Note: Descriptions are shown in the official language in which they were submitted.
~W095128469 F PCTIUS95/04205
..... . ._. ... - y : : 3,. 4!
1.
m .,2187437
DETERGENTS CONTAINING A BUILDER AND A DELAYED RELEASE ENZYME
~.f. ~ :~~Y.~
~. 1~i . t1 .I ~ , i
This invention relates to detergent compositions containing a water-soluble
builder
and an enzyme, wherein a means is provided for delaying the release to the
wash
solution of said enzyme relative to the release of said water-soluble builder.
The satisfactory removal of enzyme sensitive soilslstains such as blood, egg,
chocolate, gravy from soiled/stained substrates is a particular challenge to
the
formulator of a detergent composition for use in a washing method such as a
laundry or machine dishwashing method.
Commonly, the removal of such soilslstains has been enabled by the use of
enzyme components, proteolytic,. amylolytic, lipolytic and cellulolytic
enzymes.
The Applicants have now found that where a composition containing both a water-
soluble builder and an enzyme is employed, and wherein a means is provided for
delaying the release to a wash solution of the enzyme relative to the release
of the
water-soluble builder enhanced stain/soil removal may be obtained.
The Applicants have in addition found that stain/soil removal benefits may be
obtained when a soiled substrate is pretreated with a solution containing a
water-
soluble builder, prior to being washed in a method using an enzyme containing
detergent product.
It is therefore an object of the present invention to provide compositions
suitable
for use in laundry and machine dishwashing methods having enhanced stain
removal.
It is a related object of the present invention to provide a stain/soil
pretreatment
method involving pretreating the soiled substrate with a solution containing a
water-soluble builder, prior to washing with an enzyme containing detergent
product.
summary of the Invention
According to the present invention there is provided a detergent composition
containing
W0 95128469 PCTIUS95I04205
2
2187437
(a) a water-soluble builder; and
(b) an enzyme
wherein a means is provided for delaying the release to a wash solution of
said ,
enzyme relative to the release of said water-soluble builder such that in the
TSO
test method herein described the time to achieve a concentration that is 5096
of the
ultimate concentration of said water-soluble builder is less than 60 seconds
and the
time to achieve a concentration that is 50°b of the ultimate
concentration of said
enzyme is more than 90 seconds.
According to another aspect of the present invention there is provided a
washing
method comprising the steps of:
(1) applying an enzyme-free solution of a composition containing a water-
soluble builder to a soiled substrate;
(2) allowing said solution to remain in contact with said soiled substrate for
an
effective time interval;
(3) washing said soiled substrate using a washing method involving use of an
enzyme-containing detergent composition.
water-aninble builder compound
The detergent compositions of the present invention may contain a water-
soluble
builder compound, typically present at a level of from I °~ to
80°~ by weight,
preferably from 10~ to 7096 by weight, most preferably from 2096 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,
carbonates,
bicarbonates, borates, phosphates, silicates and mixtures of any of the
foregoing.
CA 02187437 1999-09-17
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, malefic acid, diglycolic acid,
tartaric
acid, tartronic acid and fumaric acid, as well as the ether carboxylates and
the
sutfinyl 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.
Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-
tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-
tetrahydrofuran -
cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates,
2,2,5,5-
tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane - hexacarboxylates and
carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol
and
xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid
and the
phthalic acid derivatives disclosed in British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydmxycarboxylates containing
up to three carboxy groups per molecule, more particularly citrates.
W0 95128469 PCTlUS95f04205
2181437
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents
or riiixtures 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 can also be used but
are
not preferred at wash conditions less that about 50°C, especially less
than about
40°C.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates,
including sodium carbonate and sesqui-carbonate and mixtures thereof with
ultra-
fine calcium carbonate as disclosed in German Patent Application No. 2,321,001
published on November 15, 1973.
Specific 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 polymetalphosphate in which the degree of polymerization ranges from
about 6 to 21, and salts of phytic acid.
Suitable silicates include the water soluble sodium silicates with an Si02:
Na20
ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 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.
Silicates are preferably present in the detergent compositions in accord with
the
invention at a level of from 5~ to 50~ by weight of the composition, more
preferably from 10~ to 40~ by weight.
~yme
The detergent compositions contain an enzyme. Suitable enzymatic materials
include the commercially available lipases, amylases, neutral and alkaline
proteases, esterases, cellulases, pectinases, lactases and peroxidases
conventionally
incorporated into detergent compositions. Suitable enzymes are discussed in US
Patents 3,519,570 and 3,533,139.
CA 02187437 1999-09-17
5
Preferred commercially available protease enzymes include those sold under the
trademarks Alcalase, Savinase, Primase, Durazym, and Esperase by Novo
Industries A/S (Denmark), those sold under the trademarks Maxatase, Maxacal
and
Maxapem by Gist-Brocades, those sold by Genencor International, and those sold
under the trademarks 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 °.6 to 4 96 active enzyme by weight
of the
composition.
Preferred amylases include, for example, a-amylases obtained from a special
strain of B licheniformis, described in more detail in GB-1,269,839 (Novo).
Preferred commercially available amylases include for example, those sold
under
the trademark Rapidase by Gist-Brocades, and those sold under the trademark
Termamyl and BAN by Novo Industries A/S. Amylase enzyme may be
incorporated into the composition in accordance with the invention at a level
of
from 0.00019b to 2 Yb active enzyme by weight of the composition.
Lipolytic enzyme (lipase) may be present at levels of active lipolytic enzyme
of
from 0.0001 ~ to 2 ~ by weight, preferably 0.0019 to 196 by weight, most
preferably from 0.001 ~ to 0.5 9~ by weight of the compositions.
The lipase may be fungal or bacterial in origin being obtained, for example,
from
a lipase producing strain of Humicola sp., Tlrermomyces sp. or Pseudomonas sp.
including Pseudomonas pseudoalcali~enes or Pseudomas fluorescens. Lipase from
chemically or genetically modified mutants of these strains are also useful
herein.
A preferred lipase is derived from Pseudomonas ttseudoalcaligenes, which is
described in Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola
lanueirrosa and expressing the gene in A~pereillus , as host, as described in
European Patent Application, EP-A-0258 068, whfch is commercially available
from Novo Industri AIS, Bagsvaerd, Denmark, under the trade mark Lipolase.
This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al,
issued
March 7, 1989.
WO 95128469 - PCT/US95/04205
2187437
Where the enzyme is a protease, the ultimate amount in a typical wash solution
is
from 0.1 to 100 ICNPU, but preferably is from 0.5 to 50 IUVPU, more preferably
from 3 to 30 KNPU and most preferably from 6 to 30 KNPU.
Where the enzyme is an amylase, the ultimate amount in a typical wash solution
is
from 1 to 200 K1VLT, but preferably is from 10 to 100 KNU, more preferably
from
40 to 80 KNU.
Where the enzyme is a lipase, the ultimate amount in a typical wash solution,
is
from I to 300 KLU, but preferably is from 10 to 200 ICLU, more preferably from
l O to l00 KLU. _ _
Where the enzyme is a cellulase,_the ultimate amount in the wash is typically
from
to 1200 CEVLT, but preferably is from 30 to 1000 CEVLT, more preferably
from 80 to 500 CEVLJ.
Enzyme Stabilizing System
Preferred enzyme-containing compositions herein may comprise from about
0.00136 to about 1096, preferably from about 0.005 to about 8~,most
preferably from about 0.0196 to about 696, by weight of an enzyme stabilizing
system. The enzyme stabilizing system can be any stabilizing system which is
compatible with the detersive enzyme. Such stabilizing systems can comprise
calcium ion, boric acid, propylene glycol, short chain carboxylic acid,
boronic
acid, and mixtures thereof. Such stabilizing systems can also comprise
reversible
enzyme inhibitors, such as reversible protease inhibitors.
The compositions herein may further comprise from 0 to about 1096, preferably
from about 0.0196 to about 636 by weight, of chlorine bleach scavengers, added
to
prevent chlorine bleach species present in many water supplies from attacking
and
inactivating the enzymes, especially under alkaline conditions. While chlorine
levels in water may be small, typically in the range from about 0.5 ppm to
about
1.75 ppm, the available chlorine in the total volume of water that comes in
contact
with the enzyme during washing is usually large; accordingly, enzyme stability
in-
use can be problematic.
~W0 95128469 PCT/US95/04205
2187437
Suitable chlorine scavenger anions are widely available, and are illustrated
by salts
confaining ammonium rations or sulfite, bisulfate, thiosulfite, thiosulfate,
iodide,
etc. Antioxidants such as carbamate, ascorbate, etc., organic amines such as
ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof,
monoethanolamine (MEA), and mixtures thereof can likewise be used. Other
conventional scavengers such as bisulfate, nitrate, chloride, sources of
hydrogen
peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate
and sodium percarbonate, as well as phosphate, condensed phosphate, acetate,
benzoate, citrate, formate, lactate, maLite, tartrate, salicylate, etc. and
mixtures
thereof can be used if desired.
uPlative relea ce l ;ne ; .r
In an essential aspect of the invention a means is provided for delaying the
release
to a wash solution of the enzyme relative to the release of the water-soluble
builder.
Said means may comprise a means for delaying the release of the enzyme to the
wash solution.
Alternatively said means may comprise a means for enhancing the rate of
release
of the water-soluble builder to the solution.
The delayed release means can include coating the enzyme with any suitable
component with a coating designed to provide the delayed release. The coating
may therefore, for example, comprise a poorly water soluble material, or be a
coating of sufficient thickness that the kinetics of dissolution of the thick
coating
provide the controlled rate of release.
~ The coating material may be applied using various methods. Any coating
material
is typically present at a weight ratio of coating material to bleach of from
1:99 to
1:2, preferably from 1:49 to 1:9.
WO 95128469 - _ PCTlUS95104205
8 2187437
Suitable coating materials include triglycerides (e.g. partially) hydrogenated
vegetable oil, soy bean oil, cotton seed oil) mono or diglycerides,
microcrystalline
waxes, gelatin, cellulose, fatty acids and any mixtures thereof.
Other suitable coating materials can comprise the alkali and alkaline earth
metal
sulphates, silicates and carbonates, including calcium carbonate.
