Note: Descriptions are shown in the official language in which they were submitted.
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1
s Detergent Compositions
Technical Field
~ to The present invention relates to detergent compositions or components
thereof containing
cationic surfactant and a proteolytic enzyme for use in laundry and dish
washing processes to
provide enhanced greasy stain removal and cleaning benefits.
Bactcground to the Invention
It is known to use cationic surfactants in detergent compositions. For
example, GB 2040990A
describes granular detergent compositions comprising cationic surfactants.
Other detergent components often employed in detergent compositions are
proteolytic enzymes
2 o which are known to assist in breakdown and removal of proteinaceous
stains.
The Applicant has found that in some cases, particularly from some body soils,
for example on
collar and cuff stains, oily, greasy soils may contain proteinaceous soils
which are difficult to
break down because the greasy, oily soil component protects the proteinaceous
component of
the stain.
The Applicant has found that using a specific class of cationic surfactant in
combination with a
proteolytic enzyme, the greasy component of the stain is removed, exposing the
previously
protected proteinaceous stain and making it available for enzyme action. The
combination
3 o provides improved cleaning benefits coupled with enhanced residual stain
removal. the
continued use of a detergent formulation according to the invention maintains
good stain
removal benefits prolonging the new look of washed garments.
Furthermore, generally, the stain removal performance of proteolytic enzymes
is directly related
to their concentration in the detergent composition, so that an increase in
the amount of
proteolytic enzyme increases the stain removal performance. It has however
been observed that
under stressed conditions, such as the use of short washing machine cycles, or
at tow
temperatures or in the presence of highly stained substrates, the optimum
performance of the
protease enzyme is limited beyond a certain level. Increasing the level of
protease enzyme
4 o beyond this amount does not result in increased stain removal performance
benefits.
The Applicant has now found that these problems can be ameliorated by a
detergent
composition comprising a combination of a specific quaternary ammonium
cationic surfactant
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and a proteolytic enzyme. The invention has been found to be particularly
beneficial in detergent
compositions which additionally comprise anionic surfactants.
Without wishing to be bound by theory, the Applicant believes that the
particular cationic
surfactants used in the detergent compositions of the present invention have
surprisingly good
i o solubility and form an association in the presence of anionic components
to produce surprisingly
soluble anionic/cationic complexes which lead to unexpected performance
benefits.
Furthermore, it is believed that following breakdown of the oily soil by the
enzyme, the cationic
surfactants used in the present invention may also form complexes with the
fatty acids and any
other negatively charged breakdown product produced, increasing their
solubility and enhancing
z5 greasy, oily soil removal and overall cleaning performance.
All documents cited in the present description are incorporated herein by
reference.
2 o Summary of the invention
The present invention relates to a detergent composition or component thereof
which comprises
(a) a proteolytic enzyme; and
(b) a cationic surfactant of formula I:
R1 R2 R3 R4 N+ X' (I)
3 o in which RI is a hydroxyalkyl group having no greater than 6 carbon atoms;
each of RZ
and R3 is independently selected from C 1 _4 alkyl or alkenyl; R4 is a CS_ 11
alkyl or
alkenyl; and X' is a counterion.
Unless otherwise stated alkyl or alkenyl as used herein may be branched,
linear or substituted.
Substituents may be for example, aromatic groups, heterocyclic groups
containing one or more
N, S or O atoms, or halo substituents.
Detailed description of the invention
4 o Cationic surfactant
The cationic surfactant is generally present in the composition or component
thereof in an
amount no greater than 60% by weight, preferably no greater than 10% by
weight, most
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preferably in an amount no greater than 4.5% or even 3% by weight. The
benefits of the
invention are found even with very small amounts of the cationic surfactant of
formula I.
Generally there will be at least 0.01 % by weight, preferably at least 0.05%
or at least 0.1 % by
weight of the cationic surfactant in the detergent compositions of the
invention.
1o Preferably R1 in formula I is a hydroxyalkyl group, having no greater than
6 carbon atoms and
preferably the ---OH group is separated from the quaternary ammonium nitrogen
atom by no
more than 3 carbon atoms. Preferred R 1 groups are -CH2CH20H, --CH2CH2CH20H, -
CH2CH(CH3)OH and--CH(CH3)CH20H.
-CH2CH20H and --CH2CH2CH20H are more preferred and ---CH2CH20H is particularly
i5 preferred. Preferably R2 and R3 are each selected from ethyl and methyl
groups and most
preferably both R2 and R3 are methyl groups. Preferred R4 groups have at least
6 or even at.
least 7 carbon atoms. R4 may have no greater than 9 carbon atoms, or even no
greater than 8 or
7 carbon atoms Preferred R4 groups are linear alkyl groups. Linear R4 groups
having from 8 to
11 carbon atoms, or from 8 to 10 carbon atoms are preferred. Preferably each
of R2 and R3 is
2 o selected from C 1 _4 alkyl and R4 is C6_ 11 alkyl or alkenyl.
Whilst pure or substantially pure cationic compounds are within the ambit of
this invention, it
has been found that mixtures of the cationic surfactants of formula I may be
particularly
effective. Mixtures of cationic surfactants of the present invention may
comprise mixtures of
25 formula I, preferably where there is at least 10%, or even at least 20%, or
at least 50% by weight
cationic surfactant of formula I and wherein R4 is C5_9 alkyl or alkenyl.
Other useful examples
of surfactant mixtures include those in which R4 may be a combination of Cg
and C 10 linear
alkyl groups, or Cg and C 11 alkyl groups. According to one aspect of the
invention a mixture of
cationic surfactants of formula I is present in the composition, the mixture
comprising a shorter
3 o alkyl chain surfactant of formula I and a longer alkyl chain surfactant of
formula I. Preferably
in the mixture of shorter and longer alkyl chain surfactants, there will be
from S to 95% by
weight shorter alkyl chain surfactant or at least 30% by weight shorter alkyl
chain surfactant
and preferably from 40 to 95% of the shorter alkyl chain cationic. Generally
the amount of
longer chain cationic surfactant will be from 5 to 95% by weight preferably
from 5 to 70% by
35 weight, more preferably from 35 to 75% by weight of the cationic
surfactant, preferably at least
50% by weight longer alkyl chain surfactant. The longer alkyl chain cationic
surfactant is
selected from the surfactants of formula I where R4 is an alkyl group having n
carbon atoms
where n is from 8 to 11; the shorter alkyl chain surfactant is preferably
selected from those of
formula I where R4 is an alkyl group having (n-2) carbon atoms.
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X in formula I may be any counterion providing electrical neutrality, but is
preferably selected
from the group consisting of halide, methyl sulfate, sulfate and nitrate, more
preferably being
selected from methyl sulfate, chloride, bromide and iodide. The halide ions,
especially chloride
are most preferred.
io Proteolytic Enzyme
The granular detergent compositions or component thereof in accordance with
the present
invention also comprises a proteolytic enzyme.
The weight ratio of proteolytic enzyme to cationic surfactant is generally
from I :l5000 to I0:1,
is more preferably from 1:10000 to 5: l, most preferably from l:5000 to 1:1,
based on % by weight
active enzyme of the detergent composition.
In the detergent compositions of the present invention, the proteolytic enzyme
component is
generally present at levels of from 0.0000S% to 2% of active enzyme by weight
of the detergent
2 o composition, preferably 0.000l % to 0.2% by weight, most preferably from
0.0002% to 0.0S%
by weight active enzyme in the detergent composition.
Examples of suitable proteolytic enzymes for use in the detergent compositions
of the present
invention are the subtilisins which are obtained from particular strains of B.
subtilis and B.
25 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~~
3 o 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 I99,404, Venegas, published October 29; 1986, which refers
to a modified
3 s bacterial serine protealytic enzyme which is called "Protease A" herein.
Suitable 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 valine at
position 104, serine
replaced asparagine at position 123, and alanine replaced threonine at
position 274. Protease C is
described in EP 90915958:4, corresponding to WO 91I06637, Published May 16,
1991.
4 o Genetically modified variants, particularly of Protease C, are also
included herein.
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5
A preferred 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
io amino acid residue positions equivalent to those selected from the group
consisting of +99,
+101, +103, +104, +107, +123, t27, +10S, +109, +126, +l28, +135, +156, +166,
+19S, +197,
+204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to
the
numbering of Bacillus amyloliguefaciens subtilisin, as described in W09S/1
OS91 and in the
patent application of C. Ghosh, et al, "Bleaching Compositions Comprising
Protease Enzymes"
~s having US Serial No. 08/322,677, filed October 13, 1994.
Also suitable for the present invention are proteases described in patent
applications EP 25l 446
and WO 91/06637, protease BLAP~ described in W091/02792 and their variants
described in
WO 9S/23221.
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 92/03S29 A to Novo. When desired, a
protease having
decreased adsorption and increased hydrolysis is available as described in WO
9S/07791 to
Procter & Gamble. A recombinant trypsin-like protease for detergents suitable
herein is
described in WO 94/25S83 to Novo. Other suitable proteases are described in EP
S 16 200 by
Unilever.
The protease enzyme or mixture of protease enzymes may be added to the
detergent
3 o composition as a separate ingredient leg, in the form of a prill,
granulate, stabilized liquid, etc.)
or as a mixture with two or more protease enzymes or protease and an
additional enzyme, for
example as part of a co-granulate.
Additional detergent components
The detergent compositions or components thereof in accordance with the
present invention may
also contain additional detergent components. The precise nature of these
additional
components, and levels of incorporation thereof will depend on the physical
form of the
composition or component thereof, and the precise nature of the washing
operation for which it
4 o is to be used.
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The compositions or components thereof, of the invention preferably contain
one or more
additional detergent components selected from additional surfactants,
builders, sequestrants,
bleach, bleach precursors, bleach catalysts, organic polymeric compounds,
additional enrymes,
suds suppressors, lime soap dispersants, additional soil suspension and anti-
redeposition agents
io soil releasing agents, perfumes and corrosion inhibitors.
Additional surfactant
The detergent compositions or components thereof in accordance with the
invention preferably
i s contain an additional surfactant selected from anionic, nonionic,
cationic, ampholytic,
amphoteric and zwitterionic surfactants and mixtures thereof.
A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes,
and species of these
surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Heuring on
December 30, l975.
2 o Further examples are given in "Surface Active Agents and Detergents" (Vol.
I and II by
Schwartz, Perry and Berch). A list of suitable cationic surfactants is given
in U.S.P. 4,2S9,217
issued to Murphy on March 31, 1981.
Where present, ampholytic, amphoteric and zwitteronic surfactants are
generally used in
2s combination with one or more anionic and/or nonionic surfactants.
Anionic surfactant
In a particularly preferred embodiment of the invention, the detergent
compositions additionally
comprise an anionic surfactant. Any anionic surfactant useful for detersive
purposes is suitable.
3 o These can include salts (including, for example, sodium, potassium,
ammonium, and substituted
ammonium salts such as mono-, di- and triethanolamine salts) of the anionic
sulfate, sulfonate,
carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are
preferred.
Other suitable anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl
3s taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates, monoesters of
suifosuccinate (especially saturated and unsaturated C 12-C 18 monoesters)
diesters of
sulfosuccinate (especially saturated and unsaturated C6-C 14 diesters), N-acyl
sarcosinates.
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 tallow
oil.
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Anionic sulfate surfactant
Anionic sulfate surfactants suitable for use in the compositions of the
invention include the
linear and branched primary and secondary alkyl sulfates, alkyl
ethoxysulfates, fatty oleoyl
glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the CS-C 1 ~
acyl-N-(C 1-C4 alkyl)
and -N-(C 1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of
alkylpolysaccharides such as
1o the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds
being described herein).
