Note: Descriptions are shown in the official language in which they were submitted.
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Bleaching Compositions
Technical field
The present invention relates to bleach-containing compositions, suitable for
use in
laundry washing methods.
Background to the Invention
In the past decades research efforts have been directed towards the
development of
bleaching systems, based on organic peroxyacids, which can provide effective
stain
and/or soil removal from fabrics at lower wash temperatures. The organic
peroxyacids are often obtained by the in situ perhydrolysis of organic
peroxyacid
bleach precursor compounds (bleach activators).
A commonly employed precursor compound is tetraacetyl ethylene diamine (TAED)
which provides effective hydrophilic cleaning especially on beverage stains.
To achieve efl:'~ctive bleaching of a detergent, both hydrophobic and
hydrophilic
stains need to lbe bleached by the bleach system. Further organic peroxyacid
precursors have thus been developed to deal with hydrophobic stains and soils.
Various documents disclose the use of mixtures of hydrophobic and hydrophilic
bleaches in detergents, for example JP 7-238298 DE 196,16, 782, W094/28103.
However, the inventors have found that most prior art bleaching compositions
do not
always perform satisfactory when used under stressed conditions, such as low
temperature washing, washing with limited agitation, use of low quantities of
detergent actives, highly soiled fabrics, presence of high levels of metal
ions, or after
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storage under :humid or high temperature. These problems occur in particular
in low
density detergents, in particular when the overall level of the bleach system
in the
detergent composition is low, and also in detergents which contain high levels
of
phosphate-builder, which may introduce metal ions to the wash.
Furthermore, to achieve an efficient bleach system, the system should provide
excellent bleaching at iow levels, thereby minimizing the chance of damage to
the
fabrics.
Thus, there is a need to provide detergent compositions which comprise low
levels of
a bleaching system, which has a very ei~ective bleaching performance under
stressed
conditions, on both hydrophobic soils and hydrophilic soils.
The inventors have now surprisingly found that improved bleaching under
stressed
conditions can be achieved by use of a bleaching-composition containing a low
level
of bleach activators anti peroxide source, namely having an available oxygen
(Av0)
derived from hydrophobic and hydrophilic bleach activators of less than 5000
ppm,
and having a specific ratio of Av0 of the hydrophobic activator to the Av0 of
the
hydrophilic activator, namely from 3:1 to I :50, and a specific ratio of the
total Av0
to the Av0 of the activators, namely more than 2:1. The bleach system has been
found to be particularly useful in low density detergents, in hand washing
detergents,
in phosphate-containing compositions, and also in washing processes where a
low
concentration of detergent is used.
In general, bleach and in particular hypochlorite bleach is known to kill
bacteria.
High levels of bleach are normally required to provide a suf~rcient reduction
of the
bacteria's or to eliminate the bacteria's. Therefore, most detergents which
comprise
bleach systems known in the art, which only comprise low levels of bleach, are
not
effective as biocide agents for sanitization.
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The inventors have found that mixed bleach systems, comprising specific levels
and
ratios of hydrophobic" hydrophilic bleach additives and peroxide sources are
very
useful as biocide agents.
They have found that even the use of low levels of specific bleach
compositions in
wash solutions or in detergents or cleaning agents, provides effective
sanitization of
the washed fabrics or surfaces, or effective reduction of the bacterias when
the
bleaching components are used in the specific ratios, mentioned herein.
All documents cited in the present description are, in relevant part,
incorporated
herein by referE;nce.
Summary of the Invention
The present invention relates to a detergent composition, having a density
from
330g/litre to 71)Og/litre, comprising a bleaching system containing a
hydrophilic and a
hydrophobic peracid bleach or peracid bleach presursor and a peroxide source,
characterized in that the total level of Available Oxygen from the hydrophilic
and
hydrophobic peracid bleach or bleach precursors (Av0-a) is less than 5000 ppm,
the
ratio of Available Oxygen of the hydrophobic peracid or precursor (Av0-hb) to
the
Available Oxygen of the hydrophilic peracid or precursor (Av0-hp) is from 3:1
to
1:50 and the ratio of the Available Oxygen of the peroxide source (Av0-o) to
the
Av0-a is at least 2: I .
Detailed Description of the Invention
In the detergent compositions of the invention, the total level of Available
Oxygen
from the hydrophilic and hydrophobic peracid bleach or bleach precursors (Av0-
a) is
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less than 5000 ppm, or even less than 4000ppm or even less than 3000ppm or
even
less than 2500ppm.
The ratio of Available Oxygen of the hydrophobic peracid or precursor (Av0-hb)
to
the Available C)xygen of the hydrophilic peracid or precursor (Av0-hp) is from
3:1
to 1:50, more preferably from 2.5:1 to 1:30, or even 2:1 to1:20.
The ratio of the Available Oxygen of the peroxide source (Av0-o) to the Av0-a
is at
least 2:1, preferably at least 3:1 or even 4:1.
The compositions preferably have a density from 370g/litre to 700g/litre, or
even to
650g/litre or even to 600g/litre.
It may be prefi:rred that the composition is a low density granular
composition, in
particular phosphate-containing compositions and in particular high sudsing
compositions, soaking or pre-treatment compositions, hand washing
compositions.
Thus, the invention also relates to a method of washing laundry by hand or pre
treating or soaking of laundry, whereby a detergent composition according to
the
invention.
The invention also relates to the use of bleaching compositions, comprising
hydrophobic a.nd hydrophilic peracid bleach or precursors thereto, and a
peroxide
source for reduction ofthe activity of bacteria, whereby the ratio of Av0-hb
to Av0-
hp is from 3 :1 to 1:50, preferably 2.5:1 to 1:10 as even 2:1 to 1:20 and
whereby the
ratio of Av0-~o to Av0-a is at least 2:1, preferably at least 3:1 or even 4:1.
When used herein, "reduction of the activity of bacteria" includes killing of
the
bacteria or part thereof and inhibition of further growth or development of
bacteria.
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Preferably the bleaching compositions are used for sanitisation of the fabrics
or
surfaces, cleaning with t:he bleaching compositions. Then, it is preferred
that the
sanitization method involves contacting the fabrics or surfaces containing
bacteria's,
in particularly present in stain on the fabrics or surfaces, with the
compositions. Thus,
the invention aliso encornpasses a method for sanitisation of fabrics whereby
the
fabrics are contacted with a composition or a solution of a composition,
comprising
a hydrophilic and hydrophobic peracid bleach or precursors thereto and a
peroxide
source, characl:erized in that the ratio of Available Oxygen of the
hydrophobic
peracid or precursor (Av0-hb) to the Available Oxygen of the hydrophilic
peracid or
precursor (Av0-hp) is from 3 :1 to 1:50 and the ratio of the Available Oxygen
of the
peroxide source (AvO-0) to the total level of Available Oxygen from the
hydrophilic
and hydrophobic peracid bleach (Av0-a) is at least 2:1.
The bleaching compositions are preferably present in cleaning compositions for
cleaning fabrics or surfaces, preferably laundry or dishwashing detergents or
hard-
surface cleaners. Preferred are laundry detergent compositions for comprising
the
ingredients described herein.
Preferably the level of .AvO-a in the cleaning compositions or detergent
composition,
or solutions thereof, which contain the bleaching composition and which are
for use
of reducing the activity of bacteria, is up to 10,000 ppm, more preferably, up
to
S,OOOppm or even 4,000ppm or even 3,OOOpppm or 2,SOOppm.
Preferred hydrophilic and hydrophobic peracid bleaches or precursors thereto
and
preferred peroxide sources are described hereinafter.
Hydrophobic an_ d hvdroahilic aeracids or peracid precursors
An essential feature of detergent compositions of the invention is a
hydrophobic
peracid or precursor thereto.
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The bleaching system preferably comprising a hydrophobic percarboxylic acid
and/ or
precursor thereto, of the formula
R1 - C03M
wherein Rl has at least 6 carbon atoms, and M is a counterion; or of formula
Rl -CO-L
wherein L is a leaving group which is linked to the Rl - CO- group with an
oxygen
atom, and Rl has at least 6 carbon atoms. Preferred leaving groups are benzoic
acid
and derivative;. thereof and especially benzene sulphonate.
Percarboxylic .acid bleach precursor are compounds which react with hydrogen
peroxide in a Frerhydrolysis reaction to produce a percarboxylic acid.
The counterion M of the percarboxylic acid is preferably sodium, potassium or
hydrogen.