Preferred coating material is sodium silicate of Si02 : 1Va20 ratio from 1.6 :
1 to
3.4 : 1, preferably 2.8 : 1, applied as an aqueous solution to give a level of
from
29& to 14?&, (normally from 3~~ to 5~) of silicate solids by weight of the
percarbonate. Magnesium silicate can also be included in the coating.
Any inorganic salt coating materials may be combined with organic binder
materials to provie composite inorganic salt/organic binder coatings. Suitable
binders include the Ci0-C2p alcohol ethoxylates containing from 5 - 100 moles
of
ethylene oxide per mole of alcohol and more preferably the Clg-C24 P~m'Y
alcohol ethoxylates containing from 20 - 100 moles of ethylene oxide per mole
of
alcohol.
Other preferred binders include certain polymeric materials.
Polyvinylpyrrolidones with an average molecular weight of from 12,000 to
700,000 and polyethylene glycols (PEG) with an average molecular weight of
from 600 to 10,400 are examples of such polymeric materials. Copolymers of
malefic anhydride with ethylene, methylvinyl ether or methacrylic acid, the
malefic
anhydride constituting at least 20 mole percent of the polymer are further
examples of polymeric materials useful as binder agents. These polymeric
materials may be used as such or in combination with solvents such as water,
propylene glycol and the above mentioned C10-C2p alcohol ethoxylates
containing
from 5 - 100 moles of ethylene oxide per mole. Further examples of binders
include the Cl0-C20 mono- and diglycerol ethers and also the C10-C20 fatty
acids.
Cellulose derivatives such as methylcellulose, carboxymethylcellulose and
hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their
salts are other examples of binders suitable for use herein.
~W O 95!28469 PCT/US95104205
2187437
One method for applying the coating material involves agglomeration. Preferred
agglomeration processes include the use of any of the organic binder materials
described hi;reinabove. Any conventional agglomerator/mixer may be used
including, but not limted to pan, rotary drum and vertical blender types.
Molten
coating compositions may also be applied either by being poured onto, or spray
atomized onto a moving bed of bleaching agent.
Other means of providing the required delayed release include mechanical means
for altering the physical characteristics of any enzyme containing particulate
to
control its solubility and rate of release. Suitable protocols could include
compaction, mechanical injection, manual injection, and adjustment of the
solubility of the bleach compound by selection of particle size of any
particulate
component.
Whilst the choice of particle size will depend both on the composition of the
particulate component, and the desire to meet the desired delayed release
kinetics,
it is desirable that the particle size should be more than 500 micrometers,
preferably having an average particle diameter of from 800 to 1200
micrometers.
Additional protocols for providing the means of delayed release include the
suitable choice of any other components of the detergent composition matrix
such
that when the composition is introduced to the wash solution the ionic
strength
environment therein provided enables the required delayed release kinetics to
be
achieved.
All suitable means for enhancing the rate of release of the water-soluble
builder to
the solution are envisaged.
The enhanced release means can include coating any suitable component with a
coating designed to provide the enhanced release. The coating may therefore,
for
example, comprise a highly, or even effervescently, water soluble material.
Other means of providing the required delayed release include mechanical means
for altering the physical characteristics of the water-soluble builder to
enhance its
solubility and rate of release.
~, fr;
WO 95128469 PCTIU595/04205
2187437
A suitable protocol could include deliberate selection of the particle size of
any
water-soluble builder containing component. The choice of particle size will
depend both on the composition of the particulate component, and the desire to
meet the desired enhanced release kinetics. It is desirable that the particle
size
should be less than 1200 micrometers, preferably having an average particle
diameter of from 1100 to 500 micrometers.
Additional protocols for providing the means of delayed release include the
suitable choice of any other components of the detergent composition matrix,
or of
any particulate component containing the water-soluble builder, such that when
the
composition is introduced to the wash solution the ionic strength environment
therein provided enables the required enhanced release kinetics to be
achieved..
. 1. - ai. .... 3.
W 0 95/28469 PCT/US95104205
11
Relative rate of rel se - kinetic narameterc 218 7 ~ 3 7
The release of the enzyme relative to the water-soluble builder is such that
in the
T50 test method herein described the time to achieve a concentration that is
5096
of the ultimate concentration of said water-soluble builder is less than 60
seconds,
preferably less than 50 seconds, more preferably less than 40 seconds, and the
time to achieve a concentration that is 5096 of the ultimate concentration of
said
enzyme is more than 90 seconds, preferably more than 120 seconds, more
preferably more than 150 seconds.
The ultimate wash concentration of the water-soluble builder is typically from
0.0005 ~ to 0.4 ~ , preferably from 0.005 96 to 0.35 9& , more preferably from
0.01~to0.396.
The ultimate wash concentration of the enzyme is typically from 0.000001 ~ to
0.0196 by weight of active enzyme, but preferably is from 0.0000196 to
0.0019b,
more preferably from 0.00005 ~ to 0.0005 96.
The delayed release kinetics herein are defined with respect to a 'TA test
method'
which measures the time to achieve AR6 of the ultimate concentration/level of
that
component when a composition containing the component is dissolved according
to
the standard conditions now set out.
The standard conditions involve a 1 litre glass beaker filled with 1000 ml of
distilled water at 20oC, to which lOg of composition is added. The contents of
the
beaker are agitated using a magnetic stirrer set at 100 rpm. The ultimate
concentration/level is taken to be the concentration/level attained 10 minutes
after
addition of the composition to the water-filled beaker.
Suitable analytical methods are chosen to enable a reliable determination of
the
incidental, and ultimate in solution concentrations of the component of
concern,
subsequent to the addition of the composition to the water in the beaker.
WO 95!28469 PCTIUS95/04205
12 2187437
Such analytical methods can include those involving a continuous monitoring of
the level of concentration of the component, including for example photometric
and conductrimetric methods.
Alternatively, methods involving removing titres from the solution at set time
intervals, stopping the disssolution process by an appropriate means such as
by
rapidly reducing the temperature of the titre, and then determining the
concentration of the component in the titre by any means such as chemical
titrimetric methods, can be employed.
Suitable graphical methods, including curve fitting methods, can be employed,
where appropriate, to enable calculation of the the TA value from raw
analytical
results.
The particular analytical method selected for determining the concentration of
the
component, will depend on the nature of that component, and of the nature of
the
composition containing that component.
,9dditional detergent com oo nents
The detergent compositions of the 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, and
the
nature of the cleaning operation for which it is to be used.
The compositions of the invention may for example, be formulated as hand and
machine laundry detergent compositions, including laundry additive
compositions
and compositions suitable for use in the pretreatment of stained fabrics and
machine dishwashing compositions.
When formulated as compositions suitable for use in a machine washing method,
eg: machine laundry and machine dishwashing methods, the compositions of the
invention preferably contain one or more additional detergent components
selected
from surfactants, builders, organic polymeric compounds, bleaches, suds
suppressors, Lime soap dispersants, soil suspension and anti-redeposition
agents
and corrosion inhibitors. Laundry compositions can also contain, as additional
detergent components, softening agents.
~O 95!28469 v - - - PC1'IUS95104205
287437
nt
The detergent compositions of the invention may contain as an additional
detergent
component a surfactant selected from anionic, cationic, nonionic ampholytic,
amphoteric and zwitterionic surfactants and mixtures thereof.
The surfactant is typically present at a level of from 0.1 ~b to 60 k by
weight.
More preferred levels of incorporation of surfactant are from 1 ~ to 35 % by
weight, most preferably from 1 °h to 20°6 by weight.
The surfactant is preferably formulated to be compatible with any enzyme
components present in the composition. In liquid or gel compositions the
surfactant is most preferably formulated such that it promotes, or at least
does not
degrade, the stability of any enzyme in these compositions.
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 Beroh). 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 andlor nonionic surfactants.
Anionic surfactant
Essentially any anionic surfactants usefulfor detersive purposes can be
included in
the compositions. These can include salts (including, for example, sodium,
potassium, ammotuum, and substituted ammonium salts such as mono-, di- and
triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and
sarcosinate
surfactants.
Other 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
W O 95128469 PCT/US95/04205
2187437
C12 CI8 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.
~O 95!28469 ~ PCT/US95/04205
21g7437
Anionic sulfate s,~_rfactant
Anionic sulfate surfactants suitable for use herein include the linear and
branched
primary alkyl sulfates, alkyl ethoxysulfates, fatty oleyl glycerol sulfates,
alkyl
phenol ethylene oxide ether sulfates, the CS-Cl~ aryl-N-(Cl-C4 alkyl) and -N-
(Cl-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides
such as the sulfates of allcylpolyglucoside (the nonionic nonsulfated
compounds
being described herein).
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting
of the C6-Clg alkyl sulfates which have been ethoxylated with from about 0.5
to
about 20 moles of ethylene oxide per molecule. More preferably, the alkyl
ethoxysulfate surfactant is a C6-Clg alkyl sulfate which has been ethoxylated
with
from about 0.5 to about 20, preferably from about 0.5 to about 5, moles of
ethylene oxide per molecule.
Anionic sulfonate surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of Cg-
C20
linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C~ primary or
secondary alkane sulfonates, C6-C24 oleFm sulfonates, sulfonated
polycarboxyiic
acids, alkyl glycerol sulfonates, fatty aryl glycerol sulfonates, fatty oleyl
glycerol
sulfonates, and any mixtures thereof.
Anionic carboxylate surfactants suitable for use herein include the alkyl
ethoxy
carboxylates, the allcyl polyethoxy polycarboxylate surfactants and the soaps
('alkyl carboxyls'), especially certain secondary soaps as described herein.
Preferred alkyl ethoxy carboxylates for use herein include those with the
formula
RO(CH2CH20)x CH2C00-M-~' wherein R is a C6 to Clg 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 about 20 % , and the amount of
material where x is greater than 7, is less than about 25 ~, the average x is
from
about 2 to 4 when the average R is C13 or less, and the average x is from
about 3
to 10 when the average R is greater than C13, and M is a ration, preferably
W0 95128469 pCT/US95104205
2187437
chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-
ethaiiol-ammonium, most preferably from sodium, potassium, ammonium and
mixtures thereof with magnesium ions. The preferred alkyl ethoxy carboxylates
are those where R is a CI2 to Clg alkyl group.
