Note: Descriptions are shown in the official language in which they were submitted.
CA 02275290 1999-06-14
WO 98128394 PCT1US96/20876
1
DETERGENT COMPOSITIONS COMPRISING CHOLESTEROL ESTERASE
10
~ 5 ~ Field of the invention
The present invention relates to detergent compositions, including
laundry and dishwashing compositions, comprising a cholesterol esterase
20 enzyme.
Back4round of the invention
The overall performance of a detergent product for use in washing or
cleaning method such as laundry or dishwashing, is judged by a number of
factors, including the ability to remove greasy / oily soils and the ability
to
3o prevent redeposition of the soils or the breakdown products of the soils on
the articles in the wash.
' The complex nature of everyday "body" soils 'typically found on
pillow cases, T-shirts, collars and socks, provides a thorough cleaning
challenge for detergents. These soils are difficult to remove completely and
often residues build up on fabric leading to dinginess and yellowing.
CA 02275290 1999-06-14
WO 98128394 PCT/U596I20876
2
Greasy / oily soils and stains represent also a well-known cleaning
challenge often met by the inclusion of lipolytic enzymes in detergent
compositions. Lipolytic enzymes far enhanced removal of trigiycerides
containing soils and stains from fabrics are indeed well-known in the art.
Examples are US Patent 4,769,173; US Patent 5,069,809; WO 94/03578;
WO 96/12004; WO 96/16153, .
It is therefore an object of the present invention to provide detergent
compositions, including laundry and dishwashing compositions which
1 o provide cleaning performance on body soils and/or oily / greasy soils and
stains.
The above objective has been met by formulating detergent
compositions, including laundry and dishwashing compositions comprising a
~ 5 cholesterol esterase at a level of from 0.0001 % to 5%, preferably 0.001
to 2% pure enzyme by weight of total composition.
It is a further object of the invention to provide detergent
compositions) including laundry and dishwashing compositions comprising a
2o cholesterol esterase for improved cleaning performance on body soils and/or
oily / greasy soils and stains.
The above objective has been met by formulating detergent
25 compositions, including laundry and dishwashing compositions further
comprising a surfactant selected from nonionic and/or anionic and/or
cationic and/or ampholytic and/or zwitterionic and/or semi-polar surfactants
and/or mixtures thereof, a lipolytic andlor proteolytic enzyme, a hydrophobic
bleach activator, a soil release polymer and/or a dispersant.
It has been indeed surprisingly found that cholesterol esterase is an
enzyme which boosts cleaning performance by hydrolysing the cholesterol
esters present in body soils and/or greasy / oily soils and stains. It is
believed that said enzymatic hydrolysis products are rendered more soluble
and their removal by the detergent actives is thereby facilitated.
CA 02275290 1999-06-14
WO 98128394 PCT/US96I20876
3
Cholesterol esterase is commonly used in the medical context of
- cholesterol diagnostic and treatment such as described in J081 16996, AU
9 534 240, EP 709 456, US 5 484 777, US 5 474 993, J07222586,
J07070102, J07069885 and AU 9 466 101.
WO 94/23052 describes a method of hydrolysing cholesterol esters
o by treating the cholesterol esters with a cholesterol esterase enzyme
obtained from a strain of Pseudomonas fragi. Said method is useful for the
treatment of eggs, papermaking pulp, sterols, lanolin and for cleaning
purposes, especially gel cleaning agents for industrial hard surface cleaning.
However, the detergent compositions of the present invention have not
~ 5 been exemplified and the cleaning performance on body soils and/or oily /
greasy soils and stains of laundry and dishwashing compositions has not
been therein recognised.
Summary of the invention
The present invention relates to detergent compositions, including
laundry and dishwashing compositions, comprising a cholesterol esterase
enzyme at a level of from 0.0001 % to 5%, preferably 0.001 % to 2% pure
enzyme by weight of total composition for improved cleaning performance
on body soils and/or oily / greasy soils and stains.
The present invention also relates to detergent compositions,
' including laundry and dishwashing compositions comprising a cholesterol
esterase in combination with a surfactant selected from nonionic and/or
anionic and/or cationic and/or ampholytic andlor zwitterionic and/or semi
polar surfactants and/or mixtures thereof, a lipolytic andlor proteolytic
CA 02275290 1999-06-14
WO 98128394 PCT/US96I20876
4
enzyme, a hydrophobic bleach activator, a soil release polymer and/or a
dispersant.
Detailed description of the invention
The cholesterol esterase enzyme
An essential component of the detergent compositions of the
o invention is a cholesterol esterase falling under the EC classification EC
3.1.1.1 3.
This cholesterol esterase is incorporated into the detergent
compositions in accordance with the invention at a level of from 0.0001
~ 5 to 5%, preferably from 0.001 % to 2% pure enzyme by weight of the
composition.
Suitable cholesterol esterases for use in the present invention are
described in WO 93/10224 and in WO 94/23052 by Novo Nordisk A/S
2o wherein a cholesterol esterase acting lipase from respectively Pseudomonas
cepacia or fragi are disclosed and in 107203959 disclosing a DNA encoding
a stable cholesterol esterase, related vectors and transformed microbes, for
the large scale production of the enzyme.
25 Commercially available cholesterol esterases are Sigma bovine
pancrease Cholesterol esterase (Sigma 37fi6) or Bohringar Mannheim
Pseudomonas fluorescens cholesterol esterase.
Preferred cholesterol esterases are alkaline cholesterol esterases, ie
3o enzymes having an enzymatic activity of at least 10%, preferably 25%,
more preferably 40% of its maximum activity at a pH ranging from 7 to 1 1.
More preferred cholesterol esterases are enzymes having their maximum
activity at a pH ranging from 7 to 1 1.
35 The cholesterol esterase can be produced by the so called wild-type
organism or by any host organism in which the gene responsible for the
production of the cholesterol esterase, has been cloned and expressed.
CA 02275290 1999-06-14
WO 98/28394 PCT/US96/20876
Nowadays, it is common practice to modify wild-type enzymes via
protein / genetic engineering techniques in order to optimise their
performance efficiency in the detergent compositions of the invention. For
5 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.
The surfactant system
The detergent compositions according to the present invention can
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.
Indeed, it has been surprisingly found that the combination of
cholesterol esterase with a surfactant provides enhanced cleaning
3o performance on body soils and/or oily / greasy soils and stains.
The surfactant is typically present at a level of from 0.1 % to 60% by
weight. More preferred levels of incorporation are 1 % to 35% by weight,
most preferably from 1 % to 30% by weight of detergent compositions in
accord with the invention.
CA 02275290 1999-06-14
WO 98128394 PCT/US96I20876
6
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.
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
~ 5 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
2o nonionic surfactants of this type include IgepaITM CO-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).
25 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
3o 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 7 0 to about 18 carbon atoms, with from about
2 to about 10 moles of ethylene oxide per mole of alcohol. About 2 to
about 7 motes of ethylene oxide and most preferably from 2 to 5 moles of
35 ethylene oxide per mole of alcohol are present in said condensation
products. Examples of commercially available nonionic surfactants of this
type include TergitoITM 15-S-9 (the condensation product of C 1 1-C 15
CA 02275290 1999-06-14
WO 98/28394 PCT/L1S96/20876
7
linear alcohol with 9 moles ethylene oxide), TergitoITM 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 Corporation; NeodoITM 45-9 (the condensation product of C 14-C 15
linear alcohol with 9 moles of ethylene oxide), NeodoITM 23-3 (the
condensation product of C 12-C 13 linear alcohol with 3.0 moles of ethylene
oxide), NeodoITM 45-7 (the condensation product of C 14-C 15 linear alcohol
with 7 motes of ethylene oxide), NeodoITM 45-5 (the condensation product
of C14-C15 linear alcohol with 5 moles of ethylene oxide) marketed by
Shell Chemical Company, KyroTM EOB (the condensation product of C13
C 15 alcohol with 9 moles ethylene oxide), marketed by The Procter &
Gamble Company, and Genapol LA 030 or 050 (the condensation product
of C 12-C 14 alcohol with 3 or 5 moles of ethylene oxide) marketed by
Hoechst. Preferred range of HLB in these products is from 8-1 1 and most
3 5 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
20 containing from about 6 to about 30 carbon atoms, preferably from about
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
25 can be used, e.g., glucose, galactose and galactosyl moieties can be
substituted far the glucosyl moieties (optionally the hydrophobic group is
attached at the 2-, 3-, 4-, etc. positions thus giving a 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
30 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
The preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(glycosyltx
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl
CA 02275290 1999-06-14
WO 98128394 PCTIUS96/20876
8
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 f attachment at the 1-
position). The additional glycosyl units can then be attached between their
1-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 poiyoxyethylene 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
2o to the point where the polyoxyethylene content is about 50% of the total
weight of 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
3o 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
1 1,000. Examples of this type of nonionic surfactant include certain of the
commercially available TetronicTM compounds, marketed by BASF.