Preferably such hydrophobic peracids or precursors thereto are those whose
parent
carboxylic acid has a critical micelle concentration less than 0.5 moles/litre
and
wherein said critical micelle concentration is measured in aqueous solution at
20°-
50°C.
The percarbo~rylic acid, preferably formed from the precursor, preferably
contains at
least 7 carbon atoms, or at least 8 or even 9 carbon atoms, and it may be
preferred
that it contains from 7 to 12 carbon atoms, more preferably from 8 to 11
carbon
atoms, most preferably 9 or 10 carbon atoms. In a preferred aspect the
percarboxylic
acid formed from the precursor or the peroxy acid has an alkyl chain
comprising at
least 7 carbon atoms, more preferably at least 8 carbon atoms, most preferably
9
carbon atoms..
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The percarboxylic acid precursor can be any ester which had been described as
a
bleach activator for use in laundry detergents, for instance alkyl
percarboxylic acid
precursors described herein, sugar esters, such as pentaacetylglucose, esters
of imidic
acids such as ethyl benzimidate triacylcyanurates, such as triacetylcyanurate
and
tribenzoylcyanurate an esters giving relatively surface active oxidising
products for
instance of C&,s-alkanoic or-aralkanoic acids such as described in GB-A-
864798,
GB-A-1147871 and the esters described in EP-A-98129 and EP-A-106634.
Preferred can be phenyl esters of Cmz2- alkanoic or alkenoic acids, esters of
hydroxylamine, geminal diesters of lower alkanoic acids and gem-idols, such as
those
described in El'-A-012781 especiallyl,l,5-triacetoxypent-4-ene and 1,1,5,5-
tetraacetoxypentane and the corresponding butene and butane compounds,
ethylidene
benzoate acetate and bis(ethylidene acetate) adipate and enol esters, for
instance as
described inEP~-A-0140648 and EP-A-0092932.
Other highly preferred hydrophobic alkyl percarboxylic acid precursors include
decanoly oxy benzoic acid or salt thereof, dodecanoyloxy-benzenesulphonate
sodium
or potassium salt, decanoyloxy - benzenesulphonate sodium or potassium salt
(ROBS) , ben::oyloxy - benzenesulphonate sodium or potassium salt salt (BOBS),
more preferred sodium or potassium 3,5,5-tri-methyl hexanoyloxybenzene
sulfonate
(iso-NOBS) and even more preferred sodium or potassium nonanoyloxybenzene
sulfonate (HOBS).
Amide substiti.~ted bleach activator compounds may also be useful herein, such
as
those described in EP-A-0170386. Suitable examples of this class of agents
include
the precursors. or the acids such as (6-hexylamino)-6-oxo-caproic acid(6-
octylamino}-6-oxo-caproic acid, (6-nonylamino)-6-oxo-caproic acid, (6-
decylamino)-
6-oxo-caproic acid, magnesium monoperoxyphthalate hexahydrate, the salt of
meta-
chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and
diperoxydodecanedioic; acid, or precursors thereof, in particlarly having a
benzene
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sulphonate lea~ring group. Such bleaching agents are disclosed in U. S.
4,483,781,
U.S. 4,634,551, EP 0,133,354, U.S. 4,412,934 and EP 0,170,386.
Other suitable organic peroxyacids include diperoxyalkanedioc acids having
more
than 7 carbon atoms, such as diperoxydodecanedioc acid (DPDA),
diperoxytetradecanediac acid and diperoxyhexadecanedioc acid. Mono- and
diperazelaic acrid, mono- and diperbrassylic acid and N-
phthaloylaminoperoxicaproic acid (PAP), nonanoylamido peroxo-adipic acid
(NAPAA) anda hexane sulphenoyl peroxypropionic acid and are also suitable
herein.
The compositions also comprise hydrophilic peracids or precursors thereto,
preferably of t!he formula
Rl - C03M
wherein R1 ha.s at less than 6 carbon atoms, and M is a counterion; or of
formula
R1 -CO-L
wherein L is a leaving group which is linked to the R1 - CO- group with an
oxygen
atom, and Rl has less then 6 carbon atoms.
A preferred hydrophilic precursor is TAED.
Peroxide source
Inorganic perihydrate salts are a preferred source of peroxide. Preferably
these salts
are present at a level o~f from 0.01% to 30% by weight, more preferably of
from 0.5%
to 10%.
Examples of iinorganic perhydrate salts include perborate, percarbonate,
perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts
are
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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 salt in
the granular
product. 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 formula NaB02H202 or the tetrahydrate
NaB02H202.3H20.
Alkali metal percarbonates, particularly sodium percarbonate are preferred
perhydrates hE;rein. Sodium percarbonate is an addition compound having a
formula
corresponding; to 2Na2;C03.3H202, and is available commercially as a
crystalline
solid.
Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in
the
detergent compositions herein.
Additional Detergent Components
The detergent compositions in accord with the invention may also contain
additional
detergent connponents. The precise nature of these additional components, and
levels
of incorporatiion thereof will depend on the physical form of the composition
or
component, and the precise nature of the washing operation for which it is to
be
used.
The compositions of the invention preferably contain one or more additional
detergent components selected from additional surfactants, additional
bleaches,
bleach catalysts, alkalinity systems, builders, phosphate-containing builders,
organic
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polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil
suspension and anti-redeposition agents soil releasing agents, perfumes,
brightners,
photobleachin~; agents and additional corrosion inhibitors.
Bleach Catalyst
The bleach system can contain a transition metal containing bleach catalyst.
One suitable type of bleach catalyst is a catalyst system comprising a
transition metal
ration of defined bleach catalytic activity, such as copper, iron or manganese
rations,
an auxiliary metal canon having little or no bleach catalytic activity, such
as zinc or
aluminum rations, and a sequestrant having defined stability constants for the
catalytic and auxiliary metal rations, particularly
ethylenediatninetetraacetic acid,
ethylenediatninetetra(methylenephosphonic acid) and water-soluble salts
thereof.
Such catalysts are disclosed in U.S. Pat. 4,430,243.
Other types oi-,"bleach catalysts include the manganese-based complexes
disclosed in
U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples ofthese
catalysts
include MnIV2(u-O)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-tria~zacyclononane)4-(C104)2, MnIIIMnIV4(u-O)1(u-OAc)2-(1,4,7-
trimethyl-1,4,7-triazacyclononane)2-(CI04)3, and mixtures thereof. Others are
described in l:;uropean 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. S~~e 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).
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Still another type of bleach catalyst, as disclosed in U. S. Pat. 5,114,606,
is a water-
soluble complex of rnar~ganese (III), and/or (IV) with a ligand which is a non-
carboxylate pa~lyhydroxy compound having at least three consecutive C-OH
groups.
Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol,
arabitol,
adonitol, mesa.-erythritol, meso-inositol, lactose, and mixtures thereof.
U. S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of
transition
metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said
ligands
are of the formula:
R2 R3
R~ -N=C-B-C=N-R4
wherein Rl, R 2, R3, and R4 can each be selected from H, substituted alkyl and
aryl
groups such that each :ftl-N=C-R2 and R3-C=N-R4 form a five or six-membered
ring. Said ring can further be substituted. B is a bridging group selected
from O, S.
CRSR6, NR~ and C=O, wherein R5, R6, and R~ can each be H, alkyl, or aryl
groups,
including subsetituted or unsubstituted groups. Preferred ligands include
pyridine,
pyridazine, pyrimidine" pyrazine, imidazole, pyrazole, and triazole rings.
Optionally,
said rings may be substituted with substituents such as alkyl, aryl, alkoxy,
halide, and
vitro. Particularly preferred is the ligand 2,2'-bispyridylamine. Preferred
bleach
catalysts include Co, C;u, Mn, Fe,-bispyridylmethane and -bispyridylamine
complexes.
Highly preferred catalysts include Co(2,2'-bispyridylamine)C12,
Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II)
perchlorate, (:0(2,2-bispyridylamine)202C104, Bis-(2,2'-bispyridylamine)
copper(II)
perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures
thereof. Highly
preferred may be manganese bridged cyclams, such as Mn dichloro cyclam or Mn
1,4,8,11 tetra. azacyclotetradecane.
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Other example:~ include binuclear Mn complexed with tetra-N-dentate and bi-N-
dentate ligands, including N4MnIlI(u_O)2~,IVN4)+and [Bipy2MnIII(u-
O)2MnIVbipY21-(C104;13.
Other bleach catalysts are described, for example, in European patent
application,
publication no. 408,131 (cobalt complex catalysts), European patent
applications,
publication no~~. 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 on aluminosilicate
catalyst), U.S. 4,601,84.5 (aluminosilicate support with manganese and zinc or
magnesium salt), U.S. 4,626,373 (manganese/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). Highly preferred may be pentaamine cobalt (III) acetate
dichloride salt.