Alkyl polyethoxy polycarboxylate surfactants suitable for use herein include
those
having the formula RO-(CHItl-CFiR2-O)-R3 wherein R is a C6 to Clg alkyl
group, x is from I to 25, Rl and R2 are selected from the group consisting of
hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid
radical,
and mixtures thereof, wherein at least one Rl or R2 is a succinic acid radical
or
hydroxysuccinic acid radical, and Rg is selected from the group consisting of
hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8
carbon
atoms, and mixtures thereof.
Preferred soap surfactants are secondary soap surfactants which contain a
carboxyl
unit connected to a secondary carbon. The secondary carbon can be in a ring
structure, e.g. as in p-octyt benzoic acid, or as in alkyl-substituted
cyclohexyl
carboxylates. The secondary soap surfactants should preferably contain no
ether
linkages, no ester linkages and no hydroxyl groups. There should preferably be
no nitrogen atoms in the head-group (amphiphilic portion). The secondary soap
surfactants usually contain 11-15 total carbon atoms, although slightly more
(e.g.,
up to 16) can be tolerated, e.g. p-octyl benzoic acid.
The following general structures further illustrate some of the preferred
secondary
soap surfactants:
A. A highly preferred class of secondary soaps comprises the secondary
carboxyl materials of the formula R3 CH(R4)COOM, wherein R3 is
CHg(CH~x and R4 is CH3(CH2)y, wherein y can be O or an integer from 1 to
4, x is an integer from 4 to 10 and the sum of (x + y) is 6-10, preferably 7-
9, most preferably 8.
B. Another preferred class of secondary soaps comprises those carboxyl
compounds wherein the carboxyl substituent is on a ring hydrocarbyl unit,
i.e., secondary soaps of the formula R$-R6-COOM, wherein RS is C~-
~WO 95!28469 PCT/US95104205
2181437
C10 preferably C8-C9, alkyl or alkenyl and R6 is a ring structure, such as
benzene, cyclopentane and cyclohexane. (Note: RS can be in the ortho,
meta or para position relative to the carboxyl on the ring.)
C. Still another preferred class of secondary soaps comprises secondary
carboxyl compounds of the fommla CH3(CHR)k-(CHZ)m-(CHR)n
CH(COOM)(CHR)o-(CH2)p (CHR)q CH3, wherein each R is Cl-C4
alkyl, wherein k, n, o, q are integers in the range of 0-8, provided that the
total number of carbon atoms (including the carboxylate) is in the range of
to 18.
In each of the above formulas A, B and C, the species M can be any suitable,
especially water-solubilizing, counterion.
Especially 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 acid, 2-butyl-
1-
octanoic acid and 2-pentyl-1-heptanoic acid.
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-
CON (Rl) CH2 COOM, wherein R is a CS-C1~ linear or branched alkyl or
alkenyl group, Rl is a C1-C4 alkyl group and M is an alkali metal ion.
Preferred
examples are the myristyl and oleyl methyl sarcosinates in the form of their
sodium salts.
Nonionic surfactant
Essentially any anionic surfactants useful for detersive purposes can be
included in
the compositions. Exemplary, non-Limiting classes of useful nonionic
surfactants
are listed below.
Nonionic ~lyjtydroxy fatty acid amide cnrfac an
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural formula R2CONR1Z wherein : Rl is H, Cl-Cq hydrocarbyl, 2-hydroxy
y 4-.
w0 95128469 PCT/US95104205
a e;
.18 2181437
ethyl, 2-hydroxy propyl, or a mixture thereof, preferable C1-C4 alkyl, more
prei~erably Ci or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R2 is
a
CS-C31 hydrocarbyl, preferably straight-chain Cg-Ci9 alkyl or alkenyl, more
preferably straight-chain Cg-C i ~ alkyl or alkenyl, most preferably straight-
chain
Cl1-CIA alkyl or alkenyl, or mixture thereof; and Z is a
polyhydroxyhydrocarbyl
having a linear hydnxarbyl 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 condensates of alkyl phenols
The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl
phenols are suitable for use herein. In general, the polyethylene oxide
condensates
are preferred. These compounds include the condensation products of alkyl
phenols having an alkyl group containing from about 6 to about 18 carbon atoms
in either a straight chain or branched chain co~guration with the alkylene
oxide.
Nonionic ethoxyrlated alcohol surfactant
The alkyl ethoxylate condensation products of aliphatic alcohols with from
about 1
to about 25 moles of ethylene 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 aicohois having an alkyl group containing from 8 to
20
carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of
alcohol.
The ethoxylated C6-Clg fatty alcohols and C6-Clg mixed
ethoxylatedlpropoxylated fatty alcohols are suitable surfactants for use
herein,
particularly where water soluble. Preferably the ethoxylated fatty alcohols
are the
Cl0-Clg ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to
50,
most preferably these are the C12-Clg ethoxylated fatty alcohols with a degree
of
ethoxylation from 3 to 40. Preferably the mixed ethoxylated/propoxylated fatty
"~ r~ w, .
"WO 95128469 PCT/US95I04205
2187437
alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of
ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.
Nonionic EOIPO condensates with Rm_Ry(ene glLo_I
The condensation products of ethylene oxide with a hydrophobic base formed by
the condensation of propylene oxide with propylene glycol are suitable for use
herein. The hydrophobic portion of these compounds preferably has a molecular
weight of from about 1500 to about 1800 and exhibits water insolubility.
Examples of compounds of this type include certain of the commercially-
available
PlurorucTM surfactants, marketed by BASF.
Nonionic EO condensation products with nronvlene oxidelethvlene diamine
The condensation products of ethylene oxide with the product resulting from
the
reaction of propylene oxide and ethylenediamine are suitable for use herein.
The
hydrophobic moiety of these products consists of the reaction product of
ethylenediamine and excess propylene oxide, and generally has a molecular
weight
of from about 2500 to about 3000. Examples of this type of nonionic surfactant
include certain of the commeroially available TetronicTM compounds, marketed
by BASF.
Nonionic alky_Ipolysaccharide 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 about 6 to about 30 carbon atoms, preferably from about 10 to
about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic
group containing from about 1.3 to about 10, preferably from about 1.3 to
about
3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing
saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose,
galactose
and galactosyl moieties can be substituted for the glucosyl moieties.
(Optionally
the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus
giving a
glucose or galactose as opposed to a glucoside or galactoside.) The
intersaccharide bonds can be, e.g., between the one position of the additional
saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding
saccharide
units.
WO 95128469 PCT/US95/04205
2187437
The preferred alkylpolyglycosides 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, preferably from 12 to 14, carbon atoms; n is 2 or 3; t
is
from 0 to 10, preferably 0, and X is from 1.3 to 8, preferably from 1.3 to 3,
most
preferably from 1.3 to 2.7. The gIycosyl is preferably derived from glucose.
~O 95128469 PC1'IUS95/04205
21
~lonionic fly acid amide surfactant
2187437
Fatty acid amide surfactants suitable for use herein are 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-Cq alkyl, CI-C4 hydroxyalkyl, and -(C2H40)xH, where x is in the
renge of from 1 to 3.
Am~hoteric surfactant
Suitable amphoteric surfactants for use herein include the amine oxide
surfactants
and the alkyl amphocarboxylic acids.
A suitable example of an alkyl aphodicarboxylic acid for use herein is
Miranol(TM) C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.
Amine Oxide surfactant
Amine oxides useful herein include those compounds having the formula
R3(OR4)xlVp(RS)2 wherein R3 is selected from an alkyl, hydroxyalkyl,
acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from
8
to 26 carbon atoms, preferably 8 to 18 carbon atoms; R4 is an alkylene or
hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2 carbon
atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each
RS
is an alkyl or hydyroxyalkyl group containing from I to 3, preferably from I
to 2
carbon atoms, or a polyethylene oxide group containing from 1 to 3, preferable
1,
ethylene oxide groups. The RS groups can be attached to each other, e.g.,
through an oxygen or nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include CIO-Clg alkyl dimethyl
amine
oxides and Cg-Clg alkoxy ethyl dihydroxyethyl amine oxides. Examples of such
materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-
hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide,
dipropyltetradecylamine oxide, methylethylhexadecylamine oxide,
dodecylamidopropyl dimethylamine oxide, cetyl dimethylamine oxide, stearyl
dimethylamine oxide, tallow dimethylamine oxide and dimethyl-2-
R'O 95128469 PCT/US95104205
as
hydroxyoctadecylamine oxide. Preferred are C10-C18 ~Yl dimethyLimine oxide,
and C10-18 acylamido allcyl dimethylamine oxide.
Zwitterionic cnrfa .tant
Zwitterionic surfactants can also be incorporated into the detergent
compositions
hereof. 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
zwittetionic
surfactants for use herein.
The betaines useful herein are those compounds having the formula
R(R')2N+R2C00- wherein R is a C6-Clg hydrocarbyl group, preferably a C10-
C16 alkyl group or C10-16 acylamido alkyl group, each Rl is typically Cl-C3
alkyl, preferably methyl,m and R2 is a Cl-Cg hydrocarbyl group, preferably a
Cl-C3 alkylene group, more preferably a Cl-C2 allrylene group. Examples of
suitable betaines include coconut acyLunidopnopyldimethyl betaine; hexadecyl
dimethyl betaine; C12-14 acylamidopropylbetaine; Cg-14 acylamidohexyldiethyl
betaine; 4[Ci~l6 ~Y~ethylamidodiethylammonio]-1-carboxybutane; C16-18
acylamidodimethylbetaine; C12-16 acYlamidopentanediethyl-betaine; [C12-16
acylmethylamidodimethylbetaine. Preferred betaines are C12-18 d~ethyl-
ammonio hexanoate and the C10-18 acY~dopropane (or ethane) dimethyl (or
diethyl) betaines. Complex betaine surfactants are also suitable for use
herein.
The sultaines useful herein are those compounds having the formula
(R(Rl)ZN-~R2503- wherein R is a C6-Clg hydrocarbyl group, preferably a C10-
C16 alkyl group, more preferably a C12-C13 allryl group, each Rl is typically
C1-
C3 alkyl, preferably methyl, and R2 is a Cg-C6 hydrocarbyl group, preferably a
Cl-C3 alkylene or, preferably, hydroxyalkylene group.
-WO 95!28469 PCTlUS95104205
23 -2187437
Ampholytic surfactants can be incorporated into the detergent compositions
herein.