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the Cg-C22
alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of
ethylene oxide per
molecule. More preferably, the alkyl ethoxysulfate surfactant is a C 11-C 1 g,
most preferably
i5 C11-.C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7,
preferably from 1 to 5,
moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the
preferred alkyl sulfate
and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT
Patent
2o Application No. WO 93/18124.
Anionic sulfonate surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of CS-
C2p linear
alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary
alkane sulfonates,
2 s C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol
sulfonates, fatty acyl
glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures
thereof.
Particularly preferred compositions of the present invention additionally
comprise an anionic
surfactant, selected from alkyl sulfate and/or alkylbenzene sulphonate
surfactants of formulae II
3 o and III, respectively:
RSOS03-M+ (II)
R6 S O 3 'M~+ (III)
wherein RS is a linear or branched alkyl or alkenyl moiety having from 9 to 22
carbon atoms,
preferably C 12 to C 1 g alkyl or as found in secondary alkyl sulfates; R6 is
C 10-C 16
alkylbenzene, preferabiy C 11-C 13 alkylbenzene; M+ and M~+ can vary
independently and are
selected from alkali metals, alkaline earths, alkanolammonium and ammonium.
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Particularly preferred compositions of the invention comprise both an alkyl
sulfate surfactant
and an alkyl benzene surfactant, preferably in ratios of II to III of from I
5: I to I :2, most
preferably from 12:1 to 2: I .
Amounts of the one or mixtures of more than one anionic surfactant in the
preferred
1 o composition may be from 1 % to 50%, however, preferably anionic surfactant
is present in
amounts of from 5% to 40% by weight of the composition. Preferred amounts of
the alkyl
sulfate surfactant of formula II are from 3% to 40%, or more preferably 6% to
30~fo by weight of
the detergent composition. Preferred amounts of the alkyl benzene sulphonate
surfactant of
formula III in the detergent composition are from at least I %, preferably at
least 2%, or even at
15 least 4% by weight. Preferred amounts of the alkyl benzene sulphonate
surfactant are up to
23%, more preferably no greater than 20%, most preferably up to I S% or even
10%.
The performance benefits which result when an anionic surfactant is also used
in the
compositions of the invention are particularly useful for longer carbon chain
length anionic
z o surfactants such as those having a carbon chain length of C 12 or greater,
particularly of C 14/1 S
or even up to C I 6-I 8 carbon chain lengths.
In preferred embodiments of the detergent compositions of the invention
comprising anionic
surfactant there will be a significant excess of anionic surfactants,
preferably a weight ratio of
25 anionic to cationic surfactant of from 50:1 to 2:1, most preferably 30:1 to
8: I . However, the
benefits of the invention are also achieved where the ratio of cationic
surfactant to anionic
surfactant is substantially stoichiometric, for example from 3:2 to 4:3.
In a preferred embodiment of the invention the essential cationic surfactant
of formula I is
3 o intimately mixed with one or more anionic surfactants prior to addition of
the other detergent
composition components.
Anionic carboxylate surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxylates, the alkyl
35 polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'),
especially certain
secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20~
CH2C00'
M+ wherein R is a C6 to C I g alkyl group, x ranges from O to 10, and the
ethoxylate distribution
4 o is such that, on a weight basis, the amount of material where x is 0 is
less than 20 % and M is a
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9
cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those
having the formula
RO-(CHR 1-CHR2-O)-R3 wherein R is a C6 to C ~ g alkyl group, x is from 1 to
25, RI and R2
are selected from the group consisting of hydrogen, methyl acid radical,
succinic acid radical,
hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from
the group consisting
of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8
carbon atoms,
io and mixtures thereof
Suitable soap surfactants include the secondary soap surfactants which contain
a carboxyl unit
connected to a secondary carbon. Preferred secondary soap surfactants for use
herein are water-
soluble members selected from the group consisting of the water-soluble salts
of 2-methyl-1-
undecanoic acid, 2-ethyl-I-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-
octanoic acid and
2-pentyl-1-heptanoic acid. Certain soaps may also be included as suds
suppressors.
Alkali metal sarcosinate surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON (RI) CH2
2 o COOM, wherein R is a C5-C 1 ~ linear or branched alkyl or alkenyl group,
R1 is a C 1-C4 alkyl
group and M is an alkali metal ion. Preferred examples are the myristyl and
oleoyl methyl
sarcosinates in the form of their sodium salts.
Aikoxylated nonionic surfactant
Essentially any alkoxylated nonionic surfactants are suitable herein. The
ethoxylated and
propoxylated nonionic surfactants are preferred. Linear or branched
alkoxylated groups are
suitable.
Preferred alkoxylated surfactants can be selected from the classes of the
nonionic condensates of
3 o alkyl phenols, nonionic ethoxylated alcohols, nonionic
ethoxylated/propoxylated fatty alcohols,
nonionic ethoxylate/propoxylate condensates with propylene glycol, and the
nonionic ethoxylate
condensation products with propylene oxide/ethylene diamine adducts.
Nonionic alkoxvlated alcohol surfactant
The condensation products of aliphatic alcohols with from 1 to 25 moles of
alkylene oxide,
particularly ethylene oxide and/or propylene oxide, are suitable for use
herein. The alkyl chain
of the aliphatic alcohol can either be straight or branched, primary or
secondary, and generally
contains from 6 to 22 carbon atoms. Particularly preferred are the
condensation products of
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alcohols having an alkyl group containing from 8 to 20 carbon atoms with from
2 to 10 moles of
ethylene oxide per mole of alcohol.
Nonionic polyhydroxy fatty acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural formula
1 o R2CONR 1 Z wherein : R 1 is H, C 1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-
hydroxy propyl, ethoxy,
propoxy, or a mixture thereof, preferable C 1-C4 alkyl, more preferably C 1 or
C2 alkyl, most
preferably C 1 alkyl (i.e., methyl); and R2 is a CS-C31 hydrocarbyl,
preferably straight-chain CS-
C 19 alkyl or alkenyl, more preferably straight-chain Cg-C 17 alkyl or
alkenyl, most preferably
straight-chain C 11-C 17 alkyl or alkenyl, or mixture thereof; and Z is a
polyhydroxyhydrocarbyl
~5 having a linear hydrocarbyl chain with at least 3 hydroxyls directly
connected to the chain, or an
alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z
preferably will be
derived from a reducing sugar in a reductive amination reaction; more
preferably Z is a glycityl.
Nonionic fatty acid amide surfactant
2 o Suitable fatty acid amide surfactants include those having the formula:
R6CON(R7)2 wherein
R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon
atoms and each R7
is selected from the group consisting of hydrogen, C 1-C4 alkyl, C 1-C4
hydroxyalkyl, and -
(C2H40)xH, where x is in the range of from 1 to 3.
25 Nonionic alkyiuolysaccharide surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent
4,S6S,b47, Llenado,
issued January 21, 1986, having a hydrophobic group containing from 6 to 30
carbon atoms and
a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3
to 10 saccharide
units.
Preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(glYcosyI~
wherein R2,is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from 10 to 18
carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The
glycosyl is preferably
derived from glucose.
4 o Amyhoteric surfactant
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11
Suitable amphoteric surfactants for use herein include the amine oxide
surfactants and the alkyl
amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula
R3(OR4)xN0(R$)2 wherein
R3 is selected from an alkyl, hydroxyalkyl, acyiamidopropoyl and alkyl phenyl
group, or
to mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene
or hydroxyalkylene
group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to
5, preferably from
0 to 3; and each RS is an alkyl or hydroxyalkyl group containing from 1 to 3,
or a polyethylene
oxide group containing from I to 3 ethylene oxide groups. Preferred are C I 0-
C I g alkyl
dimethylamine oxide, and C I 0_ I g acylamido alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxyiic acid is Miranol(TM) C2M Conc.
manufactured
by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant
2 o Zwitterionic surfactants can also be incorporated into the detergent
compositions or components
thereof in accord with the invention. 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. Betaine and sultaine surfactants are exemplary zwitterionic
surfactants for use
herein.
Suitable betaines are those compounds having the formula R(R')2N+R2C00-
wherein R is a
C6-C 1 g hydrocarbyl group, each RI is typically C 1-C3 alkyl, and R2 is a C I-
CS hydrocarbyl
group. Preferred betaines are C 12- I 8 dimethyl-ammon io hexanoate and the C
I p- I 8
3 o acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex
betaine surfactants are
also suitable for use herein.
Additional Cationic surfactants
The compositions of the invention are preferably substantially free of
quaternary ammonium
compounds of formula I but wherein one or RI, R2, R3 or R4 is an alkyl chain
group longer
than C 1 I . Preferably the composition should contain less than I %,
preferably less than 0. I % by
weight or even less than 0.05% and most preferably less than 0.01 % by weight
of compounds of
formula I having a linear (or even branched) alkyl group having 12 or more
carbon atoms.
4 o Another suitable group of cationic surfactants which can be used in the
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iz
detergent compositions of the invention are cationic ester surfactants. The
cationic ester
surfactant is a compound having surfactant properties comprising at least one
ester (i.e. -COO-)
linkage and at least one cationically charged group. Preferred cationic ester
surfactants are
water dispersible.
to Suitable cationic ester surfactants, including choline ester surfactants,
have for example been
disclosed in US Patents Nos. 4228042, 4239660 and 4260529.
In preferred cationic ester surfactants the ester linkage and cationically
charged group are
separated from each other in the surfactant molecule by a spacer group
consisting of a chain
15 comprising at least three atoms (i.e. of three atoms chain length),
preferably from three to eight
atoms, more preferably from three to five atoms, most preferably three atoms.
The atoms
forming the spacer group chain are selected from the group consisting of
carbon, nitrogen and
oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or
oxygen atom in
said chain connects only with carbon atoms in the chain. Thus spacer groups
having, for
2 o example, -O-O- (i.e. peroxide), -N-N-, and -N-O- linkages are excluded,
whilst spacer groups
having, for example -CH2-O- CH2- and -CH2-NH-CH2- linkages are included. In a
preferred
aspect the spacer group chain comprises only carbon atoms, most preferably the
chain is a
hydrocarbyl chain.
25 Alkalinity
In the detergent compositions of the present invention preferably an
alkalinity system is present
to achieve optimal cationic surfactant performance. The alkalinity system
comprises
components capable of providing alkalinity species in solution. Examples of
alkalinity species
include carbonate, bicarbonate, hydroxide, the various silicate anions,
percarbonate, perborates,
3 o perphosphates, persulfate and persilicate. Such alkalinity species can be
formed for example,
when alkaline salts selected from alkali metal or alkaline earth carbonate,
bicarbonate,
hydroxide or silicate, including crystalline layered silicate, salts and
percarbonate, perborates,
perphosphates, persulfate and persilicate salts and any mixtures thereof are
dissolved in water.
3 s Examples of carbonates are the alkaline earth and alkali metal carbonates,
including sodium
carbonate and sesqui-carbonate and any mixtures thereof with ultra-fine
calcium carbonate such
as are disclosed in German Patent Application No. 2,321,001 published on
November 15, 1973.
Suitable silicates include the water soluble sodium silicates with an
Si02:NA20 ratio of from
40 1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0 ratio
being most preferred. The
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13
silicates may be in the form of either the anhydrous salt or a hydrated salt.
Sodium silicate with
an Si02:Na20 ratio of 2.0 is the most preferred silicate.
Preferred crystalline layered silicates for use herein have the general
formula
i o NaMSix02x+1.yH20
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number
from 0 to 20.
