Note: Descriptions are shown in the official language in which they were submitted.
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Detereent Compositions Comprising an Amylolytic Enzyme and a Cationic
Surfactant
Technical Field
The present invention relates to detergent compositions or components thereof
containing
cationic surfactant and an amylolytic enzyme for use in laundry and dish
washing processes to
provide enhanced greasy stain removal and cleaning benefits in particular in
body soils.
BacUround 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 frequently employed in detergents are amylolytic
enzymes, which
are known to be used in detergent compositions to aid the removal of soils
such as blood stains.
Generally, the stain removal performance of amylolytic enzymes is directly
related to their
concentration in the detergent composition, so that an increase in the amount
of amylolytic
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
low temperatures or
in the presence of highly stained substrates, the optimum performance of the
amylolytic enzyme
is limited beyond a certain level. Increasing the level of amylolytic enzyme
beyond this amount
does not result in increased stain removal performance benefits.
The Applicants have now found that these problems can be ameliorated by a
detergent
composition comprising a combination of a specific quaternary ammonium
cationic surfactant
and an amylolytic enzyme. Employing both of these components in combination
has been found
to deliver surprisingly better greasy stain removal and cleaning performance
than that of
detergent compositions employing either of the two components individually.
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
solubility and form an association in the presence of anionic components to
produce surprisingly
soluble anionic/cationic complexes which lead to unexpected performance
benefits. The good
solubility of the cationic surfactants essential to the present invention, and
of any anionic-
cationic complexes formed, ensure that greasy oily soils are rapidly broken
down, enabling rapid
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contact of the enzymes with stains and highly effective stain removal,
particularly for residual
sebaceous secretions. 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 greasy, oily soil removal and overall cleaning
performance.
Summary of the invention
The present invention relates to a granular detergent composition having a
bulk density of at least
400 g/l comprising: (a) an amylolytic enzyme; and (b) a cationic surfactant
comprising: a first
compound of formula I :
R 1 R2 R3 R4 N+ X' (I)
in which R1 is a hydroxyalkyl group having from 1 to 6 carbon atoms; each of
R2 and R3 is
independently selected from C1-4 alkyl or alkenyl; R4 is a higher alkyl group
having n carbon
atoms where n is from 8 to 11; and X- is a counterion; and a second compound
of formula I in
which RI is a hydroxyalkyl group having from 1 to 6 carbon atoms; each of R2
and R3 is
independently selected from C1-4 alkyl or alkenyl; R4 is a lower alkyl group
having n-2 carbon
atoms where n is as defined above, the lower alkyl group is 2 carbons less
than the higher alkyl
group; and X" is a counterion.
Detailed descriation of the invention
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
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.
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Preferably RI 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 I groups are -CH2CH2OH, -CH2CH2CH2OH, -
CH2CH(CH3)OH and -CH(CH3)CH2OH.
-CH2CH2OH and -CH2CH2CH2OH are most preferred and -CH2CH2OH is particularly
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. Generally each of
R2 and R3 is
selected from C 1-4 alkyl and R4 is C6-1 I 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. Examples of suitable mixtures include those where at least 10%,
preferably at least
20% by weight of the cationic surfactants of formula I have R4 which is a C5-9
alkyl or alkenyl.
Other suitable examples include surfactant mixtures in which R4 may be a
combination of Cg
and C 10 linear alkyl groups, or Cq and C I 1 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 alkyl chain surfactant of formula I and a longer
alkyl chain
surfactant of formula I. 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 selected from those of formula I
where R4 is an alkyl
group having (n-2) carbon atoms. Generally in such mixtures there will be from
5 to 95%,
preferably from 35 to 70% or even 65% by weight and most preferably at least
40% by weight
of the shorter alkyl chain surfactant, and from 5 to 95%, preferably from 30
to 95% by weight
and mot preferably at least 50% by weight longer chain surfactant.
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.
Amylolytic Enzyme
The granular detergent compositions or component thereof in accordance with
the present
invention also comprises an amylolytic enzyme.
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The weight ratio of amylolytic enzyme to cationic surfactant is generally from
1:15000 to 10:1,
more preferably from 1:10000 to 5:1, most preferably from 1:5000 to 1:1, based
on % by weight
active enzyme of the detergent composition.
The amylolytic enzymes will generally be 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.
The detergent compositions of the invention may also contain one or a mixture
of more than one
amylase enzyme (a and/or (3). W094/02597, Novo Nordisk A/S published February
03, 1994,
describes cleaning compositions which incorporate mutant amylases. See also
W095/10603,
Novo Nordisk A/S, published April 20, 1995. Other amylases known for use in
cleaning
compositions include both a- and 13-amylases. a-Amylases are known in the art
and include
those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR
2,676,456; EP
285,123; EP 525,610; EP 368,341; and British Patent specification no.
1,296,839 (Novo). Other
suitable amylases are stability-enhanced amylases described in W094/18314,
published August
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).
Examples of commercial a-amylases products are Purafect Ox Am from Genencor
and
Termamyl8, Ban Fungamyl and Duramyl , all available from Novo Nordisk A/S
Denmark. W095/26397 describes other suitable amylases : a-amylases
characterised by having
a specific activity at least 25% higher than the specific activity of Termamyl
at a temperature
range of 25 C to 55 C and at a pH value in the range of 8 to 10, measured by
the Phadebas a-
amylase activity assay. 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.
The amylase enzyme or mixture of amylase enzymes may be added to the detergent
composition
as a separate ingredient (eg. in the form of a prill, granulette, stabilized
liquid, etc.) or as a
mixture with two or more amylase enzymes or amylase and an additional enzyme,
for example
as part of a co-granulate.
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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
is to be used.
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 enzymes,
suds suppressors, lime soap dispersants, additional soil suspension and anti-
redeposition agents
soil releasing agents, perfumes and corrosion inhibitors.
Additional surfactant
The detergent compositions or components thereof in accordance with the
invention preferably
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, 1975.
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. 4,259,217
issued to Murphy on March 31, 1981.
Where present, ampholytic, amphoteric and zwitteronic surfactants are
generally used in
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.