These surfactants can be broadly described as aliphatic derivatives of
secondary or
tertiary amines, or aliphatic derivatives of heterocyclic secondary and
tertiary
amines in which the aliphatic radical can be straight chain or branched.
Cationic surfactants __
Cationic surfactants can also be used in the detergent compositions herein.
Suitable
cationic surfactants include the quaternary ammonium surfactants selected from
mono C6-C16, preferably C6-Cl0 N-alkyl or alkenyl ammonium surfactants
wherein the remaining N positions are substituted by methyl, hydroxyethyl or
hydroxypropyl groups.
Partia lv soluble or insoluble builder compound
The detergent compositions of the present invention may contain a partially
soluble
or insoluble builder compound, typically present at a level of from 1 % to 80%
by
weight, preferably from 10~ to 7096 by weight, most preferably from 2096 to
609b weight of the composition.
Examples of partially water soluble builders include the crystalline layered
silicates. Examples of largely water insoluble builders include the sodium
aluminosilicates.
Crystalline layered sodium silicates have the general formula
NaMSix02x+ 1 ~YH20
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number
from 0 to 20. Crystalline layered sodium silicates of this type are disclosed
in EP-
A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and
DE-A-3742043. For the purpose of the present invention, x in the general
formula above has a value of 2, 3 or 4 and is preferably 2. The most preferred
material is &-Na2Si205, available from Hoechst AG as NaSKS-6.
The crystalline layered sodium silicate material is preferably present in
granular
detergent compositions as a particulate in intimate admixture with a solid,
water-
W0 95128469 PCT/US95/04205
24 2187437
soluble ionisable material. The solid, water-soluble ionisable material is
selected
from organic acids, organic and inorganic acid salts and mixtures thereof.
Suitable aluminosilicate zeo&tes have the unit cell formula
Naz[(A102)z(SiO~y~.
XH20 wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to
0.5
and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to
264.
The aluminosilicate material are in hydrated form and are preferably
crystalline,
containing from 10 % to 28 % , more preferably from 18 ~ to 22 ~ water in
bound
form.
The aluminosilicate ion exchange materials 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, Zeoilte MAP, Zeolite HS and mixtures thereof. Zeolite A
has the formula
Na 12 [A102). 12 (Si02)127. xH20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
[('°'10~86(Si02)106~. 276 H20.
The detergent compositions of the invention contain as a preferred optional
component an organic peroxyacid bleach source. The peroxyacid bleach source
may be the organic peroxyacid per se, or it may be a peroxyacid bleach
precursor
compound.
Where the source is a peroxyacid bleach precursor compound, the production of
the peroxyacid occurs by an in situ reaction of the precursor with a source of
hydrogen peroxide. Suitable sources of hydrogen peroxide include inorganic
perhydrate bleaches.
The organic peroxyacid bleach source is preferably also provided with means
for
delaying its release to the wash solution, such that in the T50 test, the time
to
achieve a concentration that is 50 % of the ultimate concentration of the
peroxyacid
-W0 95128469 PCT/US95104205
z5 2181437
bleach is more than 180 seconds, preferably more than 240 seconds. Any of the
means herein described for achieving the delayed release can be employed.
Peroxvacid bleach precursors
Peroxyacid bleach precursors (bleach activators) are preferred peroxyacid
sources.
Peroxyacid bleach precursors are normally incorporated at a level of from 1 ~b
to
20~ by weight, more preferably from 2Y6 to 53b by weight, most preferably from
336 to 10~ by weight of the compositions.
Suitable peroxyacid bleach precursors typically contain one or more N- or O-
aryl
groups, which precursors can be selected from a wide range of classes.
Suitable
classes include anhydrides, esters, imides and acylated derivatives of
imidazoles
and oximes, and examples 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..The acylation products of sorbitol, glucose and all saccharides
with
benzoylating agents and acetylating agents are also suitable.
Specific O-acylated precursor compounds include 2,3,3-tri-methyl hexanoyl
oxybenzene sulfonates, benzoyl oxybenzene sulfonates, nonanoyl-6-amino caproyl
oxybenzene sulfonates, monobenzoyltetraacetyl glucose benzoyl peroxide and
catiotric derivatives of any of the above, including the alkyl ammonium
derivatives
and pentaacetyl glucose. Phthalic anhydride is a suitable anhydride type
precursor.
Specific cationic derivatives of the O-aryl precursor compounds include 2-
(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride,
and any of the alkyl ammonium derivatives of the benzoyl oxybenzene sulfonates
including the 4-(trimethyl ammonium) methyl derivative.
Useful N-aryl compounds are disclosed in GB-A-855735, 907356 and GB-A-
1246338.
Preferred precursor compounds of the imide type include N-benzoyl succinimide,
tetrabenzoyl ethylene diamine, N-benzoyl substituted ureas and the N-,N,N1N1
R'O 95/28469 PCT/US95/04205
zs 2187437
tetra acetylated allcylene diamines wherein the allcylene group contains from
I to 6
carbbn atoms, particularly those compounds in which the alkylene group
contains
1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly
preferred.
N-acyhtted precursor compounds of the lactam class are disclosed generally in
GB-
A-955735. Whilst the broadest aspect of the invention contemplates the use of
any
lactam useful as a peroxyacid precursor, preferred materials comprise the
caprnlactams and valerolactams.
~O 95/28469 PCT/US95/04205
a~ 2187437
Suitable N-acylated lactam precursors have the formula:
0
II
Rs-C N CH2-CH2
- ~C H2~ ~ H2 ]~
wherein n is from 0 to about 8, preferably from 0 to 2, and R6 is H, an alkyl,
aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbons, or a
substituted
phenyl group containing from 6 to 18 carbon atoms
Suitable caprolactam bleach precursors are of the formula:
0
0 C CH2 CH2
CH2
R1- C - N
C 2 - CH2
wherein R1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from
1
to 12 carbon atoms, preferably from 6 to 12 carbon atoms, most preferably Rl
is
phenyl.
Suitable valero lactams have the formula:
0
0 C - CH2 - CH2
Rl -- C - N
CH2 - CH2
W0 95128469 .. .. PCT/US95104205
28
wherein R1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from
l
to 12 carbon atoms, preferably from 6 to 12 carbon atoms. In highly preferred
embodiments, RI is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-
trimethylpentyl, decenyl and mixtures thereof.
The most preferred materials are those which are normally solid at <
30°C,
particularly the phenyl derivatives, ie. benzoyl valerolactam, benzoyl
caprolactam
and their substituted benzoyl analogues such as chloro, amino alkyl, alkyl,
aryl
and alkoxy derivatives.
Caprolactam and valerolactam precursor materials wherein the RI moiety
contains
at least 6, preferably from 6 to 12, carbon atoms grovide peroxyacids on
perhydrolysis of a hydrophobic character which afford nucleophilic and body
soil
clean-up. Precursor compounds wherein Rl comprises from 1 to 6 carbon atoms
provide hydrophilic bleaching species which are particularly efficient for
bleaching
beverage stains. Mixtures of 'hydrophobic' and 'hydrophilic' caprolactams and
valero lactams, typically at weight ratios of 1:5 to 5:1, preferably I:1, can
be used
herein for mixed stain removal benefits.
I~ghly preferred caprolactam and valerolactam precursors include benzoyl
capralactam, nonanoyl capro-Lictam, benzoyl valerolactam, nonanoyl
valerolactam, 3,5,5-trimethylhexanoyl caprolactam, 3,5,5-trimethylhexanoyl
valerolactam, octanoyl caprolactam, octanoyl valerolactam, decanoyl
caprolactam,
decanoyl valerolactam, undecenoyl caprolactam, undecenoyl valerolactam, (6-
octanamidocaproyl)oxybenzene-sulfonate, (6-
nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)-
oxybenzenesulfonate, and mixtures thereof. Examples of highly preferred
substituted benzoyl lactams include methylbenzoyl caprolactam, methylbenzoyl
valerolactam, ethylbenzoyl caprolactam, ethylbenzoyl valerolactam,
propylbenzoyl
caprolactam, propylbenzoyl valerolactam, isopropylbenzoyl caprolactam,
isopropylbenzoyl valerolactam, butylbenzoyl caprolactam, butylbenzoyl
valerolactam, tent-butylbenzoyl caprolactam, tert-butylbenzoyl valerolactam,
pentylbenzoyl caprolactam, pentylbenaoyl valerolactam, hexylbenzoyl
caprolactam, hexylbenzoyl valerolactam, ethoxybenzoyl caprolactam,
ethoxybenzoyl valerolactam, propoxybenzoyl caprolactam, propoxybenzoyl
valerolactam, isopropoxybenzoyl caprolactam, isopropoxybenzoyl valerolactam,
butoxybenzoyl caprolactam, butoxybenzoyl valerolactam, tert-butoxybenzoyl
~0 95128469 _ PGT/US95104205
29 2187437
caprolactam, tert-butoxybenzoyl valerolactam, pentoxybenzoyl caprolactam,
pentoxybenzoyl valerolactam, hexoxybenzoyl caprolactam, hexoxybenzoyl
valerolactam, 2,4,6-trichlorobenzoyl caprolactam, 2,4,6-trichlorobenzoyl
valerolactam, pentafluorobenaoyl caprolactam, pentafluorobenzoyl valerolactam,
dichlorobenzoyl caprolactam, dimethoxybenzoyl caprolactam, 4-chlorobenzoyl
caprolactam, 2,4-dichlororbenzoyl caprolactam, terephthaloyl dicaprolactam,
pentafluorobenzoyl caprolactam, pentafluorobenzoyl valerolactam,
dichlorobenzoyl valerolactam, dimethoxybenzoyl valerolactam, 4-chlorobenzoyl
valerolactam, 2,4-dichlororbenzoyl valerolactam, terephthaloyl divalerolactam,
4-
nitrobenzoyl caprolactam, 4-nitrobenzoyl valerolactam, and mixtures thereof.