CA 02275290 1999-06-14
WO 98128394 PCT/US96120876
9
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-C 1 q, alkyl phenol ethoxylates
' having from 3 to 15 ethoxy groups and Cg-C 1 g alcohol ethoxylates
(preferably C 10 avg.) having from 2 to 10 ethoxy groups, and mixtures
thereof.
~ o Highly preferred nonionic surfactants are polyhydroxy fatty acid amide
surfactants of the formula.
R2 -C-N-Z,
~5 O R1
wherein R 1 is H, or R 1 is C ~ _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
2o hydroxyls directly connected to the chain, or an alkoxylated derivative
thereof. Preferably, R 1 is methyl, R2 is a straight C 1 1-15 alkyl or C 16-18
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 S03
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:
0
CA 02275290 1999-06-14
WO 98128394 PCT/US96/20876
R3 - CH - C - OR4
S03M
5 wherein R3 is a Cg-C2p hydrocarbyl, preferably an alkyl, or combination
thereof, R4 is a C 1-Cg 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
10 ammonium cations, such as monoethanolamine, diethanotamine, and
triethanolamine. Preferably, R3 is C 1 p-C 1 g alkyl, and R4 is methyl, ethyl
or
isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is
C1 p-C1 g alkyl.
Other suitable anionic surfactants include the alkyl sulfate surfactants
~ 5 which are water soluble salts or acids of the formula ROS03M wherein R
preferably is a C1 p-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl
having a C1 p-C2p alkyl component, more preferably a C12-C1 g 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.
2o 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
25 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 detergent compositions of the present invention. These can
3o 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
35 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
CA 02275290 1999-06-14
WO 98128394 PCT/US96/20876
11
sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates,
alkyl
phosphates, isethionates such as the acyl isethionates, N-acyl taurates,
alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates
' (especially saturated and unsaturated C12-C1 g monoesters) and diesters of
sulfosuccinates (especially saturated and unsaturated Cg-C ~ 2 diesters), acyl
' sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of
alkylpolygfucoside (the nonionic nonsulfated compounds being described
below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates
such as those of the formula RO(CH2CH20)k-CH2CO0-M + wherein R is a
o Cg-C22 alkyl, k is an integer from 1 to 10, 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.
i 5 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 1 % 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 C10-C24 alkyl or hydroxyalkyl
group having a C10-C24 alkyl component, preferably a C~ 2-C2p alkyl or
hydroxyalkyl, more preferably C 12-C 1 g 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.), 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 quaternary
ammonium cations such as tetramethyl-ammonium and dimethyl
CA 02275290 1999-06-14
WO 98!28394 PCT/US96120876
12
piperdinium
cations and
those derived
from alkylamines
such as ethylamine,
diethylamine, triethylamine, mixtures thereof) like. Exemplary
and the
surfactants re C 12-C 18 alkyl polyethoxylate sulfate (C
a ( 1.0) 12-
CIgE(1.0)M), C12-C1g alkyl polyethoxylate (2.25)sulfate (C12-
C~ gEf2.25)M),C12-C1 g alkyl polyethoxylate (3.0)sulfate (C~
2-
C1 gE(3.0)M), and C12-C1 g alkyl polyethoxylate sulfate (C12-
(4.0)
C1 gE(4.0)M), wherein M is conveniently selected
from sodium and
potassium.
The detergent 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 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 alkyltrimethylammonium halogenides, and
those surfactants having the formula
2o fR2(OR3)yl(R4(OR3)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(CH20H)-, -CH2CH2CH2-,
and mixtures thereof; each R4 is selected from the group consisting of C ~ -
C4 alkyl, C 1-C4 hydroxyalkyl, benzyl ring structures formed by joining the
two R4 groups, -CH2CHOH-CHOHCOR6CHOHCH20H wherein R6 is any
hexose or hexose 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
3o 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):
CA 02275290 1999-06-14
WO 98/28394 PCT/US96120876
13
Rz ~ s,,,.,,R4
R ~ N''
1~0 ~R5
X'
Formula I
whereby R 1 is a short chainlength alkyl (Cfi-C 10) or alkylamidoalkyl of the
formula (11)
Cs Cro~N~CH~
z
O
Formula II
y is 2-4, preferably 3.
whereby R2 is H or a C1-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 (C1-C3) or alkoxylated alkyl of the formula Ill,
whereby X- is a counterion, preferably a halide, e.g. chloride or
~ 5 methylsulfate.
Rs
O~z
Formula III
R6 is C 1-C4 and z is 1 or 2.
2o Preferred quat ammonium surfactants are those as defined in formula
I whereby
R ~ is Cg, C 10 or mixtures thereof, x = o,
Rg, R4 = CH3 and R5 = CH2CH20H.
25 Highly preferred cationic surfactants are the water-soluble quaternary
ammonium compounds useful in the present composition having the
' formula
R1 R2R3R4N+X_ (i)
CA 02275290 1999-06-14
WO 98/28394 PCT/US96I20876
14
wherein R1 is Cg-C1 g alkyl, each of R2, R3 and R4 is independently C1-C4
alkyl, C1-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. Preferred groups for R2Rg and R4 are methyl and hydroxyethyl
o 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
~ 5 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 12-15 dimethyl hydroxyethyl ammonium chloride or bromide;
2o coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxyy4 ammonium chloride or bromide;
choline esters (compounds of formula f i) wherein R1 is
25 CH2-CH2-O-C-C12-14 alkyl and R2R3R4 are methyl).
O
di-alkyl imidazolines [compounds of formula (i)].
3o 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-
35 insoluble quaternary-ammonium fabric softening actives, the most
commonly used having been di-long alkyl chain ammonium chloride or
methyl sulfate.
CA 02275290 1999-06-14
WO 98/28394 PCTIUS96120876
Preferred cationic softeners among these include the following:
1 ) ditallow dimethylammonium chloride (DTDMAC);
2) dihydrogenated tallow dimethylammonium chloride;
5 3) dihydrogenated tallow dimethylammonium methylsulfate;
4) distearyl dimethylammonium chloride;
5) dioleyl dimethylammonium chloride;
fi) dipalmityl hydroxyethyl methylammonium chloride;
7) stearyl benzyl dimethylammonium chloride;
8) tallow trimethylammonium chloride;
9) hydrogenated tallow trimethylammonium chloride;
10) 012-14 alkyl hydroxyethyl dimethylammonium chloride;
1 1 ) 012-18 alkyl dihydroxyethyl methylammonium chloride;
7 2) di(stearoyloxyethyl) dimethylammonium chloride (DSOEDMAC);
~ 5 13) di(tallowoyloxyethyl) dimethylammonium chloride;
14) ditallow imidazolinium methylsulfate;
15) 1-(2-tallowyfamidoethyl)-2-tallowyl irnidazolinium
meth ylsulfate.
2o 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
+ N yH2~_Q-'T 1 X' + N WCH2)n-CH -CH2 X '
I R3 Q ~?
RI I I
T~ T?
or
CA 02275290 1999-06-14
WO 98128394 PCTIUS96120876
16
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 C 1-Cq. alkyl or C 1-Cq. hydroxyaikyl or H;
R4 is H or C 1-C4 alkyl or C 1-Cq, hydroxyalkyl;
T1, T2, T3, T4, T5 are independently C1 ~ -C22 alkyl or alkenyl;
n and m are integers from 1 to 4; and
o 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.
Tallow is a convenient and inexpensive source of long chain alkyl and
aikenyl material. The compounds wherein T 1, 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
26
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;
3o 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;
35 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
CA 02275290 1999-06-14
WO 98/28394 PCT/US96I20876
17
8? 1,2-ditallowyi-oxy-3-trimethylammoniopropane chloride;
and mixtures of any of the above materials.
When included therein, the detergent 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.
Amphofytic surfactants are also suitable for use in the detergent
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 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 feast one contains an anionic water-
solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No.
3,929,678 to Laughiin et al., issued December 30, 1975 at column 19,
lines 18-35, for examples of ampholytic surfactants.