The bleach catalyst is typically used in a catalytically effective amount in
the
compositions and processes herein. By "catalytically effective amount" is
meant an
amount which is sufl~cient, under whatever comparative test conditions are
employed, to <;nhance bleaching and removal of the stain or stains of interest
from the
target substrate. The test conditions will vary, depending on the type of
washing
appliance used and the habits of the user. Some users elect to use very hot
water;
others use wamn or even cold water in laundering operations. Of course, the
catalytic
performance of the bleach catalyst will be affected by such considerations,
and the
levels of bleach catalyst used in fully-formulated detergent and bleach
compositions
can be appropriately adjusted. As a practical matter, and not by way of
limitation,
the compositions and processes herein can be adjusted to provide on the order
of at
least one part per ten million of the active bleach catalyst species in the
aqueous
washing liquor, and will preferably provide from about 0.2 ppm to about 200
ppm,
preferably 0.4 ppm to 100 ppm of the catalyst species in the wash liquor. To
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illustrate this point further, on the order of 3 micromolar manganese catalyst
is
effective at 40°C, pH 1.0 under European conditions using perborate and
a bleach
precursor. An increase in concentration of 3-5 fold may be required under U.S.
conditions to .achieve the same results.
urfa
The detergent compositions in accord with the invention preferably contain one
or
more surfactants selected from anionic, nonionic, cationic, ampholytic,
amphoteric
and zwitterioruc 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 Detergent.." (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, amphoter~ic and zwitteronic surfactants are
generally used
in combination with one or more anionic and/or nonionic surfactants.
Anionic Surfa.ct n
The detergent; compositions in accord with the present invention preferably
comprise
an additional .anionic surfactant. Essentially any anionic surfactants useful
for
detersive puposes can be comprised in the detergent composition. 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 and
sulfonate
surfactants are preferred.
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Highly prefen-ed are surfactants systems comprising a sulfonate and a sulfate
surfactant, preferably a linear or branched alkyl benzene sulfonate and alkyl
ethoxylsulfate~s, as described herein, preferably combined with a cationic
surfactants
as described herein.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-aryl
taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates,
monoesters o:f sulfosuccinate (especially saturated and unsaturated C12 C18
monoesters) diesters of sulfosuccinate (especially saturated and unsaturated
C6 C14
diesters), N-aryl 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 sulfal:e surfactants suitable for use herein include the linear and
branched
primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl
glycerol
sulfates, alkyl phenol ethylene oxide ether sulfates, the CS-C 1 ~ acy!-N-(C 1-
C4 alkyl)
and -N-(C1-C;2 hydroxyalkyl) glucanune sulfates, and sulfates of
alkylpolysaccharides
such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds
being
described herein).
Alkyl sulfate surfactants are preferably selected from the linear and branched
primary
C l p-C 1 g alkyl sulfates, more preferably the C 11-C 15 branched chain alkyl
sulfates
and the C 12'x =14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of
the C l 0-C 1 g alkyl sulfates which have been ethoxylated with from 0. 5 to
20 moles of
ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate
surfactant is a
C 11-C 1 g, most preferably 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.
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A particularly preferred aspect of the invention employs mixtures of the
preferred
alkyl sulfate and/ or sulfonate 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 CS-
C20
linear alkylber~zene sulfonates, alkyl ester sulfonates, C6-C22 primary or
secondary
alkane sulfona~tes, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids,
alkyl
glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol
sulfonates, and
any mixtures thereof.
Anionic CarboxXlate Surfact n
Suitable anionoc carboxylate surfactants include the alkyl ethoxy
carboxylates, the
alkyl poIyetho~xy polycarboxylate surfactants and the soaps ('alkyl
carboxyls'),
especially certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20~
CH2C00-M+ wherein R is a C6 to C 1 g alkyl group; x ranges from O 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 C 1 g 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.
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Suitable soap surfactants include the secondary soap surfactants which contain
a
carboxyl unit connected to a secondary carbon. Preferred secondary soap
surfactants
for use herein are water-soluble members selected from the group consisting of
the
water-soluble; salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-
propyl-
1-nonanoic arid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.
Certain soaps may also be included as suds suppressors.
Alkali Metal ~arcosinate Surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON
(R1) CH2 COOM, wherein R is a CS-C1~ linear or branched alkyl or alkenyl
group,
R1 is a C1-C,4 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.
Alkox~rlated Nonionic Surfactant
Essentially any alkoxylated nonionic surfactants are suitable herein. The
ethoxylated
and propoxylated nonionic surfactants are preferred.
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 Alb;oxXlated Alcohol Surfactant
The condensation products of aliphatic alcohols with from 1 to 25 moles of
alkylene
oxide, particularly ethylene oxide and/or propylene oxide, are suitable for
use herein.
The alkyl chain of the aliphatic alcohol can either be straight or branched,
primary or
secondary, and generally contains from 6 to 22 carbon atoms. Particularly
preferred
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17
are the condensation products of alcohols having an alkyl group containing
from 8 to
20 carbon atorns with from 2 to 10 moles of ethylene oxide per mole of
alcohol.
Nonionic Polvih~rdrox~r :Fatty Acid Amide Surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural
formula R2CONR1Z wherein : R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-
hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl,
more
preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is
a CS-C31
hydrocarbyl, preferably straight-chain CS-C 1 g 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 Fattv Acid Arnide Surfactant
Suitable fatty accid amide surfactants include those having the formula:
R6CON(R7)2
wherein R6 is arr 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, C1-C4
alkyl,
C1-C4 hydroxyalkyl, and -(C2H40)xH, where x is in the range of from 1 to 3.
Nonionic Alkv~olysaccharide 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 alkylp~olyglycosides have the formula:
R20(CnH2n0)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 deryved from glucose.
Amhhoteric Surfa n
Suitable amphol:eric surfactants for use herein include the amine oxide
surfactants and
the alkyl amphocarboxyiic acids.
Suitable amine oxides include those compounds having the formula
R3(OR4)xN0(R.5)2 wherein R3 is selected from an alkyl, hydroxyalkyl,
acylamidopropo~yl 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, o~r mixtures thereof; x is from 0 to 5, preferably from 0 to 3;
and each
RS is an alkyl on hydroxyalkyl group containing from 1 to 3, or a polyethylene
oxide
group containing from 1 to 3 ethylene oxide groups. Preferred are C 1 p-C 1 g
alkyl
dimethylamine oxide, and CIO-18 acylamido alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) CZM Conc.
manufactured b:y Miranol, Inc., Dayton, NJ.
Zwitterionic Surfactant
Zwitterionic surfactants can also be incorporated into the detergent
compositions in
accord with the invention. These surfactants can be broadly described as
deryvatives
of secondary and tertiary amines, derivatives of heterocyclic secondary and
tertiary
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19
amines, or derivatives of quaternary ammonium, quaternary phosphonium or
tertiary
sulfonium compounds. Betaine and sultaune 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-C18 hydrocarbyl group, each R1 is typically C1-C3 alkyl, and
R2
is a C1-CS hydrocarbyl group. Preferred betaines are C12-18 dimethyl-ammonio
hexanoate anti the CIO-lg acylamidopropane (or ethane) dimethyl (or diethyl)
betaines. Complex betaine surfactants are also suitable for use herein.
Cationic Surfactants
Suitable cationic surfactants to be used in the detergent herein include the
quaternary
ammonium surfactant:.. Preferably the quaternary ammonium surfactant is a mono
C6-C16, preferably C~~-Clp N-alkyl or alkenyl ammonium surfactants wherein the
remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl
groups. Preferred are also the mono-alkoxylated and his-alkoxylated amine
surfactants.
Another suitable group of cationic surfactants which can be used in the
detergent compositions or components thereof herein are cationic ester
surfactants.
The cationicester surfactant is a, preferably water dispersible, compound
having
surfactant properties comprising at least one ester (i.e. -COO-) linkage and
at least
one cationically charged group.
Suitable cationic ester surfactants, including choline ester surfactants, have
for
example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
In one preferred aspect 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
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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 a.ny nitrogen or oxygen atom in said chain connects only with
carbon
atoms in the chain. Thus spacer groups having, for example, -O-O- (i.e.
peroxide), -
N-N-, and -N-O- linkages are excluded, whilst spacer groups having, for
example -
CH2-O- CH2- and -CI-I2-NH-CH2- linkages are included. In a preferred aspect
the
spacer group chain comprises only carbon atoms, most preferably the chain is a
hydrocaxbyl chain.