Suitable imidazoles include N-benzoyl imidazole and N-benzoyl benzimidazole
and other useful N-acyl group-containing peroxyacid precursors include N-
benzoyl
pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
Another preferred class of peroxyacid bleach activator compounds are the amide
substituted compounds of the Following general formulae:
R~-C-N-R2-C-L R~-N-C-R2-CL
O R5 O or R5 0 O
wherein Rl is an aryl or allcaryl group with from 1 to 14 carbon atoms, R2 is
an
alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms,
and
RS is H or an allcyl, aryl, or alkaryl group containing 1 to 10 carbon atoms
and L
can be essentially any leaving group. Rl preferably contains from 6 to 12
carbon
atoms. R2 preferably contains from 4 to 8 carbon atoms. Rl may be straight
chain or branched alkyl, substituted aryl or alkylaryl containing branching,
substitution, or both and may be sourced from either synthetic sources or
natural
sources including for example, tallow fat. Analogous structural variations are
permissible for R2. The substitution can include alkyl, aryl, halogen,
nitrogen,
sulphur and other typical substituent groups or organic compounds. RS is
preferably H or methyl. Rl and RS should not contain more than 18 carbon atoms
in total. Amide substituted bleach activator compounds of this type are
described
in EP-A-0170386.
WO 95!28469 PCT/US95104205
217437
The L group must be sufficiently reactive for the 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.
These
characteristics are generally paralleled by the pKa of the conjugate acid of
the
leaving group, although exceptions to this convention are known. Ordinarily,
leaving groups that exhibit such behavior are those in which their conjugate
acid
has a pKa in the range of from 4 to 13, preferably from 6 to 11 and most
preferably from 8 to 11.
Preferred bleach precursors are those wherein Rl, R2 and RS are as defined for
the amide substituted compounds and L is selected from the group consisting
of:
-O~Y, -O~Y , and -~R3Y
0 O
-N-C-Ri -N N -N-C-CH-R4 ,
R3 , ~ , Ra Y
i
Y
R3 Y
I I
-0-CH=C-CH=CH2 -O-CH=C-CH=CH2
, ,
_O-~-Rt
,
R3 O Y
-O-C=CHR4 , and -N-S-CH-R4
R3 0
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
containing
from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon
atoms, R4 is H or R3, and Y is H or a solubilizing gmup.
"WO95l28469 ~ . PCTIUS95I04205
l' . ,! 31
The preferred solubilizing groups are -S03 M+, -C02 M+, -S04 M+,
-N~(R3) X and O <--N(R3)3 and most preferably -S03 M+ and -C02 M+
wherein R~ is an alkyl chain containing from 1 to 4 carbon atoms, M is a canon
which provides solubility to the bleach activator and X is an anion which
provides
solubility to the bleach activator. Preferably, M is an alkali metal, ammonium
or
' substituted ammonium cation, with sodium and potassium being most preferred,
and X is a halide, hydroxide, methyisulfate or acetate anion. It should be
noted
that bleach activators with a leaving group that does not contain a
solubilizing
groups should be well dispersed in the bleaching solution in order to assist
in their
dissolution.
Preferred examples of bleach precursors of the above formulae include (6-
octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfo-
nate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof.
Other preferred precursor compounds include those of the benzoxazin-type,
having
the formula:
O
C~
0
I
~N C-Rt
including the substituted benzoxazins ofthe type
-R1
wherein Rl is H, alkyl, alkaryl, aryl, aryLilkyl, and wherein R2, R3, R4, and
RS
may be the same or different substituents selected from H, halogen, alkyl,
alkenyl,
aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (wherein R6 is H or an
alkyl group) and carbonyl functions.
An especially preferred precursor of the benzoxazin-type is:
t.. :f..a ... .
W0 95128469 PCT/US95104205
32 2~ 87437
An especially preferred precursor of the benzoxazin-type is:
Or is peroxy .;~a _
The detergent compositions may also contain organic peroxyacids typically at a
level of from 19b to 15 96 by weight, more preferably from 196 to 10 96 by
weight
of the composition.
A preferred class of organic peroxyacid compounds are the amide substituted
compounds of the following general formulae:
R~ - II - ~ -R2- ~~ -OOH
0 R5 O or
R~ -R-OI -R2- ~~ -OOH
b 0
wherein Rl is an aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is
an
alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms,
and
RS is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
RI
preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4
to
8 carbon atoms. Rl may be straight chain or branched alkyl, Substituted aryl
or
alkylaryl containing branching, substitution, or both and may be sourced from
either synthetic sources or natural sources including for example, tallow fat.
Analogous structural variations are permissible for R2. The substitution can
include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent
groups
or organic compounds. RS is preferably Her methyl. Rl and RS should not
contain more than 18 carbon atoms in total. Amide substituted organic
peroxyacid
compounds of this type are described in FP-A-0170386.
0 95128469 ~ PCTIUS95/04205
33 218737
Other organic peroxyacids include diperoxy dodecanedioc acid, diperoxy tetra
decanedioc acid, diperoxyhexadecanedioc acid, mono- and diperazelaic acid,
mono- and diperbrassylic acid, monoperoxy phthalic acid, perbenzoic acid, and
their salts as disclosed in, for example, EP-A-0341 947.
Inorg m~c perh5rdrate bleaches
The compositions preferably include, as a hydrogen peroxide source, an
inorganic
perhydrate salt, most especially when the organic peroxyacid source is a
peroxyacid bleach precursor compound.
The inorganic perhydrate salts are normally incorporated in the form of the
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 I to 25 % by weight of the compositions.
Examples of inorganic perhydrate salts include perborate, percarbonate,
peiphosphate, 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'salt
in the granular product.
Sodium perborate can be in the form of the monohydrate of nominal formula
NaB02H202 or the tetrahydrate NaB02H202.3H20.
Sodium percarbonate, which is a preferred perhydrate for inclusion in
detergent
compositions in accordance with the invention, is an addition compound having
a
formula corresponding to 2Na2C03.3H202, and is available commercially as a
crystalline solid. The percarbonate is most preferably incorporated into such
compositions in a coated form which provides in product stability.
A suitable coating material providing in product stability comprises mixed
salt of
a water soluble alkali metal sulphate and carbonate. This coating however
allows
for rapid release of the percarbonate bleach to the wash solution and is
therefore
not a suitable means for providing delayed release of the percarbonate bleach
into
a wash solution. Such coatings together with coating processes have previously
.. a .l_3'_ '!Ia~'w. ".
WO 95!28469
PCT/US95/04205
34
been described in GS-1,466,799, granted to Interox on 9th March 1977. The
weight ratio of the mixed salt coating material to percarbonate lies in the
range
from 1 : 200 to I : 4, more preferably from I : 99 to 1 : 9, and most
preferably
from 1 : 49 to 1 : 19. Preferably, the mixed salt is of sodium sulphate and
sodium
carbonate which has the general formula Na2S04.n.Na2C03 wherein n is form
0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to
0.5.
Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in
the
detergent compositions herein.
~O 95128469 PCT/U595104205
Bleach catalyst
The invention also encompasses compositions containing a catalytically
effective
amount of a bleach catalyst such as a water-soluble manganese salt.
The bleach catalyst is used in a catalytically effective amount in the
compositions
and processes herein. By "catalytically effective amount" is meant an amount
which is sufficient, under whatever comparative test conditions are employed,
to
enhance bleaching and removal of the stain or stains of interest from the
target
substrate. Thus, in a fabric laundering operation, the target substrate will
typically
be a fabric stained with, for example, various food stains. For automatic
dishwashing, the target substrate may be, for example, a porcelain cup or
plate
with tea stain or a polyethylene plate stained with tomato soup. The test
conditions will vary, depending on the type of washing appliance used and the
habits of the user. Thus, front-loading laundry washing machines of the type
employed in Europe generally use less water and higher detergent
concentrations
than do top-loading U.S.-style machines. Some machines have considerably
longer wash cycles than others. Some users elect to use very hot water; others
use
warm or even cold water in fabric 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 I ppm to
about 200 ppm of the catalyst species in the laundry liquor. To illustrate
this point
further, on the order of 3 micromolar manganese catalyst is effective at
40°C, pH
10 under European conditions using perborate and a bleach precursor (e.g.,
benzoyl caprolactam). An increase in concentration of 3-5 fold may be required
under U.S. conditions to achieve the same results. Conversely, use of a bleach
precusor and the manganese catalyst with perborate may allow the formulator to
achieve equivalent bleaching at lower perborate usage levels than products
without
the manganese catalyst.
The bleach catalyst material herein can comprise the free acid or be in the
form of
any suitable salts.
w0 95/28469 PCTIUS95104205
36
One type of bleach catalyst is a catalyst system comprising a heavy metal
ration of
defined bleach catalytic activity, such as copper, iron or manganese rations,
an
auxiliary metal radon 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 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 Mn~2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2,
Mn~2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2,
Mn~4(u-O)6(1,4,7-triazacyclononane)4-(C104)2, Mn~Mn~4(u-O)1(u-OAc)2-
(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)3, and mixtures thereof.
Others
are described in European patent application publication no. 549,272. Other
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.
The bleach catalysts useful in the compositions herein may also be selected as
appropriate for the present invention. 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, I 14,606,
is a
water-soluble complex of manganese ()Z), (~, and/or (IV) with a ligand which
is
a non-carboxylate polyhydroxy compound having at least three consecutive C-OH
groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol,
xylithol,
arabitol, adonitol, meso-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:
~O 95!28469 k PCT'/US95/04205
37
R2 R3
R~-N=C-B-C=N-R4
wherein R1, R2, R3, and R4 can each be selected from H, substituted alkyl and
aryl groups such that each Rl-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 substituted or unsubstituted groups.
Preferred
ligands include pyridine, pyridazine, pyrimidine, pyrezine, imidazole,
pyraaole,
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, Cu, Mn, Fe,-
bispyridyhnethane and -bispyridylamine complexes. Highly preferred catalysts
include Co(2,2'-bispyridylamine)C12, Di(isothiocyanato)bispyridylamine-cobalt
(I)], trisdipyridylamine-cobalt()1) perchlorate, Co(2,2-
bispyridylamine)202C104,
Bis-(2,2'-bispyridylamine) copper(J~ perchlorate, tris(di-2-pyridylamine)
iron()1)
perchlorete, and mixtures thereof.
Other examples include Mn gluconate, Mn(CF3S03)2, Co(NHg)SCI, and the
binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands,
including
N4Mn~(u-O)2Mn~N4)+and [Bipy2Mn~(u-O)2Mn~bipy2]-(C104)3.
