Note: Descriptions are shown in the official language in which they were submitted.
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Deter~ent compositions
Technical field
The present invention relates to detergent compositions comprising a
cationic ester surf~çt~nt and an ~lk~linity system, wherein is provided a
means to delay the release of the ~Ik~linity system to the wash solution.
Background to the invention
The satisfactory removal of greasy soils/stains, that is soils/stains having a
high proportion of triglycerides or fatty acids, is a challenge faced by the
formulator of detergelll compositions for use in machine laundry and
dishwashing methods. Surfactant components have traditionally been
employed in detergent products to facilitate the removal of such greasy
soils/stains. In particular, surfactant systems comprising cationic esters
have been described for use in greasy soil/stain removal.
For example, EP-B-21,491 discloses detergent compositions cont~inin~ a
nonionic/cationic surfactant mixture and a builder mixture comprising
aluminosilicate and polycarboxylate builder. The cationic surfactant may
be a cationic ester. Improved particulate and greasy/oily soil removal is
described.
US-A-4,228,042 discloses biodegradable cationic surfactants, including
cationic ester surf~ct~nt~ for use in detergent compositions to provide
greasy/oily soil removal. The combination of these cationic surf~ct~nts
with nonionic surfactants in compositions designed for particulate soil
removal is also described. Anionic surfactants are disclosed as optional
components of the compositions, but are present at low levels relative to
the cationic surfactant component.
US-A-4,239,660 discloses laundry detergent compositions cont~ining
cationic ester surfactant and nonionic surfactant at defined weight ratios
.. .... . . .. . ....
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and an high ~lk~linity source. The ~lk~linity source enables a wash
solution having a pH of from 8 to 10 to be formed within 3 minutes of
dissolution of the composition in water at 100~F (37~C) at a solution
concentration of 0.15 % . This is achieved by the use of highly soluble
~lk~linity sources.
US-A-4,260,529 discloses laundry detergent compositions having a pH of
no greater than 11 con~ining cationic ester surfactant and nonionic
surfactant at defined weight ratios. Anionic surfactants are disclosed as
optional components of the compositions, but are present at low levels
relative to the cationic ester surfactant component.
The Applicants have now found that a problem with the use of certain
cationic ester surf~ct~nt~ is the tendency for the ester linkage to
hydrolytically cleave, thereby bre~king up the surfactant molecule, under
the wash conditions of a typical laundry or dishwashing method and under
the typical ~lk~linity conditions of such laundry and dishwashing methods
employing cationic surfactants. Precisely the high ~lk~linity sources,
taught by the prior art to be essential for the optimal surfactant
performance of the cationic ester surf~ct~ntc, can be the cause of the
hydrolytic cleavage of the ester linkage, which can compromise the
surfactant performance in the wash.
It has now been found that a solution to this problem is provided when the
cationic ester surfactant is employed in a detergent composition providing
a means to delay the release or establishment of the ~lk~linity in the wash
solution. Such a means provides a reduced ~lk~linity at the beginning of
the wash and thereby an overall reduction or delay of the hydrolytic
cleavage of the ester linkage is achieved during the wash. Overall,
sufficient ~lk~linity is delivered to the wash to allow the cationic ester
surfactant to perform optimal greasy soil/ stain removal during the wash.
Thus, introduction of such a means in a detergent composition will
optimise the overall surfactant performance in the wash.
All documents cited in the present description are, in relevant part,
incorporated herein by reference.
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S~lmm~ry of the Invention
According to the present invention there is provided a detergent
composition cont~inin~
(a) a cationic ester surf~ct~nt: and
(b) an ~lk~linity system,
wherein a means is provided for delaying the release to a wash solution of
said ~lk~linity system relative to the release of said cationic ester
surfactant such that in the T50 test me~ho~ herein described the time to
achieve a collce~ alion that is 50% of the ~ s~e coneclllra~ion of said
cationic ester ~ul r~cl; nt is at least 120 secullds less than the time to
achieve a concentration that is 50% of the ~ ;..-Ate collce~ alion of said
~lk~linity system.
In a preferred aspect, the cationic ester surfactant is selected from those
having the formula:
Rs 1 +
Rl-- (~ (CH)nO b (X)U ( C H 2 )m--(Y)v--(C H 2 )t--N--R3 M
- a R4
wller~ill Rl is a Cs-C3 1 linear or br~n~l~e~l alkyl, alkenyl or alkaryl chain
or M- N~ 7R8)(CH2)s; X and Y, independently, are selecte~ from
the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO,
OCONH and NHCOO wherein at least one of X or Y is a COO, OCO,
OCOO, OCONH or NHCOO group; R2, R3, R4, R6, R7, and R8 are
independently selected from the group con~ tin~ of alkyl, alkenyl,
hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4
carbon atoms; and Rs is independently H or a Cl-C3 alkyl group;
wherein the values of m, n, s and t independently lie in the range of from
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0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u
and v independently are either 0 or 1 with the proviso that at least one of
u or v must be 1; and wherein M is a counter anion.
The ~k~linity system preferably comprises alkaline salts selected from the
group consisting of alkali metal or ~lk~line earth carbonate, bicarbonate,
hydroxide or silicate salts, crystalline layered silicate and inorganic
perhydrate salts and any mixtures thereof.
Detailed description of the invention
Cationic ester surfactant
An essential element of the detergent compositions of the invention is a
cationic ester surfactant preferably present at a level from 0.1 % to
20.0%, more preferably from 0.5% to 10%, most preferably from 1.0%
to 5.0% by weight of the detel~el.t composition.
The cationic ester surfactant of the present invention is a, preferablywater dispersible, compound having surfactant properties comprising at
least one ester (i.e. -COO-) linkage and at least one cationically charged
group.
Suitable cationic ester surfactants, including choline ester surfactants,
have for example been disclosed in US Patents No.s 4228042, 4239660
and 4260529.
In one preferred aspect the ester linkage and cationically charged group
are separated from each other in the surfactant molecule by a spacer
group con~ tin,e of a chain comprising at least three atoms (i.e. of three
atoms chain length), preferably from three to eight atoms, more
preferably from three to five atoms, most preferably three atoms. The
atoms forming the spacer group chain are selected from the group
consisting of carbon, nitrogen and oxygen atoms and any mixtures
thereof, with the proviso that any nitrogen or oxygen atom in said chain
connects only with carbon atoms in the chain. Thus spacer groups
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having, for example, -O-O- (i.e. peroxide), -N-N-, and -N-O- linkages
are excluded, whilst spacer groups having, for example -CH2-O- CH2-
and -CH2-NH-CH2- linkages are included. In a preferred aspect the
spacer group chain comprises only carbon atoms, most preferably the
chain is a hydrocarbyl chain.
Preferred cationic ester surfactants are those having the formula:
R5
Rl - ~ - (CH)no (x)u - ( CH2)m-(~V-(cH2)t N R3 M
- a
R4
wherein Rl is a Cs-C31 linear or branched alkyl, alkenyl or alkaryl chain
or M-. N+(R6R7Rg)(CH2)S; X and Y, independently, are selected from
the group consisting of COO, OCO, O, CO, OCOO, CONH,NHCO,
OCONH and NHCOO wherein at least one of X or Y is a COO, OCO,
OCOO,OCONH or NHCOO group; R2, R3, R4, R6, R7, and R8 are
independently selected from the group consisting of alkyl, alkenyl,
hydroxyalkyl and hydroxy-alkenyl groups having from 1 to 4 carbon
atoms and alkaryl groups; and Rs is independently H or a C1-C3 alkyl
group; wherein the values of m, n, s and t independently lie in the range
of from 0 to 8, the value of b lies in the range from 0 to 20, and the
values of a, u and v independently are either 0 or 1 with the proviso that
at least one of u or v must be 1; and wherein M is a counter anion.
Preferably M is selected from the group consisting of halide, methyl
sulfate, sulfate, and nitrate, more preferably methyl sulfate, chloride,
bromide or iodide.
In a preferred aspect, the cationic ester surfactant is selected from those
having the formula:
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- R2
R5
R1---- O--(CH)nO (X)--(CH2)m N -- R3 M
b a
R4
wherein R1 is a Cs-C31 linear or branched alkyl, alkenyl or alkaryl
chain; X is selected from the group consisting of COO, OCO, OCOO,
OCONH and NHCOO; R2, R3, and R4 are independently selected from
the group consisting of alkyl and hydroxyalkyl groups having from 1 to 4
carbon atoms; and Rs is independently H or a C1-C3 alkyl group;
wherein the value of n lies in the range of from 0 to 8, the value of b lies
in the range from 0 to 20, the value of a is either 0 or 1, and the value of
m is from 3 to 8.
More preferably R2, R3 and R4 are independently selected from a C1-C4
alkyl group and a C 1-C4 hydroxyalkyl group. In one preferred aspect at
least one, preferably only one of R2, R3 and R4 is a hydroxyalkyl group.