Crystalline layered sodium silicates of this type are disclosed in EP-A-
0164514 and methods for
their preparation are disclosed in DE-A-3417649 and DE-A-3742043. Herein, x in
the general
1s formula above preferably has a value of 2, 3 or 4 and is preferably 2. The
most preferred
material is 8-Na2Si205, available from Hoechst AG as NaSKS-6.
Water-soluble builder compound
The detergent compositions in accordance with the present invention preferably
contain a water-
2 o soluble builder compound, typically present in detergent compositions at a
level of from 1 % to
80% by weight, preferably from 10% to 70% by weight, most preferably from 20%
to 60% by
weight of the composition.
Suitable water-soluble builder compounds include the water soluble monomeric
2s polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic
acids or their salts in
which the polycarboxylic acid comprises at least two carboxylic radicals
separated from each
other by not more that two carbon atoms, borates, phosphates, and mixtures of
any of the
foregoing.
3o The carboxylate or polycarboxylate builder can be monomeric or oligomeric
in type although
monomeric polycarboxylates are generally preferred for reasons of cost and
performance.
Suitable carboxylates containing one carboxy group include the water soluble
salts of lactic acid,
glycolic acid and ether derivatives thereof. Polycarboxylates containing two
carboxy groups
3 s include the water-soluble salts of succinic acid, malonic acid,
(ethylenedioxy) diacetic acid,
malefic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid,
as well as the ether
carboxylates and the sulfinyl carboxylates. 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,
40 lactoxysuccinates described in British Patent No. 1,389,732, and
aminosuccinates described in
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14
Netherlands Application 7205873, and the oxypolycarboxylate materials such as
2-oxa-1,1,3-
propane tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in British
Patent No. 1,261,829, l,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane
tetracarboxylates and
i o I, i,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo
substituents include the
sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,42l and
1,398,422 and in U.S.
Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in
British Patent No.
l,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to
three carboxy
groups per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents or mixtures
thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are
also contemplated as
useful builder components.
2o Borate builders, as well as builders containing borate-forming materials
that can produce borate
under detergent storage or wash conditions are useful water-soluble builders
herein.
Suitable examples of water-soluble phosphate builders are the alkali metal
tripolyphosphates,
sodium, potassium and ammonium pyrophosphate, sodium and potassium and
ammonium
2 5 pyrophosphate, sodium and potassium orthophosphate, sodium
polymeta/phosphate in which the
degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
Partially soluble or insoluble builder compound
The detergent compositions or components thereof, of the present invention may
contain a
3 o partially soluble or insoluble builder compound, typically present in
detergent compositions at a
level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most
preferably
from 20% to 60% weight of the composition.
Examples of largely water insoluble builders include the sodium
aluminosilicates.
Suitable aluminosilicate zeolites have the unit cell formula
Naz[(A102)z(Si02)y]. xH20
wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5
and x is at least 5,
preferably from 7.5 to 276, more preferably from 10 to 264. The
aluminosilicate materials are
in hydrated form and are preferably crystalline, containing from 10% to 28%,
more preferably
4 o from I 8% to 22% water in bound form.
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5
The aluminosilicate zeolites can be naturally occurring materials, but are
preferably
synthetically derived. Synthetic crystalline aluminosilicate ion exchange
materials are available
under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS
and mixtures
thereof. Zeolite A has the formula
to
Na 12 L(A102) 12 (Si02)12~~ Q20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
[(A102)86(Si02)1061. 276 H20.
Another preferred aluminosilicate zeolite is zeolite MAP builder.
The zeolite MAP can be present at a level of from 1% to 80%, more preferably
from 15%
to 40% by weight of the compositions.
2o Zeolite MAP is described in EP 384070A (Unilever). It is defined as an
alkali metal
alumino-silicate of the zeolite P type having a silicon to aluminium ratio not
greater than
1.33, preferably within the range from 0.9 to 1.33 and more preferably within
the range of
from 0.9 to 1.2.
Of particular interest is zeolite MAP having a silicon to aluminium ratio not
greater than
1.1 S and, more particularly, not greater than 1.07.
In a preferred aspect the zeolite MAP detergent builder has a particle size,
expressed as a
d50 value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0
micrometres,
3o most preferably from 2.5 to S.0 micrometres.
The d50 value indicates that 50% by weight of the particles have a diameter
smaller than
that figure. The particle size may, in particular be determined by
conventional analytical
techniques such as microscopic determination using a scanning electron
microscope or by
means of a laser granulometer. Other methods of establishing d50 values are
disclosed in
EP 384070A.
Heavy metal ion sequestrant
The detergent compositions or components thereof in accordance with the
present invention
4 o preferably contain as an optional component a heavy metal ion sequestrant.
By heavy metal ion
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16
sequestrant it is meant herein components which act to sequester (chelate)
heavy metal ions.
These components may also have calcium and magnesium chelation capacity, but
preferentially
they show selectivity to binding heavy metal ions such as iron, manganese and
copper.
Heavy metal ion sequestrants are generally present at a level of from 0.005%
to 20%, preferably
to from 0.1% to 10%, more preferably from 0.25% to 7.5% and most preferably
from 0.5% to S%
by weight of the compositions.
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates, such as the
amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy
disphosphonates
and nitrilo trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta (methylene
phosphonate),
ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra
(methylene
phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic acid and
polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenetriamine pentacetic
acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-
hydroxypropylenediamine disuccinic acid or any salts thereof. Especially
preferred is
2 s ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline
earth metal,
ammonium, or substituted ammonium salts thereof, or mixtures thereof.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic
acid derivatives
such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid,
described in EP-A-317,542
3o and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid
and aspartic acid
N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-
A-516, I02
are also suitable herein. The (~alanine-N,N'-diacetic acid, aspartic acid-N,N'-
diacetic acid,
aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants
described in EP-A-
509,382 are also suitable.
EP-A-476,2S7 describes suitable amino based sequestrants. EP-A-510,331
describes suitable
sequestrants derived from collagen, keratin or casein. EP-A-528,8S9 describes
a suitable alkyl
iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-
tricarboxylic acid
are also suitable. Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-
N'-diglutaric
4 o acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are
also suitable.
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t7
Or ag nic peroxyacid bleachine system
A preferred feature of detergent compositions or component thereof in
accordance with the
invention is an organic peroxyacid bleaching system. In one preferred
execution the bleaching
system contains a hydrogen peroxide source and an organic peroxyacid bleach
precursor
i o compound. The production of the organic peroxyacid occurs by an in situ
reaction of the
precursor with a source of hydrogen peroxide. Preferred sources of hydrogen
peroxide include
inorganic perhydrate bleaches. In an alternative preferred execution a
preformed organic
peroxyacid is incorporated directly into the composition. Compositions
containing mixtures of a
hydrogen peroxide source and organic peroxyacid precursor in combination with
a preformed
i5 organic peroxyacid are also envisaged.
Inorganic perhvdrate bleaches
Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These
salts are normally
incorporated in the form of the alkali metal, preferably sodium salt at a
level of from 1 % to 40%.
2 o by weight, more preferably from 2% to 30% by weight and most preferably
from 5% to 25% by
weight of the compositions.
Examples of inorganic perhydrate salts include perborate, percarbonate,
perphosphate, persulfate
and persilicate salts. The inorganic perhydrate salts are normally the alkali
metal salts. The
25 inorganic perhydrate salt may be included as the crystalline solid without
additional protection.
For certain perhydrate salts however, the preferred executions of such
granular compositions
utilize a coated form of the material which provides better storage stability
for the perhydrate
salt in the granular product and/or delayed release of the perhydrate salt on
contact of the
granular product with water. Suitable coatings comprise inorganic salts such
as alkali metal
3o silicate, carbonate or borate salts or mixtures thereof, or organic
materials such as waxes, oils, or
fatty soaps.
Sodium perborate is a preferred perhydrate salt and can be in the form of the
monohydrate of
nominal formula NaB02H202 or the tetrahydrate NaB02H202.3H20.
Alkali metal percarbonates, particularly sodium percarbonate are preferred
perhydrates herein.
Sodium percarbonate is an addition compound having a formula corresponding to
2Na2C03.3H202, and is available commercially as a crystalline solid.
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Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in
the detergent
compositions herein.
Peroxyacid bleach precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide
in a
io perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach
precursors may be
represented as
O
X-C-L
i 5 where L is a leaving group and X is essentially any functionality, such
that on perhydrolysis the
structure of the peroxyacid produced is
O
X-C-OOH
2 o Peroxyacid bleach precursor compounds are preferably incorporated at a
level of from 0.5% to
20% by weight, more preferably from 1% to 15% by weight, most preferably from
1.5% to 10%
by weight of the detergent compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or more N-
or O-acyl
25 groups, which precursors can be selected from a wide range of classes.
Suitable classes include
anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and
oximes. Examples
of useful materials within these classes are disclosed in GB-A-1586789.
Suitable esters are
disclosed in GB-A-836988, 864798, 1147871, 214323l and EP-A-0170386.
3 o Leavine groins
The leaving group, hereinafter L group, must be sufficiently reactive for the
perhydrolysis
reaction to occur within the optimum time frame (e.g., a wash cycle). However,
if L is too
reactive, this activator will be difficult to stabilize for use in a bleaching
composition.
35 Preferred L groups are selected from the group consisting of:
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19
Y R3 RSY
i~ ; 1. i
,~(~ ~,~i,
-O-~,\, y , O ~' ~~ -Y ~ and -0~.~
\~
O
N-C-RI , -N N , -N-C-CH-R4 ,
RS R3 Y
Y
R3 Y
I I
-O-C H=C-C H=C HZ -O-C H=C-C H=C H2
O C H -C Y O
II ~ z ~ r ~NR4
-O-C-R~ -N~C,NR4 , -NBC/ ,
p O
R3 O Y
-O-C=CHR4 , and -N-S-CH-R4
R3 O
io
and mixtures thereof, wherein RI is an alkyl, aryl, or alkaryl group
containing from i to 14
carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is
H or R3, RS is an
alkenyl chain containing from I to 8 carbon atoms and Y is H or a solubilizing
group. Any of
RI, R3 and R4 may be substituted by essentially any functional group
including, for example
i5 alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or
alkyl ammonium
groups.
The 3 referred solubilizing groups are+S03 M+, -C02 M~, -SO~ M+, -N+(R3)4X and
O<--
N(R )3 and most preferably -S03-M and -C02 M wherein R is an alkyl chain
containing
2 o from 1 to 4 carbon atoms, M is a canon which provides solubility to the
bleach activator and X
is an anion which provides solubility to the bleach activator. Preferably, M
is an alkali metal,
ammonium or substituted ammonium cation, with sodium and potassium being most
preferred,
and X is a halide, hydroxide, methylsulfate or acetate anion.
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Alkyl percarboxylic acid bleach precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on
perhydrolysis. Preferred
precursors of this type provide peracetic acid on perhydrolysis.
1o Preferred alkyl percarboxylic precursor compounds of the imide type include
the N-,N,N1N1
tetra acetylated alkylene diamines wherein the alkylene group contains from 1
to 6 carbon
atoms, particularly those compounds in which the alkylene group contains 1, 2
and 6 carbon
atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
1s Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-
tri-methyl
hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate
(HOBS),
sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide substituted alkyl peroxvacid precursors
2 o Amide substituted alkyl peroxyacid precursor compounds are suitable
herein, including those of
the following general formulae:
R~ C-NR2CL R~ N-C-R2CL
O R5 O or R5 O O
wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene
group
containing from 1 to 14 carbon atoms, and RS is H or an alkyl group containing
1 to 10 carbon
atoms and L can be essentially any leaving group. Amide substituted bleach
activator
compounds of this type are described in EP-A-0170386.