The bleach catalysts of the present invention may also be prepared by
combining a
water-soluble ligand with a water-soluble manganese salt in aqueous media and
concentrating the resulting mixture by evaporation. Any convenient water-
soluble
salt of manganese can be used herein. Manganese (II), (~, (IV) and/or (~ is
readily available on a commercial scale. In some instances, sufficient
manganese
may be present in the wash liquor, but, in general, it is preferred to add Mn
cations in the compositions to ensure its presence in catalytically-effective
amounts. Thus, the sodium salt of the ligand and a member selected from the
group consisting of MnS04, Mn(C104)2 or MnCl2 (least preferred) are dissolved
in water at molar ratios of ligand:Mn salt in the range of about 1:4 to 4:1 at
neutral or slightly alkaline pH. The water may first be de-oxygenated by
boiling
and cooled by sparging with nitrogen. The resulting solution is evaporated
(under
N2, if desired) and the resulting solids are used in the bleaching and
detergent
compositions herein without further purification.
W0 95128469 PCT/US95/04205
38 21 87437
In an alteinate mode, the water-soluble manganese source, such as MnS04, is
added to the bleach/cleaning composition or to the aqueous bleaching/cleaning
bath which comprises the ligand. Some type of complex is apparently formed in
situ, and improved bleach performance is secured. In such an in situ process,
it is
convenient to use a considerable molar excess of the ligand over the
manganese,
and mole ratios of Iigand:Mn typically are 3:1 to 15:1. The additional ligand
also
serves to scavenge vagrant metal ions such as iron and copper, thereby
protecting
the bleach from decomposition. One possible such system is described in
European patent application, publication no. 549,271.
While the structures of the bleach-catalyzing manganesecomplexes of the
present
invention have not been elucidated, it may be speculated that they comprise
chelates or other hydrated coordination complexes which result from the
interaction of the carboxyl and nitrogen atoms of the ligand with the
manganese
ration. Likewise, the oxidation state of the manganese ration during the
catalytic
process is not known with certainty, and may be the (+7T), (+)I)], (+IV) or
(+V) valence state. Due to the ligands' possible six points of attachment to
the
manganese ration, it may be reasonably speculated that mold-nuclear species
and/or "cage" structures may exist in the aqueous bleaching media. Whatever
the
form of the active Mrrligand species which actually exists, it functions in an
apparently catalytic manner to provide improved bleaching performances on
stubborn stains such as tea, ketchup, coffee, blood, and the like.
Other bleach catalysts are described, for example, in European patent
application,
publication 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 on
aluminosilicate catalyst), U.S. 4,601,845 (aIuminosilicate 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 rations and non-catalytic metal rations),
and
U:S. 4,728,455 (manganese gluconate catalysts).
-WO 95128469 PCTIUS95104205
39
The detergent compositions of the invention may contain 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.
FIeavy metal ion sequestrants are preferably present at a level of from 0.005
~ to
20 ~ , more preferably from 0.196 to 10 ~ , most preferably from 0.5 36 to 5
96 by
weight of the compositions.
Heavy metal ion sequestrants, which are acidic in nature, having for example
phosphoric acid or carboxylic acid functionalities, may be present either in
their
acid form or as a complex/salt with a suitable counter cation such as an
alkali or
alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures
thereof. Preferably any salts/complexes are water soluble. The molar ratio of
said
counter ration to the heavy metal ion sequestrant is preferably at least 1:1.
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 sequestrutt 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. Preferred EDDS compounds are the free acid form and the
sodium or magnesium salt or complex thereof. Examples of such preferred
sodium salts of EDDS include Na2EDDS and NagEDDS. Examples of such
preferred magnesium complexes of EDDS include MgEDDS and Mg2EDDS.
W0 95128469 PCT/US95104205
2187~~37
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 F.P-A-509,382 are also suitable.
EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331
describes suitable sequestiants 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) is also suitable.
Organic polymeric compounds are particularly preferred components of the
detergent compositions in accord with the invention. By organic polymeric '
compound it is meant essentially any polymeric organic compound commonly used
as dispersants, and anti-redeposition and soil suspension agents in detergent
compositions.
Organic polymeric compound is typically incorporated in the detergent
compositions of the invention at a level of from 0.1 ~ to 30~, preferably from
0.5 ~ to 15 9b, 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. Bxamples of such salts are polyacrylates of MWt
2000-5000 and their copolymers with malefic anhydride, such copolymers having
a
molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.
~O 95128469 PCT/US95104205
4~ 2187437
Other suitable organic polymeric compounds include the polymers of acrylamide
and acrylate having a molecular weight of from 3,000 to 100,000, and the
aciylatelfumarate copolymers having a molecular weight of from 2,000 to
80,000.
The polyamino 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.
Other organic polymeric compounds suitable for incorporation in the detergent
compositions herein include cellulose derivatives such as methylcellulose,
carboxymethylcellulose 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 preferably about 4000.
Lime soap dispersant compound
The compositions of the invention may contain a lime soap dispersant compound,
which has a lime soap dispersing power (LSDP), as defined hereinafter of no
more
than 8, preferably no more than 7, most preferably no more than 6. The lime
soap
dispersant compound is preferably present at a level of from 0.1 ~ to 40 ~ by
weight, more preferably 1 ~ to 209b by weight, most preferably from 2 ~ to 10
~
by weight of the compositions.
A lime soap dispersant is a material that prevents the precipitation of alkali
metal,
ammonium or amine salts of fatty acids by calcium or magnesium ions. A
numerical measure of the effectiveness of a lime soap dispersant is given by
the
lime soap dispersing power (I,SDP) which is determined using the lime soap
dispersion test as described in an article by H.C. Borghetty and C.A. Bergman,
J.
Am. Oil. Chem. Soc., volume 27, pages 88-90, (1950). This lime soap
dispersion test method is widely used by practitioners in this art field being
referred to , for example, in the following review articles; W.N. Linfield,
Surfactant Science Series, Volume 7, p3; W.N. Linfield, Tenside Surf. Det. ,
Volume 27, pages159-161, (1990); and M.K. Nagarajan, W.F. Masler, Cosmetics
and Toiletries, Volume 104, pages 71-73, (1989). The LSDP is the 9& weight
ratio of dispersing agent to sodium oleate required to disperse the lime soap
CA 02187437 1999-09-17
42
deposits formed by 0.0258 of sodium oleate in 30m1 of water of 333ppm CaC03
(Ca:Mg=3:2) equivalent hardness.
Surfactants having good lime soap dispersant capability will include certain
amine
oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated
alcohols.
Exemplary surfactants having a LSDP of no more than 8 for use in accord with
the
invention include C 16-C 1 g dimethyl amine oxide, C 12-C 1 g alkyl
ethoxysulfates
with an average degree of ethoxyladon of from 1-5, particularly C12-C15 ~yl
ethoxysulfate surfactant with a degree of ethoxyladon of about 3 (L,SDP=4),
and
the C13-C15 ethoxylated alcohols with an average degree of ethoxyladon of
either
12 (L,SDP=6) or 30, sold under the trade marks Lutensol A012 and Lutensol
A030 respectively, by BASF GmbH.
Polymeric lime soap dispersants suitable for use herein are described in the
article
by M.K. Nagaiajan and W.F. Masler, to be found in Cosmetics and Toiletries,
Volume 104, pages 71-73, (1989). Examples of such polymeric lime soap
dispersants include certain water-soluble salts of copolymers of acrylic acid,
methacrylic acid or mixtures thereof, and an acrylamide or substituted
acrylamide,
where such polymers typically have a molecular weight of from 5,000 to 20,000.
Suds su ressing 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 ~o to 15 ~b , preferably from 0.05 °b to 10 ~ ,
most preferably
fmm 0.1 ~6 to 5 9~ 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,
2-alkyl and alcanol antifoam compounds.
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.
- W O 95/28469 PCT/US95104205
43 218737
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
to about 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 Clg-C4p 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.
Copolymers of ethylene oxide and propylene oxide, particularly the mixed
ethoxylated/propoxylated fatty alcohols with an alkyl chain length of from 10
to
16 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of
propoxylation of from 1 to 10, are also suitable antifoam compounds for use
herein.
Suitable 2-alley-alcanols antifoam compounds for use herein have been
described in
DE 44 21 265._ The 2-alkyl-alcanols suitable for use herein consist of a C6 to
C16
alkyl chain carrying a terminal hydroxy group, and said alkyl chain is
substituted
in the a position by a C1 to C10 alkyl chain. Mixtures of 2-alkyl-alcanols can
be
used in the compositions according to the present invention.
CA 02187437 1999-09-17
94
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 SO % to 99 % , preferably
75 % to 95 % by weight of the silicone antifoam compound; and
(ii) silica, at a level of from I % 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. S % to 10 % , preferably 1 % to 10 % by weight; a particularly preferred
silicone glycol rake copolymer of this type is DG0544, commercially
available from DOW Corning 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 S to 50,
preferably 8 to 15, at a level of from 5 % to 80 % , preferably 10 % to 70 % ,
by weight;
A preferred particulate suds suppressor system useful herein comprises a
mixture
of an alkylated siloxane of the type hereinabove disclosed and solid silica.
The solid silica can be a fumed silica, a precipitated silica or a silica,
made by the
gel formation technique. The silica particles suitable have an average
particle size
of from 0.1 to 50 micrometers, preferably from 1 to 20 micrometers and a
surface
area of at least SOm2/g. These silica particles can be rendered hydrophobic by
treating them with dialkylsilyl groups and/or trialkylsilyl groups either
bonded
directly onto the silica or by means of a silicone resin. It is preferred to
employ a
silica the particles of which have been rendered hydrophobic with dimethyl
and/or
CA 02187437 1999-09-17
45
trimethyl silyl groups. A preferred particulate antifoam compound for
inclusion in
the detergent compositions in accordance with the invention suitably contain
an
amount of silica such that the weight ratio of silica to silicone lies in the
range
from 1:100 to 3:10, preferably from 1:50 to 1:7.
Another suitable particulate suds suppressing system is represented by a
hydrophobic silanated (most preferably trimethyl-silanated) silica having a
particle
size in the range from 10 nanometers to 20 nanometers and a specific surface
area
above SOm2/g, intimately admixed with dimethyl silicone fluid having a
molecular
weight in the range from about 500 to about 200,000 at a weight ratio of
silicone
to silanated silica of from about 1:1 to about 1:2.
A highly preferred particulate suds suppressing system is described in EP-A-
0210731 and comprises a silicone antifoam compound and an organic can-ier
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 capon 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.