Cationic mono-alko~lated amine surfactants
I~ghly preferred herein are cationic mono-alkoxylated amine surfactant
preferably of
the general formula I:
ApRa
~N+~.. X-
2 R3
R (I)
wherein Rl is an alkyl or alkenyl moiety containing from about 6 to about 18
carbon
atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to
about
14 carbon atoms; R2 and R3 are each independently alkyl groups containing from
one to about three carbon atoms, preferably methyl, most preferably both R2
and R3
are methyl groups; R'1 is selected from hydrogen (preferred), methyl and
ethyl; X- is
an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to
provide
electrical neutrality; A is a alkoxy group, especially a ethoxy, propoxy or
butoxy
group; and p~ is from'0 to about 30, preferably 2 to about 15, most preferably
2 to
about 8.
Preferably the ApR4 is a hydroxyalkyl group, having no greater than 6 carbon
atoms
whereby the -OH group is separated from the quaternary ammonium nitrogen atom
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21
by no more than 3 carbon atoms. Particularly preferred ApR4 groups are -CH2-
CH20H, -C:H2CH2CH20H, -~H2CH(CH3)OH and -CH(CH3)CH20H, with
-CH2CH2C>H being particularly preferred. Preferred R1 groups are linear alkyl
groups. Linear Rl groups having from 8 to 14 carbon atoms are preferred.
Another highly prefen-ed cationic mono-alkoxylated amine surfactants for use
herein
are of the formula
R1 /(CH2CH20)2-SH
N+/ X(O
CH3/ 'CH3
wherein Rl is C 1 p-C 1 g hydrocarbyl and mixtures thereof, especially C 1 p-C
14 alkyl,
preferably C 10 and C il2 alkyl, and X is any convenient anion to provide
charge
balance, prefi~rably chloride or bromide.
As noted, compounds of the foregoing type include those wherein the ethoxy
(CH2CH20) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH20] and
[CH2CH(CH:30] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or
Pr
and/or i-Pr unts.
The levels of the cationic mono-alkoxylated amine surfactants used in
detergent
compositions of the invention is preferably from 0.1% to 20%, more preferably
from
0.2% to 7%, most preferably from 0.3% to 3.0% by weight of the composition.
Cationic bis-alkoxXlated amine surfactant
The cationic bis-alkoxylated amine surfactant preferably has the general
formula II:
R~ /APR3
R2~ ~A,qRa
(II)
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22
wherein R1 is an alkyl or alkenyl moiety containing from about 8 to about 18
carbon
atoms, prefer~~bly 10 to about 16 carbon atoms, most preferably from about 10
to
about 14 carbon atoms; R2 is an alkyl group containing from one to three
carbon
atoms, preferably methyl; R3 and R4 can vary independently and are selected
from
hydrogen (pre:ferred), methyl and ethyl, X- is an anion such as chloride,
bromide,
methylsulfate, sulfate, or the like, su~cient to provide electrical
neutrality. A and A'
can vary independently and are each selected from C1-C4 alkoxy, especially
ethoxy,
(i.e., -CH2CH:20-), propoxy, butoxy and mixtures thereof; p is from 1 to about
30,
preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4,
and
most preferably both p and q are 1.
Highly preferred cationic bis-alkoxylated amine surfactants for use herein are
of the
formula
+/CHZCH20H
N X
l~H3~ ~'CH2CH20H
wherein R 1 is C 10-C 18 hydrocarbyl and mixtures thereof, preferably C 10, C
12, C 14
alkyl and mixtures thereof. X is any convenient anion to provide charge
balance,
preferably chloride. With reference to the general cationic bis-alkoxylated
amine
structure noted above, since in a preferred compound R1 is derived from
(coconut)
C 12-C 14 alkyl fraction fatty acids, R2 is methyl and ApR3 and A'qR4 are each
monoethoxy.
Other cationic: bis-alkoxylated amine surfactants useful herein include
compounds of
the formula:
/(CH2CH20~H
N+ X -
R2~ ~{CH2CH20)qH
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23
wherein R1 is C 10-C 1 g hydrocarbyl, preferably C 1 p-C 14 alkyl,
independently p is 1
to about 3 and q is 1 to about 3, R2 is C1-C3 alkyl, preferably methyl, and X
is an
anion, especu~lly chloride or bromide.
Other compounds of the foregoing type include those wherein the ethoxy
(CH2CH20) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH20]
and [CH2CH(CH30] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO
and/or
Pr and/or i-Pn units.
Water-Soluble Builder Compound
The detergent compositions in accord 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 60% by weight, most
preferably from 15% t:o 40% by weight of the composition.
The detergent compositions of the invention preferably comprise phosphate-
containing builder material. Preferably present at a level of from 0.5% to
60%, more
preferably from 5% to 50%, more preferably from 8% to 40.
The phosphate-containing builder material preferably comprises tetrasodium
pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.
Suitable watf;r-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, and
mixtures
of any of the foregoing.
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24
The carboxyLate or polycarboxylate builder can be momomeric or oligomeric in
type
although monomeric polycarboxylates are generally preferred for reasons of
cost and
performance.
Suitable carb~oxylates 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,
(ethyienedioxy) diacetic acid, malefic acid, diglycolic acid, tartaric acid,
tartronic acid
and fumaric acid, as well as the ether carboxylates and the sulfinyl
carboxylates.
Polycarboxyl;ates or their acids containing three carboxy groups include, in
particular,
water-soluble. citrates, aconitrates and citraconates as well as succinate
derivatives
such as the crrrboxymethyloxysuccinates described in British Patent No.
1,379,241,
lactoxysuccinates described in British Patent No. 1,389,732, and
aminosuccinates
described in I'~letherlands Application 7205873, and the oxypolycarboxylate
materials
such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No.
1,387,447. Tlhe most preferred polycarboxylic acid containing three carboxy
groups
is citric acid, preferably present at a level of from 0.1% to I S%, more
preferably from
0.5% to 8% by weight of the composition. -
Polycarboxyl,ates 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, I,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
polycarboxyl;ates are hydroxycarboxylates containing up to three carboxy
groups per
molecule, mare particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents or
mixtures thereof with their salts, e.g. citric acid or citrate;/citric acid
mixtures are also
contemplated as useful builder components.
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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 :;alts of phytic acid.
Partiall~r Soluble or Insoluble Builder Compound
The detergent compositions in accord with the present invention may contain a
partially soluble or insoluble builder compound, typically present in
detergent
compositions at a level of from 0.5% to 60% by weight, preferably from 5% to
50%
by weight, most preferably from 8% to 40% weight of the composition.
Examples of llargely water insoluble builders include the sodium
aluminosilicates.
Suitable alumunosilicate zeolites have the unit cell formula
Naz[(A102)z(Si02)y].
xH20 wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to
0.5 and x
is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The
alumunosilicate maternal are in hydrated form and are preferably crystalline,
containing
from 10% to 28%, more preferably from 18% to 22% water in bound form.
The aluminos.ilicate 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
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26
HS and mixtures thereof. Zeolite A has the formula:
Na 12 [A102) 12 ~Sr02)12~~ ~ZO
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
IW02)86~5102)106~. 276 H20.
Another prefE;rred alwninosilicate zeolite is zeolite MAP builder.
The zeolite N(AP 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 a.15 and, more particularly, not greater than 1.07.
In a preferred aspect the zeolite MAP detergent builder has a particle size,
expressed as a ds0 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 ds0 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 ds0 values are disclosed in EP 384070A.
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Heavy metal ion sequestrant
The compositions of the invention preferably contain as an optional component
a
heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein
components vrhich 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 10%,
preferably from 0.1% 1:0 5%, more preferably from 0.25% to 7.5% and most
preferably from 0.3% to 2% by weight of the compositions or component
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates,
such as the annino 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 (methyle,ne phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1
hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphoric
acid.
Other suitable; heavy metal ion sequestrant for use herein include
nitrilotriacetic acid
and polyaminocarbaxylic acids such as ethylenediaminotetracetic acid,
ethylenediami,ne disuccinic acid, ethylenediamine diglutaric acid, 2-
hydroxypropylenedianune disuccinic acid or any salts thereof.