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.
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Other suitable anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl
taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates, monoesters of
sulfosuccinate (especially saturated and unsaturated C 12-C 18 monoesters)
diesters of
sulfosuccinate (especially saturated and unsaturated C6-C14 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.
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 C5-C 17
acyl-N-(C 1-C4 alkyl)
and -N-(C 1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of
alkylpolysaccharides such as
the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being
described herein).
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the C9-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 I I-C 18,
most preferably
C 11-C 15 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
Application No. WO 93/18124.
Anionic sulfonate surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of C5-
C20 linear
alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary
alkane sulfonates,
C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol
sulfonates, fatty acyl
glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures
thereof.
Particularly prefenred compositions of the present invention additionally
comprise an anionic
surfactant, selected from alkyl sulfate and/or alkylbenzene sulphonate
surfactants of formulae II
and III, respectively:
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R5 O S O 3-M+ (II)
R6303-1y'+ (III)
wherein R5 is a linear or branched alkyl or alkenyl moiety having from 9 to 22
carbon atoms,
preferably C 12 to C 18 alkyl or as found in secondary alkyl sulfates; R6 is C
10-C 16
alkylbenzene, preferably C 11-C 13 alkylbenzene; M+ and M'+ can vary
independently and are
selected from alkali metals, alkaline earths, alkanolammonium and ammonium.
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
15:1 to 1:2, most
preferably from 12:1 to 2:1.
Amounts of the one or mixtures of more than one anionic surfactant in the
preferred
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% 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 1%, preferably at
least 2%, or even at
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 15% 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
surfactants such as those having a carbon chain length of C 12 or greater,
particularly of C 14/ 15
or even up to C 16-18 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
anionic to cationic surfactant of from 50:1 to 2:1, most preferably 30:1 to
8:1. 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
intimately mixed with one or more anionic surfactants prior to addition of the
other detergent
composition components.
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Anionic carboxylate surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxylates, the alkyl
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)x
CH2C00'
M+ wherein R is a C6 to C 18 alkyl group, x ranges from 0 to 10, and the
ethoxylate distribution
is such that, on a weight basis, the amount of material where x is 0 is less
than 20 % and M is a
cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those
having the formula
RO-(CHR1-CHR2-O)-R3 wherein R is a C6 to C18 alkyl group, x is from 1 to 25,
R1 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,
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-l-
undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-l-
octanoic acid and
2-pentyl-l-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 (R1) CH2
COOM, wherein R is a C5-C 17 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.
Alkoxylated 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.
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Preferred alkoxylated surfactants can be selected from the classes of the
nonionic condensates of
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 alkoxylated alcohol surfactant
The condensation products of aliphatic alcohols with from I 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
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 fattv acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural formula
R2CONRIZ wherein : R1 is H, CI-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl, ethoxy,
propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably CI or
C2 alkyl, most
preferably C 1 alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl,
preferably straight-chain C5-
C 19 alkyl or alkenyl, more preferably straight-chain C9-C 17 alkyl or
alkenyl, most preferably
straight-chain C 11-C 17 alkyl or alkenyl, or mixture thereof; and Z is a
polyhydroxyhydrocarbyl
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
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, CI-C4 alkyl, CI-C4
hydroxyalkyl, and -
(C2H4O)xH, where x is in the range of from I to 3.
Nonionic alkylpolysaccharide surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent
4,565,647, 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.
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Preferred alkylpolyglycosides have the formula
R2O(CnH2nO)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from 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.
Amphoteric surfactant
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(R5)2 wherein
R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl
group, or
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 R5 is an alkyl or hydroxyalkyl group containing from t to 3,
or a polyethylene
oxide group containing from 1 to 3 ethylene oxide groups. Preferred are C I O-
C 18 alkyl
dimethylamine oxide, and C10-18 acylamido alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured
by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant
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 18 hydrocarbyl group, each R I is typically C I-C3 alkyl, and R2 is a C I-
C5 hydrocarbyl
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group. Preferred betaines are C 12-18 dimethyl-ammonio hexanoate and the C 10-
18
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 11. Preferably the composition should contain less than 1%, preferably
less than 0.1 % by
weight or even less than 0.05% and most preferably less than 0.0 1% by weight
of compounds of
formula I having a linear (or even branched) alkyl group having 12 or more
carbon atoms.
Another suitable group of cationic surfactants which can be used in the
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.
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
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
example, -0-0- (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.
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
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include carbonate, bicarbonate, hydroxide, the various silicate anions,
percarbonate, perborates,
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.
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:NA2O ratio of from
1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0 ratio
being most preferred. The
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
NaMSixO2x+1.yH2O
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
formula above preferably has a value of 2, 3 or 4 and is preferably 2. The
most preferred
TM
material is 8-Na2Si2O5, available from Hoechst AG as NaSKS-6.
Water-soluble builder compound
The detergent compositions in accordance with the present invention preferably
contain a water-
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
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.
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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
include the water-soluble salts of succinic acid, malonic acid,
(ethylenedioxy) diacetic acid,
maleic 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,
lactoxysuccinates described in British Patent No. 1,389,732, and
aminosuccinates described in
Canadian Patent No. 973,771, and the oxypolycarboxylate materials such as 2-
oxa-1,1;3-
propane tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in British
Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane
tetracarboxylates and
1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo
substituents include the
sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and
1,398,422 and in U.S.
Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in
British Patent No.
1,439,000. 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 mix!-ares
thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are
also contemplated as
useful builder components.
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
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
CA 02268772 1999-04-14
WO 98/17767 PCT/US97/17815
14
The detergent compositions or components thereof, of the present invention may
contain a
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[(AIO2)z(SiO2)y). xH2O
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 hy.drated form and are preferably crystalline, containing from 10% to 28%,
more preferably
from 18% to 22% water in bound form.
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
Na 12 [(A102) 12 (Si02)121= xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86
[(AI02)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.
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
1.15 and, more particularly, not greater than 1.07.