Other highly preferred particulate suds suppressing systems are described in
CA 2,099,129 which systems comprise silicone antifoam compound, a carrier
material, an organic coating material and glycerol at a weight ratio of
glycerol
silicone antifoam compound of 1:2 to 3:1. CA 2,110,409 also discloses
highly preferred particulate suds suppressing systems
comprising silicone antifoam compound, a carrier material, an organic coating
material and crystalline or amorphous aluminosilicate at a weight ratio of
aluminosilicate : silicone antifoam compound of 1:3 to 3:1. The preferred
carltier
material in both of the above described highly preferred granular suds
controlling
agents is starch.
An exemplary particulate suds suppressing system for use herein is a
particulate
agglomerate component, made by an agglomeration process, comprising in
combination
W0 95128469 PCTIU595/04205
46
(i) from 5 ~ to 30 % , preferably from 8 ~ to 15 ~ by weight of the component
of silicone antifoam compound, preferably comprising in combination
polydimethyl siloxane and silica;
(ii) from 50 % to 90 ~ , preferably from 60 ~ to 80 ~ by weight of the
component, of carrier material, preferably starch;
(iii) from 5 % to 30 ~, preferably from 10 % to 20 % by weight of the
component of agglomerate binder compound, where herein such compound
can be any compound, or mixtures thereof typically employed as binders
for agglomerates, most preferably said agglomerate binder compound
comprises a C16-Clg ethoxylated alcohol with a degree of ethoxylation of
from 50 to 100; and
(iv) from 29b to 15 ro, preferably from 3 % to 1036, by weight of CI2-C22
hydrogenated fatty acid.
'WO95128469 ~ PCT/US95/04205
2187437
Polymeric dye transfer inhibiting ggentc
The detergent compositions herein may also comprise from 0.01 ~ to 10 ro,
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-
vinyIimidazole, polyvinylpyrrolidone polymers or combinations thereof.
al Polyamine N-oxide poll
Polyamine N-oxide polymers suitable for use herein contain units having the
following structure formula
P
(I)
R
wherein P is a polymerisable unit, whereto the R-N-O group can be attached to,
or
wherein the R-N-O group forms part of the poIymerisable unit or a combination
of
both.
O O O
A is NC, C0, C, -O-, -S-, -N-; x is O or 1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic
groups
or any combination thereof whereto the nitrogen 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
WO 95/28469 PCTIUS95104205
48 2187437
0
0
~R~ ) x _ ~ _~R2)y 1
(R3)Z or =N-(R~ )x
wherein Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic
groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the
nitrogen of the N-O group 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 pyrridine, pyrrole, imidazole,
pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
Another class of said polyamine N-oxides comprises the group of polyamine N-
oxides wherein the nitrogen of the N-O group is attached to the R-group.
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O
group is attached to the polymerisable unit.
Preferred class of these polyamine N-oxides are the polyamine N-oxides having
the general formula ()] wherein R is an aromatic,heterocyclic or alicyclic
groups
wherein the nitrogen of the N-0 functional group is part of said R group.
Examples of these classes are polyamine oxides wherein R is a heterocyclic
compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the polyamine oxides having
the general formula (n wherein R are aromatic, heterocyclic or alicyclic
groups
wherein the nitrogen of the N-0 functional group is attached to said R groups.
'WO95128469 ' PCTIU595/04205
49 2187437
fixamples of these classes are polyamine oxides wherein R groups can be
aromatic
such as phenyl.
Any polymer backbone can be used as long as the amine oxide polymer formed is
water-soluble and has dye transfer inhibiting properties. Examples of suitable
polymeric backbones are polyvinyls, polyallcylenes, polyesters, polyethers,
polyamide, polyimides, polyacrylates and mixtures thereof.
The amine N-oxide polymers of the present invention typically have a ratio of
amine to the amine N-oxide of 10:1 to 1:1000000. However the amount of amine
oxide groups present in the polyamine oxide polymer can be varied by
appropriate
copolymerization or by appropriate degree of N-oxidation. Preferably, the
ratio of
amine to amine N-oxide is from 2:3 to 1:1000000. More preferably from 1:4 to
1:1000000, most preferably from 1:7 to 1:1000000. The polymers of the present
invention actually encompass random or block copolymers where one monomer
type is an amine N-oxide and the other monomer type is either an amine N-oxide
or not. The amine oxide unit of the polyamine N-oxides has a PKa < 10,
preferably PKa < 7, more preferred PKa < 6.
The polyamine oxides can be obtained in almost any degree of polymesisation.
The degree of polymerisation is not critical provided the material has the
desired
water-solubility and dye-suspending power. Typically, the average molecular
weight is within the range of 500 to 1000,000; preferably from 1,000 to
50,000,
more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
bl CoRolymers of N-vinylpyrro&done an~i N-~inylimidawle
Preferred polymers for use herein may comprise a polymer selected from N-
vinylimidazole N-vinylpyrrolidone copolymers wherein said polymer has an
average molecular weight range from 5,000 to 50,000 more preferably from 8,000
to 30,000, most preferably from 10,000 to 20,000. The preferred N-
vinylimidazole N-vinylpyrrolidone copolymers have a molar ratio of N-
vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8
to
0.3, most preferably from 0.6 to 0.4 .
cl PolyvinylQyrrolidone
WO 95128469 PCTlUS95104205
So 2187437
The detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP"
having an average molecular weight of from 2,500 to 400,000, preferably from
5,000 to 200,000, more preferably from 5,000 to 50,000, and most preferably
from 5,000 to 15,000. Suitable polyvinylpyrrolidones are commercially vailable
from ISP Corporation, New York, NY and Montreal, Canada under the product
names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average
molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000),
and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available
from ISP Corporation. Other suitable polyvinylpyrrolidones which are
commercially available from BASF Cooperation include Sokalan HP 165 and
Sokalan HP 12.
Polyvinylpyrrolidone may be incorporated in the detergent compositions herein
at
a level of from 0.01 ~ to 5 ~ by weight of the detergent, preferably from 0.05
~
to 3 9b by weight, and more preferably from 0.1 % to 2 % by weight. The amount
of polyvinylpyrrolidone delivered in the wash solution is preferably from 0.5
ppm
to 250 ppm, preferably from 2.5 ppm to 150 ppm, more preferably from 5 ppm to
l00 ppm.
The detergent compositions herein may also utilize polyvinyloxazolidones as
polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an
average molecular weight of from 2,500 to 400,000, preferably from 5,000 to
200,000, more preferably from 5,000 to 50,000, and most preferably from 5,000
to 15,000.
The amount of polyvinyloxazolidone incorporated in the detergent compositions
may be from 0.01 ~ to 5 Rb by weight, preferably from 0.05 ~ to 3 °k by
weight,
and more preferably from 0.1 ~ to 2 ~ by weight. The amount of
polyvinyloxazolidone delivered in the wash solution is typically from 0.5 ppm
to
250 ppm, preferably from 2.5 ppm to 150 ppm, more preferably from 5 ppm to
100 ppm.
el Polyvinylimidazole
R'O 95128469 PCTIUS95104205
~ ~ 81437
The detergent compositions herein may also utilize polyvinylimidazole as
polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably
have
an average molecular weight of from 2,500 to 400,000, more preferably from
5,000 to 50,000, and most preferably from 5,000 to 15,000.
The amount of polyvinylimidazole incorpoarted in the detergent compositions
may
be from 0.01 % to 5 % by weight, preferably from 0.05 36 to 3 Y6 by weight,
and
more preferably from 0.136 to 2 h by weight. The amount of polyvinylimidazole
delivered in the wash solution is from 0.5 ppm to 250 ppm, preferably from 2.5
ppm to 150 ppm, more preferably from 5 ppm to 100 ppm.
CA 02187437 1999-09-17
52
tical brightener
The detergent compositions herein may also optionally contain from about 0.005
~
to 5 ~ by weight of certain types of hydrophilic optical brighteners which
also
provide a dye transfer inhibition action. If used, the compositions herein
will
preferably comprise from about 0.01 qb to 1 ~ by weight of such optical
brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having
the structural formula:
R~ R2
~N H H N
N N
C C ~ N--~~ N
/ N H H N
S03M S03M
wherein RI is selected from anilino, N-2-bis-hydmxyethyl 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 radon such
as sodium or potassium.
When in the above formula, RI is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
ration such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium
salt. This particular brightener species is commercially marketed under the
trademark Tinopal-LTNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is
the preferred hydrophilic optical brightener useful in the detergent
compositions
herein.
When in the above formula, RI is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a ration such as sodium, the brightener is 4,4'-bis[(4-
anilino-6-(N-2-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 SBM-GX by Ciba-Geigy
Corporation.
'-WO 95/28469 PCTIUS95104205
53 2187437
When in the above formula, Rl is anilino, R2 is morphilino and M is a canon
such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-
2-
yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener
species is commercially marketed under the tradename Tinopal AMS-GX by Ciba
Geigy Corporation.
The specific optical brightener species selected for use in the present
invention
provide especially effective dye transfer inhibition performance benefits when
used
in combination with the selected polymeric dye transfer inhibiting agents
hereinbefore described. The combination of such selected polymeric materials
(e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g.,
Tinopal
UNPA-GX, Tinopal SBM-GX and/or Tinopal AMS-GX) provides significantly
better dye transfer inhibition in aqueous wash solutions than does either of
these
two detergent composition components when used alone. Without being bound by
theory, it is believed that such brighteners work this way because they have
high
affinity for fabrics in the wash solution and therefore deposit relatively
quick on
these fabrics. The extent to which brighteners deposit on fabrics in the wash
solution can be defined by a parameter called the "exhaustion coefficient".
The
exhaustion coefficient is in general as the ratio of a) the brightener
material
deposited on fabric to b) the initial brightener concentration in the wash
liquor.
Brighteners with relatively high exhaustion coefficients are the most suitable
for
inhibiting dye transfer in the context of the present invention.
Of course, it will be appreciated that other, conventional optical brightener
types
of compounds can optionally be used in the present compositions to provide
conventional fabric "brightness" benefits, rather than a true dye transfer
inhibiting
effect. Such usage is conventional and well-known to detergent formulations.