When included therein, the detergent 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 detergent
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 detergent 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
CA 02275290 1999-06-14
WO 98/28394 PCTIITS96120876
18
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 selected from the group consisting of alkyl groups
and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms;
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
1 o surfactants having the formula
0
T
R3 ( OR4 ) xN ( R5 ) 2
~ 5 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 0 to about 3; and each R5 is an alkyl or
hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a
2o 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 C10-C1 g alkyl
25 dimethyl amine oxides and Cg-C12 alkoxy ethyl dihydroxy ethyl amine
oxides.
When included therein, the detergent compositions of the present
invention typically comprise from 0.2% to about 7 5%, preferably from
3o about 1 % to about 10% by weight of such semi-polar nonionic surfactants.
The detergent 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 R1 NH2 wherein R1 is a Cg-C12~ preferably Cg-C10 alkyl chain or
CA 02275290 1999-06-14
WO 98128394 PCTIUS96120876
19
R4X/CH2)n, X is -O-,-C(O)NH- or -NH-~ R4 is a Cg-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 1-hexylamine, 1
octylamine, 1-decylamine and laurylamine. Other preferred primary amines
include C8-C 10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl
oxypropyiamine, lauryi amido propyiamine and amido propylamine.
Suitable tertiary amines for use herein include tertiary amines having
the formula R1R2R3N wherein R1 and R2 are C1-Cg alkylchains or
Rs
I
-C CHz-CH-p~H
R3 is either a C6-C12~ preferably Cg-C10 alkyl chain, or R3 is R4X(CH2)n,
~5 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 rnay be interrupted
with up to 12, preferably less than 5, ethylene oxide moieties.
2o Preferred tertiary amines are R1 R2R3N where R1 is a C6-C12 alkyl
chain, R2 and R3 are C 1-C3 alkyl or
Rs
I
-<\ CH,-CH-O~H
where R5 is H or CH3 and x = 1-2.
Also preferred are the amidoamines of the formula:
O
R i -C-NH-( CH2 n N-( R2 a
wherein R1 is Cg-C12 alkyl; n is 2-4,
3o preferably n is 3; R2 and R3 is C1-C4
Most preferred amines of the present invention include 1-octylamine,
1-hexylamine, 1-decylamine, 1-dodecylamine,CB-1 Ooxypropylamine, N coco
CA 02275290 1999-06-14
WO 98/28394 PCT/US96I20876
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
5 amidopropyldimethylamine.
The most preferred amines for use in the compositions herein are 1-
hexylamine, 1-octyiamine, 1-decylamine, 1-dodecylamine. Especially
desirable are n-dodecyldimethylamine and bishydroxyethylcoconutalkylamine
1 o and oleylamine 7 times ethoxylated, lauryl amido propylamine and
cocoamido propylamine.
The lipolytic enzyme
It has also been surprisingly found that the combination of cholesterol
esterase with a lipolytic enzyme provides enhanced cleaning performance on
body soils and/or oily / greasy soils and stains.
In the present context, the term "lipolytic enzyme" is intended to
indicate an enzyme exhibiting a lipid degrading capability, such as a
capability of degrading a triglyceride, a phospholipid, a wax-ester or cutin.
The lipolytic enzyme may, e.g., be a lipase, a phospholipase, an esterase or
a cutinase.
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
3o 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. iipolyticum NRRLB 3673 from Toyo Jozo Co.,
Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical
Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex
CA 02275290 1999-06-14
WO 98/28394 PCTIL1S96/20876
21
Pseudomonas gladioli. Especially suitable fipases are lipases such as M 1
LipaseR and LipomaxR (Gist-Brocades) and LipolaseR and Lipolase
UItraR(Novo) which have found to be very effective when used in
' combination with the compositions of the present invention.
' Preferred lipolytic enzymes include variants of lipolytic enzymes
producible by Humicola lanuginosa and Thermomyces lanuginosus, or by
cloning and expressing the gene responsible for producing said variants into
a host organism, e.g. Aspergillus oryzae as described in European Patent
io Application 0 258 068, incorporated herein by reference.
Other preferred lipolytic enzymes are variants of the native lipase
derived from Humicola ianuginosa as described in US Serial No.
08/341,826. Preferably the Humicola lanuginosa strain DSM 4106 is used.
~ 5 An example of said variants is D96L lipolytic enzyme as described in
patent
application WO 92/05249.
Afso 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
2o activation. Suitable cutinases are described in WO 94/14963 and WO
94/14964. Addition of cutinases to detergent compositions have been
described in e.g. WO-A-88/09367 (Genencorl.
Other suitable second lipolytic enzymes are phospholipases and esterases.
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 proteolytic enzyme
ft has also been surprisingly found that the combination of cholesterol
esterase with a proteolytic enzyme provides enhanced cleaning performance
on body soils and/or oily / greasy soils and stains.
CA 02275290 1999-06-14
WO 98128394 PCT/ITS96/20876
22
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 Gist-
Brocades. Proteolytic enzymes also encompass modified bacterial serine
proteases, such as those described in European Patent Application Serial
Number 87 303761.8, filed April 28, 1987 (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 proteaiytic 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 Bacillus in which lysine replaced
arginine at position 27, tyrosine replaced vaiine at position 104, serine
replaced asparagine at position 123, and alanine replaced threonine at
2o position 274. Protease C is described in EP 90915958:4, corresponding to
WO 91 /06637, Published May 16, 1991. Genetically modified variants,
particularly of Protease C, are also included herein. 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. When desired, a protease having decreased adsorption and
increased hydrolysis is available as described in WO 95/07791 to Procter &
Gamble. 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 group consisting of + 99, + 101, + 103, + 104,
CA 02275290 1999-06-14
WO 98/28394 PCT/1JS96/20876
23
+ 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 W091 /06637 and protease BLAP~
described in W091102792.
0
The proteolytic enzymes are incorporated in the detergent compositions of
the present invention a level of from 0.0001 % to 2%, preferably from
0.001 % to 0.2%, more preferably from 0.005% to 0.1 % pure enzyme by
weight of the composition.
The Hvdrophobic bleach activator
It has also been surprisingly found that the combination of cholesterol
esterase with a hydrophobic bleach activator provides enhanced cleaning
performance on body soils and/or oily / greasy soils and stains.
An essential element of the present invention is a hydrophobic bleach
activator within a bleaching system. The bleaching system wherein a bleach
activator is used, also comprises as an essential component a peroxygen
bleach capable of releasing hydrogen peroxide in aqueous solution.
It is generally believed that the bleach activator indergoes nucleophilic
attack by a perhydroxide anion, which is generated from the hydrogen
peroxide evolved by the peroxygen bleach, to form a peroxycarboxylic acid.
3o This reaction is commonly referred to as perhydrolysis.
The detergent compositions of the present invention include
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.
CA 02275290 1999-06-14
WO 98/28394 PCT/U896/20876
24
When present oxygen bleaching compounds will typically be present at
levels of from about 1 % to about 25%.
The hydrogen peroxide releasing agents are used in combination with
bleach activators such as nonanoyloxybenzene-sulfonate (NOBS, described
in US 4,412,934), 3,5,-trimethylhexanoioxybenzenesulfonate fISONOBS,
described in EP 120,591 )or Phenolsulfonate ester of N-nonanoyl-6-
aminocaproic acid (NACA-OBS, described in W094/28106), which are
perhydrolyzed to form a peracid as the active bleaching species, leading to
1 o improved bleaching effect. Their acid form can also be used such as the
nonyl amide of peroxy succinic acid, nonylamide of peraxy adipic acid or
nonanoyl axybenzene peroxy acid as described in our co-pending application
USSN 08/136,626.
~ 5 Useful bleaching agents, including peroxyacids and bleaching systems
comprising bleach activators and peroxygen bleaching compounds for use in
detergent compositions according to the invention as the N-acyl lactam
bleach described in W095/27773 and some bleach activators disclosed in
our co-pending application PCTlUS95/07823 USSN.
The dispersant
It has also been surprisingly found that the combination of cholesterol
esterase with a dispersant provides enhanced cleaning performance on body
soils and/or oily / greasy soils and stains.
Suitable dispersant for the detergent composition of the present
invention : 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 malefic
anhydride, such copolymers having a molecular weight of from 1,000 to
100,000.
CA 02275290 1999-06-14
WO 98128394 PCTlUS96/20876
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 detergent compositions of the
' present invention.
5
Other suitable dispersant for the detergent compositions of the
invention is a lime soap dispersant 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
i o dispersant compound is present at a level of from 0.1 % to 40% by weight,
more preferably 1 % to 20% by weight, most preferably from 2% to 10%
by weight of the compositions.
