-14 alkenyl 3.0 8.0 10.0 -
succinic acid
Citric acid 10.0 15.0 2.0 2.0
25AS acid form 8.0 8.0 - 15.0
25AE2S acid form- 3.0 - 4.0
25AE7 - 8.0 - 6.0
25AE3 8.0 - _ _
CFAA _ _ _ 6.0
DETPMP 0.2 - 1.0 1.0
Fatt acid - - - 10.0
Oleic acid 1.8 - 1.0 -
Ethanol 4.0 4.0 6.0 2.0
Pro anediol 2.0 2.0 6.0 10.0
CA 02227752 1998-O1-23
WO 97/04067 PCT/US96/11898
X lanase 0.05 0.0 0.05 0.0
Am lace 0.005 0.01 0.2 0.0001
Coco-alkyl dimethyl- - 3.0 -
hydroxy ethyl '
ammonium chloride
Smectite cla - 5.0 -
PVP 1.0 2.0 - _
Perborate - 1.0 - _
Phenol sul honate- 0.2 -
Peroxidase 0.01 -
NaOH H7.5 H7.5 H7.5 H7.5
Water/minors to 100% to 100%to 100% to 100%
Amylase enzymes include: Termamyl~, Genecor's Purafact Ox Am~, and
Duramyl~.
EXAMPLE IV
Heavy duty liquid fabric cleaning compositions in accord with the invention
are nrenared as followsv
I II III
CFAA S.0 4.5 3.9
25AS acid form 15.0 13.0 7.5
25AE2S acid form 9.0 8.0 11.0
Amine surfactants C8-10 2.0 2.0 2.5
amine
Fatt acid builder 5.0 4.0 3.5
Citric acid 4.0 3.5 3.0
Carze me cellulase 0.27 0.0 0.05
Li olase 1i ase 0.15 0.0 0.075
Protease D 0.05 0.05 -
Protease - - 0.1
X lanase 0.05 0.05 0.05
Am lase 0.015 0.05 0.1
DETPMP chelant 1.0 1.0 0.75
Soil release of er 0.2 0.25 0.15
Dis ersin a ent 0.25 0.7 1.2
Waters/minors U to %
100
Amylase enzymes include: Termamyl~, Genecor's Purafact Ox Am~, and
Duramyl~.
CA 02227752 1998-O1-23
WO 97/04067 PCT/LTS96/11898
- , 31
EXAMPLE V
Granular fabric cleaning compositions in accord with the invention are
prepared
as follows:
A B
' LAS 22.0 22.0
Phos hate 23.0 23.0
Carbonate 23.0 23.0
Silicate 14.0 14.0
Zeolite A 8.2 8.2
DETPMP 0.4 0.4
Sodium Sulfate5.5 5.5
Protease 0.01 0.02
Cellulase 0.001 -
Am lase* 0.01 0.1
Water/minorsto 100% to 100%
*Amylase enzymes include: Termamyl~, Genecor's Purafact Ox Am~, and
Duramyl~.
Aqueous crutcher mixes of heat and alkali stable components of the
detergent compositions are prepared and spray-dried and the other ingredients
are
dry-mixed so that they contain the ingredients tabulated at the levels shown.
EXAMPLE VI
Granular fabric cleaning compositions in accord with the invention are
prepared
as follows:
A B
LAS 12.0 12.0
Zeolite A 26.0 26.0
SS 4.0 4.0
SAS 5.0 5.0
Citrate 5.0 5.0
Sodium Sulfate17.0 17.0
Perborate 16.0 16.0
TAED 5.0 -
' Protease 0.06 0.03
Am lase* 0.01 0.2
Water/minors up to 100%up to
100%
CA 02227752 1998-O1-23
WO 97/04067 PC'H'/US96/11898
32
*Amylase
enzymes
include:
Termamyl~,
Genecor's
Purafact
Ox
Am~,
and
Duramyl~.
Aqueous mixes
crutcher of heat
and alkali
stable
components
of the
'
detergent
compositions
are
prepared
and
spray-dried
and
the
other
ingredients
are
dry-mixed
so
that
they
contain
the
ingredients
tabulated
at
the
levels
shown.