The hydroxyalkyl preferably has from 1 to 4 carbon atoms, more
preferably 2 or 3 carbon atoms, most preferably 2 carbon atoms. In
another preferred aspect at least one of R2, R3 and R4 is a C2-C3 alkyl
group, more preferably two C2-C3 alkyl groups are present.
Highly preferred water dispersible cationic ester surfactants are the esters
having the formula:
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O CH3
R1--C -- O--(CH2)m N+--CH3 M-
CH3
where m is from 1 to 4, preferably 2 or 3 and wherein Rl is a Cl 1-Clg
linear or branched alkyl chain.
Particularly preferred choline esters of this type include the stearoylcholine ester quaternary methylammonium halides (R1=C17 alkyl),
palmitoyl choline ester quaternary methylamrnonium halides (R1=C1s
alkyl), myristoyl choline ester quaternary methyl~mmonium halides
(R1=C13 alkyl), lauroyl choline ester methylammonium halides
(Rl=C11 alkyl), cocoyl choline ester quaternary methylamrnonium
halides (R1=C11 C13 alkyl), tallowyl choline ester quaternary
methylammonium halides (R1=C1s C17 alkyl), and any mixtures thereof.
Other suitable cationic ester surfactants have the structural formulas
below, wherein d may be from 0 to 20.
Rl--~--C--~CH2)d C--O--CH2CH2--I--CH3 M-
CH3
CH3 0 0 CH3
M CH3--I--CH2--CH2--O--C--(CH2)d C--O--CH2--CH2--I--CH3M
CH3 CH3
In a preferred aspect the cationic ester surfactant is hydrolysable under the
conditions of a laundry wash method.
The particularly preferred choline esters, given above, may be preparedby the direct esterif1cation of a fatty acid of the desired chain length with
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dimethylaminoethanol, in the presence of an acid catalyst. The reaction
product is then quaternized with a methyl halide, preferably in the
presence of a solvent such as ethanol, water, propylene glycol or
preferably a fatty alcohol ethoxylate such as C1o-C1g fatty alcohol
ethoxylate having a degree of ethoxylation of from 3 to 50 ethoxy groups
per mole forming the desired cationic material. They may also be
prepared by the direct esterification of a long chain fatty acid of the
desired chain length together with 2-haloethanol, in the presence of an
acid catalyst material. The reaction product is then quaternized with
trimethyl~mine, forrning the desired cationic material.
Alk~linity system
Another essential aspect of the deterge.lt composition of the present
invention is an ~lk~linity system, comprising components capable of
providing ~lk~linity species in solution. By ~lk~linity species it is meant
for the purposes of this invention: carbonate, bicarbonate, hydroxide, the
various silicate anions, inorganic perhydrate anions and crystalline
layered silicates. Such ~lk~linity species can be formed for example, when
~lk~lin~ salts selected from alkali metal or ~lk~line earth carbonate,
bicarbonate, hydroxide or silicate salts, crystalline layered silicate or
inorganic perhydrate salts, preferably alkali metal percarbonate, perborate
and persilicate salts and any mixtures thereof, are dissolved in water.
Preferably, the ~lk~lin~ earth and alkali metal carbonates and bicarbonates
are selected from sodium carbonate, potassium carbonate, sodium
bicarbonate and potassium bicarbonate and mixtures thereof, and
including sodium carbonate, sesqui-carbonate and any mixtures thereof
with ultra-fine calcium carbonate such as are disclosed in German Patent
Application No. 2,321,001 published on November 15, 1973. Suitable
mixtures include mixtures of sodium carbonate with sodium bicarbonate,
sodium carbonate with potassium carbonate and sodium carbonate with
sodium bicarbonate and potassium carbonate. More preferably, the
~lk~linity system is subst~nti~lly free from carbonate salts, but may
comprise bicarbonate salts.
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The carbonate and bicarbonate preferably have a amorphous structure.
Preferably the carbonate and bicarbonates are coated with coating
materials, described below in the section 'delayed rate of release -
means' .
The particles of carbonate and bicarbonate can have a mean particle size
of 250~m or greater, preferably 500~1m or greater. It is preferred that
fewer than 20% of the particles have a particle size below 500,um.
The mean particle size of the particles of carbonate and bicarbonate
herein is deterrnined by reference to a method involving choice of varied
sizes of sieve through which the sample is attempted to be passed. The
mean particle size of a sample is given by the diameter of sieve through
which half of the mass of the sample will pass, and accordingly through
which half of the sample will not pass.
Suitable silicates include the sodium silicates with an SiO2: Na20 ratio of
from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0
ratio being most preferred. The silicates may be in the form of either the
anhydrous salt or a hydrated salt. Sodium silicate with an SiO2: Na20
ratio of 2.0 is the most preferred silicate. Preferably the silicates have an
amorphous structure.
Alkali metal percarbonate salts are also suitable ~lk~linity species and are
described in more detail in the section 'inorganic perhydrate salts' herein.
The alkali metal percarbonate used may preferably be sodium
percarbonate or pot~si~m percarbonate, more preferably sodium
percarbonate. The percarbonate is generally in particulate form. The
percarbonate particles generally have a mean particle diameter of 150-
1200~1m, preferably 500-900,um. Preferably, the particles of percarbonate
are coated. Alkali metal persilicates, as described in the section 'inorganic
perhydrate salts', are also suitable ~lk~linity species.
Another suitable ~Ik~linity species include a crystalline layered silicate,
preferably a crystalline ~-layered silicate, and most preferably the
cryst~lline ~-layered silicate is a crystalline ~-layered sodium silicate with
the general formula
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NaMSix02 + 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. The most preferred material is ~-Na2Si20s,
available from Hoechst AG as NaSKS-6.
The crystalline layered silicate material is preferably present in granular
detergent compositions as a particulate in intim~te admixture with a solid,
water-soluble ionisable material. The solid, water-soluble ionisable
material is selected from organic acids, organic and inorganic acid salts
and mixtures thereof. In accord with the invention, the crystalline layered
silicate ~lk~linity species is preferably coated with a coating material such
as citric acid, as described in the section 'delayed release-means'.
The ~lk~linity system is preferably present in an amount of from 1% to
75%, more preferably in an amount of from 10% to 40% by weight of the
deter~ent composition.
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11
Relative release kinetics
An essential aspect of the invention is a means, which is provided for
delaying the release to a wash solution of the ~lk~linity system relative to
the release of the cationic ester surfactant.
Delayed rate of release - means
The means preferably provide for delayed release of the ~lk~linity system
itself to the wash solution. The delayed release means can include coating
any suitable ~lk~linity species 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
~lk~linity species of from 1:99 to 1:2, preferably from 1:49 to 1:9.
Suitable coating materials include triglycerides (e.g. partially)
hydrogenated vegetable oil, soy bean oil, cotton seed oil) mono or
diglycerides, microcryst~llin~ waxes, gelatin, cellulose, fatty acids and
any mixtures thereof.
Other suitable coating materials can comprise the alkali and ~Ik~line earth
metal sulphates. An other suitable coating material can comprise citric
acid.
A preferred coating material is sodium silicate of SiO2: Na2O ratio from
1.6: 1 to 3.4: 1, ylefelably 2.8: 1, applied as an aqueous solution to
give a level of from 2~o to 10%, (normally from 3% to 5%) of silicate
solids by weight of the percarbonate. Magnesium silicate can also be
included in the coating.
Other suitable coating materials for use herein include polymers derived
from amino acids such as polygl~ mine acid, as disclosed in GB 91-
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12
20653.2, and polyaspartic acid, as disclosed in EP 305 282, and EP 351
629. EP-A-0382464 discloses coating materials such as polyacrylic acid
and cellulose acetate phthalate. These polymeric coating materials are
water-soluble (acidic) polymers which are preferably used as coating
material for inorganic perhydrate salts and peroxyacid bleach precursors.
Suitable polymers for use herein have a molecular weight in the range of
from 1000 to 280,000, preferably from 1500 to 150,000. Preferably, the
polymers have a melting point superior to 30~C.
Any coating materials may be combined with organic binder materials to
provide composite inorganic salt/organic binder coatings. Suitable binders
include the C1o-C20 alcohol ethoxylates cont~ining from 5 - 100 moles of
ethylene oxide per mole of alcohol and more preferably the C1s-C20
primary alcohol ethoxylates cont~ining 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 10,000 are examples of such polymeric materials.
Copolymers of maleic anhydride with ethylene, methylvinyl ether or
methacrylic acid, the maleic 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 Clo-C20 alcohol ethoxylates cont~ining from 5 - 100 moles of
ethylene oxide per mole. Further examples of binders include the C1o-
C20 mono- and diglycerol ethers and also the C1o-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.
One method for applying the coating material involves agglomeration.
Preferred agglomeration processes include the use of any of the organic
binder materials described hereinabove. Any conventional
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agglomerator/mixer may be used including, but not limited 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. Preferred methods for applying coating materials are
described in WO 93/ 918259.
Other means of providing the required delayed release include mechanical
means for altering the physical characteristics of the ~lk~linity system to
control its solubility and rate of release. Suitable means could include
compaction, mechanical injection, m~ml~l injection.