A lime soap dispersant is a material that prevents the precipitation of
~ 5 alkali metal, ammonium or amine salts of fatty acids by calcium or
magnesium ions. A numerical measure of the effectiveness of a time soap
dispersant is given by the lime soap dispersing power (LSDP) which is
determined using the lime soap dispersion test as described in an article by
H.C. Borghetty and C.A. Bergman, J. Am. Oil. Chem. Soc., volume 27,
2o 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, p3; W.N. Linfield, Tenside Surf. Det. , Volume 27, pages 159-161,
11990); and M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, Volume
25 104, 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 30m1 of water of 333ppm
CaC03 (Ca: Mg = 3:2) equivalent hardness.
3o In the Borghetty/Bergman lime soap dispersion test 5ml of a 0.5% by
weight solution of sodium oleate is added to a test tube, followed by 10m1
of a hard water solution containing 600ppm Ca2 + and 400ppm Mg2 +
(1000ppm as CaC03 equivalent, 70° Clark Hardness) which will cause
formation of a time soap deposit (or curd). An arbitrary amount (less than
15m1) of dispersing agent as a 0.25% by weight solution is then added to
the test tube. The total volume of solution in the test tube is then made up
to 30m1 and the test tube is stoppered, inverted 20 times and then allowed
CA 02275290 1999-06-14
WO 98128394 PCT/US96/20876
26
to stand for 30 seconds. The contents of the test tube are then visually
inspected to check if the lime soap deposits are still intact or whether they
have been dispersed into the solution. The test procedure is repeated using
different amounts of dispersing agent solution until the minimum amount of
dispersing agent solution which will cause dispersion of the lime soap
deposits is obtained.
The lime soap dispersing power is then obtained as:
o LSDP = (weight of lime soap dispersing agent) x 100
(weight of sodium oleate)
Thus in accord with the test method described above a material with a
lower LSDP is a more effective time soap dispersant than one with a higher
~5 LSDP.
A listing of suitable lime soap dispersants for use in accord with the
invention is given in the above mentioned review by M. Linfield to be found
in Tenside. Sust. Det., Volume 27, pages 159-161 (1990).
Polymeric lime soap dispersants suitable for use herein are described
in the above mentioned article by M.K. Nagarajan and W.F. Masier, to be
found in Cosmetics and Toiletries, Volume 104, pages 71-73, ( 1989).
Examples of such polymeric lime soap dispersants include certain water-
soluble salts of copolymers of acrylic acid, methacrylic acid or mixtures
thereof, and an acrylamide or substituted acrylamide, where such polymers
typically have a molecular weight of from 5,000 to 20,000.
Surfactants having good lime soap dispersant capability will include
3o 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 invention include C 16-C 1 g dimethyl amine oxide, C 12-C 18
alkyl ethoxysulfates with an average degree of ethoxylation of from 1-5,
particularly C12-C15 alkyl ethoxysulfate surfactant with a degree of
ethoxyfation of about 3 (LSDP = 4), and the C 13-C 15 ethoxylated alcohois
CA 02275290 1999-06-14
WO 98128394 PCTIUS96/20876
27
with an average degree of ethoxylation of either 12 (LSDP = 6) or 30, sold
under the trade names Lutensol A012 and Lutensol A030 respectively, by
BASF GmbH.
Polymeric time soap peptisers suitable for use herein are described in
' the article by M. K. Nagarajan, W. F. Master, to be found in Cosmetics and
Toiletries, volume 104, pages 71-73, ( 1989).
Hydrophobic bleaches such as 4-[N-octanoyl-6-aminohexanoyl]benzene
o 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 / hydrophobic
bleach formulations can also be used as lime soap peptisers compounds.
'f 5
The soil release pol~,mer
It has also been surprisingly found that the combination of cholesterol
esterase with a soil release polymer hereinafter "SRP", provides enhanced
2o cleaning performance on body soils and/or oily / greasy soils and stains.
SRP's will generally be comprised from 0.01 % to 10.0%, typically
from 0.1 % to 5%, preferably from 0.2% to 3.0% by weight, of the
compositions.
Preferred SRP's typically have hydrophilic segments to hydrophilize the
surface of hydrophobic fibers such as polyester and nylon, and hydrophobic
segments to deposit upon hydrophobic fibers and remain adhered thereto
through completion of washing and rinsing cycles, thereby serving as an
3o anchor for the hydrophilic segments. This can enable stains occurring
subsequent to treatment with the SRP to be more easily cleaned in later
washing procedures.
SRP's can include a variety of charged, e.g., anionic or even cationic
species, see U.S. 4,956,447, issued September 1 1, 1990 to Gosselink, et
al., as well as noncharged monomer units, and their structures may be
linear, branched or even star-shaped. They may include capping moieties
CA 02275290 1999-06-14
WO 98128394 PCT/L1S96I2087b
28
which are especially effective in controlling molecular weight or altering the
physical or surface-active properties. Structures and charge distributions
may be tailored for application to different fiber or textile types and for
varied detergent or detergent additive products.
Preferred SRP's include oligomeric terephthalate esters, typically
prepared by processes involving at least one
transesterification/oligomerization, often with a metal catalyst such as a
titanium(IV) alkoxide. Such esters may be made using additional monomers
0 capable of being incorporated into the ester structure through one, two,
three, four or more positions, without, of course, forming a densely
crosslinked overall structure.
Suitable SRP's include a sulfonated product of a substantially linear
~ 5 ester oligomer comprised of an oligomeric ester backbone of terephthaloyl
and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal
moieties covalently attached to the backbone, for example as described in
U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b)
20 reacting the product of (a) with dimethyl terephthalate ("DMT") and 1 (2-
propylene glycol ("PG") in a two-stage transesterification/oligomerization
procedure; and (c) reacting the product of (b) with sodium metabisulfite in
water. Other SRP's include the nonionic end-capped 1 (2-
propylene/polyoxyethylene terephthalate polyesters of U.S. 4,71 1 (730,
25 December 8, 1987 to Gosselink et al., for example those produced by
transesterification / oligomerization of poly(ethyleneglycol) methyl ether,
DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of SRP's
include: the partly- and fully- anionic-end-capped otigomeric esters of U.S.
4,721,580, January 26, 1988 to Gosselink, such as oligomers from
3o ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-
hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric
compounds of U.S. 4,702,857, October 27, 1987 to Gosselink, for
example produced from DMT, methyl (Me)-capped PEG and EG and/or PG,
or a combination of DMT, EG andlor PG, Me-capped PEG and Na-dimethyl-
35 5-sulfoisophthalate; and the anionic, especially sutfoaroyl, end-capped
terephthalate esters of U.S. 4,877,89fi, October 31, 1989 to Maldonado,
Gosselink et al., the latter being typical of SRP's useful in both laundry and
CA 02275290 1999-06-14
WO 98/28394 PCT/US96/20876
29
fabric conditioning products, an example being an ester composition made
from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but
preferably further comprising added PEG, e.g., PEG 3400.
SRP's also include: simple copolymeric blocks of ethylene terephthalate
or propylene terephthalate with polyethylene oxide or polypropylene oxide
terephthalate, see U:S. 3,959,230 to Hays, May 25, 1976 and U.S.
3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the
hydroxyether cellulosic polymers available as METHOCEL from Dow; the
C1-C4 alkyl celluloses and C4 hydroxyaikyi celluloses, see U.S. 4,000,093,
December 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having
an average degree of substitution (methyl) per anhydroglucose unit from
about 1.6 to about 2.3 and a solution viscosity of from about 80 to about
120 centipoise measured at 20°C as a 2% aqueous solution. Such
materials are available as METOLOSE SM100 and METOLOSE SM200,
which are the trade names of methyl cellulose ethers manufactured by Shin-
etsu Kagaku Kogyo KK.
Suitable SRP's characterised by polyvinyl ester) hydrophobe segments
2o include graft copolymers of polyvinyl ester), e.g., C 1-Cg vinyl esters,
preferably polyvinyl acetate), grafted onto polyalkylene oxide backbones.
See European Patent Application 0 219 048, published April 22, 1987 by
Kud, et al. Commercially available examples include SOKALAN SRP's such
as SOKALAN HP-22, available from BASF, Germany. Other SRP's are
polyesters with repeat units containing 10-15% by weight of ethylene
terephthalate together with 80-90% by weight of polyoxyethylene
terephthalate derived from a poiyoxyethylene glycol of average molecular
weight 300-5,000. Commercial examples include ZELCON 5126 from
Dupont and MILEASE T from ICI.