Other suitable: heavy metal ion sequestrants for use herein are iminodiacetic
acid
derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic
acid,
described in EP-A-31'7,542 and EP-A-399,133. The iminodiacetic acid-N-2-
hydroxyprop~,rl sulfonic acid and aspartic acid N-carboxymethyl N-2-
hydroxypropyl-
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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 acrid and inunodisuccinic acid sequestrants described in EP-A-
509,382
are also suital:de.
EP-A-476,25') describes suitable amino based sequestrants. EP-A-S 10,331
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.
Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine-
N,N'-disuccinic acid (E:DDS), 1,1 hydroxyethane diphosphonic acid and 1,1
hydroxyethane dimethylene phosphoric acid or the alkali metal, alkaline earth
metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
Enzyme
Another preferred ingredient useful in the detergent compositions is one or
more
additional enzymes.
Preferred additional enzymatic materials include the commercially available
lipases,
cutinases, amylases, neutral and alkaline proteases, cellulases, endolases,
esterases,
pectinases, lactases and peroxidases conventionally incorporated into
detergent
compositions. Suitable enzymes are discussed in US Patents 3,519,570 and
3,533,139.
Preferred commercially available protease enzymes include those sold under the
tradenames Alicalase, Savinase, Primase, Durazym, and Esperase by Novo
Industries
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A/S (Denmark:), those sold under the tradename Maxatase, Maxacal and Maxapem
by Gist-Brocades, those sold by Genencor International, and those sold under
the
tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be
incorporated into the compositions in accordance with the invention at a level
of from
0.0001% to 4°.~o active enzyme by weight of the composition.
Preferred amyllases include, for example, a-amylases obtained from a special
strain of
B licheniformi;s, described in more detail in GB-1,269,839 (Novo). Preferred
commercially available amylases include for example, those sold under the
tradename
Rapidase by Gist-Brocades, and those sold under the tradename Termamyl,
Duramyl
and BAN by Novo Industries A/S. Highly preferred amylase enzymes maybe those
described in P'CT/ US 9703635, and in W095/26397 and W096/23873.
Amylase enzyme may be incorporated into the composition in accordance with the
invention at a .level of from 0.0001 % to 2% active enzyme by weight of the
composition.
Lipolytic enzyme may be present at levels of active lipolytic enzyme of from
0.0001%
to 2% by weight, preferably 0.001% to 1% by weight, most preferably from
0.001%
to 0.5% by weight ofthe compositions.
The lipase may be fungal or bacterial in origin being obtained, for example,
from a
lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp.
including Pseudomonas pseudoalcali eg nes or Pseudomas fluorescens. Lipase
from
chemically or genetically modified mutants of these strains are also useful
herein. A
preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is
described
in Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola
lanuginosa and expressing the gene in Aspergillus orXza, as host, as described
in
European Patent Application, EP-A-0258 068, which is commercially available
from
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Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This
lipase
is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7,
1989.
Organic Polymeric Compound
Organic polyrr~eric compounds are preferred additional components of the
detergent
compositions and are preferably present as components of any particulate
components where they may act such as to bind the particulate component
together.
By organic pollymeric compound it is meant herein essentially any polymeric
organic
compound commonly used as dispersants, and anti-redeposition and soil
suspension
agents in detergent compositions, including any of the high molecular weight
organic
polymeric compounds described as clay flocculating agents herein, including
quaternised etlzoxylated (poly) amine clay-soil removal/ anti-redeposition
agent in
accord with the invention.
Organic polymeric compound is typically incorporated in the detergent
compositions
of the invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%,
most
preferably frorn 0.5% to 10% by weight of the compositions.
Examples of organic polymeric compounds include the water soluble organic homo-
or co-polymeric polyca.rboxylic acids or their salts in which the
polycarboxylic acid
comprises at l~;ast two carboxyl radicals separated from each other by not
more than
two carbon atoms. Pol'~ymers of the latter type are disclosed in GB-A-
1,596,756.
Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymers
with malefic anhydride, such copolyrrters having a molecular weight of from
2000 to
100,000, especially 40,000 to 80,000.
The polyanuno compounds are useful herein including those derived from
aspartic
acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
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Terpolymers containing monomer units selected from malefic acid, acrylic acid,
polyaspartic acid and vinyl alcohol, particularly those having an average
molecular
weight of from 5,000 to 10,000, are also suitable herein.
Other organic polymeric compounds suitable for incorporation in the detergent
compositions :herein include cellulose derivatives such as methylcellulose,
carboxymethylcellulose, hydroxypropylmethylcellulose and
hydroxyethylcellulose.
Further useful organic polymeric compounds are the polyethylene glycols,
particularly those of molecular weight 1000-10000, more particularly 2000 to
8000
and most prefi~rably about 4000.
Highly preferred polymeric components herein are cotton and non-cotton soil
release
polymer according to IJ.S. Patent 4,968,451, Scheibel et al., and U.S. Patent
5,415,807, Gosselink et al., and in particular according to US application
no.60/OS 1 S 17.
Another orgatuc compound, which is a preferred clay dispersant/ anti-
redeposition
agent, for use herein, can be the ethoxylated cationic monoamines and diamines
of
the formula:
H3 ~ H3
X-(-OCH2C:H2)n- i +-CH2-CH2-(-CH2)a b i +-CH2CH20~X
(CH2CH20 ~X (CH2CH20 ~X
wherein X is a nonionic group selected from the group consisting ofH, C1-C4
alkyl
or hydroxyalkyi 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 1 or 0;
for
cationic monoamines (b=0), n is at least 16, with a typical range of from 20
to 35; for
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32
cationic dialnines (b=1 ), n is at least about I2 with a typical range of from
about 12
to about 42.
Other dispersants/ anti-redeposition agents for use herein are described in EP-
B-
011965 and US 4,659,802 and US 4,664,848.
Suds Suppres:,in tem
The detergent compositions of the invention, when formulated for use in
machine
washing compositions, may comprise a suds suppressing system present at a
level of
from 0.01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to
3% 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.
By antifoam compound it is meant herein any compound or mixtures of compounds
which act suclh 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. ouch silicone antifoam compounds also typically contain a silica
component. 'lChe 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 a.re the siloxanes, particularly the polydimethylsiloxanes
having
trimethylsilyl ~~nd blocking units.
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33
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 2T, 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: antifoarn compounds include, for example, high molecular
weight fatty
esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent
alcohols, aliphatic
C1 g-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to
hexa-
alkylmelamines or di- to tetra alkyIdiamine 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
(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by
weight of the silicone/silica antifoam compound;
where:in said silica/silicone antifoam compound is incorporated at a level of
from S% to 50%, preferably 10% to 40% by weight;
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(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 weight; a particularly preferred silicone glycol
rake copolymer of this type is DC0544, commercially available from DOW
Corning under the tradename 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 comprise 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
corriprises a rnonoester 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 systc;ms 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.
Other highly preferred suds suppressing systems comprise polydimethylsiloxane
or
mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and
polycarboxylic
polymers, such as copolymers of laic and acrylic acid.
Polymeric D;, e~ Transfer Inhibiting Agents
The detergent compositions herein may also comprise from 0.01% to 10 %,
preferably from 0.05°.~o 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,
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polyvinylpyrrolidonepalymers or combinations thereof, whereby these polymers
can
be cross-linked polymers.
Q~tical Brighi:ener
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:
Rt R2
--N H H N
N( C C N
N H H N
R2 S03M S03M Rl
wherein Rl is selected from arulino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl;
R2 is selected from N-~2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino, chloro and amino; and M is a salt-forming cation such as sodium or
potassium.
When in the above formula, Rl is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
cation such as sodium;, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-
s-triazine-2-y:l)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This
particular
brightener species is commercially marketed under the tradename Tinopal-UNPA-
GX
by Ciba-Geigy Corporation. Tinopal-CBS-X and Tinopal-UNPA-GX is the preferred
hydrophilic optical bri,ghtener useful in the detergent compositions herein.
When in the above formula, Rl is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino
and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-{N-2-
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36
hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid
disodium salt. This particular brightener species is commercially marketed
under the
tradename Tinopal ABM-GX by Ciba-Geigy Corporation.
When in the above formula, Rl 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'-
stilbenedisulfi~nic acid, sodium salt. This particular brightener species are
commercially marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX
by Ciba Geigy Corporation. ,
Polxmeric Soil Release Agent
Known polynneric 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 hydroplhobic fibers and remain adhered thereto through completion of
washing
and rinsing cycles, thereby serving as an anchor for the hydrophilic segments.
This
can enable strains occurnng 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 titanum(IV) alkoxide. Such esters may be made using
additional
monomers capable of being incorporated into the ester structure through one,
two,
three, four o:r more positions, without, of course, forming a densely
crosslinked
overall structure.