CA 02268772 1999-04-14
WO 98/17767 PCT/US97/17815
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,
most preferably from 2.5 to 5.0 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 seauestrant
The detergent compositions or components thereof in accordance with the
present invention
preferably contain as an optional component a heavy metal ion sequestrant. By
heavy metal ion
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
from 0.1% to 10%, more preferably from 0.25% to 7.5% and most preferably from
0.5% to 5%
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
ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline
earth metal,
ammonium, or substituted ammonium salts thereof, or mixtures thereof.
CA 02268772 1999-04-14
WO 98/17767 PCTIUS97/17815
16
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
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-516,102
are also suitable herein. The (3-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-476,257 describes suitable amino based sequestrants. EP-A-510,331
describes suitable
sequestrants derived from collagen, keratin or casein. EP-A-528,859 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
acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are
also suitable.
Organic peroxyacid bleachin¾ 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
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 altemative 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
organic peroxyacid are also envisaged.
Inoreanic 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%
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
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
CA 02268772 2003-08-05
17
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
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 forrnula NaBO2H2O2 or the tetrahydrate NaBO2H2O2.3H20.
Alkali metal percarbonates, particularly sodium percarbonate are preferred
perhydrates herein.
Sodium percarbonate is an addition compound having a formula corresponding to
2Na2CO3.3H2O2, and is available commercially as a crystalline solid.
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
perhydrolysis reaction to produce a peroxvacid. Generally peroxyacid bleach
precursors may be
represented as
O
11
X-C-L
where L is a leaving group and X is essentially any functionality, such that
on perhydrolysis the
structure of the peroxyacid produced is
O
II
'X-C-OOH
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 0-acyl
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
CA 02268772 2003-08-05
18
of useful materials within these classes are disclosed in GB-A-1586789.
Suitable esters are
disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
Leaving grouDs
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.
Preferred L groups are selected from the group consisting of:
Y R3 R5Y
-O -O Y and
-O
C 1~
~i
O
Il ~ , ~
-N-C- RI , - + N , --i--C-iH-R4 ,
RS R3 Y
Y
R3 Y
I I
-O-C H=C-C H=C H2 --O-C H=C-C H=C H2
. 0
Y 0 11 O
CH2-C r~ 4
11
-O-C-R' -N\C jNR4 -NCNR
~ p O
R3 O Y
1 II 1
-O-C=CHR4 , and --N-S-CH-R4
R3 O
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, R5 is an
alkenyl chain containing from I to 8 carbon atoms and Y is H or a solubilizing
group. Any of
R1, R3 and R4 may be substituted by essentially any functional group
including, for example
CA 02268772 2003-08-05
19
alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl
ammonium
groups.
The 3 preferred solubilizing groups are+SO3 M+, CO2 M+, -SO4 M+, -N+(R3)4X and
O<--
N(R )3 and most preferably -SO3 M and -CO2 M wherein R is an alkyl chain
containing
from 1 to 4 carbon atoms, M is a catiori 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.
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.
Preferred alkyl percarboxylic precursor compounds of the imide type include
the N-,N,NIN1
tetra acetylated alkylene diamines wherein the alkylene group contains from I
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.
Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-
methyl
hexanoyloxybenzene sulfonate (iso-NC)BS), sodium nonanoyloxybenzene sulfonate
(NOBS),
sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide substituted alkyl neroxyacid precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable herein,
including those of
the following general formulae:
R' -C-N-R2-C-L R' -N-C-R2-C-L
~~ ~ 1 . I I 11 11
O R5 O or R5 O O
wherein RI is an alkyl group with from I to 14 carbon atoms, R2 is an alkylene
group
containing from I to 14 carbon atoms, and R5 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-0 1703 86.
CA 02268772 2003-08-05
Perbenzoic acid precursor
Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
Suitable 0-
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.
Cationic aeroxyacid 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.
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
.7ompound or
an amide substituted alkyl peroxyacid precursor as described hereinafter
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406;
4,751,015; 4,988,451;
4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP
475,512, 458,396
and 284,292; and in JP 87-318,332.
Examples of preferred cationic peroxyacid precursors are described in
WO 95/29160 and US Patent Nos. 5,686,015; 5,460,747; 5,578,136 and 5,584,888.
Suitable cationic peroxyacid precursors include any of the ammonium or alkyl
ammonium
substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams,
and
CA 02268772 2003-08-05
21
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 or ag nic peroxyacid precursors
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:
O
I I
O
O ~ .
N C-Rt
wherein RI is H, alkyl, alkaryl, aryl, or arylalkyl.
Preformed organic perox vacid
The organic peroxyacid bleaching system may contain, in addition to, or as an
altetnative 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.
A preferred class of organic peroxyacid compounds are the amide substituted
compounds of the
following general formulae:
R1-C-N-R2-C-OOH R' - N - C - R2 - C - OOH
I 1 f 11 ~ 11 ~~
O R5 0 or R5 O 0
wherein RI is an alkyl, aryl or alkaryl group with from I to 14 carbon atoms,
R2 is an alkylene,
arylene, and alkarylene group containing from I to 14 carbon atoms, and R5 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-0 1703 86.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetradecanedioic acid and
diperoxyhexadecanedioc acid.
CA 02268772 1999-04-14
WO 98/17767 PCT/US97/17815
22
Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-
phthaloylaminoperoxicaproic
acid are also suitable herein.
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
cations, and a sequestrant having defined stability constants for the
catalytic and auxiliary metal
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.
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-
(CIO4)2,
MnIIIMnIV4(u-O)I(u-OAc)2-(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(CI04)3,
and mixtures
thereof. Others are described in European patent application publication no.
549,272. Other
ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-
triazacyclododecane, 2-methyl-
1,4,7-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. 4,246,612 and U.S. Pat
5,227,084. See
also U.S. Pat. 5,194,416 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. 5,114,606, 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-
dentate and bi-N-dentate ligands, including N4MnIII(u-O)2MnIVN4)+ and
[BiPY2MnII1(u-
O)2Mn1Vb1PY2)-(C1O4)3.
Further suitable bleach catalysts are described, for example, in European
patent application No.