Another preferred SRP is an oligomer having empirical formula
(CAP)2(EG/PG)5(T)5(SIP)1 which comprises terephthaloyl (T),
sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units
and which is preferably terminated with end-caps (CAP), preferably modified
isethionates, as in an oligomer comprising one sulfoisophthaloyl unit, 5
terephthaloyl units, oxyethyieneoxy and oxy-1,2-propyleneoxy units in a
defined ratio, preferably about 0.5:1 to about 10:1, and two end-.cap units
CA 02275290 1999-06-14
WO 98128394 PCT/US96/20876
derived from sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said SRP
preferably further comprises from 0.5% to 20%, by weight of the oligomer,
of a crystallinity-reducing stabiliser, for example an anionic surfactant such
as linear sodium dodecylbenzenesulfonate or a member selected from
5 xylene-, cumene-, and toluene- sulfonates or mixtures thereof, these
stabilizers or modifiers being introduced into the synthesis vessel, all as
taught in U.S. 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16,
1995. Suitable monomers for the above SRP include Na-2-(2
hydroxyethoxy)-ethanesulfonate, DMT, Na-dimethyl-5-sulfoisophthalate, EG
o and PG .
Yet another group of preferred SRP's are oligomeric esters comprising:
( 1 ) a backbone comprising (a) at least one unit selected from the group
consisting of dihydroxysulfonates, polyhydroxy sulfonates, a unit which is
15 at least trifunctional whereby ester linkages are formed resulting in a
branched oligomer backbone, and combinations thereof; (b1 at least one
unit which is a terephthaloyl moiety; and (c) at least one unsulfonated unit
which is a 1,2-oxyalkyleneoxy moiety; and (2) one or more capping units
selected from nonionic capping units, anionic capping units such as
2o alkoxylated, preferably ethoxylated, isethionates, alkoxylated
propanesulfonates, alkoxylated propanedisulfonates, alkoxylated
phenolsulfonates, sulfoaroyl derivatives and mixtures thereof. Preferred are
esters of the empirical formula:
25 t(CAP)x(EG/PG)y'(DEG)y"(PEG)y"'(T)z(SIP)z'(SEG)q(B)m}
wherein CAP, EG/PG, PEG, T and SIP are as defined hereinabove, (DEG)
represents di(oxyethylene)oxy units, (SEG) represents units derived from the
sulfoethyl ether of glycerin and related moiety units, (B) represents
3o branching units which are at least trifunctional whereby ester linkages are
farmed resulting in a branched oligomer backbone, x is from about 1 to
about 12, y' is from about 0.5 to about 25, y" is from 0 to about 12, y"' is
from 0 to about 10, y' + y" + y"' totals from about 0.5 to about 25, z is
from about 1.5 to about 25, z' is from 0 to about 12; z + z' totals from
about 1.5 to about 25, q is from about 0.05 to about 12; m is from about
0.01 to about 10, and x, y', y", y"') z, z', q and m represent the average
CA 02275290 1999-06-14
WO 98128394 PCT/US96120876
31
number of moles of the corresponding units per mole of said ester and said
ester has a molecular weight ranging from about 500 to about 5,000.
Preferred SEG and CAP monomers for the above esters include Na-2-
(2-,3-dihydroxypropoxy)ethanesuifonate ("SEG"), Na-2-{2-(2-
' hydroxyethoxy) ethoxy} ethanesulfonate ("SE3") and its homologs and
mixtures thereof and the products of ethoxylating and sulfonating allyl
alcohol. Preferred SRP esters in this class include the product of
transesterifying and oligomerizing sodium 2-{2-(2-hydroxy-
o ethoxy)ethoxy}ethanesulfonate and/or sodium 2-[2-{2-(2-hydroxy-
ethoxy)ethoxy}ethoxy)ethanesulfonate, DMT, sodium 2-(2,3-
dihydroxypropoxy) ethane sulfonate, EG, and PG using an appropriate Ti(IV)
catalyst and can be designated as (CAP)2(T)5(EG/PG) 1.4(SEG)2.5(B)0.13
wherein CAP is (Na+-03S[CH2CH20]3.5)- and B is a unit from glycerin
~ 5 and the mole ratio EG/PG is about 1.7:1 as measured by conventional gas
chromatography after complete hydrolysis.
Additional classes of SRP's include: (I) nonionic terephthalates using
diisocyanate coupling agents to link polymeric ester structures, see U.S.
2o 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II)
SRP's with carboxylate terminal groups made by adding trimellitic anhydride
to known SRP's to convert terminal hydroxyl groups to trimellitate esters.
With the proper selection of catalyst, the trimellitic anhydride forms
linkages
to the terminals of the polymer through an ester of the isolated carboxylic
25 acid of trimellitic anhydride rather than by opening of the anhydride
linkage.
Either nonionic or anionic SRP's may be used as starting materials as long
as they have hydroxyl terminal groups which may be esterified. See U.S.
4,525,524 Tung et al.. Other classes include: (III) anionic terephthalate-
based SRP's of the urethane-linked variety, see U.S. 4,201,824, Violland et
3o al.; (IV) poiy(vinyl caprolactam) and related co-polymers with monomers
such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate, including
both nonionic and cationic polymers, see U.S. 4,579,fi81 ( Ruppert et al.;
(V) graft copolymers, in addition to the SOKALAN types 'from BASF, made
by grafting acrylic monomers onto sulfonated polyesters. These SRP's
35 assertedly have soil release and anti-redeposition activity similar to
known
cellulose ethers: see EP 279,134 A, 1988, to Rhone-Poulenc Chemie. Still
other classes include: (VI) grafts of vinyl monomers such as acrylic acid and
CA 02275290 1999-06-14
WO 98/28394 PCT/US96I20876
32
vinyl acetate onto proteins such as caseins, see EP 457,205 A to BASF
( 1991 ); and (VII) polyester-polyamide SRP's prepared by condensing adipic
acid, caprolactam, and polyethylene glycol, especially for treating polyamide
fabrics, see Bevan et al., DE 2,335,044 to Unilever N. V., 1974. Other
useful SRP's are described in U.S. Patents 4,240,918, 4,787,989 and
4,525,524.
Other suitables SRP for the purpose of present invention are
described in US Patent Nos. US5,541,341; US4,715,990; US5,496,490
and in W095/32997.
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-0 272
033 has the formula
(CH3(PEG)43)0.75(POH)0.25(T-PO)2_g(T-PEG)0.4]T(PO-
H)0.25(IPEG)43CH3)p.75
where PEG is -(OC2H4)O-,PO is (OC3Hg0) 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
CA 02275290 1999-06-14
WO 98128394 PCT/US961Z0876
33
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 31 1 342.
Detergient components
The detergent compositions of the invention may also contain
1 o 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 detergent 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. Compositions containing
such cholesterol esterase can also be formulated as softening compositions.
Such compositions containing cholesterol esterase can provide fabric
cleaning, stain removal, whiteness maintenance, softening, color
3o 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
compounds, suds enhancing agents, group II metal ions, solvents,
hydrotropes and additional enzymes.
CA 02275290 1999-06-14
WO 98128394 PCT/US96/20876
34
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.
0
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
2o 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 10%,
most preferably not exceeding 5% by weight of the composition.
3o 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
CA 02275290 1999-06-14
WO 98128394 PCT/US96/20876
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
5 preferably less than 40%, more preferably less than 30%, most preferably
' less than 20% by weight of the detergent composition.
Conventional detergent enzymes
The detergent compositions can in addition to cholesterol esterase
further comprise one or more enzymes which provide cleaning performance
and/or fabric care benefits.
~ 5 Said enzymes include enzymes selected from cellulases, hemicellulases,
peroxidases, gluco-amylases, amylases, xylanases, cutinases, pectinases,
keratanases, reductases, oxidases, phenoloxidases, lipoxygenases,
ligninases, pulluianases, tannases, pentosanases, malanases, f3-glucanases,
arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof.
A preferred combination is a detergent composition having cocktail of
conventional applicable enzymes like protease, amylase, lipase, cutinase
and/or celluiase in conjunction with one or more plant cell wall degrading
enzymes.
The cellutases 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
3o insoiens. 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.
CA 02275290 1999-06-14
WO 98128394 PCT/US96120876
36
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; and a "'43kD endoglucanase derived from
Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred
endoglucanase component has the amino acid sequence disclosed in PCT
Patent Application No. WO 91 /17243. Also suitable cellulases are the EG111
cellulases from Trichoderma longibrachiatum described in W094/21801,
Genencor, published September 29, 1994. Especially suitable cellulases are
the cellulases having color care benefits. Examples of such cellulases are
o cellufases 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 W091117243.