Another means to delay the ~lk~linity release can include a suitable choice
of ~Ik~linity species with an amorphous structure. These are known to
dissolve relatively slowly in comparison to ~Ik~linity species with a
crystalline structure. Thus, a suitable choice of amorphous ~lk~linity
species will provide a delay of ~lk~linity release.
Additionally, a means of delayed release may include a 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.
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14
Relative rate of release - kinetic parameters
The release of the cationic ester surfactant relative to that of the ~lk~linity
system is such that in the T50 test method herein described the time to
achieve a concentration that is 50% of the ultimate concentration of the
cationic ester surfactant is at least 120 seconds less than the time to
achieve a concentration of that is 50% of the ultimate concentration of
said ~lk~linity system.
Preferably, the time to achieve a concentration that is 50 % of the ultimate
concentration of the cationic ester surfactant is more than 300 seconds less
than the time to achieve a concentration that is 50% of the ultimate
concentration of the ~lk~linity system.
Delayed release - test method
The delayed release kinetics herein are defined with respect to a 'TA test
method' which me~llres the time to achieve A% of the ultimate
concentration/level of that component when a composition cont~ining 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 20~C, to which 10g of composition is added. The
contents of the beaker are agitated using a magnetic stirrer set at 100 rpm.
The ~lltim~te concentration/level is taken to be the concentration/level
in~l 15 minlltes 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.
Such analytical methods can include those involving a continuous
monitoring of the level of concentration of the component, including for
example photometric and conductimetric methods.
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Alternatively, methods involving removing titres from the solution at set
time intervals, stopping the dissolution 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 cune 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 cont~ining that
component.
Additional detergent components
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 precise nature of the washing operation for which it
is to be used.
The compositions of the invention preferably contain one or more
additional detergent components selected from additional surfactants,
bleaches, builders, organic polymeric compounds, enzymes, suds
suppressors, lime soap dispersants, soil suspension and anti-redeposition
agents and corrosion inhibitors.
Additional surfactant
The detergent compositions of the invention preferably contains one or
more additional surfactants selected from anionic, nonionic, non-ester
cationic, ampholytic, amphoteric and zwitterionic surfactants and
mixtures thereof.
....~ ., .
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16
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 ~ ghlin and Heuring on December 30, 1975. Further examples
are given in "Surface Active Agents and Detergents" (Vol. I and II by
Schwartz, Perry and Berch). A list of suitable cationic surfactants is given
in U.S.P. 4,259,217 issued to Murphy on ~Iarch 31, 1981.
Where present, ampholytic, arnphoteric and zwitteronic surfactants are
generally used in combination with one or more anionic and/or nonionic
surfactants.
Anionic surfactant
A preferred additional component of the detergent composition of the
invention is an anionic surfactant. Essentially any anionic surf~ct~n
useful for detersive purposes are suitable. These can include salts
(including, for example, sodium, potassium, ammonium, and substituted
ammonium salts such as mono-, di- and triethanol~mine salts) of the
anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.
Anionic sulfate surfactants are preferred.
Other anionic surf~ct~ntc 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 llns~tllrated C12-C18 monoesters) diesters of sulfosuccinate
(especially saturated and ~ln~tllrated C6-C14 diesters), N-acyl
sarcosin~tec. 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.
The weight ratio of anionic surf~ct~nt to cationic ester surfactant in the
surfactant system is from 3: 1 to 15: 1, preferably from 4: 1 to 12: 1, most
preferably from 5:1 to 10:1.
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17
Anionic sulfate surfactant
Anionic sulfate surfactants suitable for use herein include the linear and
branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty
oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the
Cs-C17 acyl-N-(Cl-C4 alkyl) and -N-(Cl-C2 hydroxyalkyl) gll1c~mine
sulfates, and sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described
herein).
Alkyl sulfate surfactants are preferably selected from the linear and
branched primary Clo-Clg alkyl sulfates, more preferably the C11-C1s
branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the C1o-C1g alkyl sulfates which have been ethoxylated with
from 0.5 to 20 moles of ethylene oxide per molecule. More preferably,
the alkyl ethoxysulfate surfactant is a C1 1-cl8~ most preferably C1 1-Cls
alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably
from 1 to 5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the
preferred alkyl sulfate and alkyl ethoxysulfate surf~ct~nts. Such mixtures
have been disclosed in PCT Patent Application No. WO 93/18124.
Anionic sulfonate surfactant
Anionic sulfonate surf~ct~nt~ suitable for use herein include the salts of
Cs-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22
primary or secondary alkane sulfonates, C6-C24 olefin sulfonates,
sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl
glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures
thereof.
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Anionic carboxylate surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the
soaps ('alkyl carboxyls'), especially certain secondary soaps as described
herein.
Suitable alkyl ethoxy carboxylates include those with the formula
RO(CH2CH20)X CH2COO-M+ wherein R is a C6 to C1g alkyl group, x
ranges from O to 10, and the ethoxylate distribution is such that, on a
weight basis, the amount of material where x is 0 is less than 20 % and M
is a cation. Suitable alkyl polyethoxy polycarboxylate surf~ct~nt~ include
those having the formula RO-(CHR1-CHR2-O)-R3 wherein R is a C6 to
Clg alkyl group, x is from 1 to 25, R1 and R2 are selected from the
group consisting of hydrogen, methyl acid radical, succinic acid radical,
hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected
from the group consisting of hydrogen, substituted or unsubstitllte~l
hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
Suitable soap surf~ct~nts include the secondary soap surf~ct~ntc which
contain a carboxyl unit connected to a secondary carbon. Preferred
secondary soap surfactants for use herein are water-soluble members
selected from the group consisting of the water-soluble salts of 2-methyl-
n-lec~noic acid, 2-ethyl-1-clec~noic acid, 2-propyl-1-nonanoic acid, 2-
butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may
also be included as suds suppressors.
Alkali metal sarcosinate surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates offormula R-CON (Rl) CH2 COOM, wherein R is a Cs-C17 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 oleoyl methyl
sarcosinates in the form of their sodium salts.
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19
Alkoxylated nonionic surfactant
A preferred additional surfactant in accord with the detergent composition
of the invention is a nonionic surfactant present at a level of from 0.1~ to
20%, more preferably from 0.2% to 10% by weight, most preferably
- from 0.5 % to 5 % by weight of the detergent composition.
Essentially any alkoxylated nonionic surfactants are suitable herein. The
ethoxylated and propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surf~ct~nt~ can be selected from the classes of the
nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols,
nonionic ethoxylated/propoxylated fatty alcohols, nonionic
ethoxylate/propoxylate condensates with propylene glycol, and the
nonionic ethoxylate condensation products with propylene oxide/ethylene
min~ cts.
Nonionic alkoxylated alcohol surfactant
The condensation products of aliphatic alcohols with from 1 to 25 moles
of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are
suitable for use herein. The alkyl chain of the aliphatic alcohol can either
be straight or branched, primary or secondary, and generally contains
from 6 to 22 carbon atoms. Particularly preferred are the condensation
products of alcohols having an alkyl group cont~ining from 8 to 20 carbon
atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Nonionic polyhydroxy fatty acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural forrnula R2CONR1Z wherein: Rl is H, Cl-C4 hydrocarbyl, 2-
hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof,
preferable Cl-C4 alkyl, more preferably Cl or C2 alkyl, most preferably
Cl alkyl (i.e., methyl); and R2 is a Cs-C31 hydrocarbyl, preferably
straight-chain Cs-C1g alkyl or alkenyl, more preferably straight-chain
Cg-C17 alkyl or alkenyl, most preferab1y straight-chain C11-C17 alkyl or
alkenyl, or mixture thereof; and Z is a po1yhydroxyhydrocarbyl having a
. .
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linear hydrocarbyl chain with at least 3 hydroxyls directly connected to
the chain, or an alkoxylated derivative (preferably ethoxylated or
propoxylated) thereof. Z preferably will be derived from a reducing
sugar in a reductive ~min~tion reaction; more preferably Z is a glycityl.
A preferred nonionic polyhydroxy fatty acid amide surfactant for use
herein is a C1s-C17 alkyl N-methyl glucamide. The ratio of polyhydroxy
fatty acid amide to cationic ester surfactant is preferably between 1:1 to
1:8, more preferably 1:2.5. ~t has been found that such surfactant systems
are able to reduce 'lime soap' formation and deposition of encrustation on
the fabric.
Nonionic fatty acid amide surfactant
Suitable fatty acid amide surfactants include those having the formula:R6CoN(R7)2 wherein R6 is an alkyl group cont~ining from 7 to 21,
preferably from 9 to 17 carbon atoms and each R7 is selected from the
group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -
(C2H4O)XH, where x is in the range of from 1 to 3.
Nonionic alkylpolysaccharide surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent
4,565,647, Llenado, issued January 21, 1986, having a hydrophobic
group cont~ining from 6 to 30 carbon atoms and a polysaccharide, e.g., a
polyglycoside, hydrophilic group cont~inin~ from 1.3 to 10 saccharide
units.