408,131 (cobalt complex catalysts), European patent applications, publication
nos. 384,503, and
306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate
ligand catalyst),
U.S. 4,711,748 and European patent application, publication no. 224,952,
(absorbed manganese
CA 02268772 2003-08-05
23
on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with
manganese and zinc
or magnesium salt), U.S. 4,626,373 (inanganese/ligand catalyst), U.S.
4,119,557 (ferric complex
catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst)
Canadian 866,191
(transition metal-containing salts), U.S. 4,430,243 (chelants with manganese
cations and non-
catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts).
Additional Enzymes
The compositions of the present invention may comprise one or more additional
enzymes.
Preferred additional enzymatic materials include the commercially available
enzymes. Said
enzymes include enzymes selected from cellulases, hemicellulases, peroxidases,
proteases,
gluco-amylases, lipases, xylanases, phospholipases, esterases, cutinases,
pectinases, keratanases,
reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases,
tannases,
pentosanases, malanases, R-glucanases, arabinosidases, hyaluronidase,
chondroitinase, laccase or
mixtures thereof.
A preferred combination of additional enzymes in a cleaning composition has a
mixture of
conventional applicable enzymes such as protease, lipase, cutinase and/or
cellulase in
conjunction with one or more plant cell wall degrading enzymes. Suitable
enzymes are
exemplified in US Patents 3,519,570 and 3,533,139.
Suitable proteases are the subtilisins which are obtained from particular
strains of B. subtilis and
B. lichenlormis (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 ,
IVIAXACALO, PROPERASE and MAXAPEMO (protein engineered Maxacal) from Gist-
Brocades. Proteolytic enzymes also encompass modified bacterial serine
proteases, such as
those described in European Patent Application 251,446 published January 7,
1988
(particularly pages 17, 24 and 98), and which is called herein "Protease B",
and in European
Patent Application 199,404, Venegas, published October 29, 1986, which refers
to a modified
bacterial serine protealytic enzyme which is called "Protease A" herein.
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
CA 02268772 2003-08-05
24
described in WO 91/06637, Published May 16, 1991.
Genetically modified variants, particuiariy of Protease C, are also included
herein.
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
amino acid residue positions equivalent to those selected from the group
consisting of +99,
+101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166,
+195, +197,
+204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to
the
numbering of Bacillus amyloliquefaciens subtilisin, as described in W095/10591
and in the
patent of C. Ghosh, et al, "Bleaching Compositions Comprising Protease
Enzymes" having US
Patent No. 5,677,272 issued October 14, 1997.
Also suitable for the present invention are proteases described in patent
applications EP 251 446-
and WO 91/06637, protease BLAP described in W091/02792 and their variants
described in
WO 95/23221.
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 92/03529 A to Novo. When desired, a
protease having
decreased adsorption and increased hydrolysis is available as described in WO
95/07791 to
Procter & Gamble. A recombinant trypsin-like protease for detergents suitable
herein is
described in WO 94/25583 to Novo. Other suitable proteases are described in EP
516 200 by
Unilever.
One or a mixture of proteolytic enzymes may be incorporated in the detergent
compositions of
the present invention, generally at a level of from 0.0001 % to 2%, preferably
from 0.001 % to
0.2%, more preferably from 0.005% to 0.1% pure enzyme by weight of the
composition.
The detergent composition of the invention may also contain lipolytic enzymes.
Suitable
lipolytic enzymes for use include those produced by micro-organisms of the
Pseudomonas
group, such as Pseudomonas stuizeri ATCC 19.154, 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
CA 02268772 2003-08-05
mark Lipase P "Amano," hereinafter referred to as "Amano-P." Other suitable
commercial
lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter
viscosum
var. lipolyticum NRRLB 3673, 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 M 1 Lipase and Lipomax (Gist-Brocades) and Lipulase and Lipolase Ultra
{Novo)
which have found to be very effective when used in combination with the
compositions of the
present invention. Also suitable are the lipolytic 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.
Also suitable are cutinases [EC 3.1.1.50) which can be considered as a special
kind of lipase,
namely lipases which do not require interfacial activation. Addition of
cutinases to detergent
compositions have been described in e.g. WO-A-88/09367 (Genencor); 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
341,947) 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
enzyme D96L the standard LU assay may be used (Analytical method, internal
Novo Nordisk
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.
In the detergent compositions of the present invention, the lipolytic enzyme
component is
generally present at levels of from 0.00005% to 2% of active enzyme by weight
of the detergent
composition, preferably 0.001 % to 1% by weight, most preferably from 0.0002%
to 0.05% by
weight active enzyme in the detergent composition.
CA 02268772 2003-08-05
26
The detergent compositions of the invention may additionally incorporate one
or more cellulase
enzymes. Suitable cellulases 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
Humicola
insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes
cellulases isolated
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
are cellulases originated from Humicola insolens having a molecular weight of
about 50KDay an
isoelectric point of 5.5 and containing 415 amino acids; and a`43kD
endoglucanase derived
from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred
endoglucanase
component has the amino acid sequence disclosed in PCT Patent Application No.
WO 91/17243.
Also suitable cellulases are the EGIII cellulases from Trichoderma
longibrachiatum described in
W094/2 1 80 1, Genencor, published September 29, 1994. Especially suitable
cellulases are the
cellulases having color care benefits. Examples of such cellulases are
cellulases described in
United States Patent No. 5,520,838 (Novo). CarezymeTM and
TM
Celluzyme (Novo Nordisk A/S) are especially useful. See also WO91/17244 and
W09 1 /2 1 80 1.
Other suitable cellulases for fabric care and/or cleaning properties are
described in
W096/34092, W096/17994 and W095/24471.
Peroxidase enzymes may also be incorporated into the detergent compositions of
the invention.
Peroxidasis are used in combination with oxygen sources, e.g. percarbonate,
perborate,
persulfate, hydrogen peroxide, etc. They are used for "solution bleaching",
i.e. to prevent
transfer of dyes or pigments removed from substrates during wash operations to
other substrates
in the wash solution. Peroxidase enzymes are known in the art, and include,
for example,
horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-
peroxidase.