Peroxidase enzymes are used in combination with oxygen sources,
e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are
used for "solution bleaching", i.e. to prevent transfer of dyes or pigments
removed from substrates during wash operations to other substrates in the
wash solution. Peroxidase enzymes are known in the art, and include, for
example, horseradish peroxidase, ligninase and haloperoxidase such as
2o chloro- and bromo-peroxidase. Peroxidase-containing detergent
compositions are disclosed, for example, in PCT International Application
WO 89!099813, W089/09813 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 phenthiazine 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
3o alkyl syringates) and phenols. Sodium percarbonate or perborate are
preferred sources of hydrogen peroxide.
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.
CA 02275290 1999-06-14
WO 98!28394 PCT/CTS96I20876
37
Amylases (a and/or f3) can be included for removal of carbohydrate-
based stains. 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 and
W095/10603, Novo Nordisk A/S, published April 20, 1995. Other
amylases known for use in cleaning compositions include both a- and (3-
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 368,347 ; and British Patent specification no.
o 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 W096/05295, Genencor, published Februaury 22, 1996 and
amylase variants having additional modification in the immediate parent
available from Novo Nordisk A/S, disclosed in WO 95/10603, published
~ 5 April 95.
Examples of 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
20 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
25 level are described in W095/35382.
The above-mentioned enzymes may be of any suitable origin, such as
vegetable, animal, bacterial, fungal and yeast origin. Origin can further
be mesophilic or extremophilic (psychrophific, psychrotrophic, thermophilic,
3o barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-
purified
forms of these enzymes may be used. Also included by definition, are
mutants of native enzymes. Mutants can be obtained e.g. by protein and/or
genetic engineering, chemical and/or physical modifications of native
enzymes. Common practice as well is the expression of the enzyme via host
35 organisms in which the genetic material responsible for the production of
the enzyme has been cloned.
CA 02275290 1999-06-14
WO 98/28394 PCT/ITS96120876
38
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
(grills, granulates, stabilized liquids, etc... containing one enzyme 1 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
o 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
~ 5 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, 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
20 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. AC 13 giving proteases) xylanases
25 and ceilulases, is described in WO 9401532 A to Novo.
Color care benefits
Technologies which provide a type of color care benefit can also be
3o included. Examples of these technologies are metallo catalysts for color
maintenance. Such metallo catalysts are described in copending European
Patent Application No. 92870181.2.
Other bleaching agent
One category of oxygen bleaching agent that can be used encompasses
percarboxylic acid bleaching agents and salts thereof. Suitable examples of
CA 02275290 1999-06-14
WO 98/28394 PCT/US96/20876
39
this class of agents include magnesium monoperoxyphthalate hexahydrate,
the magnesium salt of meta-chloro perbenzoic acid, 4-nonyiamino-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
i 0 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
other bleach activators such astetraacetylethylenediamine (TAED) or
pentaacetylglucose (PAG), which are perhydrolyzed to form a peracid as the
active bleaching species, leading to improved bleaching effect. Also suitable
activators are acylated citrate esters such as disclosed in Copending
European Patent Application No. 91870207.7.
Metal-containing catalysts for use in bleach compositions, include
cobalt-containing catalysts such as Pentaamine acetate cobalt(///) 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 5,1 14,fi1 1. 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
CA 02275290 1999-06-14
WO 98/28394 PCT/US96/20876
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 wilt contain about 0.025% to
about 1.25%, by weight, of sulfonated zinc phthalocyanine.
5
Useful bleaching agents, including peroxyacids and bleaching systems
comprising bleach activators and peroxygen bleaching compounds for use in
detergent compositions according to the invention are described in our co-
pending applications W095/27772, W095/27774 and W095/27775.
0
Builder system
The compositions according to the present invention may further
comprise a builder system. Any, conventional builder system is suitable for
15 use herein including aluminosilicate materials, silicates,
polycarboxylates,
alkyl- or alkenyl-succinic acid and fatty acids, materials such as
ethylenediamine tetraacetate, diethylene triamine pentamethyleneacetate,
metal ion sequestrants such as aminopolyphosphonates, particularly
ethylenediamine tetramethylene phosphoric acid and diethylene triamine
2o 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
25 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 (Na2Si205).
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, malefic 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
CA 02275290 1999-06-14
WO 98/28394 PCT/US96I20876
41
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 tricarboxyiates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include
0 oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane
tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane
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
~ 5 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-
20 cis,cis,cis-tetracarboxylates, cyciopentadienide 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
25 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
30 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 carboxyfate chelating agent
35 such as citric acid.
CA 02275290 1999-06-14
WO 98128394 PCT/(TS96I20876
42
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 malefic
2o 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.
Chelant
The detergent compositions herein may also optionally contain one or
3o more iron and/or manganese chelating agents. Such chelating agents can
be selected from the group consisting of amino carboxylates, amino
phosphonates, polyfunctionalfy-substituted aromatic chelating agents and
mixtures therein, all as hereinafter defined. Without intending to be bound
by theory, it is believed that the benefit of these materials is due in part
to
their exceptional ability to remove iron and manganese ions from washing
solutions by formation of soluble chelates.
CA 02275290 1999-06-14
WO 98/28394 PCT/US96120876
43
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,
' nitrifotriacetates, ethylenediamine tetraproprionates, triethylenetetraamine
hexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali
' metal, ammonium, and substituted ammonium salts therein and mixtures
therein.
0 Amino phosphonates are also suitable for use as chelating agents in
the compositions of the invention when at lease low levels of total
phosphorus are permitted in detergent compositions, and include
ethylenediaminetetrakis /methylenephosphonates) as DEQUEST. Preferred,
these amino phosphonates to not contain alkyl or alkenyl groups with more
~ 5 than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful
in the compositions herein. See U.S. Patent 3,812,044, issued May 21,
1974) to Connor et al. Preferred compounds of this type in acid form are
2o dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
A preferred biodegradable cheiator for use herein is ethylenediamine
disuccinate ("EDDS"), especially the (S,S] isomer as described in U.S.
Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
The compositions herein may also contain water-soluble methyl
gfycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder
useful with, for example, insoluble builders such as zeolites, layered
silicates and the like.
If utilized, these chelating agents will generally comprise from about
0.1 % to about 15% by weight of the detergent compositions herein. More
preferably, if utilized, the chelating agents will comprise from about 0.1
to about 3.0% by weight of such compositions.
Suds suppressor
CA 02275290 1999-06-14
WO 98!28394
PCT/US96120876
44
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
o 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
2o 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, 1992.
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.
3o 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 detergent compositions may be employed,
such as soil-suspending agents, optical brighteners, abrasives, bactericides,
CA 02275290 1999-06-14
WO 98/28394 PCTlUS96I20876
tarnish inhibitors, coloring agents, and/or encapsulated or non-encapsulated
perfumes.
Especially suitable encapsulating materials are water soluble capsules
5 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
o 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
~ 5 starch is modified by adding monofunctionai substituted groups such as
octenyl succinic acid anhydride.
Antiredeposition and soil suspension agents suitable herein include
cellulose derivatives such as methylcellulose, carboxymethylcellulose and
2o hydroxyethylcellulose, and homo- or co-polymeric polycarboxyiic 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
25 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
3o 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
35 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-
CA 02275290 1999-06-14
WO 98/28394 PCT/US96/20876
46
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.
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
2o composition, in the formulas will provide improved through the wash
stability of the detergent enzymes. 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
3o every 7-8 acrylate units. The side-chains are of the formula
-(CH2CH20)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 poiycarboxylates can
comprise from about 0.05% to about 10%, by weight, of the compositions
herein.
CA 02275290 1999-06-14
WO 98/28394 PCT/US96/20876
47
Softening agents
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-A1 514 276 and EP-BO 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 2% to 20%,
more preferably from 5% 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 5% by
weight, normally from 1 % 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.
Dye transfer inhibition
The detergent compositions of the present invention can also include
compounds for inhibiting dye transfer from one fabric to another of
solubilized and suspended dyes encountered during fabric laundering
operations involving colored fabrics.
Polymeric dye transfer inhibiting agents
CA 02275290 1999-06-14
WO 98128394 PCT/US96/20876
48
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.