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Suitable SRA''s include a sulfonated product of a substantially linear ester
oligomer
comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy
repeat units and allyl-derived sulfonated terminal moieties covalently
attached to the
backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J.
Scheibel and E.P. Gosselink. Such ester oligomers can be prepared by: (a)
ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl
terephthalate
("DMT") and 1,2-propylene glycol ("PG") in a two-stage
transesterifica~tion/oligomerization procedure; and (c) reacting the product
of (b) with
sodium metab~isulfite in water. Other SItA's include the nonionic end-capped
1,2-
propylene/pol~yoxyethylene terephthalate polyesters of U.S. 4,711,730,
December 8,
1987 to Gosselink et al., for example those produced by
transesterifica~tion/oligomerization of poly(ethyleneglycol) methyl ether,
DMT, PG
and poly(ethyleneglycol) ("PEG"). Other examples of SItA'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 o~f U.S. 4,702,857, October 27; 1987 to Gosselink, for example
produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination
of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-S-sulfoisophthalate; and
the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S.
4,8?7,896,
October 31, 1989 to Maldonado, Gosselink et al., the latter being typical of
S1:ZA'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.
S1ZA's also include: simple copolymeric blocks of ethylene terephthalate or
propylene
terephthalate 'with polyethylene oxide or polypropylene oxide terephthalate,
see U. S.
3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975;
cellulosic derivatives such as the hydroxyether cellulosic polymers available
as
METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses,
see U.S. 4,000,093, December 28, 1976 to Nicol, et al.; and the methyl
cellulose
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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 SMI00 and METOLOSE SM200, which are the trade names of
methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
Additional classes of SRA's include: (I) nonionic terephthalates using
diisocyanate
coupling agents to link: polymeric ester structures, see U.S. 4,201,824,
Violland et al.
and U.S. 4,2440,918 Lagasse et al.; and (II) SRA's with carboxylate ternunal
groups
made by adding trimellitic anhydride to known SRA's to convert terminal
hydroxyl
groups to trinnellitate 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: (III) anionic terephthalate-
based SRA's
of the urethane-linked variety, see U.S. 4,201,824, Violland et al.;
Other Optional In redients
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.
Highly preferred may be the inclusion of speckle particles. The following
speckle
particle is a ~areferred speckle particle: Sodium carbonate particles, having
75 ~ of
particles having a particle size of from 600 microns to $SO microns and 25 %
of
particles having a particle size of from 425 microns to 600 microns are
obtained
by agglomerating and sieving sodium carbonate powder. The thus obtained
particles are sprayed with a Monastral blue BV paste solution and subsequently
dried, obtaining speckle particles comprising about 1000ppm of dye.
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Highly prefewed compositions contain from about 2% to about 10% by weight of
an
organic acid, preferably citric acid. Also, preferably combined with a
carbonate salt,
minor amounta (e.g., less than about 20% by weight) of neutralizing agents,
buffering
agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids,
suds
regulants, opacifiers, anti-oxidants, bactericides and dyes, such as those
described in
US Patent 4,2;85,841 to Barrat et al., issued August 25, 1981 (herein
incorporated by
reference), can be present.
Form of the Compositions
The detergent composition of the invention can be made via a variety of
methods,
including dry-mixing and agglomerating and/ or spray-drying of the various
compounds comprised in the detergent component.
The compositions in accordance with the invention can take a variety of
physical
forms including liquid and solid forms such as tablet, flake, pastille and
bar, and
preferably granular forms.
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.
Chlorine-Basgd Bleach
The detergent compositions can include as an additional component a chlorine-
based
bleach. However, since preferred detergent compositions of the invention are
solid,
most liquid chlorine-based bleaching will not be suitable for these detergent
compositions and only granular or powder chlorine-based bleaches will be
suitable.
Alternatively, the detergent compositions can be formulated such that they are
chlorine-based bleach-compatible, thus ensuring that a chlorine based bleach
can be
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added to the detergent composition by the user at the beginning or during the
washing proceas.
The chlorine-based bleachis such that a hypochlorite species is formed in
aqueous
solution. The hypochlorite ion is chemically represented by the formula OCI'.
Those bleaching agents which yield a hypochlorite species in aqueous solution
include alkali metal and alkaline earth metal hypochlorites, hypochlorite
addition
products, chloramines, chlorimines, chloramides, and chlorimides. Specific
examples
of compounds. of this tvype include sodium hypochlorite, potassium
hypochlorite,
monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated
trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium
dichloroisocyanurate sodium dichloroisocyanurate dihydrate, trichlorocyanuric
acid,
1,3-dichToro-_'i,5-dimet:hylhydantoin, N-chlorosulfamide, Chloramine T,
Dichloramine
T, chloramine B and Dichloramine B. A preferred bleaching agent for use in the
compositions of the instant invention is sodium hypochlorite, potassium
hypochlorite,
or a mixture thereof . .A preferred chlorine-based bleach can be Triclosan
(trade
name).
Most of the above-described hypochlorite-yielding bleaching agents are
available in
solid or concentrated form and are dissolved in water during preparation of
the
compositions of the instant invention. Some of the above materials are
available as
aqueous solutions.
The mean particle size; of the components of the granular compositions in
accordance
with the invention, should preferably be such that no more that 25% of the
particles
are greater than 1.8mm in diameter and not more than 25% 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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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.
Laundry Waslv-ng Met'hQd_
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 3008 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.
In a preferred use aspect the detergent composition is formulated such that it
is
suitable for hand washing.
In another preferred aspect the detergent composition is a pre-treatment or
soaking
composition., to be used to pre-treat or soak soiled and stained fabrics.
Abbreviations used in Examples
In the deterf;ent compositions, the abbreviated component identifications have
the
following meanings:
LAS : Sodium linear C11-13 alkyl benzene sulfonate
TAS : Sodium tallow alkyl sulfate
CxyAS : Sodium Clx - Cly alkyl sulfate
C46SAS : Sodium C14 - C16 secondary (2,3) alkyl sulfate
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CxyEzS : Sodium C 1 x-C 1 y alkyl sulfate condensed with z
moles of ethylene oxide
CxyEz : C 1 x-C 1 y predominantly linear primary alcohol
condensed with an average of z moles of ethylene
oxide
QAS : R2.N+(CH3~(C2H40H) with R2 = C 12 - C
14
QAS 1 : R2.N+(CH3)2(C2H40I-~ with R2 = Cg - C11
SADS : Sodium C,a-CZZ alkyl disulfate of formula
2-(R).C4
H,.-1,4-(S04-)z where R = C,~C~s
SADE2S : Sodium C,e-Czz alkyl disulfate of formula
2-(R).C4
H~.-1,4-(SOa-)2 where R = C,o-C~g, condensed
with z
moles of ethylene oxide
MES : x-sulpho methylester of C18 fatty acid
App ; Cg - C 10 amido propyl dimethyl anune
Soap : Sodium linear alkyl carboxylate derived
from an 80/20
mixture of tallow and coconut fatty acids
STS : Sodium toluene sulphonate
CFAA : C 12-C 14 (coco) alkyl N-methyl glucamide
TFAA : C 16-C 1 g alkyl N-methyl glucamide
TPKFA : C 16-C 18 topped whole cut fatty acids
STPP : Anhydrous sodium tripolyphosphate
TSPP : Tetrasodium pyrophosphate
Zeolite A : Hydrated sodium aluminosilicate of formula
Nal2(A102Si02)12~2~H20 having a primary
particle
size in the range from 0.1 to 10 nucrometers
(weight
expressed on an anhydrous basis)
NaSKS-6 : Crystalline layered silicate of formula
8- Na2Si205
Citric acid : Anhydrous citric acid
Borate : Sodium borate
Carbonate : Anydrous sodium carbonate with a particle
size
between 200pm and 900um
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Bicarbonate Anhydrous sodium bicarbonate with a particle
: size
distribution between 400~.m and 1200wm
Silicate : Amorphous sodium silicate (Si02:Na20 =
2.0:1)
Sulfate : Anhydrous sodium sulfate
Mg sulfate : Anhydrous magnesium sulfate
Citrate : Tri-sodium citrate dihydrate of activity
86.4% with a
particle size distribution between 425um
and 850wm
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 70,000
MA/AA ( 1 ) Copolymer of 4:6 maleic/acrylic acid, average
:
molecular weight about 10,000
pp : Sodium polyacrylate polymer of average
molecular
weight 4,500
CMC : Sodium carboxymethyl cellulose
Cellulose etherMethyl cellulose ether with a degree of
: polymerization
of 650 available from Shin Etsu Chemicals
Protease : Proteolytic enzyme, having 3.3% by weight
of active
enzyme, sold by NOVO Industries A/S under
the
tradename Savinase
Protease I : Proteolytic enzyme, having 4% by weight
of active
enzyme, as described in WO 95/10591, sold
by
Genencor Int. Inc.