Fabric softening agents can also be incorporated into laundry detergent
compositions in accordance with the present invention. These agents may be
inorganic or organic in type. Inorganic softening agents are exemplified by
the
smectite clays disclosed in GB-A-1 400 898. Organic fabric softening agents
include the water insoluble tertiary amines as disclosed in GB-A-1 514 276 and
EP-B-0 011 340.
WO 95!28469 PCTIUS95/04205
54 2187437
Levels of smectite clay are normally in the range from 5 ~ to 15 % , more
preferably from 8 % to 12 ~ by weight, with the material being added as a dry
mixed component to the remainder of the formulation. Organic fabric softening
agents such as the water-insoluble tertiary amines or dilong chain amide
materials
are incorporated at levels of from 0.5 ~ to 5 ~ by weight, normally from 1 ~
to
3 9& by weight, whilst the high molecular weight polyethylene oxide materials
and
the water soluble cationic materials are added at levels of from 0.1 ~ to 2 J
,
normally from 0.15 l to 1.5 % by weight.
Other optional ing iii .n c
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.
The detergent compositions of the invention can be formulated in any desirable
form such as powders, granulates, pastes, liquids, tablets and gels.
The detergent compositions of the present invention may be formulated as
liquid
detergent compositions. Such liquid detergent compositions typically comprise
from 94 k to 35 % by weight, preferably from 90 °6 to 40 ~ by weight,
most
preferably from 80~ to SO Y6 by weight of a liquid carrier, e.g., water,
preferably
a mixture of water and organic solvent.
The detergent compositions of the present invention may also be in the form of
gels. Such compositions are typically formulated with polyakenyl polyether
having a molecular weight of from about '750,000 to about 4,000,000.
- W095128469 ~ a,- _ _ ' ~ -i PCT/IJ595104205
55 2187437
The detergent compositions of the invention are preferably in the form of
solids,
such as powders and granules.
The particle size of the components of granular compositions in accordance
with
the invention should preferably be such that no more that 5 °.6 of
particles are
greater than 1.4mm in diameter and not more than 5 % of particles are less
than
O.lSmm in diameter.
The bulls density of granular detergent compositions in accordance with the
present
invention typically have a bulk density of at least 450 g/litre, more usually
at least
600 g/litre and more preferably from 650 gllitre to 1200 gllitre.
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
afigned cylindrial cup disposed below the funnel. The funnel is 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 S00 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 e.g. a knife, across its upper edge. The filled cup
is
then weighed and the value obtained for the weight of powder doubled to
provide
the bulk density in g/litre. Replicate measurements are made as required.
Making processes - eranular com ositions
In general, granular detergent compositions in accordance with the present
invention can be made via a variety of methods including dry mixing, spray
drying, agglomeration and granulation.
Washing methods
s~ ~i,J~.r ,~ 'y ~ -
WO 95!28469 =r PCTIUS95104205
2187437
The compositions of the invention may be used in essentially any washing or
cleaning method, including machine laundry and dishwashing methods.
A preferred machine dishwashing method comprises treating soiled articles
selected from crockery, glassware, hollowware 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 inevntion. 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.
Machine laundry methods herein 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. The detergent can be added to the wash solution either via the
dispenser
drawer of the washing machine or by a dispensing device. By an effective
amount
of the detergent composition it is meant from 40g 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.
In a preferred washing method herein a dispensing device containing an
effective
amount of detergent product is introduced into the drum of a front-loading
washing machine before the commencement of the wash cycle.
The dispensing device is a container for the detergent product which is used
to
deliver the product directly into the drum of the washing machine. Its volume
,
capacity should be such as to be able to contain sufficient detergent product
as
would normally be used in the washing method. .
Once the washing machine has been loaded with laundry the dispensing device
containing the detergent product is placed inside the drum. At the
commencement
~W 0 95128469 PCT/US95104205
5' 2187437
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 immersion in 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 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 in accord with 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".
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 arrangemnt 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.
Pretreatment washing method
n x t~. 6....
W0 95/28469 PCTIUS95I04205
Sa 2181431
In a pretreatment wash method aspect of the invention a soiled/stained
substrate is
treated with an effective amount of a pretreatment solution containing a water-
soluble builder, but no enzyme components. The solution might optionally
contain other non-enzyme detergent components such as surfactants, builders,
and
detergent polymers. Preferably the solution also contains water-soluble
builder.
The level of the water-soluble builder in said pretreatment solution is
typically
from 0.05% to 809&, and preferably is more than 1 ~.
The pretreatment solution is allowed to remain in contact with the soiled
substrate
for an effective time interval. Said time interval will typically be from 10
seconds
to 1800 seconds, more preferably from 60 seconds to 600 seconds.
The soiled substrate is then washed using a suitable washing method wherein an
enzyme-containing detergent product is employed. The washing method may for
example, be any of the machine dishwashing or machine laundry washing methods
described herein.
In the detergent compositions, the abbreviated component identifications have
the
following meanings:
XYAS . Sodium C1X - Cly alkyl sulfate
~~' : -A CI2_IS P~ominantly linear primary alcohol
condensed with an average of Y moles of ethylene
oxide
~Z . A Clx - Cly predominantly linear primary alcohol
condensed with an average of Z moles of ethylene
oxide
~S ~ C1X - C1Y sodium alkyl sulfate condensed with an
average of Z moles of ethylene oxide per mole
'AAA . C16-Clg alkyl N-methyl glucamide.
~WO 95/28469 - - PGT/US95/04205
59 2187437
Silicate . Amorphous Sodium Silicate (Si02:Na20 ratio = 2.0)
NaSKS-6 . Crystalline layered silicate of formula b-Na2Si205
Carbonate . Anhydrous sodium carbonate
Polycarboxylate . Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 80,000 -
Zeolite A . Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si0~12. 27H20 having a primary particle
size in the range from 1 to 10 micrometers
Citrate . Tri-sodium citrate dihydrate
Percarbonate (fast release . Anhydrous sodium percarbonate bleach of empirical
particle) formula 2Na2C03.3H202 coated with a mixed salt of
formula Na2SO4.n.Na2C03 where n is 0.29 and
where the weight ratio of percarbonate to mixed salt is
39:1
Percarbonate (slow release . Anhydrous sodium percarbonate bleach coated with
a
particle) coating of sodium silicate (Si20:Na20 ratio = 2:1) at
a weight ratio of percarbonate to sodium silicate of
39:1
TAB . Tetraacetyl ethylene diamine
TAED (slow release . Particle formed by agglomerating TAED with citric
particle) acid and polyethylene glycol (PEG) of Mw=4,000
with a weight ratio of components of TAED:citric
acid:PEG of 75:10:15, coated with an external coating
of citric acid at a weight ratio of agglomerate: citric
acid coating of 95:5.
CA 02187437 1999-09-17
60
Benzoyl Caprolactam (slow . Particle formed by agglomerating benzoyl
caprolactam
release particle) (BzCI) with citric acid and polyethylene glycol (PEG)
of Mw=4,000, with a weight ratio of components of
BzCl:citric acid:PEG of 63:21:16, coated with an
external coating of citric acid at a weight ratio of
agglomerate:citric acid coating of 95:5
TAED (fast release . Particle formed by agglomerating TAED with partially
particle) neutralised polycarboxylate at a ratio of
TAED:polycarboxylate of 93:7, coated with an
external coating of polycarboxylate at a weight ratio of
agglomerate:coating of 96:4
EDDS (fast release . Particle formed by spray-drying EDDS with MgS04 at
particle) a weight ratio of 26:74
Protease . Proteolytic enzyme sold under the trademark Savinase
by Novo Industries A/S with an activity of 13
KNPU/g.
Protease (slow release . An enzyme prill containing proteolytic enzyme sold
particle) under the tradename Savinase by Novo Industries A/S
with an activity of 13 KNPU/g coated with a coating
of sodium silicate (Si02:Na20 ratio = 2:1) at a
coating level of 5 ~ .
Amylase . Amylolytic enzyme sold under the trademark
Termamyl 60T by Novo Industries A/S with an activity
of 300 KNU/g
Cellulase . Cellulosic enzyme sold by Novo Industries A/S with an
activity of 1000 CEVU/g
Lipase . Lipolytic enzyme sold under the trademark Lipo(ase by
Novo Industries A/S with an activity of 165 KLU/g
~W095128469 ~ . PCTlUS95104205
61 21874-37
CMC . Sodium carboxymethyl cellulose
1,1-hydroxyethane diphosphonic acid
EDDS . Ethylenediamine -N, N'- disuccinic acid, [S,S] isomer
in the form of the sodium salt.
PVN~ . Poly (4-vinylpyridine)-N-oxide copolymer of
vinylimidaxole and vinylpyrrolidone
Granular Suds Suppressor . 129b Silicone/silica, 18 % stearyl alcoho1,709b
starch in
granular form
. ., a.
WO 95128469 PCT/US95104205
62 2137437
The following laundry detergent compositions were prepared values being
expressed as percentages by weight of the compositions: Composition A is a
prior
art composition, compositions B to D are in accord with the invention:
A B C D
45AS/25AS (3:1) 9.1 9.1 9.1 9.1
35AE3S 2.3 2.3 2.3 2.3
24E5 4.5 4.5 4.5 4.5
TFAA 2.0 2.0 2.0 2.0
Z.eoHte A 13.2 13.2 13.2 13.2
Na SKS-6/citric acid 15.6 15.6 15.6 15.6
(79:21)
Carbonate 7.6 7.6 7.6 7.6
TAED (fast release 6.3 - - -
particle)
TAED (slow release - 5.0 - 2.3
particle)
Benzoyl Caprolactam - - g,0 2.~
(slow
release particle)
Percarbonate (fast 22.5 - - 22.5
release
particle)
Percarbonate (slow - 22.5 22.5 -
release
particle)
~O 95128469 " PCT/US95/04205
~~~7437
DETPMP 0.5 0.8
EDDS (fast release particle)- - 0.3 0.75
Protease 0.55 - - _
Protease (slow release - 1.27 0.55 1.27
article
Lipase 0.15 0.15 0.15 0.15
Cellulase 0.28 0.28 0.28 0.28
Amylase 0.27 0.27 0.27 0.27
Polycarboxylate 5.1 5.1 5.1 5.1
CMC 0.4 0.4 0.4 0.4
PVNO 0.03 0.03 0.03 0.03
Granular suds suppressor1.5 1.5 1.5 1.5
Minorslmisc to 10036