Peroxidase-containing detergent compositions are disclosed, for example, in
PCT International
Application WO 89/099813, WO 89/09813 and in Canadian Patent application No.
2,122,987,
filed on October 28, 1992 and EP 927,242 published July 7, 1999. Also suitable
is the laccase
enzyme.
Preferred enhancers are substituted phenthiazine and phenoxasine 10-
Phenothiazinepropionicacid (PPT), l0-ethylphenothiazine-4-carboxylic acid
(EPC), 10-
CA 02268772 2004-09-16
27
phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO
94/12621) and
substituted syringates (C3-C5 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
composition at levels from 0.0001 % to 2% of active enzyme 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
additional enzymes can be added as separate single ingredients (prills,
granulates, stabilized
liquids, etc. containing one enzyme ) or as mixtures of two or more enzymes (
e.g. cogranulates ).
Enzyme Oxidation Scavengers
Other suitable detergent ingredients that can be added are enzyme oxidation
scavengers which
are described in European Published Patent application 553,607.
Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene
polyamines.
Enzyme Materials
A range of enzyme materials and means for their incorporation into synthetic
detergent
compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor
International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to
McCarty et al.
Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978,
and in U.S.
4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid
detergent formulations,
and their incorporation into such formulations, are disclosed in U.S.
4,261,868, Hora et al, April
14, 1981. Enzymes for use in detergents can be stabilised by various
techniques. Enzyme
stabilisation techniques are disclosed and exemplified in U.S. 3,600,319,
August 17, 1971,
Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme
stabilisation
systems are also described, for example, in U.S. 3,519,570. A useful Bacillus,
sp. AC13 giving
proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.
Organic polymeric compound
Organic polymeric compounds are preferred additional components of the
detergent
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 sucti
CA 02268772 1999-04-14
WO 98/17767 PCTIUS97/17815
28
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
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 15%,
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 maleic 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
polyaspartic acid and such as those disclosed in EP-A-305282, EP-A-305283 and
EP-A-351629.
Terpolymers containing monomer units selected from maleic acid, acrylic acid,
aspartic acid and
vinyl alcohol or acetate, particularly those having an average molecular
weight of from 1,000 to
30,000, preferably 3,000 to 10,000, are also suitable for incorporation into
the compositions of
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
hydroxyethylcellulose.
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.
Cationic soil removal/anti-redeposition compounds
CA 02268772 2003-08-05
29
The detergent composition or components thereof of the invention may comprise
water-soluble
cationic ethoxylated amine compounds with particulate soil/clay-soil removal
and/or anti-
redeposition properties. These cationic compounds are described in more detail
in EP-B-
111965, 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 fonnula:
IH3 1C H3
X OCH2CH2)n 1~ +- CH2 -- CH2 -(- CH2)a b N+- CH2CH2O ~ X
1
(CH2CH2O +n_ X (CH2CH2O -)n-- X
wherein X is a nonionic group selected from the group consisting of H, C1-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
0.01 to 30% by weight, preferably 0.05 to 10% by weight.
Suds suppressin¾ 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.
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.
CA 02268772 1999-04-14
WO 98/17767 PCTIUS97/17815
By antifoam compound it is meant herein any compound or mixtures of compounds
which act
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
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.
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 18-C40
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
(i) polydimethyl siloxane, at a level of from 50% to 99%,
preferably 75% to 95% by weight of the silicone antifoam compound; and
... , .. , .. i .
CA 02268772 2003-08-05
31
(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight
of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of
from 5% to 50%,
preferably 10% to 40% by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol rake
copolymer
with a polyoxyalkylene 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
TM
weight; a particularly preferred silicone glycol rake copolymer of this type
is DC0544,
commercially available from DOW Coming under the trademark DC0544;
(c) an inert carrier fluid compound, most preferably comprising a C 16-C 18
ethoxylated
alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at
a level of
from 5% to 80%, preferably 10% to 70%, by weight;
A highly preferred particulate suds suppressing system is described in EP-A-
0210731 and
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
atoms, or a mixture thereof, with a melting point of from 45 C to 80 C.
Polymeric dye transfer inhibitin pY 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,
polyvinylpyrrolidone
polymers or combinations thereof, whereby these polymers can be cross-linked
polymers.
a) Polyamine N-oxide polymers
Polyamine N-oxide polymers suitable for use herein contain units having the
following structure
formula :
CA 02268772 2003-08-05
32
P
= (
(~) Ax
I
R
wherein P is a polymerisable unit, and
~1 RIO ~1
A is-C-N-, -N-C-, CO, C, -0-, -S-, -N-; xis 0 or 1;
R 1 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
~
I 0
(Rj) x -N-(R2)y; ~
(R3)z or --- N-(Rl)x
wherein RI, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic groups or
combinations thereof, x or/and y or/and z is 0 or I and wherein the nitrogen
of the N-O group
can be attached or wherein the nitrogen of the N-O group forms part of these
groups. The N-O
group can be part of the polymerisable unit (P) or can be attached to the
polymeric backbone or
a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the
polymerisable unit
comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic,
alicyclic or
heterocyclic groups. One class of said polyamine N-oxides comprises the group
of polyamine N-
oxides wherein the nitrogen of the N-O group forms part of the R-group.
Preferred polyamine
N-oxides are those wherein R is a heterocyclic group such as pyridine, N-
substituted pyrrole,
imidazole, N-substituted pyrrolidine, piperidine, quinoline, acridine and
derivatives thereof.