3 o Perbenzoic acid precursor
Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
Suitable O-
acylated perbenzoic acid precursor compounds include the substituted and
unsubstituted benzoyl
oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and
all saccharides
with benzoylating agents, and those of the imide type including N-benzoyl
succinimide,
tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable
imidazole type
perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl
benzimidazole. Other
useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl
pyrrolidone,
dibenzoyl taurine and benzoyl pyroglutamic acid.
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21
Cationic peroxvacid precursors
Cationic peroxyacid precursor compounds produce cationic peroxyacids on
perhydrolysis.
Typically, cationic peroxyacid precursors are formed by substituting the
peroxyacid part of a
suitable peroxyacid precursor compound with a positively charged functional
group, such as an
ammonium or alkyl ammonium group, preferably an ethyl or methyl ammonium
group.
Cationic peroxyacid precursors are typically present in the solid detergent
compositions as a salt
with a suitable anion, such as a halide ion.
15 The peroxyacid precursor compound to be so cationically substituted may be
a perbenzoic acid,
or substituted derivative thereof, precursor compound as described
hereinbefore. Alternatively,
the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor
compound or
an amide substituted alkyl peroxyacid precursor as described hereinafter
2o Cationic peroxyacid precursors are described in U.S. Patents 4,904,406;
4,751,01S; 4,988,451;
4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,3 82,594; EP
475,512, 458,396
and 284,292; and in JP 87-318,332.
Examples of preferred cationic peroxyacid precursors are described in UK
Patent Application
25 No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650,
08/298904 and
08/298906.
Suitable cationic peroxyacid precursors include any of the ammonium or alkyl
ammonium
substituted alkyl or benzoyl oxybenzene sulfonates, N-acyiated caprolactams,
and
3 o monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic
peroxyacid precursors of
the N-acylated caprolactam class include the trialkyl ammonium methylene
benzoyl
caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
Benzoxazin oreanic peroxvacid precursors
35 Also suitable are precursor compounds of the benzoxazin-type, as disclosed
for example in EP-
A-332,294 and EP-A-482,807, particularly those having the formula:
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22
O
II
C O
I
N C-R~
s
wherein R1 is H, alkyl, alkaryl, aryl, or arylalkyl.
Preformed organic peroxyacid
1o The organic peroxyacid bleaching system may contain, in addition to, or as
an alternative to, an
organic peroxyacid bleach precursor compound, a preformed organic peroxyacid ,
typically at a
level of from 1 % to 15% by weight, more preferably from 1 % to 10% by weight
of the
composition.
i5 A preferred class of organic peroxyacid compounds are the amide substituted
compounds of the
following general formulae:
R~ --C-N-R2-C-OOH R~ N-C-R2C-OOH
O R~ O or R~ O O
2o wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon
atoms, R2 is an alkylene,
arylene, and alkarylene group containing from 1 to 14 carbon atoms, and RS is
H or an alkyl,
aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide substituted
organic peroxyacid
compounds of this type are described in EP-A-017038b.
25 Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetradecanedioic acid and
diperoxyhexadecanedioc acid.
Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-
phthaloylaminoperoxicaproic
acid are also suitable herein.
3o Bleach catalyst
The compositions of the invention optionally contain a transition metal
containing bleach
catalyst. One suitable type of bleach catalyst is a catalyst system comprising
a heavy metal
cation of defined bleach catalytic activity, such as copper, iron or manganese
cations, an
auxiliary metal cation having little or no bleach catalytic activity, such as
zinc or aluminum
3 s cations, and a sequestrant having defined stability constants for the
catalytic and auxiliary metal
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23
cations, particularly ethylenediaminetetraacetic acid,
ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts
thereof. Such catalysts
are disclosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the manganese-based complexes
disclosed in U.S. Pat.
io 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts
include MnIV2(u-
0)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnIII2(u-O)1(u-
OAc)2(1,4,7-trimethyl-
1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-O)6(1,4,7-triazacyclononane)4-
(C104)2,
MnIIIMnIV4(u-O)I(u-OAc)2_(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)3,
and mixtures
thereof. Others are described in European patent application publication no.
549,272. Other
is Iigands suitable for use herein include 1,5,9-trimethyl-1,S,9-
triazacyclododecane, 2-methyl-
l,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-
1,4,7-
triazacyclononane, and mixtures thereof.
For examples of suitable bleach catalysts see U.S. Pat. 4,246,6I2 and U.S. Pat
5,227,084. See
2 o also U.S. Pat. 5, I94,416 which teaches mononuclear manganese (IV)
complexes such as
Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH3)3_(PF6). Still another type
of bleach
catalyst, as disclosed in U.S. Pat. 5, I 14,606, is a water-soluble complex of
manganese (III),
and/or (IV) with a ligand which is a non-carboxylate polyhydroxyl compound
having at least
three consecutive C-OH groups. Other examples include binuclear Mn complexed
with tetra-N-
2s dentate and bi-N-dentate ligands, including N4MnIII{u_O)2MnIVN4)~ and
[Bipy2Mnlll(u-
p)2~IVbipY2l-(C104)3.
Further suitable bleach catalysts are described, for example, in European
patent application No.
408,13l {cobalt complex catalysts), European patent applications, publication
nos. 384,503, and
3 0 306,089 (metalto-porphyrin catalysts), U.S. 4,728,45S
(manganese/multidentate ligand catalyst),
U.S. 4,7I 1,748 and European patent application, publication no. 224,952,
(absorbed manganese
on aluminosilicate catalyst), U.S. 4,60I,845 (aluminosilicate support with
manganese and zinc
or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4, I
19,557 (ferric complex
catalyst), German Pat. specification 2,0S4,019 (cobalt chelant catalyst)
Canadian 866,191
35 (transition metal-containing salts), U.S. 4,430,243 (chelants with
manganese canons and non-
catalytic metal cations), and U.S. 4,728,4S5 (manganese gluconate catalysts).
Additional Enzymes
The compositions of the present invention may comprise one or more additional
enzymes.
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24
Preferred additional enzymatic materials include the commercially available
enzymes. Said
enzymes include enzymes selected from cellulases, hemicellulases, peroxidases,
gluco-
amylases, amylases, xylanases, phospholipases, esterases, cutinases,
pectinases, keratanases,
reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases,
tannases,
pentosanases, malanases, Q-glucanases, arabinosidases, hyaluronidase,
chondroitinase, lactase or
1o mixtures thereof.
A preferred combination of additional enzymes is a cleaning composition having
a mixture of
conventional applicable enzymes such as protease, amylase, cutinase and/or
cellulase in
conjunction with one or more plant cell wall degrading enzymes. Suitable
enzymes are
~s exemplified in US Patents 3,519,S70 and 3,533,139.
The detergent compositions of the invention may also contain one or a mixture
of more than one
amylase enzyme (a and/or Vii). W094/02597, Novo Nordisk A/S published February
03, 1994,
describes cleaning compositions which incorporate mutant amylases. See also
W095/10603,
2 o 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; W0/91/00353; FR
2,676,456; EP
285,123; EP 525,610; EP 368,341; and British Patent specification no.
1,296,839 (Novo). Other
suitable amylases are stability-enhanced amylases described in W094/18314,
published August
25 18, 1994 and W096/05295, Genencor, published February 22, 1996 and amylase
variants
having additional modification in the immediate parent available from Novo
Nordisk A/S,
disclosed in WO 95/10603, published April 95. Also suitable are amylases
described in EP 277
216, W095/26397 and W096/23873 (all by Novo Nordisk).
3 o Examples of commercial a-amylases products are Purafect Ox Am~ from
Genencor and
Termamyl~, Ban~ ,Fungamyl~ and Duramyl~, all available from Novo Nordisk A/S
Denmark. W095/26397 describes other suitable amylases : a-amylases
characterised by having
a specific activity at least 25% higher than the specific activity of
Termamyl~ at a temperature
range of 25~C to 55~C and at a pH value in the range of 8 to 10, measured by
the Phadebas~ a-
35 amylase activity assay. Suitable are variants of the above enzymes,
described in W096/23873
(Novo Nordisk). Other preferred amylolytic enzymes with improved properties
with respect to
the activity level and the combination of thermostability and a higher
activity level are described
in W095/35382.
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5 The amylolytic enzymes if present are generally incorporated in the
detergent compositions of
the present invention a level of from 0.0001 % to 2%, preferably from 0.00018%
to 0.06%, more
preferably from 0.00024% to 0.048% pure enzyme by weight of the composition.
Suitable lipolytic enzymes for use in the present invention include those
produced by micro-
i0 organisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC
19.l54, as disclosed
in British Patent 1,372,034. Suitable lipases include those which show a
positive immunological
cross-section with the antibody of the lipase produced by the microorganism
Pseudomonas
Hisorescent 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
i5 suitable commercial lipases include Amano-CES, lipases ex Chromobacter
viscosum, e.g.
Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available 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 Pseudomonas gladioli. Especially
suitable
lipases are lipases such as M1 LipaseR and LipomaxR (Gist-Brocades) and
LipolaseR and
2o Lipolase UltraR(Novo) which have found to be very effective when used in
combination with
the compositions of the present invention. Also suitable are the iipolytic
enzymes described in
EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO
95/35381 and WO 96/00292 by Unilever.
25 Also suitable are cutinases [EC 3.1.1.50J which can be considered as a
special kind of lipase,
namely lipases which do not require interfacial activation. Addition of
cutinases to detergent
compositions have been described in e.g. WO-A-88/09367 (Genencor); WO 90/09446
(Plant
Genetic System) and WO 94/14963 and WO 94/14964 (Unilever). The LIPOLASE
enzyme
derived from Humicola lanuginosa and commercially available from Novo (see
also EPO
34l,947) is a preferred lipase for use in the present invention.
Another preferred lipase for use in the present invention is D96L lipolytic
enzyme variant of the
native lipase derived from Humicola lanuginosa. Most preferably the Humicola
lanuginosa
strain DSM 4106 is used.
By D96L lipolytic enzyme variant is meant the lipase variant as described in
patent application
WO 92/05249 in which the native lipase ex Humicola lanuginosa has the aspartic
acid (D)
residue at position 96 changed to Leucine (L). According to this nomenclature
said substitution
of aspartic acid to Leucine in position 96 is shown as : D96L. To determine
the activity of the
4 o enzyme D96L the standard LU assay may be used (Analytical method, internal
Novo Nordisk
CA 02268526 1999-04-13
WO 98I17766 PCT/US97/17814
26
number AF 95/6-GB 1991.02.07). A substrate for D96L was prepared by
emulsifying glycerine
tributyrate (Merck) using gum-arabic as emulsifier. Lipase activity is assayed
at pH 7 using pH
stat. method.
The detergent compositions of the invention may additionally incorporate one
or more cellulase
enzymes. Suitable celluiases include both bacterial or fungal cellulases.
Preferably, they will
have a pH optimum of between 5 and 12 and an activity above 50 CEVU (Cellulose
Viscosity
Unit). Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard
et al, J61078384
and W096/02653 which disclose fungal cellulases produced respectively from
Humicoia
insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes
celiulases isolated
15 from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-
2.075.028; GB-A-
2.095.275; DE-OS-2.247.832 and W095/26398.
Examples of such cellulases are cellulases produced by a strain of Humicola
insolens (Humicola
grisea var. thermoidea), particularly the Humicola strain DSM 1800. Other
suitable cellulases
2 o are celiulases originated from Humicola insolens having a molecular weight
of about SOICDa, an
isoelectric point of S.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 EGIII cellulases from Trichoderma
longibrachiatum described in
25 W094/21801, Genencor, published September 29, 1994. Especially suitable
cellulases are the
cellulases having color care benefits. Examples of such cellulases are
cellulases described in
European patent application No. 91202879.2, filed November 6, 1991 (Novo).