Alcalase : Proteolytic enzyme, having 5.3% by weight
of active
enzyme, sold by NOVO Industries A/S
Cellulase : Cellulytic enzyme, having 0.23% by weight
of active
enzyme, sold by NOVO Industries A/S under
the
tradename Carezyme
Amylase : Amylolytic enzyme, having 1.6% by weight
of active
enzyme, sold by NOVO Industries A/S under
the
tradename Termamyl 120T
Amylase II : Amylolytic enzyme, as disclosed in PCT/
US9703635
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44
PCT/US98/12325
Lipase : Lipolytic enzyme, having 2.0% by weight
of active
enzyme, sold by NOVO Industries A/S under
the
tradename Lipolase
Lipase (1) : Lipolytic enzyme, having 2.0% by weight
of active
enzyme, sold by NOVO Industries A/S under
the
tradename Lipolase Ultra
Endolase; : Endoglucanase enzyme, having 1.5% by
weight of
active enzyme, sold by NOVO Industries
A/S
PB4 : Sodium perborate tetrahydrate of nominal
formula
NaB02.3H20.H202
PB 1 : Anhydrous sodium perborate bleach of
nominal
formula NaB02.H202
Percarbonate : Sodium percarbonate of nominal formula
2Na2C03.3H202
DOBS : Decanoyl oxybenzene sulfonate in the
form of the
sodium salt
DPDA : Diperoxydodecanedioc acid
NOBS : Nonanoyloxybenzene sulfonate in the
form of the
sodium salt
NACA-0135 : (6-nonamidocaproyI) oxybenzene sulfonate
LOBS : Dodecanoyloxybenzene sulfonate in the
form of the
sodium salt
DOBS : Decanoyloxybenzene sulfonate in the
form of the
sodium salt
DOBA : Decanoyl oxybenzoic acid
TAED : Tetraacetylethylenediamine
DTPA : Diethylene triamine pentaacetic acid
DTPMP : Diethylene triamine penta (methylene phosphonate),
marketed by Monsanto under the Tradename
bequest
2060
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EDDS : Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in
the form of its sodium salt.
Photoactivate:d : Sulfonated zinc phthlocyarune encapsulated in bleach
(1) dextrin soluble polymer
Photoactivate:d : Sulfonated alumino phthlocyanine encapsulated in
bleach (2) dextrin soluble polymer
Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl
Brightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-
triazin-2-yl)amino) stilbene-2:2'-disulfonate
~Dp : 1,1-hydroxyethane diphosphonic acid
HEDMP : 1,1-hydroxyethane dimethylene phosphonic
acid
PEGx : Polyethylene glycol, with a molecular weight
of x
(typically 4,000)
PEO : Polyethylene oxide, with an average molecular
weight of 50,000
TEPAE : Tetraethylenepentaamine ethoxylate
PVI : Polyvinyl imidosole, with an average molecular
weight of 20,000
pVp : Polyvinylpyrolidone polymer, with an average
molecular weight of 60,000
PVNO : Polyvinylpyridine N-oxide polymer, with
an average
molecular weight of 50,000
PVPVI : Copolymer of polyvinylpyrolidone and vinylimidazole,
with an average molecular weight of 20,000
QEA : bis((C2H50)(C2H40)n)(CH3) -~-C6H12-~-
(CH3) bis((C2H50)-(C2H40))n, wherein n =
from 20
to 30
SRP 1 : Anionically end capped poly esters
SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate) short
block polymer
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PEI : Polyethyleneimine with an average molecular weight
of 1800 and an average ethoxylation degree of 7
ethyleneoxy residues per nitrogen
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
Opacifier : Water based monostyrene latex mixture, sold by
BASF Aktiengesellschaft under the tradename Lytron
621
Wax : ParafFn wax
Speckle particle : speckle particle as described herein on p. 40
In the following examples all levels are quoted as % by weight of the
composition:
Example 1
The following; detergent formulations are in accord with the invention.
Blown powder
:115 2.0 0.5 1.0 -
SADS - - - 2.0
LAS 6.0 5.0 I1.0 6.0
TAS 2.0 - - 2.0
Zeolite A 24.0 - - 20.0
;3'fpp - 27.0 24.0 -
Sulfate 4.0 6.0 13.0 -
MA/AA 1.0 4.0 6.0 2.0
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Silicate 1.0 7.0 3.0 3.0
CMC 1.0 1.0 0.5 0.6
Brightener 1 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
Brightener 0.02 - - 0.02
C45E7 - - - 5.0
C45E2 2. 5 2. S 2.0 -
C45E3 2.6 2.5 2.0 -
Perfume 0.5 0.3 0.5 0.2
Silicone antifoam 0.3 0.3 0.3 -
Dry additives
.
(ZEA - _ - 1.0
-
EDDS 0.3 - - -
S~.lfate 2.0 3.0 5.0 10.0
Carbonate 6.0 13.0 15.0 14.0
Citric acid 2.5 - - 2.0
QAS II 0.5 - - 0.5
SKS-6 10.0 - - -
Percarbonate 4.0 3.0 - 1.9
PB4 - _ - 5.0
NOBS 0.5 - - 0.3
TAED 0.75 0.5 0.2 0.5
DOBS - -. 0.5 0.6 -
Protease 1.0 1.0 1.0 1.0
Lipase - 0.4 - 0.2
Lipase ( 1 ) 0.4 - 0.4 -
Arnylase 0.2 0.2 0.2 0.4
Brightener 1 0.05 - - 0.05
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Misc/minor to 100%
Example 2
The following granular detergent formulations are in accord with the
invention.
E F G H I J
Blown powder
LAS 23.0 8.0 7.0 9.0 7.0 7.0
QAS - - - - 1.0 -
C45AS 6.0 6.0 5.0 8.0 - -
C45A:E11S - 1.0 1.0 1.0 - -
MES 2.0 - - - 2.0 4.0
Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0
IVL~/AA - 0.5 - _ _ 2.0
MA/AA (1) 7.0 - - - - -
AA - 3.0 3.0 2.0 3.0 3.0
S ulfate 5. 0 6. 3 11.1 11.0 11.0 18.1
Silicate 10.0 1.0 1.0 1.0 1.0 1.0
Carbonate 15.0 20.0 10.0 20.7 8.0 6.0
PEG 4000 0.4 1.5 1.5 1.0 1.0 1.0
I)TPA - 0.9 0.5 - ~ 0.5
Brightener 0.3 0.2 0.3 - 0.1 0.3
2
Spray on
C;45E7 - 2.0 - - 2.0 2.0
C;25E9 3.0 - - - -
C;23E9 - - 1.5 2.0 - 2.0
Perfume 0.3 0.3 0.3 2.0 0.3 0.3
Agglomerate..
C;45AS - 5.0 5.0 2.0 - 5.0
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LAS - 2.0 2.0 - - 2.0
Zeolite A - 7.5 7.5 8.0 - 7.5
Carbonate - 4.0 4.0 5.0 - 4.0
PEG 4000 - 0.5 0.5 - - 0.5
Misc (water - 2.0 2.0 2.0 - 2.0
etc)
Dry additives
QA,S (I) _ _ _ - 1.0 -
Citric; acid i - - - - 2.0 -
PB4 - 3. 0 - - 5 -
PB 1 ' ~ - - 4 1.0 - -
Percarb~onate 2.0 - - 1.0 - 2.0
Carbonate - 5.3 1.8 - 4.0 4.0
I
rtOB S 0. - 0.4 0. 3 - 0.6
5
ROBS - 0.9 - - 0.3 -
T'A,ED 0.6 0.4 0.6 0.3 0.9 0.5
Methyl cellulose0.2 - - - - 0.5
I)TPA 0.7 0.5 1.0 0.5 0.5 1.2
S~KS-6 8.0 - - - - -
STS _ - 2.0 - 1.0 -
Cumene sulfonic- 1.0 - - - 2.0
acid
Lipase 0.2 - 0.2 - 0.2 0.4
Cel':lulase 0.2 0.2 0.2 0.3 0.2 0.2
Amylase II 0.2 - 0.1 - 0.2 -
Pr~~tease 0.5 0.5 0.5 0.3 0.5 0.5
P Vp~ - - _ 0. 5 0.1
PVP - - - _ 0.5
PVNO - 0.5 0.3
Q A - - _ ~ 1.0 ~ -
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;iRP I 0.2 0. 5 0.3 - 0.2 -
Silicone antifoam0.2 0.4 0.2 0.4 0.1 -
Mg s~.~lfate - - 0.2 - 0.2
speckle - 2.0 1.0 0.5 2.0 6.0
Misc/minors
to
100%
Examele 3
The following granular detergent formulations are in accord with the
invention.