EXAMPLE
VII
Granular
fabric
cleaning
compositions
in
accord
with
the
invention
which
are
especialluseful in
the launderin
of coloured
fabrics
are prepared
as follows:
LAS 11.4 10.7
TAS 1.8 2.4
TF~ - 3.0
45AS 3.0 5.0
45E7 4~.0 -
25E3 S - 3.0
68E11 1.8 1.8
Citrate 14.0 15.0
Citric acid 3.0 2.5
ZeoIite A 32.5 32.1
Na-SKS-6 - 9.0
MA/AA 5.0 5.0
DETPMP 1.0 0.2
X lanase 0.01 -
Protease 0.02 0.02
D96L 0.0005 0.01
Am lase* 0.03 0.2
Silicate 2.0 2.5
Sul hate 3.5 5.2
PVP 0.3 0.5
Poly (4-vinyl-- 0.2
pyridine)-N-
oxide/co-
polymer of
vinyl-imidazole
and vinyl-
olidone
Perborate 0. S 1.0
CA 02227752 1998-O1-23
WO 97/04067 PCT/US96/11898
33
Peroxidase 0.01 0.01
Phenol 0.1 0.2
' sulfonate
water/minorsa to 100% a to 100%
*Amylase enzymes
include: Termamyl~,
Genecor's Purafact
Ox Am~, and
Duramyl~.
Aqueous crutcher
mixes of heat
and alkali stable
components of
the
detergent compositions
are prepared and
spray-dried and
the other ingredients
are
dry-mixed so that
they contain the
ingredients tabulated
at the levels
shown.
EXAMPLE VIII
A laundry bar suitable
for hand-washing
soiled fabrics
is prepared comprising
the following ingredients.
Com onent Wei ht
Linear alkyl benzene30
sulfonate
Phosphate (as sodium7
tri of - hos hate
Sodium carbonate 20
Sodium o hos hate 7
Coconut 2
monoethanolamide
Zeolite A (0.1-10 5
microns
Carbo eth lcellulose0.2
Pol ac late 1400 0.2
N-a I ca rolactam 5
Sodium perborate 10
tetrah drate
Bri htener, erfume 0.2
Am lace E a 0.05
CaSO 1
M SO 1
Water 4
Filler* Balance
to
100%
Amylase enzymes include: Termamyl~, Genecor's Purafact Ox Am~, and
CA 02227752 1998-O1-23
WO 97/04067 PCT/US96/11898
34
Duramyl~.
*Can be selected from convenient materials such as CaC03, talc, clay,
silicates,
and the like.
A detergent laundry bar is extruded in conventional soap or detergent bar
making equipment as commonly used in the art.
EXAMPLE IX
A compact granular fabric cleaning composition is prepared as follows:
I II ITI
C m onent Wt % Wt % Wt
LAS - g,0 _
TAS - 2.0
45AS 8.0 - 10.0
25E3S 2.0 0.5 3.0
25E5 - 5.0 5.0
25E3 5.0 - -
TFAA 2.5 - 2.5
Coco-alkyl-dimethyl- 1.0 -
hydroxy-ethyl
ammonium chloride
Zeolite A 17.0 15.0 25.0
NaSKS-6 12.0 10.0 12.0
Citric acid 3.0 2.0 3.0
Sodium citrate - - 10.0
Carbonate 7.0 8.0 7.0
MA/AA 5.0 1.0 5.0
CMC 0.4 0.4 0.4
Poly (4-vinylpyridine)-0.2 - 0.2
N-oxide/
Protease 0.05 0.03 0.05
Li ase* 0.002 0.004 0.002
Cellulase 0.001 - 0.001
Am lase 0.01 0.006 0.006
TAED 6.0 3.0 -
Percarbonate 22.0 20.0 -
NACA-OBS - 3.0 -
CA 02227752 1998-O1-23
.,.
WO 97/04067 PCT/IJS96/11898
EDDS 0.3 0.2 0.3
Granular suds 3.5 3.0 3.5
' su ressor
water/minors sulfateU to 100%
' *Lipase is selected from LipolaseT'M or Lipolase UltraTM (known as DL96L),
both
supplied by Novo Nordisk.
EXAMPLE X
A high density, compact granular detergent composition is nrenareri ac fnliwve-
_III
Com onent Wt. % Wt. % Wt.
AS 7.4 S 16
AES 0.8 _ -
LAS 12 21 10
3 3 3
Polyhydroxy 1 - _
fatty
acid amide
Cationic quaternary1 1 1
ammonum
com ounds
Am lase E a 0.001 0.05 0.1
Biosam~ Protease0.001 0.005 -
Zeolites 17 7 27
Na SKS-6 6 3.3 -
Citric Acid 1 - _
Pol carbo late 3 7 2
Chelant 0.4 - 0.6
Carbonate 18 10 28
Silicate 4 11 0.5
Perborate 11 4 29
Nonanoyl 2.5 3
oxybenzene
sulfonate
TAED 4.8 -
Soil release 0.3 0.3 0.3
of er
PEG 0.8 - 1.5
Suds Control 0.3 0.2 0.3
Sulfate To BalanceTo Balance To Balance
Amylase enzymes include: Termamyl~, Genecor's Purafact Ox Am~, and
' Duramyl~.