Carezyme and
Celluzyme (Novo Nordisk A/S) are especially useful. See also W091/17244 and
W091/21801.
Other suitable cellulases for fabric care and/or cleaning properties are
described in
3o W096/34092, W096/17994 and W095/24471.
Peroxidase enzymes may also be incorporated into the detergent compositions of
the invention.
Peroxidases 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
3 5 transfer of dyes or pigments removed from substrates during wash
operations to other substrates
in the wash solution. Peroxidase enzymes are known in the art, and include,
for example,
horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-
peroxidase.
Peroxidase-containing detergent compositions are disclosed, for example, in
PCT International
Application WO 89/099813, W089/09813 and in European Patent application EP No.
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z7
91202882.6, filed on November 6, 199l and EP No. 96870013.8, filed February
20, 1996. Also
suitable is the laccase enzyme.
Preferred enhancers are substituted phenthiazine and phenoxasine 10-
Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid
(EPC), 10-
1o phenoxazinepropionic acid (POP) and 10-methyiphenoxazine (described in WO
94l12621) and
substituted syringates (C3-CS substituted alkyl syringates) and phenols.
Sodium percarbonate or
perborate are preferred sources of hydrogen peroxide.
Said cellulases and/or peroxidases, if present, are normally incorporated in
the detergent
i 5 composition at levels from 0.0001 % to 2% of active enryme by weight of
the detergent
composition.
Said additional enzymes, when present, are normally incorporated in the
detergent composition
at levels from 0.0001 % to 2% of active enzyme by weight of the detergent
composition. The
2o additional enzymes can be added as separate single ingredients (prills,
granulates, stabilized
liquids, etc. containing one enryme ) or as mixtures of two or more enzymes (
e.g. cogranulates
).
Enzyme Oxidation Scaven
25 Other suitable detergent ingredients that can be added are enzyme oxidation
scavengers which
are described in Copending European Patent application 92870018.6 filed on
January 31, 1992.
Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene
polyamines.
Enzyme Materials
3 o A range of enzyme materials and means for their incorporation into
synthetic detergent
compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor
International, WO 8908694 A to Novo, and U.S. 3,SS3,139, January S, 1971 to
McCarty et al.
Enzymes are further disclosed in U.S. 4,I01,457, Place et al, July 18, 1978,
and in U.S.
4,S07,219, Hughes, March 26, 198S. Enzyme materials useful for liquid
detergent formulations,
3s and their incorporation into such formulations, are disclosed in U.S.
4,261,868, Hora et al, April
14, 1981. Enzymes for use in detergents can be stabilised by various
techniques. Enzyme
stabilisation techniques are disclosed and exemplified in U.S. 3,600,319,
August 17, 1971,
Gedge et al, EP 199,40S and EP 200,S86, October 29, 1986, Venegas. Enzyme
stabilisation
systems are also described, for example, in U.S. 3,5 l9,570. A useful
Bacillus, sp. AC 13 giving
4 o proteases, xylanases and cellulases, is described in WO 940I S32 A to
Novo.
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z8
Oreanic polymeric compound
Organic polymeric compounds are preferred additional components of the
detergent
io compositions or components thereof of the present invention, and are
preferably present as
components of any particulate component of the detergent composition where
they may act such
as to bind the particulate component together. By organic polymeric compound
is .meant any
polymeric organic compound commonly used as dispersants, anti-redeposition or
soil
suspension agents in detergent compositions, including any of the high
molecular weight
15 organic polymeric compounds described as clay flocculating agents herein.
Such an organic polymeric compound is generally incorporated in the detergent
compositions of
the invention at a level of from 0.1% to 30%, preferably from 0.5% to IS%,
most preferably
from 1% to 10% by weight of the compositions.
Examples of organic polymeric compounds include the water soluble organic homo-
or co-
polymeric polycarboxylic 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 the latter type are disclosed in GB-A-1,596,756. Examples of such salts are
polyacrylic acid
or polyacrylates of MWt 1000-5000 and their copolymers with malefic anhydride,
such
copolymers having a molecular weight of from 2000 to 100,000, especially
40,000 to 80,000.
Polymaleates or polymaleic acid polymers and salts thereof are also suitable
examples.
Polyamino compounds useful herein include those derived from aspartic acid
including
3 o polyaspartic acid and such as those disclosed in EP-A-305282, EP-A-305283
and EP-A-351629.
Terpolymers containing monomer units selected from malefic acid, acrylic acid,
aspartic acid and
vinyl alcohol or acetate, particularly those having an average molecular
weight of from I,000 to
30,000, preferably 3,000 to 10,000, are also suitable for incorporation into
the compositions of
3 5 the present invention.
Other organic polymeric compounds suitable for incorporation in the detergent
compositions of
the present invention include cellulose derivatives such as methylcellulose,
carboxymethylcellulose, hydroxypropylmethylcellulose,
ethylhydroxyethylcellulose and
4 o hydroxyethylcellulose.
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29
Further useful organic polymeric compounds are the polyethylene glycols,
particularly those of
molecular weight 1000 to 10000, more particularly 2000 to 8000 and most
preferably about
4000.
1o Cationic soil removal/anti-redeposition compounds
The detergent composition or components thereof of the invention may comprise
water-soluble
cationic ethoxylated amine compounds with particulate soiUclay-soil removal
and/or anti-
redeposition properties. These cationic compounds are described in more detail
in EP-B-
11 i965, US 4659802 and US 4664848. Particularly preferred of these cationic
compounds are
ethoxylated cationic monoamines, diamines or triamines. Especially preferred
are the
ethoxylated cationic monoamines, diamines and triamines of the formula:
CH3 CH3
i
X --(-- OCH2CH2)n N+- CH2 CH2 --(- CH2)a N+CH2CH20 r X
b
(CH2CH20 -~ X (CH2CH20 -~ X
wherein X is a nonionic group selected from the group consisting of H, C 1-C4
alkyl or
hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20,
preferably from 0 to
4 (e.g. ethylene, propylene, hexamethylene) b is 2, 1 or 0; for cationic
monoamines (b=0), n is
preferably at least 16, with a typical range of from 20 to 35; for cationic
diamines or triamines, n
is preferably at least about 12 with a typical range of from about 12 to about
42.
These compounds where present in the composition, are generally present in an
amount of from
0.0l to 30% by weight, preferably 0.05 to 10% by weight.
Suds suppressing system
The detergent compositions of the invention, when formulated for use in
machine washing
compositions, preferably comprise a suds suppressing system present at a level
of from 0.01 % to
15%, preferably from 0.05% to 10%, most preferably from 0.1 % to 5% by weight
of the
composition.
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Suitable suds suppressing systems for use herein may comprise essentially any
known antifoam
compound, including, for example silicone antifoam compounds and 2-alkyl
alcanol antifoam
compounds.
By antifoam compound it is meant herein any compound or mixtures of compounds
which act
to such as to depress the foaming or sudsing produced by a solution of a
detergent composition,
particularly in the presence of agitation of that solution.
Particularly preferred antifoam compounds for use herein are silicone antifoam
compounds
defined herein as any antifoam compound including a silicone component. Such
silicone
i5 antifoam compounds also typically contain a silica component. The term
"silicone" as used
herein, and in general throughout the industry, encompasses a variety of
relatively high
molecular weight polymers containing siloxane units and hydrocarbyl group of
various types.
Preferred silicone antifoam compounds are the siloxanes, particularly the
polydimethylsiloxanes
having trimethylsilyl end blocking units.
Other suitable antifoam compounds include the monocarboxylic fatty acids and
soluble salts
thereof. These materials are described in US Patent 2,954,347, issued
September 27, 1960 to
Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as
suds suppressor
typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to
18 carbon atoms.
2s Suitable salts include the alkali metal salts such as sodium, potassium,
and lithium salts, and
ammonium and alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight
fatty esters
(e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols,
aliphatic C 1 g-C40
3 o ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa-
alkylmelamines or di- to
tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with
two or three
moles of a primary or secondary amine containing 1 to 24 carbon atoms,
propylene oxide, bis
stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium,
lithium) phosphates
and phosphate esters.
A preferred suds suppressing system comprises
(a} antifoam compound, preferably silicone antifoam compound, most preferably
a
silicone antifoam compound comprising in combination
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31
(i) polydimethyl siloxane, at a level of from SO% to 99%,
preferably 75% to 95% by weight of the silicone antifoam compound; and
(ii) silica, at a level of from 1 % to SO%, preferably 5% to 2S% by weight
of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of
from S% to 50%,
preferably 10% to 40% by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol rake
copolymer
1 s with a polyoxyalkyiene content of 72-78% and an ethylene oxide to
propylene oxide
ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, preferably 1% to
10% by
weight; a particularly preferred silicone glycol rake copolymer of this type
is DC0544,
commercially available from DOW Corning under the tradename DC0544;
2 0 (c) an inert carrier fluid compound, most preferably comprising a C 16-C 1
g ethoxylated
alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at
a level of
from S% to 80%, preferably 10% to 70%, by weight;
A highly preferred particulate suds suppressing system is described in EP-A-
0210731 and
25 comprises a silicone antifoam compound and an organic carrier material
having a melting point
in the range 50~C to 85~C, wherein the organic carrier material comprises a
monoester of
glycerol and a fatty acid having a carbon chain containing from 12 to 20
carbon atoms. EP-A-
0210721 discloses other preferred particulate suds suppressing systems wherein
the organic
carrier material is a fatty acid or alcohol having a carbon chain containing
from 12 to 20 carbon
3o atoms, or a mixture thereof, with a melting point of from 4S~C to 80~C.
Polymeric dye transfer inhibitins. agents
The detergent compositions herein may also comprise from 0.01 % to 10 %,
preferably from
0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from
polyamine N-oxide
polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinyipyrrolidone
polymers or combinations thereof, whereby these polymers can be cross-linked
polymers.
4 o al Polyamine N-oxide polymers
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32
Polyamine N-oxide polymers suitable for use herein contain units having the
following structure
formula
P
(I)
R
io wherein P is a polymerisable unit, and
O R1 R10 O O R1
A is-C-N-, -N-C-, CO, C, -O-~ -S-, -N-; x is 0 or 1;
R1 is H or C 1 _6 linear or branched alkyl; or may form a heterocyclic group
with R;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic
groups or any
combination thereof whereto the nitrogen of the N-O group can be attached or
wherein the
nitrogen of the N-O group is part of these groups.
The N-O group can be represented by the following general
structures
0
0
(R1 ) x _N_(R2)Y
(R3)z or N_(R1)x
wherein Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic groups or
combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen
of the N-O group
2 5 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
3 o comprise polyamine N-oxides wherein R is selected from aliphatic,
aromatic, alicyclic or
heterocyclic groups. One class of said polyamine N-oxides comprises the group
of polyamine N-
CA 02268526 1999-04-13
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33
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 pyridine, N-
substituted pyrrole,
imidazole, N-substituted pyrrolidine, piperidine, quinoline, acridine and
derivatives thereof.
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O
group is attached
to to the polymerisable unit. A preferred class of these polyamine N-oxides
comprises the
polyamine N-oxides having the general formula (I) wherein R is an
aromatic,heterocyclic or
alicyclic groups wherein the nitrogen of the N-O functional group is part of
said R group.
Examples of these classes are polyamine oxides wherein R is a heterocyclic
compound such as
pyridine, N-substituted pyrrole, imidazole and derivatives thereof.
The polyamine N-oxides can be obtained in almost any degree of polymerisation.