CA 02268772 2003-08-05
33
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O
group is attached
to the polymerisable unit. A preferred class of these polyamine N-oxides
comprises the
polyamine N-oxides having the general formula (1) 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-vinYlpyrrolidone and N-vinvlimidazole
Suitable herein are copolymers ofN-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 I
to 0.2.
c) Polyvinylpyrrolidone
The detergent compositions herein may also utilize polyvinylpyrrolidone
("PVP") having an
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 moleciilar weight of 160,000), 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
SokalaTMn HP 165 and Sokalan HP 12.
d) Polyvinvloxazolidone
The detergent compositions herein may also utilize poiyvinyloxazolidones as
polymeric dye
transfer inhibiting agents. Said polyvinyloxazolidones have an average
molecular weight of
from 2,500 to 400,000.
e) Polyvinylimidazole
. . , , i CA 02268772 2003-08-05
34
The detergent compositions herein may also utilize polyvinylimidazole as
polymeric dye
transfer inhibiting agent. Said polyviriylimidazoles preferably have an
average molecular weight
of from 2,500 to 400,000.
Optical brightener
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:
R, R2
)7N H H N 41"
N
O>--N O C=C N--CN
N ~
R2~N H S03M S03M H Rt
wherein R1 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, R1 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
cor-,mercially marketed under the trademark Tinopal-UNPA-GX by Ciba-Geigy
Corporation.
Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the
detergent
compositions herein.
When in the above fotmula, R1 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-
methylamino)-s-triazine-2-yi)amino]2,2'-stilbenedisulfonic acid disodium salt.
This particular
brightener species is commercially marketed under the trademark Tinopal 5BM-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)amino]2,2'-
stilbenedisulfonic
CA 02268772 2003-08-05
acid, sodium salt. This particular brightener species is commercially marketed
under the
trademark Tinopal AMS-GX by Ciba Geigy Corporation.
Polymeric Soil Release Agent
Known polymeric soil release agents, hereinafter "SRA", can optionally be
employed in the
present detergent compositions. If utilized, SRA's will generally comprise
from 0.01% to
10.0%, typically from 0.1 % to 5%, preferably from 0.2% to 3.0% by weight, of
the
compositions.
Preferred SRA's typically have hydrophilic segments to hydrophilize the
surface of hydrophobic
fibers such as polyester and nylon, and hydrophobic segments to deposit upon
hydrophobic
fibers and remain adhered thereto through completion of washing and rinsing
cycles, thereby
serving as an 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.
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 oligomeric or polymeric ester backbone of terephthaloyl and oxyalkyleneoxy
repeat units and
allyl-derived sulfonated tenninal moieties covalently attached to the
backbone, for example as
described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P.
Gosselink. Such ester
oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) 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
Gosselink et al., for example those produced by
transesterification/oligomerization of poly-
(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
CA 02268772 2003-08-05
= 36
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
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 terephthalate,
see U.S. 3,959,230
to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic
derivatives such
TM
as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1-
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 1.6 to about 2.3 and a solution viscosity of
from about 80 to
about 120 centipoise measured at 20 C as a 2% aqueous solution. Such materials
are available
as METOLOSE SM100 and METOLOSE SM200, which are the trade names of methyl
cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
Additional classes of SRA's include: (1) 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
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
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: (111) anionic terephthalate-
based SRA's of the
urethane-linked variety, see U.S. 4,201,824, Violland et al.;
Other optional ineredients
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.
Near neutral wash pH deterQent formulation
While the detergent compositions of the present invention are operative within
a wide range of
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
CA 02268772 2003-08-05
37
concentration of from about 0.1 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
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
95205 published November 30, 1983, J.H.M. Wertz and P.C.E. Goffinet.
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, 1981 .
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
non-aqueous and may be in the fonn of a gel. The compositions are particularly
the so-called
concentrated granular detergent compositions adapted to be added to a washing
machine by
means of a dispensing device placed in the machine drum with the soiled fabric
load.
Such granular detergent compositions or components thereof in accordance with
the present
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.
The compositions in accord with the present invention can also be used in or
in combination
with bleach additive compositions, for example comprising chlorine bleach.
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
15% of the
particles are greater than 18mm 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.
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38
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
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 last 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
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.
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
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
doubled to provide a bulk density in g/litre. Replicate measurements are made
as required.
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
solid has a minimum hardness of 176N to 275N, preferably from 195N to 245N,
measured by a
C100 hardness test as supplied by I. Holland instruments. This process may be
used to prepare
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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.
Laundry washing 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 l Og to 300g of product
dissolved or
dispersed in a wash solution of volume from 5 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.
The detergent composition may be dispensed 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
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
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
result of its contact with the wash water.
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
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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
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
1989, 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
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 latter Application discloses a device
comprising a
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 orifice into the washing
medium. The
support ring is provided with a masking arrangement to prevent egress of
wetted, undissolved,
product, this arrangement typically comprising radially 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
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, 0011501, 0011502, and 0011968. A convenient
form of
water frangible closure comprises a water soluble adhesive disposed along and
sealing one edge
of a pouch formed of a water impermeable polymeric film such as polyethylene
or
polypropylene.
Machine dishwashing method
. . , . . . , i .
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41
Any suitable methods for machine dishwashing or cleaning soiled tableware,
particularly soiled
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
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.
Packaging 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 WO
95/02681.