Preferred alkylpolyglycosides have the formula
R20(CnH2nO)t(glYC~sYl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the
alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0
to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from
glucose.
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Amphoteric surfactant
Suitable amphoteric surf~ct~nt~ for use herein include the amine oxide
surfactants and the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula
R3(0R4)XNO(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl,
acylamidopropoyl and alkyl phenyl group, or mixtures thereof, cont~inin~
from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group
cont~inin~ from 2 to 3 carbon atoms, or mixtures thereof; x is from O to
5, preferably from O to 3; and each R5 is an alkyl or hydroxyalkyl group
cont~ininp; from 1 to 3, or a polyethylene oxide group cont~ining from 1
to 3 ethylene oxide groups. Preferred are Clo-Clg alkyl dimethyl~min~
oxide, and C10-l8 acylamido alkyl dimethyl~mine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM)
C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant
Zwitterionic surf~ct~nt~ can also be incorporated into the detergent
compositions hereof. These surf~ct~nt~ can be broadly described as
derivatives of secondary and tertiary amines, derivatives of heterocyclic
secondary and tertiary amines, or derivatives of quaternary ammonium,
quaternary phosphonium or tertiary sulfonium compounds. Betaine and
sultaine surfactants are exemplary zwitterionic surf~ct~ntc for use herein.
Suitable bet~in~s are those compounds having the formula
R(R')2N+R2COO- wherein R is a C6-C1g hydrocarbyl group, each Rl
is typically C1-C3 alkyl, and R2 is a Cl-Cs hydrocarbyl group. Preferred
betaines are C12 18 dimethyl-ammonio hexanoate and the C10-l8
acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex
betaine surfactants are also suitable for use herein.
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Cationic surfactants
Additional 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-Clo
N-alkyl or alkenyl ammonium surfactants wherein the rem~ining N
positions are substituted by methyl, hydroxyethyl or hydroxypropyl
groups.
Water-soluble builder compound
The detergent compositions of the present invention preferably contain a
water-soluble builder compound, typically present at a level of from 1%
to ~0% by weight, preferably from 10~ to 70~ by weight, most
preferably from 20% to 60% by weight of the composition.
Suitable water-soluble builder compounds include the water soluble
monomeric polycarboxylates, or their acid forms, homo or copolymeric
polycarboxylic acids or their salts in which the polycarboxylic acid
comprises at least two carboxylic radicals separated from each other by
not more that two carbon atoms, borates, phosphates, and mixtures of any
of the foregoing.
The carboxylate or polycarboxylate builder can be momomeric or
oligomeric in type although monomeric polycarboxylates are generally
preferred for reasons of cost and performance.
Suitable carboxylates cont~inin~ one carboxy group include the water
soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
Polycarboxylates cont~ining two carboxy groups include the water-soluble
salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic
acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well
as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates
cont~ining 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.
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1,379,241, lactoxysuccinates described in British Patent No. 1,389,732,
and aminosuccinates described in Netherlands Application 7205873, and
the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane
tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates cont~inin?~ 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 cont~inin~ sulfo substituents include
the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421
and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated
pyrolysed citrates described in British Patent No. 1,439,000. Preferred
polycarboxylates are hydroxycarboxylates cont~ining up to three carboxy
groups per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate
chelating agents or mixtures thereof with their salts, e.g. citric acid or
citrate/citric acid mixtures are also contemplated as useful builder
components.
Borate builders, as well as builders cont~ining borate-forming materials
that can produce borate under detergent storage or wash conditions are
useful water-soluble builders herein.
Suitable examples of water-soluble phosphate builders are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate,
sodium and potassium and ammonium pyrophosphate, sodium and
potassium orthophosphate, sodium polymeta/phosphate in which the
degree of polymerization ranges from about 6 to 21, and salts of phytic
acld.
In a highly preferred aspect of the invention a means is also provided for
delaying the release to a wash solution of the preferred water soluble
builder component relatively to the release of the cationic ester surfactant.
Said means can comprise equivalents of any of the delayed release means
herein described for achieving the delayed release of the ~lk~linity system
or species, described hereinbefore.
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Partially 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 70% by
weight, most preferably from 20% to 60% weight of the composition.
Examples of largely water insoluble builders include the sodium
aluminosilicates .
Suitable aluminosilicate zeolites have the unit cell formula
Naz[(AlO2)z(SiO2)y]. xH2O wherein z and y are at least 6; the molar
ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to
276, more preferably from 10 to 264. The aluminosilicate material are in
hydrated form and are preferably crystalline, cont~inin~ from 10% to
28~c, more preferably from 18% to 22% water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are
preferably synthetically derived. Synthetic cryst~llin~ aluminosilicate ion
exchange materials are available under the designations Zeolite A, Zeolite
B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has
the formula
Nal2 [Alo2)l2(sio2)l2]. xH20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula
Na86 [(Alo2)86(sio2)lo6]. 276 H2O.
Another preferred builder material is a crystalline layered silicate,
preferably a crystalline ~-layered silicate, and most preferably the
crystalline ~-layered silicate is a crystalline ~-layered sodium silicate with
the general formula
NaMSix02 + 1 YH20
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wherein M is sodium or hydrogen~ x is a number from 1.9 to 4 and y is a
number from 0 to 20. Crystalline layered sodium silicates of this type are
disclosed in EP-A-0164514 and methods for their preparation are
disclosed in DE-A-3417649 and DE-A-3742043. Herein, x in the general
formula above preferably has a value of 2, 3 or 4 and is preferably 2. The
most preferred material is ~-Na2Si20s, available from Hoechst AG as
NaSKS-6.
The crystalline layered silicate material is preferably present in granular
detergent compositions as a particulate in intim~te admixture with a solid,
water-soluble ionisable material. The solid, water-soluble ionisable
material is selected from organic acids, organic and inorganic acid salts
and mixtures thereof. Most preferably this material contains citric acid.
The Applicants have found that deposition onto the fabric in the wash of
inorganic (insoluble) encrustation, for example c~llse.l by reaction of
builder material such as zeolite and cryst~lline layered silicate with alkali
metal and earth alkali metal ions, causing the hardness of the water, can
be re-l~lced by the cationic ester surfactants in accord with the present
invention. The cationic ester surfactants facilitate suspension of the
inorganic encrustation, thereby reducing the deposition of these inorganic
materials onto the fabric. Two mech~ni~m~ are believed to be responsible
therefor. Firstly, the interaction of the cationically charged ester
surf~ct~nts with the negatively charged fabric surface can modify the
fabric surface, which reduces deposition of inorganic encrustation onto
the fabric surface. Secondly, the interaction of the cationically charged
ester surfactants with anionically charged deposited builder material (such
as zeolite and crystalline layered silicate) can facilitate the suspension of
the deposited builder material, which reduces the fabric encrustation.
Organic peroxyacid bleaching system
A preferred feature of detergent compositions of the invention is an
organic peroxyacid bleaching system. In one preferred execution the
bleaching system contains a hydrogen peroxide source and an organic
peroxyacid bleach precursor compound. The production of the organic
peroxyacid occurs by an in situ reaction of the precursor with a source of
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26
hydrogen peroxide. Preferred sources of hydrogen peroxide include
inorganic perhydrate bleaches. In an alternative preferred execution a
preformed organic peroxyacid is incorporated directly into the
composition. Compositions Cont~inin~2; mixtures of a hydrogen peroxide
source and organic peroxyacid precursor in combination with a preformed
organic peroxyacid are also envisaged.
Inor~anic perhydrate bleaches
Inorganic perhydrate salts are a preferred source of hydrogen peroxide.These salts are normally incorporated in the form of the alkali metal,
preferably sodium salt at a level of from 1 % to 40% by weight, more
preferably from 2% to 30% by weight and most ~refe~ably from 5 % to
25 % by weight of the compositions.
Examples of inorganic perhydrate salts include perborate, percarbonate,perphosphate, persulfate and persilicate salts. The inorganic perhydrate
salts are normally the alkali metal salts. The inorganic perhydrate salt
may be included as the cryst~llin~ solid without additional protection. For
certain perhydrate salts however, the preferred executions of such
granular compositions utilize a coated form of the material, such as
described in the section 'delayed release-means'. Coatings can also be
used to provide better storage stability for the perhydrate salt in the
granular product. Suitable coatings therefor comprise inorganic salts such
as alkali metal silicate, carbonate or borate salts or mixtures thereof, or
organic materials such as waxes, oils, or fatty soaps.
Sodium perborate is a preferred perhydrate salt and can be in the form of
the monohydrate of nominal formula NaB02H202 or the tetrahydrate
NaB02H202 3H20
Alkali metal percarbonates, particularly sodium percarbonate are
preferred perhydrates herein. Sodium percarbonate is an addition
compound having a formula corresponding to 2Na2C03.3H202, and is
available commercially as a crystalline solid.