K L M N
Base granule
STPP - _ 22.0 - 15.0
~:eolite A 30.0 - 24.0 5.0
Sulfate 5.5 5.0 7.0 7.0
MA/AA 3.0 - - -
AA - 1.6 2.0 -
~/~ (1) - 12.0 - 6.0
LAS 14.0 10.0 9.0 20.0
C45AS 8.0 7.0 9.0 7.0
C45AEI1S - I.0 - 1.0
MES 0.5 4.0 6.0 -
SADS 2.5 - - 1.0
Silicate - 1.0 0.5 10.0
Soap - - 2.0 - -
Brightener 1 0.2 0.2 0.2 0.2
Carbonate 6.0 9.0 8.0 10.0
PEG 4000 - 1.0 1.5 -
DTPA _ 0.4 - _
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Spray on
C25E9 - - - 5.0
C45E7 1.0 1.0 - -
C23E9 - 1.0 2.5 -
'Perfume 0.2 0.3 0.3 -
Dry additives
Carbonate 5.0 10.0 13.0 8.0
PVPV1/PVNO 0.5 - 0.3 -
~Protease 1.0 1.0 1.0 0.5
Lipase 0.4 - - 0.4
Amylase 0.1 - - 0.1
Cellulase 0.1 0.2 0.2 0.1
DTPA/ HEDP 0.5 0.3 0.5 I .0
LOBS - 0.8 - 0.3
PB1 5 3.0 10 4.0
DOBA 1.0 - 0.4 -
TAED 0.5 0.3 0.5 0.6
Sulfate 4.0 5.0 - 5.0
SRPI - 0.4 - _
Sud supressor - 0.5 - -
Speckle 1.0 0.5 - 5.0
Misc/minor 1:0 100%
Example 4
The followinl~ compositions are pre-treatment compositions in accordance with
the
invention
O P Q R S T U
MES -- 1.1) 2.0 0.8 4.0 - - -
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C45E7 6.5 7.5 - - - - -
C23E3 - 2.0 S.0 S.0 7.0 9.0 3.0
C25E2.SS 10.0 14.0 17.0 8.0 5.0 15.0 20.0
SADS - - 3.0 - 1.0 1.0 2.0
Acetyltriethyl3.5 4.0 Z.5 - - 3.0 3.5
citrate
Percarbonate- - 3.0 2.0 3.0 - -
Perborate 2.CI 3.0 - - - 1.0 5.0
NACA-OBS 0.3 - - - 0.6 0.4
NOBS/ LOBS/ 1.0 - 1.0 0.2 0.4 - -
DOBS
TAED 0..'i 0.6 0.3 0.8 0.9 0.4 0.7
Chelant 0.:3 0.5 - - 0.2 - 0.8
Water and
minors
H2S04 up
to
pH 4
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Example 5
V W X Y Z ~ AA ~ BB
Sodium C 11-(% 13 12.0 16.0 23.0 19 18.0 20.0 16.0
alkylbenzenesulfonate
Sodium C14-(=15 alcohol 4.5 - - - 4.0
sulfate
C 14-C 15 alcohol - - - - -
ethoxylate
(0.5) sulfate
C,4-C,s alcohol ethoxylate- - 2.0 - 1.0 1:0 1.0
(3)
sulfate
Sodium C 14-~~ 15 2.0 2.0 - 1.3 - - 0.6
alcohol
ethoxylate {3.0)
C9-C,4 alkyl dimethyl - - 1.0 0.5 2.0
hydroxy
ethyl quaternary ammonium
salt
Tallow fatty acid - - - - 1.0
Tallow alcohol ethoxylate- - - - - - -
(50)
Sodium tripollyphosphate23.0 25.0 24.0 22,0 20.0 15.0 20.0
Sodium carbonate 15.0 12.0 15.0 10.0 13.0 11.0 10.0
Sodium Polyacrylate 0.5 0.5 0.5 0.5 - - -
(45%)
Sodium poiyacrylate/rnaleate- - 1.0 1.0 1.0 2.0 0.5
polymer
Sodium silicate (1:6 3.0 6.0 9.0 8.0 9.0 6.0 8.0
ratio
Na0/Si02)(qE6%)
Sodium sulfate 25.0 18.0 20.0 18.0 20.0 22.0 13.0
Sodium perborate 5.0 5.0 10.0 8.0 3.0 1.0 2.0
Poly(ethylennglycol),1.5 1.5 1.0 1.0 - - 0.5
MW
4000 (50%;?
Sodium carboxy methyl1.0 1.0 1.0 - 0.5 0.5 0.5
cellulose
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Citric acid - - - - - - -
NOBS/ DOB:. 0.5 1.0 0.5 0.5 1.0 0.7 0.3
TAED 1.5 1.0 2.5 3.0 0.3 0.2 0.5
Soil release pol~ 1.5 1.5 1.0 1.0 - 1.0 -
Soil release pcdymerl- - - - 1.0 - 1.0
Moisture 7.5 7.5 6.0 7.0 5.0 3.0 S.0
Magnesium sulphate - - - - 1.0 0.5 1.5
Speckle 0.5 3.0 - 5.0 2.0 - 0.2
Chelants - - - - 0.8 0.6 1.0
Enzymes, including - - - - 2.0 1.5 2.0
amylase,
amylase II, cel.lulase,
protease
and lipase
minors, e.g. perfume,1.0 1.0 1.0 1.0 0.5 1.5 1.0
brightener,photo-bleach,
dye
1. Non-cotton soil release polymer according to U.S. Patent 5,415,807,
Gosselink,
Pan, Kellett and Hall, issued May 16, 1995.
2. Non-cotton soil release polymer according to US application no.60/OS 1517
Example 6
CC DD EE FF
Sodium C11-C13 13.3 13.7 10.4 8.0
alkylbenza~nesulfonate
Sodium C1,~-C15 alcohol3.9 4.0 4.5
sulfate
C 14-C 15 alcohol 2.0 2.0 - -
ethoxylate
(0.5) sulfate
Cia-C,s alcohol ethoxylate- - - -
(3)
sulfate
Sodium C14-C15 alcohol0.5 0.5 0.5 5.0
ethoxylate (6.5;)
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Cg-C14 alkyl dimethyl 1.0 - - 0.5
hydroxy
ethyl quaternary ammonium
salt
Tallow fatty acid 0.5 - - -
Tallow alcohol ethoxylate- - 1.0 0.3
x;50)
Sodium tri.polyphosphate- 41.0 - 20.0
Zeolite A, hydrate 26.3 - 21.3 1.0
(17.1-10
micron size)
Sodium carbonate 23.9 12.4 25.2 17.0
Sodium Pol:yacrylate 3.4 0.0 2.7 -
(45%)
Sodium polyacrylate/maleate- - 1.0 1.5
polymer
Sodium siliicate (l:Ei2.4 6.4 2.1 6.0
ratio
Na0/Si02X46.~0)
Sodium sulfate 10.5 10.9 8.2 15.0
Sodium perborate 1.0 1.0 1.0 2.0
Poly(ethyleneglycol), 1.7 0.4 1.0
MW
-r40(!0 (50%)
Sodium carboxy methyl 1.0 - - 0.3
cellulose
Citric acid - - 3.0
NOBS/ DOBS 0.2 0.5 0.5 0.1
T'AED 0.6 0. 0.4 0.3
S
Soil release polymer 1.5 - - -
Soil release polymer - 1.5 1.0 1.0
Moisture 7.5 3.1 6.1 7.3
Magnesium sulphate - - - 1.0
Chelants - - ~ ~
- 0.5
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Enzymes, including - I.0 - I.5
amylase,
amylase II, c~ellulase,
protease
anti lipase
minors, e.g. perfume,1.0 1.0 1.0 1.0
brightener,photo-bleach,
dye
1. Non-cotton soil 4,968,451, Scheibel
rc;lease polymer et
according to U.S.
Patent
al., issued November 6, 1990.
2. Non-cotton soil release polymer according to US application no.60/051517