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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 I x- C I y alkyl sulfate
C46SAS . Sodium C 14 - C 16 secondary (2,3) alkyl sulfate
CxyEzS . Sodium C I x-C 1 y alkyl sulfate condensed with z
moles of ethylene oxide
CxyEz . C I x-C 1 y predominantly linear primary alcohol
condensed with an average of z moles of ethylene
oxide
QAS I . R2.N+(CH3)2(C2H4OH) with R2 = C9 - C I I linear
alkyl
QAS 2 . R2.N+(CH3)2(C2H4OH) with approximately
50% R2 = C8 linear alkyl; approximately
50%R2=C10
QAS 3 . R2.N+(CH3)2(C2H4OH) with approximately
40% R2 = C I I linear alkyl; approximately
60% R2 = C9 linear alkyl
QAS 4 . R2.N+(CH3)2(C2H4OH) with R2 = C6 linear alkyl
QAS 5 . R2.N+(CH3)2(C2H4OH) with R2 = C 10 linear alkyl
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 18 alkyl N-methyl glucamide
TPKFA . C 12-C 14 topped whole cut fatty acids
STPP . Anhydrous sodium tripolyphosphate
TSPP . Tetrasodium pyrophosphate
Zeolite A . Hydrated Sodium Aluminosilicate of formula
Na12(A102SiO2)I2.27H20 having a primary
particle size in the range from 0.1 to 10
micrometers
Zeolite MAP . Hydrated sodium aluminosilicate zeolite MAP
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43
having a silicon to aluminium ratio of 1.07
NaSKS-6 . Crystalline layered silicate of formula 8-
Na2Si2O5
Citric acid . Anhydrous citric acid
Borate . Sodium borate
Carbonate . Anydrous sodium carbonate with a particle size
between 200 m and 900 m
Bicarbonate . Anhydrous sodium bicarbonate with a particle
size distribution between 400 m and 1200pm
Silicate . Amorphous Sodium Silicate (Si02:Na20 = 2.0:1)
Sodium sulfate : Anhydrous sodium sulfate
Citrate . Tri-sodium citrate dihydrate of activity 86.4%
with a particle size distribution between 425pm
and 850 m
MA/AA . Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 70,000
AA . Sodium polyacrylate polymer of average
molecular weight 4,500
CMC Sodium carboxymethyl cellulose
Cellulose ether : Methyl cellulose ether with a degree of
polymerization of 650 available from Shin Etsu
Chemicals
Protease . Proteolytic enzyme of activity 4KNPU/g sold by
NOVO Industries A/S under the trademark
Savinase
Alcalase . Proteolytic enzyme of activity 3AU/g sold by
NOVO Industries A/S
Cellulase . Cellulytic enzyme of activity 1000 CEVU/g sold
by NOVO Industries A/S under the trademark
Carezyme
Amylase . Amylolytic enzyme of activity 120KNU/g sold by
NOVO Industries A/S under the trademark
Termamyl 120T
Lipase . Lipolytic enzyme of activity 100KLU/g sold
by NOVO Industries A/S under the trademark
Lipolase
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44
TM
Endolase . Endoglucanase enzyme of activity 3000 CEVU/g.
sold by NOVO Industries A/S
PB4 . Sodium perborate tetrahydrate of nominal formula
NaBO2.3H20.H202
PBI . Anhydrous sodium perborate bleach of nominal
formula NaBO2.H202
Percarbonate Sodium percarbonate of nominal formula
2Na2CO3.3H2O2
NOBS . Nonanoyloxybenzene sulfonate in the form of the
sodium salt
TAED Tetraacetylethylenediamine
Mn catalyst . MnlV2(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
DTPMP . Diethylene triamine penta (methylene
phosphonate), marketed by Monsanto under the
Trademark Dequest 2060
Photoactivated bleach : Sulfonated Zinc Phthlocyanine encapsulated in bleach
dextrin soluble polymer
Brightener 1 Disodium 4,4'-bis(2-sulphostyry)biphenyl
Brightener 2 . Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-
triazin-2-yl)amino) stilbene-2:2'-disulfonate
HEDP . 1,1-hydroxvethane diphosphonic acid
EDDS . Ethylenediamine-N, N-disuccinic acid
QEA . bis((C2H5O)(C2H4On)(CH3) -N+-C6H12-N+ -
(CH3) bis((C2H5O)-(C2H4O)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
TEPAE . Tetraethylenepentaamine ethoxylate
PVP . Polyvinylpyrrolidone polymer
PVNO Polyvinylpyridine N-oxide
PVPVI Copolymer of polyvinylpyrrolidone and
vinylimidazole
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SRP I . Anionically end capped esters with oxyethylene
oxy and terephtaloyl backbone
SRP 2 . Diethoxylated poly (1, 2 propylene terephthalate)
short block polymer
Silicone antifoam . Polydimethylsiloxane foam controller with
siloxane-oxyalkylene copolymer as dispersing
agent with a ratio of said foam controller to said
dispersing agent of 10:1 to 100:1
Wax . Paraffin wax
In the following examples all levels are quoted as % by weight of the
composition:
Examole 1
The following high density granular laundry detergent compositions A to F of
particular utility
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 - - -
QAS 3 - - - 1.4 1.0 -
Zeolite A 18.1 18.1 16.1 18.1 18.1 18.1
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 acid 11.0 6.0 6.0 - - 12.5
79:21)
Sodium Sulfate 26.1 26.1 25.0 17.1 24.1 9.1
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 1.5 1.5. 1.0 1.5 - 1.5
Mn Catalyst - 0.03 0.07 - - -
DTPMP 0.1 0.3 - - 0.2 0.3
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 - 0.5
Protease 0.85 0.85 0.26 0.85 0.85 0.85
Amylase 0.1 0.1 0.4 0.3 0.1 0.1
Lipase 0.05 0.6 0.7 0.1 0.07 0.1
Photoactivated 15 ppm 15 ppm 15 ppm 15 ppm 15 ppm 15 ppm
bleach (ppm)
Brightener 1 0.09 0.09 - 0.09 0.09 0.09
Perfume 0.3 0.3 0.3 0.3 0.3 0.3
Silicone antifoam 0.5 0.5 0.5 0.5 0.5 0.5
Misc/minors to 100%
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Density in g/litre 850 850 850 850 850 850
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 5.61 4.76
TAS 1.3 1.86 1.57
C45AS - 2.24 3.89
C25E3S - 0.76 1.18
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 acid - 13.0 10.6
(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 - 12.7
TAED 0.5 3.1 -
Mn Catalyst 0.04 - -
DTPMP 0.25 0.2 0.2
HEDP - 0.3 0.3
QEA 0.9 - -
Protease 0.85 2.8 0.85
Lipase 0.15 0.25 0.15
Cellulase 0.28 0.28 0.28
Amylase 0.4 0.1 0.1
PVP 0.9 1.3 0.8
Photoactivated bleach 15 ppm 27 ppm 27 ppm
(ppm)
Brightener 1 0.08 0.19 0.19
Brightener 2 - 0.04 0.04
Perfume 0.3 0.3 0.3
Silicone antifoam 0.5 2.4 2.4
Minors/misc to 1.3 1.1 0.3
100%
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Example 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
QAS2 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 antifoam 1.0 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 antifoam 0.3 0.3 0.3 -
Dry additives
Sulfate 3.0 3.0 5.0 10.0
Carbonate 6.0 13.0 15.0 11.0
PB l - - - 1.5
PB4 18.0 18.0 10.0 18.5
TAED 3.0 2.0 - 2.0
EDDS - 2.0 2.4 -
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Protease 3.25 1.0 3.25 3.25
Lipase 0.4 0.5 0.4 0.2
Amylase 0.2 0.2 0.2 0.4
Photoactivated bleach - - - 0.15
Minors/misc to 100%
ExamRie 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 0 to S are particularly suitable for use under US machine wash
conditions.