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Potassium peroxymonopersulfate is another inorganic perhydrate salt of
use in the detergent compositions herein.
In a preferred aspect of the present invention a means is provided to delay
the release to a wash solution of the preferred inorganic perhydrate salts,
- relatively to the release of the cationic ester surfactant. Said means can
comprise equivalents of any of the delayed release means herein described
for achieving the delayed release of the ~lk~linity system or species,
described hereinbefore.
Peroxyacid bleach precursors
Peroxyacid bleach precursors (bleach activators) are preferred peroxyacid
sources in accord with the invention. Peroxyacid bleach precursors are
normally incorporated at a level of from 0.5% to 20% by weight, more
preferably from 2% to 10% by weight, most preferably from 3% to 5%
by weight of the compositions.
Suitable peroxyacid bleach precursors typically contain one or more N- or
O- acyl 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 cationic derivatives of any of the above,
including the alkyl ammonium derivatives and pentaacetyl glucose.
Phthalic anhydride is a suitable anhydride type precursor.
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Specific cationic derivatives of the O-acyl precursor compounds include2-(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-acyl 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 ~ mine, N-benzoyl subst~ te~l ureas
and the N-,N,NlNl tetra acetylated alkylene tli~min~s wherein the
alkylene group contains from 1 to 6 carbon atoms, particularly those
compounds in which the alkylene group contains 1, 2 and 6 carbon atoms.
Tetraacetyl ethylene ~ minP (TAED) is particularly preferred.
Preferably, the tetraacetyl ethylene ~ mine has a compressed particle
structure, achieved by mechanically compression, to delay the desolving
of the particles into the wash solution.
N-acylated precursor compounds of the l~ct~m class are disclosed
generally in GB-A-955735. Preferred materials comprise the caprolactams
and valerolactams.
Suitable N-acylated lactam precursors have the formula:
O C--CH2--CH2
R6--C--N
--CH2~cH2 ]n
wherein n is from 0 to 8, preferably from 0 to 2, and R6 is H, an alkyl,
aryl, alkoxyaryl or alkaryl group con~inin~ from 1 to 12 carbons, or a
substituted phenyl group cont~ining from 6 to 18 carbon atoms
Suitable caprolactam bleach precursors are of the formula:
. .
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29
O C --CH2 CH2
CH2
Rl _ C N ~
CH2 CH2
wherein Rl is H or an allyl, aryl, alkoxyaryl or alkaryl group cont~inin~
from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms, most
preferably Rl is phenyl.
Suitable valero l~ct~mc have the formula:
o C CH2 CH2
~ i
Rl C N
CH2 CH2
wherein Rl is H or an alkyl, aryl, alkoxyaryl or alkaryl group cont~inin~
from 1 to 12 carbon atoms, ~l~felably from 6 to 12 carbon atoms. In
highly plefellcd embodiments, Rl is selected from phenyl, heptyl, octyl,
nonyl, 2,4,4~ n~ ylpentyl, decenyl and mixtures ~ereof.
The most prefe~led materials are those which are normally solid at
< 30~C, particularly ~e phenyl derivatives, ie. benzoyl valerol~ct~m,
benzoyl caprolact~m and their substituted benzoyl analogues such as
chloro, amino alkyl, alkyl, aryl and alkoxy derivatives.
Caprol~ m and valerol~ct~m precursor materials wherein the Rl moiety
contains at least 6, pl~felably from 6 to 12, carbon atoms provide
peroxyacids on perhydrolysis of a hydrophobic character which afford
nucleophilic and body soil clean-up. Precursor compounds wherein R
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comprises from 1 to 6 carbon atoms provide hydrophilic bleaching species
which are particularly ef~lcient for bleaching beverage stains. Mixtures
of 'hydrophobic' and 'hydrophilic' caprolactams and valero lactams,
typically at weight ratios of 1:5 to 5:1, preferably 1:1, can be used herein
for mixed stain removal benefits.
Highly preferred caprolactam and valerolactam precursors include
benzoyl caprolactam, nonanoyl capro-lactam, benzoyl valerolactam,
nonanoyl valerolactam, 3,5,5-trimethylhexanoyl caprolactam, 3,5,5-
trimethylhexanoyl valerolactam, octanoyl caprolactam, octanoyl
valerolactam, decanoyl caprolactam, decanoyl valerolactam, lln-1ecenoyl
caprolactam, lln-lecenoyl valerolactam, (6-
oct~n~midocaproyl)oxybenzene-sulfonate, (6-
non~n~midocaproyl)oxybenzenesulfonate, (6-~lec~n~mi~locaproyl)-
oxybenzenesulfonate, and mixtures thereof. Examples of highly preferred
substituted benzoyl l~rt~m~ include methylbenzoyl caprolactam,
methylbenzoyl valerolactam, ethylbenzoyl caprolactam, ethylbenzoyl
valerolactam, propylbenzoyl caprolactam, propylbenzoyl valerol~ct~m,
isopropylbenzoyl caprolactam, isopropylbenzoyl valerolactam,
butylbenzoyl caprolactam, butylbenzoyl valerolactam, tert-butylbenzoyl
caprolactam, tert-butylbenzoyl valerolactam, pentylbenzoyl caprolactam,
pentylbenzoyl valerol~ct~m, hexylbenzoyl caprolactam, hexylbenzoyl
valerolactam, ethoxybenzoyl caprolactam, ethoxybenzoyl valerol~ct~m,
propoxybenzoyl caprolactam, propoxybenzoyl valerolactam,
isopropoxybenzoyl caprolactam, isopropoxybenzoyl valerolactam,
butoxybenzoyl caprol~ct~m, butoxybenzoyl valerolactam, tert-
butoxybenzoyl caprol~rt~m, tert-butoxybenzoyl valerolactam,
pentoxybenzoyl caprol~ct~m, pentoxybenzoyl valerol~Gt~m,
hexoxybenzoyl caprolactam, hexoxybenzoyl valerolactam, 2,4,6-
trichlorobenzoyl caprolactam, 2,4,6-trichlorobenzoyl valerolactam,
pentafluorobenzoyl caprolactam, pentafluorobenzoyl valerolactam,
dichlorobenzoyl caprolactam, dimethoxybenzoyl caprolactam, 4-
chlorobenzoyl caprolactam, 2,4-dichlororbenzoyl caprolactam,
terephthaloyl dicaprolactam, pentafluorobenzoyl caprol~ct~m,
pentafluorobenzoyl valerolactam, dichlorobenzoyl valerolactam,
dimethoxybenzoyl valerolactam, 4-chlorobenzoyl valerolactam, 2,4-
dichlororbenzoyl valerolactam, terephthaloyl divalerolactam, 4-
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31
nitrobenzoyl caprolactam, 4-nitrobenzoyl valerol~ct~m, and mixtures
thereof.
Suitable imi~l~7oles include N-benzoyl imidazole and N-benzoyl
benzimidazole and other useful N-acyl group-cont~ining peroxyacid
precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl
pyroglutamic acid.
Another preferred class of peroxyacid bleach activator compounds are the
amide substit~]te~l compounds of the following general formulae:
R1 C N R2 C L R1 N--C R2 C L
O R5 O or R5 O O
wherein Rl is an aryl or alkaryl group with from 1 to 14 carbon atoms,
R2 is an alkylene, arylene, and alkarylene group con~ining from 1 to 14
carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group cont~ining 1
to 10 carbon atoms and L can be e~senti~lly 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 br~nrhe~ alkyl,
sul,sliluled aryl or alkylaryl cont~ining branching, s~bsti~tion~ or both
and may be sourced from either synthetic sources or natural sources
including ~or 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. R5 is ~referably H or methyl. Rl and R5 should not contain
more than 18 carbon atoms in total. Amide substituterl bleach activator
co,n~o.lnds of this type are described in EP-A-0170386.
The L group must be sufficiently reactive for ~e reaction to occur within
the o~ti~ l time frame (e.g., a wash cycle). However, if L is too
reactive, this activator will be ~lifflel~lt to stabilize for use in a ble~chingco~ osilioll. 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
,
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32
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 R1, R2 and R5 are as
defined for the amide substituted compounds and L is selected from the
group consisting of:
--0~ O~Y and --~~
O ~ O
--N--C--R1 --N N --N--C--CH--R4
R3 Ll R3 Y
y
R3 r
-~CH=C--CH=CH2 --O--CH=C--CH=CH2
,C H2- , ~C ~NR4
O O
R3 0 Y
--~C=CHR4 , and N i--CH--R4
R3 o
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
cont~ining from 1 to 14 carbon atoms, R is an alkyl chain cont~inin~
from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing
group.
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 R3 is an alkyl chain cont~inin~ from 1 to 4 carbon
atoms, M is a cation which provides solubility to the bleach activator and
X is an anion which provides solubility to the bleach activator.