The degree of
polymerisation is not critical provided the material has the desired water-
solubility and dye-
suspending power. Typically, the average molecular weight is within the range
of 500 to
1000,000.
b) Copolymers ofN-vin~pyrrolidone and N-vinylimidazole
Suitable herein are copolymers of N-vinylimidazole and N-vinylpyrrolidone
having a preferred
average molecular weight range of from 5,000 to 100,000, or 5,000 to 50,000.
The preferred
copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1
to 0.2.
c) Pohrvinypyrrolidone
The detergent compositions herein may also utilize polyvinylpyrrolidone
("PVP") having an
3 o average molecular weight of from 2,500 to 400,000. Suitable
polyvinylpyrrolidones are
commercially available 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 I 60,000), and PVP K-
90 (average
molecular weight of 360,000). PVP K-15 is also available from ISP Corporation.
Other suitable
polyvinylpyrrolidones which are commercially available from BASF Corporation
include
Sokalan HP 165 and Sokalan HP 12.
d) Polyvinyloxazolidone
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34
The detergent compositions herein may also utilize polyvinyioxazolidones as
polymeric dye
transfer inhibiting agents. Said polyvinyloxazolidones have an average
molecular weight of
from 2,500 to 400,000.
e) Polwinvlimidazole
i o The detergent compositions herein may also utilize polyvinyiimidazole as
polymeric dye
transfer inhibiting agent. Said polyvinylimidazoles preferably have an average
molecular weight
of from 2,500 to 400,000.
Optical briehtener
15 The detergent compositions herein also optionally contain from about 0.005%
to 5% by weight
of certain types of hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural formula:
R1 R2
H H
N~O~-N O C C 0 N---~~ N
H H
R2/ S03M S~3M Ri
wherein R I is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is
selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino, chloro and
amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, Rl is anilino, R2 is N-2-bis-hydroxyethyl and M is
a cation such as
sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-
triazine-2-yl)amino]-
2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener
species is
commercially marketed under the tradename Tinopal-IJNPA-GX by Ciba-Geigy
Corporation.
3 o Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in
the detergent
compositions herein.
When in the above formula, Rl is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a
cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-
hydroxyethyl-N-
3 s methylamino~s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium
salt. This particular
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5 brightener species is commercially marketed under the tradename Tinopal SBM-
GX by Ciba-
Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation
such as sodium,
the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)aminoJ2,2'-
stilbenedisulfonic
io acid, sodium Bait. This particular brightener species is commercially
marketed under the
tradename Tinopal AMS-GX by Ciba Geigy Corporation.
Polymeric Soil Release A~,ent
Known polymeric soil release agents, hereinafter "SRA", can optionally be
employed in the
i5 present detergent compositions. If utilized, SRA's will generally comprise
from 0.0l% to
10.0%, typically from 0.1 % to 5%, preferably from 0.2% to 3.0% by weight, of
the
compositions.
Preferred SRA's typically have hydrophilic segments to hydrophilize the
surface of hydrophobic
2 o 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 anchor for the hydrophilic segments. This can enable stains
occurring subsequent
to treatment with the SRA to be more easily cleaned in later washing
procedures.
25 Preferred SRA'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
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 SRA's include a sulfonated product of a substantially linear ester
oligomer comprised of
an oligonieric or polymeric 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. 4,9b8,451, November 6, l990 to J.J. Scheibel and E.P.
Gosselink. Such ester
3 5 oligomers can be prepared by: (a) ethoxylating al lyl alcohol; (b)
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 SRA's include the nonionic end-capped 1,2-
propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December
8, 1987 to
4 o Gosselink et al., for example those produced by
transesterification/oligomerization of poly-
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36
s (ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG").
Other examples of
SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of
U.S. 4,721,580,
January 26, 1988 to Gosselink, such as oligomers from 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
1 o DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG
and/or PG,
Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially
sulfoaroyl,
end-capped terephthalate esters of U.S. 4,877,896, October 31, 1989 to
Maldonado, Gosselink et
al., the latter being typical of SRA's useful in both laundry and fabric
conditioning products, an
example being an ester composition made from m-sulfobenzoic acid monosodium
salt, PG and
~ 5 DMT, optionally but preferably further comprising added PEG, e.g., PEG
3400.
SRA's also include: simple copolymeric blocks of ethylene terephthalate or
propylene
terephthalate with polyethylene oxide or polypropylene oxide terephthaiate,
see U.S. 3,9S9,230
to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic
derivatives such
2 o as the hydroxyether cellulosic polymers available as METHOCEL from Dow;
the C 1-C4 alkyl
celluloses and C4 hydroxyalkyl 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 i.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
25 as METOLOSE SM100 and METOLOSE SM200, which are the trade names of methyl
cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
Additional classes of SRA's include: (I) nonionic terephthalates using
diisocyanate coupling
agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al.
and U.S. 4,240,918
3 o Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by
adding trimellitic
anhydride to known SRA'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 acid of trimellitic
anhydride rather than by
opening of the anhydride linkage. Either nonionic or anionic SRA's may be used
as starting
3 s 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 SRA's of the
urethane-linked variety, see U.S. 4,201,824, Violland et al.;
Other optional ingredients
4 o Other optional ingredients suitable for inclusion in the compositions of
the invention include
perfumes, colours and filler salts, with sodium sulfate being a preferred
filler salt.
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Near neutral wash pH detereent formulation
While the detergent compositions of the present invention are operative within
a wide range of
to wash pHs (e.g. from about 5 to about 12), they are particularly suitable
when formulated to
provide a near neutral wash pH, i.e. an initial pH of from about 7.0 to about
10.5 at a
concentration of from about O.I to about 2% by weight in water at 20~C. Near
neutral wash pH
formulations are better for enzyme stability and for preventing stains from
setting. In such
formulations, the wash pH is preferably from about 7.0 to about 10.5, more
preferably from
is about 8.0 to about 10.5, most preferably from 8.0 to 9Ø
Preferred near neutral wash pH detergent formulations are disclosed to
European Patent
Application 83.200688.6, filed May 16, l983, J.H.M. Wertz and P.C.E. Goffinet.
2 o Highly preferred compositions of this type also preferably contain from
about 2 to about 10% by
weight of citric acid and minor amounts (e.g., less than about 20% by weight)
of neutralizing
agents, buffering agents, phase regulants, hydrotropes, enzymes, enzyme
stabilizing agents,
polyacids, suds regulants, opacifiers, anti-oxidants, bactericides, dyes,
perfumes and brighteners,
such as those described in US Patent 4,285,841 to Barrat et al., issued August
25, 198l (herein
2 5 incorporated by reference).
Form of the compositions
The compositions in accordance with the invention can take a variety of
physical forms
including granular, tablet, flake, pastille and bar and liquid forms. Liquids
may be aqueous or
3 o non-aqueous and may be in the form of a gel. The compositions are
particularly the so-called
concentrated granular detergent compositions adapted to be added to a washing
machine by
means ofa dispensing device placed in the machine drum with the soiled fabric
load.
Such granular detergent compositions or components thereof in accordance with
the present
3 5 invention can be made via a variety of methods, including spray-drying,
dry-mixing, extrusion,
agglomerating and granulation. The cationic quaternised surfactant can be
added to the other
detergent components by mixing, agglomeration (preferably combined with a
carrier material),
granulation or as a spray-dried component.
4 o The compositions in accordance with the present invention can also be used
in or in combination
with bleach additive compositions, for example comprising chlorine bleach.
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In one aspect of the invention the mean particle size of the components of
granular compositions
in accordance with the invention, should preferably be such that no more than
I S% of the
particles are greater than 1.8mm in diameter and not more than 15% of the
particles are less than
0.25mm in diameter. Preferably the mean particle size is such that from 10% to
50% of the
particles has a particle size of from 0.2mm to 0.7mm in diameter.
The term mean particle size as defined herein is calculated by sieving a
sample of the
composition into a number of fractions (typically 5 fractions) on a series of
sieves, preferably
Tyler sieves. The weight fractions thereby obtained are plotted against the
aperture size of the
i5 sieves. The mean particle size is taken to be the aperture size through
which 50% by weight of
the sample would pass.
In a further aspect of the invention at least 80%, preferably at least 90% by
weight of the
composition comprises particles of mean particle size at least 0.8 mm, more
preferably at least
2 0 1.0 mm and most preferably from 1.0, or 1.5 to 2.5 mm. Most preferably at
least 95% of the
particles will have such a mean particle size. Such particles are preferably
prepared by an
extrusion process. Preferably the cationic surfactant and proteoiytic enzyme
are contained in the
same particle.
25 The bulk density of granular detergent compositions in accordance with the
present invention
typically have a bulk density of at least 400, preferably at least 600
g/litre, more preferably from
650 g/litre to 1200 g/litre. Bulk density is measured by means of a simple
funnel and cup device
consisting of a conical funnel moulded rigidly on a base and provided with a
flap valve at its
lower extremity to allow the contents of the funnel to be emptied into an
axially aligned
3 o cylindrical cup disposed below the funnel. The funnel is 130 mm high and
has internal diameters
of 130 mm and 40 mm at its respective upper and lower extremities. It is
mounted so that the
lower extremity is 140 mm above the upper surface of the base. The cup has an
overall height of
90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its
nominal volume is
500 ml.
To carry out a measurement, the funnel is filled with powder by hand pouring,
the flap valve is
opened and powder allowed to overfill the cup. The filled cup is removed from
the frame and
excess powder removed from the cup by passing a straight edged implement eg; a
knife, across
its upper edge. The filled cup is then weighed and the value obtained for the
weight of powder
4o doubled to provide a bulk density in g/litre. Replicate measurements are
made as required.
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Compacted solids may be manufactured using any suitable compacting process,
such as
tabletting, briquetting or extrusion, preferably tabletting. Preferably
tablets for use in dish
washing processes, are manufactured using a standard rotary tabletting press
using compression
forces of from 5 to 13 KN/cm2, more preferably from 5 to 11 KN/cm2 so that the
compacted
io solid has a minimum hardness of 176N to 275N, preferably from 195N to 245N,
measured by a
C 100 hardness test as supplied by I. Holland instruments. This process may be
used to prepare
homogeneous or layered tablets of any size or shape. Preferably tablets are
symmetrical to
ensure the uniform dissolution of the tablet in the wash solution.
~s Laundry washine method
Machine laundry methods herein typically comprise treating soiled laundry with
an aqueous
wash solution in a washing machine having dissolved or dispensed therein an
effective amount
of a machine laundry detergent composition in accord with the invention. By an
effective
amount of the detergent composition it is meant from 10g to 300g of product
dissolved or
2o dispersed in a wash solution of volume from S to 65 litres, as are typical
product dosages and
wash solution volumes commonly employed in conventional machine laundry
methods. Dosage
is dependent upon the particular conditions such as water hardness and degree
of soiling of the
soiled laundry.
2 s The detergent composition may be dispensed for example, from the drawer
dispenser of a
washing machine or may be sprinkled over the soiled laundry placed in the
machine.
In one use aspect a dispensing device is employed in the washing method. The
dispensing
device is charged with the detergent product, and is used to introduce the
product directly into
3 o the drum of the washing machine before the commencement of the wash cycle.
Its volume
capacity should be such as to be able to contain sufficient detergent product
as would normally
be used in the washing method.
The dispensing device containing the detergent product is placed inside the
drum before the
3 s commencement of the wash, before, simultaneously with or after the washing
machine has been
loaded with laundry. At the commencement of the wash cycle of the washing
machine water is
introduced into the drum and the drum periodically rotates. The design of the
dispensing device
should be such that it permits containment of the dry detergent product but
then allows release
of this product during the wash cycle in response to its agitation as the drum
rotates and also as a
4o result of its contact with the wash water.