1 o 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
~ 5 according the invention.
a1 Polyamine N-oxide polymers
2o The polyamine N-oxide polymers suitable for use contain units having
the following structure formula
P
CI) AX
R
wherein P is a polymerisable unit, whereto the R-N-0 group can be
attached to or wherein the R-N-O group forms part of the
3o polymerisable unit or a combination of both.
0 0 0
A is NC, CO, C, -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
CA 02275290 1999-06-14
WO 98/28394 PCTIUS96120876
49
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
( R1 ) x -N- ( R2 ) y =N- ( R1 ) x
(R3 ) z
wherein R 1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic groups or combinations thereof, x or/and y or/and z is 0
or 7 and wherein the nitrogen of the N-0 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 poiyamine 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.
3o 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 pofymerisable unit.
Preferred classes of these polyamine N-oxides are the polyamine N-oxides
having the general formula (I) wherein R is an aromatic, heterocyclic or
CA 02275290 1999-06-14
WO 98/28394 PCT/US96120876
aficyciic 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 heterocyciic
5 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, heterocycfic or
alicyclic groups wherein the nitrogen of the N-0 functional group is attached
1 o to said R groups.
Examples of these classes are polyamine oxides wherein R groups can
be aromatic such as phenyl.
~ 5 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, poiyethers, 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-
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
3o 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.
CA 02275290 1999-06-14
WO 98128394 PCTIUS96120876
51
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-vinyiimidazole 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 fight 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 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.
3o 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
CA 02275290 1999-06-14
WO 98/28394 PCT/US96120876
52
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
1o PVP K-90 (average molecular weight of 360,000). Other suitable
polyvinylpyrrolidones which are commercially available from BASF
Cooperation include Sokalan HP 165 and Sokaian 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
2o 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.
e) Polyvinylimidazole
The detergent compositions of the present invention may also utilize
polyvinylimidazole as polymeric dye transfer inhibiting agent. Said
3o polyvinyfimidazoles 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
CA 02275290 1999-06-14
WO 98/28394 PCTIUS96/20876
53
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
o embodiment, the cross-linked polymers entrap the dyes by swelling.
Such cross-linked polymers are described in the co-pending patent
application 9487027 3.9
Method of washing
The compositions of the invention may be used in essentially any
washing or cleaning methods, including soaking methods, pretreatment
2o 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.
The process of the invention 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 1 1.
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 3-10 litres.
CA 02275290 1999-06-14
WO 98/28394 PCT/LTS96/20876
54
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
o 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
~ 5 compositions. The abbreviated component identifications therein have the
following meanings:
LAS . Sodium linear C 12 alkyl benzene sulphonate
TAS . Sodium tallow alkyl sulphate
CXYAS . Sodium C 1 X - C 1 Y alkyl sulfate
25EY . A C12_C15 predominantly linear primary alcohol
condensed with an average of Y moles of ethylene
oxide
CXYEZ . A C1 X - C1 Y predominantly linear primary alcohol
condensed with an average of Z moles of ethylene
oxide
XYEZS . C1X - C1Y 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
CA 02275290 1999-06-14
WO 98/28394 PCTIUS96l20876
Soap . Sodium linear alkyl carboxylate derived from a 80/20
mixture of tallow and coconut oils.
Nonionic . C 13-C 15 mixed ethoxylated/propoxylated fatty
alcohol with an average degree of ethoxyiation 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 ~ C 16-C 18 alkyl N-methyl glucamide.
TPKFA . C 1 2-C 14 topped whole cut fatty acids.
DEQA . Di-(tallow-oxy-ethyl) dimethyl ammonium chloride.
SDASA . 1:2 ratio of stearyldimethyl amineariple-pressed
stearic acid.
Neodol 45-13 . C 14-C 15 linear primary alcohol ethoxylate, sold by
Shell Chemical CO.
Tallow . Dihydrogenated taiiowamidoethyl hydroxyethylmonium
methosulfate / glycol distearate / cetyl alcohol.
Silicate : Amorphous Sodium Silicate (Si02:Na20 ratio = 2.0?
NaSKS-6 . Crystalline layered silicate of formula 8-Na2Si205.
Carbonate . Anhydrous sodium carbonate with a particle size
between 200 pm and 900~.m.
Bicarbonate . Anhydrous sodium bicarbonate with a particle size
between 400 ~,m and 1200pm.
STPP . Anhydrous sodium tripolyphosphate
CA 02275290 1999-06-14
WO 98128394 PCT/LTS96120876
56
MA/AA : Copolymer of 1:4 maleic/acryiic 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 acryiic:maleic:ethylacrylic acid
monomer units at a weight ratio of 60:20:20
480N . Random copolymer of 3:7 acrylic/methacrylic acid,
average molecular weight about 3,500.
Polyacrylate : Polyacrylate homopoiymer with an average molecular
weight of 8,000 sold under the tradename PA30 by
BASF GmbH
Zeolite A : Hydrated Sodium Aiuminosilicate of formula
Nal2(A102Si02)12. 27H20 having a primary particle
size in the range from 0.1 to 10 micrometers
Citrate : Tri-sodium citrate dehydrate 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 NaB02.H202
PB4 . Anhydrous sodium perborate tetrahydrate
Percarbonate : Anhydrous sodium percarbonate bleach of empirical
formula 2Na2C03.3H202
TAED : Tetraacetyl ethylene diamine.
CA 02275290 1999-06-14
WO 98128394 PCTlUS96/20876
57
NOBS . Nonanoyloxybenzene sulfonate in the form of the
sodium salt.
Photoactivated : Sulfonated zinc phtiocyanine encapsulated in dextrin
Bleach soluble polymer.
PAAC : Pentaamine acetate cobalt(II1) salt.
Paraffin . Paraffin oil sold under the tradename Winog 70 by
Wintershall.
BzP : Benzoyl Peroxide.
Cholesterol : Sigma bovine pancrease Cholesterol esterase (Sigma
esterase 3766) or Bohringar Mannheim Pseudomonas
fluorescens cholesterol esterase.
Protease : Proteolytic enzyme sold under the tradename
Savinase, Alcalase, Durazym by Novo Nordisk AIS,
Maxacal, Maxapem sold by Gist-Brocades and
proteases described in patents W091 /06637 and/or
W095/10591 and/or EP 251 446.
Amylase : Amylolytic enzyme sold under the tradename Purafact
Ox AmR described in WO 94/18314, W096/05295
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.
CA 02275290 1999-06-14
WO 98/28394 PCTIUS96120876
58
HEDP . 1,1-hydroxyethane diphosphonic acid.
DETPMP . Diethylene triamine penta (methylene phosphoric
acid), marketed by Monsanto under the Trade name
bequest 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)biphenyi.
Brightener 2 . Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin
2-yl) stilbene-2:2'-disulfonate.
Silicone antifoam : Polydimethylsiloxane foam controller 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 alcoho1,70% starch
Suppressor in granular form
SRP 7 : Sulfobenzoyl end capped esters with oxyethylene oxy
and terephtaloyl backbone.
SRP 2 . Diethoxylated poly (1,2 propylene terephtalate) short
block polymer.
SCS . Sodium cumene sulphonate
Sulphate . Anhydrous sodium sulphate.
HMWPEO : High molecular weight polyethylene oxide
CA 02275290 1999-06-14
WO 98128394 PCTIUS96120876
59
PEG . Polyethylene glycol.
BTA : Benzotriazole
Bismuth nitrate . Bismuth nitrate salt
NaDCC : 'Sodium dichloroisocyanurate
Encapsulated : Insoluble fragrance delivery technology utilising zeolite
perfume particles 13x, perfume and a dextrose/glycerin agglomerating
binder.
KOH : 100% Active solution of Potassium Hydroxide
pH : Measured as a 1 % solution in distilled water at 20°C.