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33
Preferably, M is an alkali metal, ammonium or substituted ammonium
cation, with sodium and potassium being most preferred, and X is a
halide, hydroxide, methylsulfate or acetate anion. 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 activators of the above formulae include (6-
oct~n~midocaproyl)oxybenzenesulfonate, (6-
non~n~midocaproyl)oxybenzenesulfo-nate, (6-
dec~n~midocaproyl)oxybenzenesulfonate, and mixtures thereof.
Other preferred precursor compounds include those of the benzoxazin-
type, having the formula:
o
1~--R~
including the substituted benzoxazins of the type
R2 ~
R ~ 'O
wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4,
and R5 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:
C
~C~
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Bleach catalyst
The detergent compositions optionally contain a transition metal
cont~ining bleach catalyst. One suitable type of bleach catalyst is a
catalyst system comprising a heavy metal cation of defined bleach
catalytic activity, such as copper, iron or m~ng~nese cations, an auxiliary
metal cation having little or no bleach catalytic activity, such as zinc or
al-lmimlm cations, and a sequestrant having defined stability con~t~nts for
the catalytic and auxiliary metal cations, particularly
ethylen~ minetetraacetic acid,
ethylen~ min~tetra(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 m~ng~nese-based complexes
disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred
examples of these catalysts include MnIV2(u-0)3(1,4,7-trimethyl-1,4,7-
triazacyclononane)2-(PF6)2, MnIII2(u-O) 1 (u-OAc)2(1,4,7-trimethyl-
1,4,7-triazacyclononane)2-(C104)2; MnIV4(u-0)6(1,4,7-
triazacyclononane)4-(C104)2, MnIIIMnIV4(u-O)l(u-OAc)2 (1,4,7-
trimethyl-1,4,7-triazacyclononane)2-(ClO4)3, and mixtures thereof.
Others are described in European patent application publication no.
549,272. Other lig~n-ls suitable for use herein include 1,5,9-trimethyl-
1,5,9-triazacyclodo~lec~n~, 2-methyl-1,4,7-triazacyclononane, 2-methyl-
1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane,
and mixtures thereof.
For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and
U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which te~ches
mononuclear m~ng~nese (IV) complexes such as Mn(1,4,7-trimethyl-
1,4,7-triazacyclononane)(OCH3)3 (PF6). Still another type of bleach
catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble complex
of m~ng~nese (III), and/or (IV) with a ligand which is a non-carboxylate
polyhydroxy compound having at least three consecutive C-OH groups.
Other examples include binuclear Mn complexed with tetra-N-dentate and
bi-N-dentate ligands, including N4MnIII(u-O)2MnIVN4)+and
~Bipy2MnIII(u-O)2MnIVbipy2] -(Cl04)3.
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Further suitable bleach catalysts are described, for example, in European
patent application No. 408,131 (cobalt complex catalysts), European
patent applications, publication nos. 384,503, and 306,089 (metallo-
porphyrin catalysts), U.S. 4,728,455 (m~ng~nese/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 (aluminosilicate support with m~ng~n~se and zinc or
magnesium salt), U.S. 4,626,373 (m~ng~nese/ligand catalyst), U.S.
4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019
(cobaltchelantcatalyst) ~n~ n 866,191 (transitionmetal-cont~ining
salts), U.S. 4,430,243 (chelants with m~ng~nese cations and non-catalytic
metal cations), and U.S. 4,728,455 (manganese gluconate catalysts).
Heavy metal ion sequestrant
The detergent compositions of the invention preferably contain as an
optional component a heavy metal ion sequestrant. By heavy metal ion
sequestrant it is meant herein components which act to sequester (chelate)
heavy metal ions. These components may also have calcium and
m~gn~sium chelation capacity, but preferentially they show selectivity to
binding heavy metal ions such as iron, m~ng~nlose and copper.
Heavy metal ion sequestrants are generally present at a level of from
0.005 % to 20%, preferably from 0.1 % to 10%, more preferably from
0.25 % to 7.5 % and most preferably from 0.5 % to 5 % by weight of the
compositions.
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates, such as the amino alkylene poly (alkylene phosphonates),
alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene
phosphonates.
Preferred among the above species are diethylene triamine penta
(methylene phosphonate), ethylene ~ mine tri (methylene phosphonate)
hexamethylene ~ min~ tetra (methylene phosphonate) and hydroxy-
ethylene 1,1 diphosphonate.
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Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic acid and polyaminocarboxylic acids such as
ethylene~ minotetracetic acid, ethylenetri~mine pentacetic acid,
ethylene~ mine disuccinic acid, ethylenediamine diglutaric acid, 2-
hydroxypropylene~ mine disuccinic acid or any salts thereof. Especially
preferred is ethylen~ mine-N,N'-disuccinic acid (EDDS) or the alkali
metal, ~lk~line earth metal, ammonium, or substituted ammonium salts
thereof, or mixtures thereof.
Other suitable heavy metal ion sequestrants for use herein are
iminodiacetic acid derivatives such as 2-hydroxyethyl ~ cetic 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 ~-
~l~nin~-N,N'-~ cetic acid, aspartic acid-N,N'-diacetic acid, aspartic
acid-N-mono~cetic acid and iminodisuccinic acid sequestrants described in
EP-A-509,382 are also suitable.
EP-A-476,257 describes suitable amino based sequestrants. EP-A-
510,331 describes suitable sequestrants derived from collagen, keratin or
casein. EP-A-528,859 describes a suitable alkyl imino~ retic acid
sequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic
acid are alos suitable. Glycinamide-N,N'-disuccinic acid (GADS),
ethylen~di~min~-N-N'-diglutaric acid (EDDG) and 2-
hydroxypropylen~di~min~-N-N'-disuccinic acid (HPDDS) are also
suitable.
Enzyme
Another preferred ingredient useful in the detergent compositions is one
or more additional enzymes.
Preferred additional enzymatic materials include the commercially
available lipases, cutinases, amylases, neutral and ~lk~line proteases,
esterases, cellulases, pectinases, lactases and peroxidases conventionally
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37
incorporated into detergent compositions. Suitable enzymes are discussed
in US Patents 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold
under the tradenames Alcalase, Savinase, Primase, Durazym, and
Esperase by Novo ~n~ stries A/S (Denmark), those sold under the
tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those
sold by Genencor International, and those sold under the tradename
Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be
incorporated into the compositions in accordance with the invention at a
level of from 0.0001% to 4% 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 tradename Rapidase by Gist-Brocades,
and those sold under the tradename 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 0.0001%
to 2% active enzyme by weight of the composition.
Preferably the detergent composition in accordance with the present
invention contains a lipolytic enzyme. It has been found that the cationic
ester surfactant enh~n~-es the performance of the lipolytic enzyme. Two
mech~ni~m~ are believed to be responsible for the improved enzyme
performance. Firstly, the fatty acids, which are formed by the enzymatic
reaction of the lipolytic enzymes with triglycerides cont~in~-l in the greasy
or oily soils, will be removed from the fabric surface by the cationic ester
surf~ct~nt This will facilitate the 'access' by the enzymes to the greasy
stains/ soils during the washing process. Secondly, the removal of fatty
acids from the fabric surface by the cationic ester surfactant will reduce
the formation and deposition onto the fabric of 'lime soap', formed
through reaction of fatty acids with calcium ions of the hardness of the
water. This will also facilitate the 'access' by the enzymes to the greasy
stains/ soils on the fabric surface.
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38
Lipolytic enzyme may be present at levels of active lipolytic enzyme of
from 0.01% to 5% by weight, preferably 0.1% to 2% by weight, most
preferably from 0. 1 % to 0. 5 % 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., Thermomyces
sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or
Pseudomas fluorescens. Lipase from chemically or genetically modified
mutants of these strains are also useful herein. A preferred lipase is
derived from Pseudomonas pseudoalcaligenes, which is described in
Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from
~Iumicola l~nll~inosa and expressing the gene in Aspergillus oryza, as
host, as described in European Patent Application, EP-A-0258 068, which
is commercially available from Novo ~n-lllstri A/S, Bagsvaerd, Denmark,
under the trade name Lipolase. This lipase is also described in U.S.
Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989. A highly
preferred lipase, which is also obtained via Humicola l~m~inosa, is a
lipase l~nown as Lipase Ultra SP514 (trade name), also available from
NOVO Industri A/S.
Organic polymeric compound
Organic polymeric compounds are preferred additional components of the
detergent compositions in accord with the invention, and are preferably
present as components of any particulate components where they may act
such as to bind the partic~ te component together. By organic polymeric
compound it is meant herein essentially any polymeric organic compound
commonly used as dispersants, and anti-redeposition and soil suspension
agents in detergent compositions, including any of the high molecular
weight organic polymeric compounds described as clay floccul~ting
agents herein.
Organic polymeric compound is typically incorporated in the detergent
compositions of the invention at a level of from 0.1% to 30%, preferably
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from 0.5 % to 15 %, most preferably from 1 % to 10 % by weight of the
composltlons.