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To allow for release of the detergent product during the wash the device may
possess a number
of openings through which the product may pass. Alternatively, the device may
be made of a
material which is permeable to liquid but impermeable to the solid product,
which will allow
release of dissolved product. Preferably, the detergent product will be
rapidly released at the
io start of the wash cycle thereby providing transient localised high
concentrations of product in
the drum of the washing machine at this stage of the wash cycle.
Preferred dispensing devices are reusable and are designed in such a way that
container integrity
is maintained in both the dry state and during the wash cycle. Especially
preferred dispensing
~5 devices for use with the composition of the invention have been described
in the following
patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-
A-
0288346. An article by J.Bland published in Manufacturing Chemist, November
l989, pages
41-46 also describes especially preferred dispensing devices for use with
granular laundry
products which are of a type commonly know as the "granulette". Another
preferred dispensing
2 o device for use with the compositions of this invention is disclosed in PCT
Patent Application
No. W094/11562.
Especially preferred dispensing devices are disclosed in European Patent
Application
Publication Nos. 0343069 & 0343070. The tatter Application discloses a device
comprising a
2 5 flexible sheath in the form of a bag extending from a support ring
defining an orifice, the orifice
being adapted to admit to the bag sufficient product for one washing cycle in
a washing process.
A portion of the washing medium flows through the orifice into the bag,
dissolves the product,
and the solution then passes outwardly through the orif ce into the washing
medium. The
support ring is provided with a masking arrangement to prevent egress of
wetted, undissolved,
3o product, this arrangement typically comprising radialiy extending walls
extending from a central
boss in a spoked wheel configuration, or a similar structure in which the
walls have a helical
form.
Alternatively, the dispensing device may be a flexible container, such as a
bag or pouch. The
3 5 bag may be of fibrous construction coated with a water impermeable
protective material so as to
retain the contents, such as is disclosed in European published Patent
Application No. 0018678.
Alternatively it may be formed of a water-insoluble synthetic polymeric
material provided with
an edge seal or closure designed to rupture in aqueous media as disclosed in
European published
Patent Application Nos. 0011500, 001150I, 0011502, and 00l 1968. A convenient
form of
4 o water frangible closure comprises a water soluble adhesive disposed along
and sealing one edge
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s of a pouch formed of a water impermeable polymeric film such as polyethylene
or
polypropylene.
Machine dishwashing method
Any suitable methods for machine dishwashing or cleaning soiled tableware,
particularly soiled
to silverware are envisaged.
A preferred machine dishwashing method comprises treating soiled articles
selected from
crockery, glassware, hollowware, silverware and cutlery and mixtures thereof,
with an aqueous
liquid having dissolved or dispensed therein an effective amount of a machine
dishwashing
1 s composition in accord with the invention. By an effective amount of the
machine dishwashing
composition it is meant from 8g to 60g of product dissolved or dispersed in a
wash solution of
volume from 3 to 10 litres, as are typical product dosages and wash solution
volumes commonly
employed in conventional machine dishwashing methods.
2 o Packa ins for the compositions
Commercially marketed executions of the bleaching compositions can be packaged
in any
suitable container including those constructed from paper, cardboard, plastic
materials and any
suitable laminates. A preferred packaging execution is described in European
Application No.
94921505.7.
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Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications have
the following
meanings:
LAS . Sodium linear C 12 alkyl benzene sulfonate
TAS . Sodium tallow alkyl sulfate
CxyAS . Sodium C 1 x - C 1 y alkyl sulfate
C46SAS . Sodium C 14 - C 16 secondary (2,3) alkyl
sulfate
1 s CxyEzS . Sodium C 1 x C 1 y alkyl sulfate condensed
with z
moles of ethylene oxide
CxyEz . C 1 x-C 1 y predominantly linear primary
alcohol
condensed with an average of z moles of
ethylene
oxide
2 o QAS 1 . R2.N+(CH3)2(C2H40H) with R2 = Cg - C 11
linear
alkyl
QAS 2 . R2.N+(CH3)2(C2H40H) with approximately
50% R2 = Cg linear alkyl; approximately
50% R2 = C 10
2s QAS 3 . R2.N+(CH3)2(C2H40H) with approximately
40% R2 = C11 linear alkyl; approximately
60% R2 = Cg linear alkyl
QAS 4 . R2.N+(CH3)2(C2H40H) with R2 = C6 linear
alkyl
QAS 5 . R2.N+(CH3)2(C2H40H) with R2 = C 10 linear
alkyl
3o Soap . Sodium linear alkyl carboxylate derived
from an
80/20 mixture of tallow and coconut oils
CFAA . C 12-C 14 (coco) alkyl N-methyl glucamide
TFAA . C 16-C 1 g alkyl N-methyl glucamide
TPKFA . C 12-C 14 topped whole cut fatty acids
3 s STPP . Anhydrous sodium tripolyphosphate
TSPP . Tetrasodium pyrophosphate
Zeolite A . Hydrated Sodium Aluminosilicate of formula
Nal2(AIOZSi02)12~2~H20 having a primary
particle size in the range from 0.1 to 10
4 o micrometers
Zeolite MAP . Hydrated sodium aluminosilicate zeolite
MAP
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having a silicon to aluminium ratio of
1.07
NaSKS-6 : Crystalline layered silicate of formula
8-
Na2Si205
Citric acid. Anhydrous citric acid
. Borate . Sodium borate
io Carbonate . Anydrous sodium carbonate with a particle
size
between 200um and 900pm
Bicarbonate. Anhydrous sodium bicarbonate with a particle
size distribution between 400pm and 1200pm
Silicate . Amorphous Sodium Silicate (Si02:Na20
= 2.0:l )
is Sodium sulfate
: Anhydrous
sodium
sulfate
Citrate . Tri-sodium citrate dehydrate of activity
86.4%
with a particle size distribution between
425pm
and 850pm
MA/AA . Copolymer of 1:4 maleic/acrylic acid,
average
2 o molecular weight about 70,000
AA . Sodium polyacrylate polymer of average
molecular weight 4,500
CMC . Sodium carboxymethyl cellulose
Cellulose r : Methyl cellulose ether with a degree
ethe of
25 polymerization of 650 available from Shin
Etsu
Chem icals
Protease . Proteolytic enzyme of activity 4KNPU/g
sold by
NOVO Industries A/S under the tradename
Savinase
3 o Alcalase . Proteolytic enzyme of activity 3AU/g
sold by
NOVO Industries A/S
Cellulase . Cellulytic enzyme of activity i 000 CEVU/g
sold
by NOVO Industries A/S under the tradename
Carezyme
35 Amylase . Amylolytic enzyme of activity 120KNU/g
sold by
NOVO Industries A/S under the tradename
Termamyl 120T
Lipase . Lipolytic enzyme of activity 1 OOKLU/g
sold
by NOVO Industries A/S under the tradename
4 o Lipolase
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Endolase . Endoglucanase enzyme of activity 3000 CEVU/g
sold by NOVO Industries A/S
PB4 . Sodium perborate tetrahydrate of nominal
formula
NaB02.3H20.H202
PB 1 . Anhydrous sodium perborate bleach of nominal
io formula NaB02.H202
Percarbonate. Sodium percarbonate of nominal formula
2Na2C03.3H202
NOES . Nonanoyloxybenzene sulfonate in the form
of the
sodium salt
TAED . Tetraacetylethylenediamine
Mn catalyst. MnIV2(m-O)3(1,4,7-trimethyl-1,4,7-
triazacyclononane)2(PF6)2, as described in
U.S.
Pat. Nos. 5,246,621 and 5,244,594.
DTPA . Diethylene triamine pentaacetic acid
2o DTPMP . Diethylene triamine penta (methylene
phosphonate), marketed by Monsanto under the
Tradename bequest 2060
Photoactivatedbleach . Sulfonated Zinc Phthlocyanine encapsulated
in bleach
dextrin soluble polymer
z Brightener . Disodium 4,4'-bis(2-sulphostyry)biphenyl
5 1
Brightener2. Disodium4,4'-bis(4-anilino-6-morpholino-1.3.5-
triazin-2-yl)amino) stilbene-2:2'-disulfonate
HEDP . 1,1-hydroxyethane diphosphonic acid
EDDS . Ethylenediamine-N, N-disuccinic acid
3o QEA . bis((C2H50)(C2H40n)(CH3) -N+-C6H12-N+ _
(CH3) bis((C2H50}-(C2H40)n), wherein n = from
20
to 30
PEGX . Polyethylene glycol, with a molecular weight
of x
PEO . Polyethylene oxide, with a molecular weight
of 50,000
3 TEPAE . Tetraethylenepentaamine ethoxylate
5
PVP . Polyvinylpyrolidone polymer
PVNO . Polyvinylpyridine N-oxide
PVPVI . Copolymer of polyvinylpyrolidone and
vinylimidazole
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5 SRP 1 . Sulfobenzoyl and capped esters with oxyethylene
oxy and terephtaioyl backbone
, SRP 2 . Diethoxylated poly (1, 2 propylene terephtalate)
short block polymer
Silicone antifoam . Polydimethylsiloxane foam controller with
1o siloxane-oxyalkylene copolymer as dispersing
agent with a ratio of said foam controller to said
dispersing agent of 10:1 to 100:1
Wax . Paraffin wax
~ 5 In the following examples all levels are quoted as % by weight of the
composition:
Example 1
The following high density granular laundry detergent compositions A to F of
particular utility
2 o under European machine wash conditions are examples of the present
invention:
A B C D E F
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
C46AS 1.0 2.0 2.5 - 3.0 4.0
C68AS 3.0 2.0 5.0 7.0 1.0 0.5
QAS 1 0.05 - - - - 0.8
QAS 2 - 0.05 0.8 - - -
QAS3 - - - 1.4 1.0 -
Zeolite A i 8.1 18.1 16. 18.1 18.1 18.
i t
Zeolite MAP - 4.0 3.5 - - -
Carbonate 12.0 12.0 13.0 26.0 26.0 26.0
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Silicate 1.4 1.4 1.4 3.0 3.0 3,0
NaSKS-6(citric 11.0 6.0 6.0 - - I2.S
acid
79:21 )
Sodium Sulfate 26.1 26.1 2S.0 17.1 24.I 9.I
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
PB4 9.0 9.0 9.0 9.0 9.0 9.0
TAED I.S 1.5. 1.0 I.S - I.S
Mn Catalyst - 0.03 0.07 - - -
DTPMP 0.2S 0.2S - 0.2S 0.2S 0.2S
HEDP 0.3 0.3 0.2 0.2 0.3 0.3
EDDS - - 0.4 0.2 -
QEA 1.0 0.8 0.7 1.2 - O.S
Protease 0.8S 0.8S 0.26 0.8S 0.8S 0.8S
Amylase 0.1 0.1 0.4 0.3 0.1 0.1
Lipase 0.05 0.6 0.7 O.I 0.07 0.1
Photoactivated I S 15 pp 1 S 1 S 1 S 1 S
bleach pp pp pp pp pp
(PPm)
Brightener 1 0.09 0.09 - 0.09 0.09 0.D9
Perfume 0.3 0.3 0.3 0.3 0.3 0.3
Silicone antifoamO.S O.S O.S O.S O.S O.S
Misclminors
to 100%
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Density in g/litre 850 850 850 850 850 850
to
Example 2
The following granular laundry detergent compositions G to I of particular
utility under
European machine wash conditions are examples of the present invention:
G H I
LAS 5.3 5.6 4.8
TAS 1.3 1.9 1.6
C45AS - 2.2 3.9
C25E3S - 0.8 1.2
C45E7 3.3 - 5.0
C25E3 - 5.5 -
QAS 1 0.8 3.0 2.5 .