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
Cholesterol 0.005 0.005 0.005 0.005 0.005 0.005
esterase
Protease 0.0026 0.0026 0.0026 0.0026 0.0026 0.0026
CA 02275290 1999-06-14
WO 98128394 PCT/ITS96/Z0876
Amylase - 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 1 0.09 0.09 0.09 0.09 0.09 0.09
Perfume 0.3 0.3 0.3 ~ 0.3 0.3 0.3
Silicone antifoam0.5 0.5 0.5 0.5 0.5 0.5
Misc/minors to
100%
Density in g/litre850 850 850 850 850 850
Example 2
5 The following granular
laundry detergent compositions
of bulk density 750
g/litre were prepared ntion:
in accord with the
inve
1 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 1 g,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,g _ _
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
Cholesterol esterase 0.005 0.005 0.005
Protease 0.0026 0.0085 0.045
Lipase 0.003 0.003 0.003
CA 02275290 1999-06-14
WO 98/28394 PCTILTS96/20876
61
Cellufase 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 bleach 15 ppm 27 ppm 27 ppm
(ppm)
Brightener 1 0.08 0.19 0.19
Brightener 2 - 0.04 0.04
Encapsulated perfume 0.3 0.3 0.3
particles
Silicone antifoam 0.5 2.4 2.4
Minors/misc to 100%
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 1 1.0
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 bleach 0.02 0.02 0.02
CA 02275290 1999-06-14
WO 98/28394 PCT/L1S96/20876
62
Cholesterol esterase 0.01 0.01 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 sulfate3.0 3.0 5.0
Balance (Moisture & 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 630 670 670
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:
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 -
Agglomerates
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
PVPVIlPVNO 0.5 0.5 0.5
Cholesterol esterase 0.01 0.01 0.01
CA 02275290 1999-06-14
WO 98J28394 PCT/L1S96/20876
63
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 (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/litrel 700 700 700
Example 5
The following detergent formulations, according to the present invention
were prepared:
i 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
Cholesterol esterase 0.01 0.01 0.01 0.01
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 70ppm 45ppm - 10ppm
bleach (ppm)
Brightener 1 0.2 0.2 0.08 0.2
PB 1 6.0 2.0 - -
CA 02275290 1999-06-14
WO 98128394 PCT/US96/20876
64
NOBS 2.0 1.0 - -
Balance (Moisture 100 100 100 100
and Miscellaneous
Examale 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 fi.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 -
Cholesterol esterase 0.01 0.01 0.01 0.01
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 0.00.02 0.0002
NOBS - 6.1 4.5 3.2
PB1 1.0 5.0 6.0 3.9
Sodium sulfate - 6.0 - to balance
CA 02275290 1999-06-14
WO 98/28394 PCT/US96120876
Balance (Moisture and 100 100 100
Miscellaneous)
Examale 7
' The following high density and bleach-containing detergent formulations,
5 according to the present invention were prepared:
I II III
Blown Powder
Zeolite A 15.0 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
PB 1 14.0 7.0 10.0
Polyethylene oxide of MW - - 0.2
5,000,000
Bentonite clay - - 10.0
Cholesterol esterase 0.01 0.01 0.01
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
CA 02275290 1999-06-14
WO 98128394 PCTIUS96120876
66
Sodium sulfate 0.0 3.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 850 850 850
ExamJole 8
The following high density detergent formulations, according to the present
invention were prepared:
Agglomerate
Spray On
Dry Adds
C45AS 1 1.0 14.0
Zeolite 15.0 fi.0
A ~
Carbonate 4.0 8.0
MA/AA 4.0 2.0
CMC 0.5 0.5
DETPMP 0.4 0.4
C25E5 5.0 5.0
Perfume 0.5 0.5
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 0.3
Cholesterol esterase0.01 0.01
Protease 0.014 0.014
Lipase 0.009 0.009
Cellulase 0.001 0.001
Amylase 0.005 0.005
Silicone antifoam 5.0 5.0
Brightener 1 0.2 0.2
Brightener 2 0.2 -
67
Image
Example 9
The following granular detergent formulations, according to the present
invention were prepared:
Image
Example 10
CA 02275290 1999-06-14
WO 98/28394 PCT1US96/20876
68
The following liquid detergent formulations, according to the present
invention were prepared:
I II III IV V VI VII V111
LAS 10.0 13.0 9.0 - 25.0 - - -
C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 15.0
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 fatty- - - 5.0 - - 4.0 4.0
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
succinic acid
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 Propanediol4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.-
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 4.3
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
Cholesterol .005 .005 .005 .005 .005 .005 .005 .005
esterase
Protease .005 .005 .004 .003 0.08 .005 .003 .006
Lipase - .002 - .000 - - .003 .003
2
CA 02275290 1999-06-14
WO 98!28394 PCTIUS96120876
69
Amylase .002 .002 .005 .004 .002 .008 .005 .005
Cellulase - - - .000 - - .000 .000
1 4 4
Boric acid 0.1 0.2 - 2.0 1.0 1.5 2.5 2.5
Na formate - - 1.0 - - - _ -
Ca chloride - 0.01 - 0.01 - - - -
Bentonite clay - - - - 4.0 4.0 - -
Suspending clay - - - - 0.6 0.3 - -
SD3
Balance 100 100 100 100 100 100 100 100
Moisture and
Miscellaneous
Examale 11
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 - 1 1.0
Zeolite A 15.0 15.0
MA/AA 4.0 4.0
DETPMP 0.4 0.4
PB1 15.0 -
Percarbonate - 15.0
TAED 5.0 5.0
Smectite clay 10.0 10.0
CA 02275290 1999-06-14
WO 98128394 PCT/US96/20876
HMWPEO - 0.1
Cholesterol esterase 0.01 0.01
Protease 0.02 0.01
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%
Examale 12
The following rinse added fabric softener composition was prepared in
5 accord with the present invention
Softener active 20.0
Cholesterol esterase 0.001
Amylase 0.001
Cellulase 0.001
HCL 0.03
Antifoam agent 0.01
Blue dye 25ppm
CaCl2 0.20
Perfume 0.90
Water / minors Up to 100%
Example 13
o The following fabric softener composition was prepared in accord with
the present invention
I II
DEQA 2.6 19.0
SDASA - - 70.0
Stearic acid of I V = 0 0.3 - _
Neodol45-13 - - 13.0
CA 02275290 1999-06-14
WO 98/28394 PCT/L1S96/20876
71
Hydrochloride acid 0.02 0.02 -
Ethanol - - 1.0
PEG - 0.6 -
Cholesterol esterase 0.001 0.001 0.001
Perfume 1.0 1.0 0.75
Digeranyl Succinate - - 0.38
Silicone antifoam 0.01 0.01 -
~
Electrolyte - 600ppm -
Dye 100ppm 50ppm 0.01
Water and minors 100% 100%
Example 14
Syndet bar fabric cleaning compositions were prepared in accord with
the present invention
I I I 111 I V
C26 AS 20.00 20.00 20.00 20.00
CFAA 5.0 5.0 5.0 5.0
LAS (C 11-131 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
Zeoiite A 5.0 5.0 5.0 5.0
CMC 0.2 0.2 0.2 0.2
Polyacrylate (MW 1400y 0.2 0.2 0.2 0.2
Coconut monethanolamide5.0 5.0 5.0 5.0
Cholesterol esterase 0.02 0.02 0.02 0.02
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
MgS04 1.0 1.0 1.0 1.0
Water 4.0 4.0 4.0 4.0
Filler " : balance100%
to
CA 02275290 1999-06-14
WO 98128394 PCTILTS96120876
72
Can be selected from convenient materials such as CaC03, talc, clay
(Kaolinite, Smectite), silicates, and the like.
Example 15
The following compact high density (0.96Kg/I) dishwashing detergent
compositions ( to VI were prepared in accord with the present invention:
I II III IV V Vl
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
Cholesterol esterase0.01 0.01 0.01 0.01 0.01 0.01
Protease 0.075 0.05 0.10 0.10 0.08 0.01
Lipase - 0.001 - 0.005 - -
Amylase 0.01 0.005 0.015 0.015 0.01 0.0025
BTA 0.3 0.3 0.3 0.3 0.3 -
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 1 1.0 10.9 10.8 10.9 9.6
Example 16
CA 02275290 1999-06-14
WO 98/28394 PCT/US96/20876
73
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
PB1 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 - - -
Cholesterol esterase0.01 0.01 0.01 0.01 0.01 0.01
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
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
Cholesterol esterase 0.01 0.01 0.01
CA 02275290 1999-06-14
WO 98/28394 PCT/US96/20876
74
Protease 0.03 0.075 0.01
Lipase 0.005 - -
Amylase 0.01 0.005 0.001
PB1 1.6 7.8 -
PB4 6.9 - 1 1.4
Nonionic 1.2 2.0 1.1
TAED ~ 4.3 2.4 0.8
HEDP 0.7 - -
DETPMP 0.65 - -
Paraffi n 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 1 1.0
Example 18
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 1.1 1.1 5
Nonionic 2.5 1.0
Paraffin 2.2 -
Cholesterol esterase 0.01 0.01
Protease 0.03 0.02
Amylase 0.005 0.0025
480N 0.50 4.00
KOH - 6.00
Sulphate 1.6 -
pH (1 % solution) 9.1 10.0