Examples of organic polymeric compounds include the water soluble
organic homo- or co-polymeric polycarboxylic acids or their salts in
which the polycarboxylic acid comprises at least two carboxyl radicals
separated from each other by not more than two carbon atoms. Polymers
of the latter type are disclosed in GB-A-1,596,756. Examples of such
salts are polyacrylates of MWt 2000-5000 and their copolymers with
maleic anhydride, such copolymers having a molecular weight of from
20,000 to 100,000, especially 40,000 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.
Terpolymers cont~ining monomer units selected from maleic acid, acrylicacid, polyaspartic acid and vinyl alcohol, particularly those having an
average molecular weight of from 5,000 to 10,000, are also suitable
herem.
-
Other organic polymeric compounds suitable for incorporation in thedetergent compositions herein include cellulose derivatives such as
methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose
and hydroxyethylcellulose.
Further useful organic polymeric compounds are the polyethylene glycols,
particularly those of molecular weight 1000-10000, more particularly
2000 to 80~)0 and most preferably about 4000.
Suds suppressing system
The detergent compositions of the invention, when form~ te~l for use in
machine washing compositions, preferably comprise a suds suppressing
system present at a level of from 0.01 % to 15%, preferably from 0.05%
to 10%, most preferably from 0.1 % to 5 % by weight of the composition.
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Suitable suds suppressing systems for use herein may comprise essentially
any known antifoam compound, including, for example silicone antifoam
compounds and 2-alkyl alcanol antifoam compounds.
By antifoam compound it is meant herein any compound or mixtures of
compounds which act such as to depress the fo~min~ or sudsing produced
by a solution of a detergent composition, particularly in the presence of
agitation of that solution.
Particularly preferred antifoam compounds for use herein are silicone
antifoam compounds defined herein as any antifoam compound including
a silicone component. Such silicone antifoam compounds also typically
contain a silica component. The term "silicone" as used herein, and in
general throughout the in~ stry, encompasses a variety of relatively high
molecular weight polymers cont~ining siloxane units and hydrocarbyl
group of various types. Preferred silicone antifoam compounds are the
siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end
blocking units.
Other suitable antifoam compounds include the monocarboxylic fatty
acids and soluble salts thereof. These materials are described in US
Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The
monocarboxylic fatty acids, and salts thereof, for use as suds suppressor
typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12
to 18 carbon atoms. Suitable salts include the alkali metal salts such as
sodium, potassium, and lithium salts, and ammonium and
alkanolammonium salts. A disadvantage associated with such fatty acid
antifoallls is their tendency to interact with any Ca+ + or Mg+ + ion
present in the wash solution, to form insoluble 'lime soaps', which can
deposit on the fabric in the wash. It has now been found that this problem
can be rerll-ce~ by the presence of cationic ester surfactants. The cationic
ester surfactant interacts with the formed 'lime soaps', thereby suspending
them in the wash solution, and thus reducing the deposition of the formed
'lime soaps' on the fabric in the wash.
Other suitable antifoam compounds include, for example, high molecular
weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of
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monovalent alcohols~ aliphatic C1g-C40 ketones (e.g. stearone) N-
alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to
tetra alkyldiamine chlortriazines formed as products of cyanuric chloride
with two or three moles of a primary or secondary amine con~inin~ 1 to
24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl
di-alkali metal (e.g. sodium, potassium, lithium) phosphates and
phosphate esters.
A preferred suds suppressing system comprises
(a) antifoam compound, preferably silicone antifoam compound, most
preferably a silicone antifoam compound comprising in combination
(i) polydimethyl siloxane, at a level of from 50% to 99%,
preferably 75 % to 95 % by weight of the silicone antifoam
compound; and
(ii) silica, at a level of from 1 % to 50%, preferably 5 % to 25 %
by weight of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level
of from 5% to 50%, preferably 10% to 40% by weight;
(b) a dispersant compound, most preferably comprising a silicone
glycol rake copolymer with a polyoxyalkylene content of 72-78 %
and an ethylene oxide to propylene oxide ratio of from 1:0.9 to
1:1.1, at a level of from 0.5% to 10%, preferably 1% to 10% by
weight; a particularly preferred silicone glycol rake copolymer of
this type is DCO544, commercially available from DOW Corning
under the tradename DCO544;
(c) an inert carrier fluid compound, most preferably comprising a C16-
C 18 ethoxylated alcohol with a degree of ethoxylation of from 5 to
50, preferably 8 to 15, at a level of from 5% to 80%, preferably
10% to 70%, by weight;
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A highly preferred particulate suds suppressing system is described in EP-
A-0210731 and comprises a silicone antifoam compound and an organic
carrier material having a melting point in the range 50~C to 85~C,
wherein the organic carrier material comprises a monoester of glycerol
and a fatty acid having a carbon chain cont~ining from 12 to 20 carbon
atoms . EP-A-0210721 discloses other preferred particulate suds
suppressing systems wherein the organic carrier material is a fatty acid or
alcohol having a carbon chain cont~ining from 12 to 20 carbon atoms, or
a mixture thereof, with a melting point of from 45~C to 80~C.
Clay softening system
The detergent compositions may contain a clay softening system
comprising a clay mineral compound and optionally a clay flocc~ ting
agent.
The clay mineral compound is preferably a smectite clay compound.
Smectite clays are disclosed in the US Patents No.s 3,862,058,
3,948,790, 3,954,632 and 4,062,647. European Patents No.s EP-A-
299,575 and EP-A-313,146 in the name of the Procter and Gamble
Company describe suitable organic polymeric clay flocc~ ting agents.
Polymeric dye transfer inhibiting a~ents
The detergent compositions herein may also comprise from 0.01 % to 10
%, preferably from O.OS % to 0.5 % by weight of polymeric dye transfer
inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from
polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-
vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
a) Polyamine N-oxide polymers
Polyamine N-oxide polymers suitable for use herein contain units having
the following structure formula:
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p
(I) Ax
R
wherein P is a polymerisable unit, and
00 0
A is NC, CO, C, -O-, -S-, -N-; x is O or1;
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 ~helein the nitrogen of the N-O group is part of these
groups.
The N-O group can be represented by the following ge,.elal
structures:
o
(R1) X- ~ -(R2)y
(R3)z or N-(R1 )x
wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic g~o~s or combinations thereof, x or/and y or/and z is 0 or 1 and
crei.l the nitrogen of the N-O group can be attached or wherein the
l~illugen of the N-O group forms part of these gl'OUlJS. 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 hetelocyclic gl'~)S. One class of
said polyanli-le N-oxides comprises the group of polyamine N-oxides
~hcleil~ the nilr~e" of the N-O group forms part of the R-group.
Preferred polyamine N-oxides are those v~herei,l R is a heterocyclic group
.
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such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline,
acridine and derivatives thereof.
Other suitable polyamine N-oxides are the polyamine oxides whereto the
N-O group is attached to the polymerisable unit. A preferred class of
these polyamine N-oxides comprises the polyamine N-oxides having the
general formula (I) wherein R is an aromatic,heterocyclic or alicyclic
groups wherein the nitrogen of the N-O functional group is part of said R
group. Examples of these classes are polyamine oxides wherein R is a
heterocyclic compound such as pyrridine, pyrrole, imidazole and
derivatives thereof.
The polyamine N-oxides can be obtained in almost any degree of
polymerisation. The degree of polymerisation is not critical provided the
material has the desired water-solubility and dye-suspending power.
Typically, the average molecular weight is within the range of 500 to
1000,000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
Suitable herein are coploymers of N-vinylimidazole and N-
vinylpyrrolidone having an average molecular weight range of from 5,000
to 50,000. The preferred copolymers have a molar ratio of N-
vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
c) Polyvinylpyrrolidone
The de~ergelll compositions herein may also utilize polyvinylpyrrolidone
("PVP") having an average molecular weight of from 2,500 to 400,000.
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 molecu~ar 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.
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d) Polyvinyloxazolidone
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.
e) Polyvinylimidazole
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.
Optical bri~htener
The detergent compositions herein also optionally contain from about
0.005 % to 5 % by weight of certain types of hydrophilic optical
brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural formula:
Rl H H~ ~N~
R2 SO3M SO3M Rl
wherein Rl is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-
hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a
salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl
and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-
(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid
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46
and disodium salt. This particular brightener species is commercially
marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy
Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical
brightener useful in the detergent compositions herein.
When in the above formula, R1 is ~nilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-
bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-
yl)aminol2,2'-stilbenedisulfonic acid disodium salt. This particular
brightener species is commercially marketed under the tradename Tinopal
SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is ~nilino, R2 is morphilino and M is a
cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-
s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This
particular brightener species is commercially marketed under the
tradename Tinopal AMS-GX by Ciba Geigy Corporation.
Cationic fabric softening agents
Cationic fabric softening agents can also be incorporated into
compositions in accordance with the present invention. Suitable cationic
fabric softening agents include the water insoluble tertiary amines or
dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0
011 340.
Cationic fabric softening agents are typically incorporated at total levels
of from 0.5~ to 15% by weight, normally from 1% to 5~ by weight.