N 0 P Q R S
Blown powder
LAS 22.0 5.0 4.0 9.0 8.0 7.0
C45AS 7.0 7.0 6.0 - - -
C46AS - 4.0 3.0 - - -
C45E35 - 3.0 2.0 8.0 5.0 4.0
QAS 1 0.5 - - - - -
QAS 2 - 0.5 - 2.0 - 3.5
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 Sulfate 6.0 3.3 2.3 24.0 13.3 19.3
Silicate 5.0 1.0 1.0 2.0 1.0 1.0
Carbonate 28.3 9.0 3.0 25.7 8.0 6.0
QEA 0.4 0.4 - - 0.5 1.1
PEG 4000 0.5 - 1.5 1.0 1.5 1.0
Sodium oleate 2.0 - - - - -
DTPA 0.4 - 0.5 - - 0.5
Brightener 0.2 0.3 0.3 0.3 0.3 0.3
Spray on
C25E5 1.0 - - - - -
C45E7 - 2.0 2.0 0.5 2.0 2.0
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Perfume 1.0 0.3 0.3 1.0 0.3 0.3
Agglomerates
C45AS - 5.0 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 etc) - 2.0 2.0 - 2.0 2.0
Dry additives
TAED 1.0 2.0 3.0 1.0 3.0 2.0
PB4 - 1.0 4.0 - 5.0 0.5
PBI 6.0 - - - - -
Percarbonate - 5.0 12.5 - - -
Carbonate - 5.3 0.8 - 2.5 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 - - 0.2
Cellulase - 0.2 0.2 - 0.2 0.2
Amylase 1.6 0.3 0.3 0.1 0.05 0.2
Protease - 1.6 1.6 - 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 are of particular utility under US machine wash
conditions. Y is of
particular utility under Japanese machine wash conditions
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T U V
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 14.0 12.0 22.0
C45AS 8.0 7.0 7.0
QAS 1 0.7 - -
QAS 2 - 2.2 -
QAS 5 - - 1.5
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 - 1.0 5.0
C45E7 1.0 1.0 1.0
Dry additives
HEDP 1.0 - -
PVPVI/PVNO 0.5 0.5 0.5
Protease 3.25 3.25 3.25
Lipase 0.4 0.1 0.2
Amylase 0.1 0.1 0.1
Cellulase 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.)
ExamBle 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 -
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QA S 4 - 0.6
Silicate 3.0 8.0
MA/AA 4.0 2.0
CMC 0.6 0.6
Brightener 1 0.2 0.2
DTPMP 0.4 0.4
Spray on
C45E7 5.0 5.0
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 bleach 15 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 and Misc.) 10.6 5.12
Density (g/litre) 700 700
Example 7
The foilowing 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
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CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
Agglomerates
LAS 5.0 5.0 5.0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
QEA - 1.0 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 12.5 5.5
Percarbonate - 7.0 10.0
TAED 6.0 2.0 5.0
PB 1 14.0 7.0 8.0
EDDS - 2.0 -
PolyethyleneoxideofMW 5,000,000 - - 0.2
Bentonite clay - - 10.0
Protease 1.0 3.25 3.25
Lipase 0.4 0.1 -
Amylase 0.6 0.6 1.0
Cellulase 0.6 0.6 -
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
Balance (Moisture and Misc.) to
100%
Density (g/litre) 850 850 850
Example 8
The following detergent formulations are examples of the present invention:
BB CC DD EE
LAS 20.0 14.0 24.0 22.0
QAS 1 0.7 1.0 0 0
QAS 2 - - 0.08 -
QAS 4 - - - 1.0
TFAA - 1.0 - -
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C25E5/C45E7 - 2.0 - 0.5
C45E3S - 2.5 - -
STPP 30.0 18.0 30.0 22.0
Silicate 9.0 5.0 10.0 8.0
Carbonate 13.0 7.5 - 5.0
Bicarbonate - 7.5 - -
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 3.25 1.6 1.6
Amylase 0.8 0.4 0.25 0.5
Lipase 0.2 0.06 - 0.1
Cellulase 0.15 0.05 - -
Photoactivated 70ppm 45ppm - 10ppm
bleach (ppm)
Brightener 1 0.2 0.2 0.08 0.2
PBI 6.0 2.0 - -
HEDP - - 2.3 -
TAED 2.0 1.0 - -
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 laurate 2.5 9.0 - - - - - -
QAS 1 - - - 0.08 - - 2.0 -
QAS2 1.5 - 0.8 - - - - -
QAS 3 - 5 - - - - - 0.1
QAS 4 - - - - 1.5 0.04 - -
QAS 5 - - - - - 0.04 - -
Zeolite A 2.0 1.25 - - - 1.25 1.25 1.25
Carbonate 20.0 3.0 13.0 8.0 10.0 15.0 15.0 10.0
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56
Calcium carbonate 21.5 - - - - - - -
Sulfate 5.0 - - - - - - -
TSPP 5.0 - 5.0 - 5.0 5.0 2.5 5.0
STPP 5.0 15.0 - - - 5.0 8.0 10.0
Bentonite clay - 10.0 - - 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 - 0.39 - - 0.26 - - -
Lipase - 0.1 - - 0.2 - 0.1 -
Amylase 0.07 0.12 0.15 0.1 0.15 0.5 0.1 0.1
Cellulase - 0.15 - - - - - -
PEO - 0.2 - 0.2 0.3 - - 0.3
Perfume 1.6 - - - - - - -