STPP 19.7 - -
Zeolite A - 19.5 19.5
Zeolite MAP 2.0 - -
NaSKS-6/citric - 13.0 10.6
acid
(79:21 )
Carbonate 5.1 18.4 21.4
Bicarbonate - 2.0 2.0
Silicate 6.8 - -
Sodium Sulfate 37.8 - 7.0
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MA/AA 0.8 1.6 1.6
CMC 0.2 0.4 0.4
PB4 5.0 12.7 -
Percarbonate 5.0 - i2.7
TAED 0.5 3.1 -
Mn Catalyst 0.04 - -
DTPMP 0.25 0.2 0.2
~Dp - 0.3 0.3
QEA 0.9 - -
Protease 0.85 2.8 0.85
Lipase 0.15 0.25 0. I 5
Cellulase 0.2 0.3 0.3
Amylase 0.4 0.1 0.1
PVP 0.9 1.3 0.8
Photoactivated 15 ppm 27 ppm 27 ppm
bleach
Brightener 1 0.08 0.19 0.19
Brightener 2 - 0.04 0.04
Perfume 0.3 0.3 0.3
Silicone antifoam0.5 2.4 2.4
Minors/misc to
100%
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Examele 3
The following detergent formulations of particular utility under European
machine wash
conditions are examples of the present invention.
J K L M
Blown powder
LAS 6.0 5.0 11.0 6.0
TAS 2.0 - - 2.0
QAS 2 0.8 1.0 - -
QAS 3 - - 1.5 0.6
Zeolite A - 27.0 - 20.0
STPP 24.0 - 24.0 -
Sulfate 6.0 6.0 9.0 -
MA/AA 2.0 4.0 6.0 4.0
Silicate 7.0 3.0 3.0 3.0
CMC 1.0 1.0 0.5 0.6
QEA - - 1.4 0.5
Brightener 0.2 0.2 0.2 0.2
Silicone antifoam1.0 1.0 1.0 0.3
DTPMP 0.4 0.4 0.2 0.4
Spray on
C45E7 - - - 5.0
C45E5 2.5 2.5 2.0 -
C45E3 2.6 2.5 2.0 -
Perfume 0.3 0.3 0.3 0.2
Silicone antifoam0.3 0.3 0.3 -
Dry additives
Sulfate 3.0 3.0 S.0 10.0
Carbonate 6.0 13.0 l5.0 14.0
PB 1 - - - 1.5
PB4 18.0 18.0 10.0 18.5
TAED 3.0 2.0 - 2.0
EDDS - 2.0 2.4 -
Protease 3.25 1.0 3.25 3.25
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Lipase 0.4 O.S 0.4 0.2
Amylase 0.2 0.3 0.2 0.4
Photoactivated - - - 0.1 S
bleach
Minors/misc to
I00%
Example 4
The following granular detergent formulations are examples of the present
invention.
Formulation N is particularly suitable for usage under Japanese machine wash
conditions.
Formulations O to S are particularly suitable for use under US machine wash
conditions.
N O P Q R S
Blown powder
LAS 22.0 S.0 4.0 9.0 8.0 7.0
C4SAS 7.0 7.0 6.0 - - -
C46AS - 4.0 3.0 - - -
C4SE3S - 3.0 2.0 8.0 S.0 4.0
QAS 1 0.S - - - - -
QAS 2 - O.S - 2.0 - 3.S
QAS 3 - - 0.8 - 3.0 -
Zeolite A 6.0 16.0 14.0 19.0 16.0 14.0
MA/AA 6.0 3.0 3.0 - - -
AA - 3.0 3.0 2.0 3.0 3.0
Sodium Sulfate6.0 3.3 2.3 24.0 l3.3 l9.3
Silicate S.0 1.0 1.0 2.0 1.0 1.0
Carbonate 24.3 9.0 3.0 2S.7 8.0 6.0
QEA 0.4 0.4 - - O.S 1.1
PEG 4000 O.S - 1.S 1.0 I.S 1.0
Sodium oleate 2.0 - - - - -
DTPA 0.4 - O.S - - O.S
Brightener 0.2 0.3 0.3 0.3 0.3 0.3
Spray on
C2SES 1.0 - - - - -
C4SE7 - 2.0 2.0 O.S 2.0 2.0
Perfume I.0 0.3 0.3 1.0 0.3 0.3
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Agglomerates
C45AS - S.0 5.0 - 5.0 5.0
LAS - 2.0 2.0 - 2.0 2.0
Zeolite A - 7.5 7.5 - 7.5 7.5
HEDP - 1.0 - - 2.0 -
Carbonate - 4.0 4.0 - 4.0 4.0
PEG 4000 - 0.5 0.5 - 0.5 0.5
Misc (water - 2.0 2.0 - 2.0 2.0
etc)
Dry additives
TAED 1.0 2.0 3.0 1.0 3.0 2.0
PB4 - 1.0 4.0 - 5.0 0.5
PB1 6.0 - - - -
Percarbonate - 5.0 12.5 - - -
Carbonate - 5.3 1.8 - 4.0 4.0
NOBS 4.5 - 6.0 - - 0.6
Cumeme sulfonic- 2.0 2.0 - 2.0 2.0
acid
Lipase - 0.4 0.4 - 0.05 0.2
Cellulase - 0.2 0.2 - 0.2 0.2
Amylase - 0.3 0.3 - - -
Protease 5.3 1.6 1.6 0.3 1.6 1.6
PVPVi - 0.5 - _ _ _
PVP 0.5 - - - - -
PVNO - 0.5 0.5 - - -
SRP1 - 0.5 0.5 - - -
Silicone antifoam- 0.2 0.2 - 0.2 0.2
Minors/misc
to
100%
Example 5
The following granular detergent formulations are examples of the present
invention.
Formulations W and X ar~ of particular utility under US machine wash
conditions. Y is of
1o particular utility under Japanese machine wash conditions
T U V
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Blown Powder
Zeolite A 30.0 22.0 6.0
Sodium Sulfate 19.0 5.0 7.0
MA/AA 3.0 2.0 6.0
LAS I4.0 12.0 22.0
C45AS 8.0 7.0 7.0
QAS 1 0.7 - -
QAS 2 - 2.2 -
QAS 5 - - I.5
Silicate - 1.0 5.0
Soap - - 2.0
Brightener 1 0.2 0.2 0.2
Carbonate 7.0 16.0 20.0
DTPMP - 0.4 0.4
Spray On - I.0 5.0
C45E7 1.0 1.0 1.0
Dry additives
HEDP 1.0 - -
PVPVI/PVNO 0.5 0.5 0.5
Protease 3.3 3.3 3.3
Lipase 0.4 0.1 0.2
Amylase 0.1 0.1 0.1
Celtulase 0.1 0.1 0.1
TAED - 6.1 4.5
PB 1 11.0 5.0 6.0
Sodium Sulfate - 6.0 -
Balance (Moisture and Misc.)
Example 6
The following granular detergent compositions of particular utility under
European wash
conditions were are examples of the present invention.
W X
Blown powder
Zeolite A 20.0 -
STPP - 20.0
LAS 6.0 6.0
C68AS 2.0 2.0
QAS 1 0.01 -
QAS 4 - 0.6
Silicate 3.0 8.0
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M,vAA 4.o z.o
CMC 0.6 0.6
Brightener 1 0.2 0.2
DTPMP 0.4 0.4
Spray on
C45E7 S.0 S.0
Silicone antifoam 0.3 0.3
Perfume 0.2 0.2
Dry additives
Carbonate 14.0 9.0
PB 1 1.5 2.0
PB4 18.5 13.0
TAED 2.0 2.0
Photoactivated bleach15 ppm 15 ppm
Protease 1.0 1.0
Lipase 0.2 0.08
Amylase 0.4 0.4
Cellulase 0.1 0.1
Sulfate 10.0 20.0
Balance (Moisture 10.6 5.12
and Misc.)
Density (gllitre) 700 700
Example 7
The following detergent compositions are examples of the present invention:
Y Z AA
Blown Powder
Zeolite A 15.0 15.0 15.0
Sodium Sulfate 0.0 0.0 0.0
LAS 3.0 3.0 3.0
QAS 2 1.0 - -
QAS 5 - 3.0 2.0
DTPMP 0.4 0.2 0.4
CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
Agglomerates
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LAS 5.0 5.0 5.0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
QEA - I .0 0.6
Mn Catalyst 0.03 - -
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 8.0
Percarbonate - 7.0 l0.0
TAED 6.0 2.0 5.0
PB 1 14.0 7.0 8.0
EDDS - 2.0 -
Poly~hyleneoxideofMW5,000,000- - 0.2
Bentonite clay - - 10.0
Protease I.0 3.3 3.3
Lipase 0.4 0.1 1.0
Amylase 0.6 0.6 -
Cellulase 0.6 0.6 -
Silicone antifoam S.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
Balance (Moisture and 5.3 0.8 0.1
Misc.)
to 100%
Density (g/litre) 850 850 850
Example 8
T'he following detergent formulations are examples of the present invention:
BB CC DD EE
LAS 20.0 14.0 24.0 22.0
QAS I 0.7 1.0 0 0
QAS 2 - - 0.08 -
QAS4 - - -
1.0
TFAA - 1.0 - -
C25E5/C45E7 - 2,0 - 0.5
C45E3S - 2.5 - -
STPP 30.0 18.0 30.0 22.0
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Silicate 9.0 5.0 I0.0 8.0
Carbonate 13.0 7.5 - 5.0
B icarbonate - 7.5 - -
Percarbonate - 5.0 9.0 15.0
DTPMP 0.7 1.0 - -
QEA 1 0.4 1.2 0.5 2.0
QEA 2 0.4 - - -
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
Protease 2.6 3.3 1.6 1.6
Amylase 0.8 0.4 - -
Lipase 0.2 0.06 0.25 0. i
Celluiase 0.15 0.0S - -
Photoactivated70ppm 45ppm - lOppm
bleach (ppm)
Brightener 0.2 0.2 0.08 0.2
i
PB 1 6.0 2.0 - -
HEDP - - 2.3
TAED 2.0 I .0 - -
Balance (Moisture
and Misc.)
to 100%
Example 9
The following laundry bar detergent compositions are examples of the present
invention.
FF GG HH II JJ KK LL MM
LAS - - 19.0 15.0 21.0 6.75 8.8 -
C28AS 30.0 13.5 - - - 15.75 11.2 22.5
Sodium iaurate2.5 9.0 - - - - - -
QAS 1 - - - 0.08 - - 2.0 -
QAS 2 1.5 - 0.8 - - - - -
QAS 3 _ S - - _ _ - 0.1
QAS 4 - - - - I.5 0.04 - -
QAS S ' - - - - - 0.04 - -
Zeolite A 2.0 1.25 - - - 1.25 1.25 1.25
Carbonate 20.0 3.0 I 3.0 8.0 10.0 1 S.0 15.0 10.0
Calcium carbonate21.5 - - - - - - -
Sulfate 5.0 - - - - - -
TSPP 5.0 - 5.0 - S.0 5.0 2.5 5.0
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STPP 5.0 15.0 - - - 5.0 8.0 10.0
Bentonite clay- l0.0 - - 5.0 - - -
DTPMP - 0.7 0.6 - 0.6 0.7 0.7 0.7
MA/AA 0.4 1.0 - - 0.2 0.4 0.5 0.4
SRP1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
Protease 0.2 0.4 0.4 0.3 0.3 1.5 0.3 0.3
Lipase - 0.1 - - 0.2 - - -
Amylase - - _ _ _ - 0.1 -
Cellulase - 0.15 - - 0.15 - - -
PEO - 0.2 - 0.2 0.3 - - 0.3
Perfume 1.6 - - - - - - -