Other optional ingredients
Other optional ingredients suitable for inclusion in the compositions of the
invention include perfumes, colours and filler salts, with sodium sulfate
being a preferred filler salt.
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47
pH of the compositions
The present compositions preferably have a pH measured as a 1%
solution in distilled water of at least 9.0, preferably from 9.0 to 11.5,
most preferably from 9.5 to 10.5 .
Form of the compositions
The compositions in accordance with the invention can take a variety of
physical forms including granular, tablet, bar and liquid forms. The
compositions are particularly the so-called concentrated granular detergent
compositions adapted to be added to a washing machine by means of a
dispensing device placed in the machine drum with the soiled fabric load.
The mean particle size of the components of granular compositions in
accordance with the invention should preferably be such that no more that
5 % of particles are greater than 1 .7mm in diameter and not more than 5 %
of particles are less than 0.15mm in diameter.
The term mean particle size as defined herein is calculated by sieving a
sample of the composition into a number of fractions (typically 5
fractions) on a series of Tyler sieves. The weight fractions thereby
obtained are plotted against the aperture size of the sieves. The mean
particle size is taken to be the aperture size through which 50% by weight
of the sample would pass.
The bulk density of granular de~ergent compositions in accordance with
the present invention typically have a bulk density of at least 600 g/litre,
more preferably from 650 g/litre to 1200 g/litre. Bulk density is measured
by means of a simple funnel and cup device consisting of a conical funnel
moulded rigidly on a base and provided with a flap valve at its lower
extremity to allow the contents of the funnel to be emptied into an axially
aligned cylindrical cup disposed below the funnel. The funnel is 130 mm
high and has internal diameters of 130 mrn 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
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48
height of 90 mm, an internal height of 87 mm and an internal diameter of
84 mm. Its nominal volume is 500 ml.
To carry out a measurement, the funnel is filled with powder by hand
pouring, the flap valve is opened and powder allowed to overfill the cup.
The filled cup is removed from the frame and excess powder removed
from the cup by passing a straight edged implement eg; a knife, across its
upper edge. The filled cup is then weighed and the value obtained for the
weight of powder doubled to provide a bulk density in g/litre. Replicate
measurements are made as required.
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49
Surfactant ag~lomerate particles
The surfactant system herein is preferably present in granular
compositions in the form of surfactant agglomerate particles, which may
take the form of flakes, prills, marumes, noodles, ribbons, but preferably
take the form of granules. The most preferred way to process the particles
is by agglomerating powders (e.g. aluminosilicate, carbonate) with high
active surfactant pastes and to control the particle size of the resultant
agglomerates within specified limits. Such a process involves mixing an
effective amount of powder with a high active surfactant paste in one or
more agglomerators such as a pan agglomerator, a Z-blade mixer or more
preferably an in-line mixer such as those manufactured by Schugi
(Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and
Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1,
Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high
shear mixer is used, such as a Lodige CB (Trade Name).
The Applicants have found that the flow properties of cationic ester
surfactant-cont~inin~ granules be improved by the addition of a desiccant
during the gr~n~ tion process. The desiccant absorbs water during the
granulation process and also absorbs atmospheric moisture during the
storage of the fini~he-l product. Such absorbance of atmospheric moisture
also improves the stability of the cationic ester surfactant which can
hydrolyse in moisturous conditions. Preferred desiccants are (anhydrous)
MgSO4 and dried sodium aluminosilicates, such as Zeolite A, and
silicates.
The Applicants have also found that stability of cationic ester surfactant-
cont~inin~ particles can be improved when the level of heavy metal ions
in the particle m~kin~ process is reduced, since heavy metal ions can
catalyse the hydrolysis of the cationic ester surfactants. This can be
achieved by limitinP~ the possible contact of cationic ester surfactants and
heavy metal ions throughout the particle m~king process, for example
through the use of vessels, which are free of or subst~nti~lly free of heavy
metal ions, such as glass vessels or synthetic plastic lined vessels. The
stability of cationic ester surfactant cont~inin~ particles can also be
improved by addition of trace levels of heavy metal ion sequestrants
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during the particle m~king process or by spraying the heavy metal ion
sequestrants onto the particles once formed. Suitable heavy metal ion
sequestrants, which can be sprayed onto or added to the particles in trace
levels up to 3 % by weight of the particles, include any of those described
herein. Other suitable sequestering agents include certain organic
polymeric compounds, including acrylic/ maleic acid copolymers.
Surfactant particle micro-pastillation
The cationic ester surfactants may be included in the form of micro-
pastilles, formed by a so called 'pastillation process'. A preferred process
for the manufacture of detergent micro-pastilles from a surfactant paste
which is subst~nti~lly in the solid phase at temperatures of 25~C and
below, comprises the steps of:
(i) mixing the surfactant paste at a temperature above its softening point,
the surfactant paste comprising at least 50~ by weight of nonionic
surfactant;
(ii) forming the molten surfactant paste into drops on a cooling belt;
(iii) forming solid pastilles by cooling the drops of molten surfactant
paste; and
(iv) removing solidified pastilles from the cooling belt.
In the process, the molten surfactant paste is preferably formed into drops
by a continuous rotary drop former comprising outer and inner coaxial
cylinders, both cylinders comprising a series of openings, at least one of
the cylinders being rotatable. The molten surfactant drops are
conveniently formed on a continuous steel cooling belt and, optionally,
cooled by spraying a cooling liquid on to the opposite side of the belt to
the side on which the drops are formed.
The micro-pastilles characteristically have a generally rounded surfaceprofile and at least one subst~nti~lly planar surface.
To improve the flow properties of the granules and to improve the
surfactant stability, the particle size of the granules should be controlled
so as to achieve the most ideal size. Therefore, the surfactant paste is
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5~
preferably undercooled before the melting process step and a crystal
growth carrier such as choline chloride can be added. Hereby will be
achieved that the granules, tablets or pastilles will have the preferred size.
Preferably a so called 'dusting agent' is added to the micro-pastilles, to
avoid product c~king and to improve the flow properties and surfactant
stability. Preferably a hydrophobic dusting agent is, such as hydrophobic
silica, is employed.
To improve the flow properties of the granules during the process (i.e. the
flow from one process step/ vessel/ container to an other) the powder
should be essentially free from water or moisture and therefore a
desiccant is preferably added during the micro-p~till~tion process.
Particle morpholo~y
The cationic ester surfactant cont~inin,e particles or micro-pastilles formed
during the gr~n~ tion process or the p~still~tion process, are susceptible
to decomposition when in ~lk~lin~, under moisturous conditions. The
particle or micro-pastille stability however can be improved, when the
particle has a specific morphology, which can been defined by a
morphology index MI. The morphology index can be calculated with the
following formula:
MI= (0.0448 x CV) + (3.61 x 106/ d3)
wherein CV is the coefficient of variation of weight average particle size
distribution and d is the weight mean average particle size in microns.
Preferably MI is less then 0.06, more preferably less than 0.04 and most
preferably less than 0.03.
n-lry washing method
Machine laundry methods herein typically comprise treating soiled
laundry with an aqueous wash solution in a washing machine having
dissolved or dispensed therein an effective amount of a machine laundry
detergent composition in accord with the invention. By an effective
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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 use aspect a dispensing device is employed in the washing
method. The dispensing device is charged with the detergent product, and
is used to introduce the product directly into the drum of the washing
machine before the commencement of the wash cycle. Its volume
capacity should be such as to be able to contain sufficient detergent
product as would normally be used in the washing method.
Once the washing machine has been loaded with laundry the dispensing
device cont~inin~ the detergent product is placed inside the drum. At the
commencement of the wash cycle of the washing machine water is
introduced into the drum and the drum periodically rotates. The design of
the dispensing device should be such that it permits cont~inment of the
dry detergent product but then allows release of this product during the
wash cycle in response to its agitation as the drum rotates and also as a
result of its contact with the wash water.
To allow for release of the detergent product during the wash the device
may possess a number of openings through which the product may pass.
Alternatively, the device may be made of a material which is permeable
to liquid but impermeable to the solid product, which will allow release of
dissolved product. Preferably, the detergent product will be rapidly
released at the 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 m~int~ined in both the dry state and during the
wash cycle. Especially preferred dispensing devices for use with the
composition of the invention have been described in the following patents;
GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345
and EP-A-0288346. An article by J.Bland published in Manufacturing
Chemist, November 1989, pages 41-46 also describes especially preferred
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53
dispensing devices for use with granular laundry products which are of a
type cornrnonly know as the "granulette". Another preferred dispensing
device for use with the compositions of this invention is disclosed in PCT
Patent Application No. WO94/11562.
Especially preferred dispensing devices are disclosed in European Patent
Application Publication Nos. 0343069 & 0343070. The latter Application
discloses a device comprising a flexible sheath in the form of a bag
extending from a support ring defining an orifice, the orifice being
adapted to admit to the bag sufficient product for one washing cycle in a
washing process. A portion of the washing medium flows through the
orifice into the bag, dissolves the product, and the solution then passes
outwardly through the orifice into the washing medium. The support ring
is provided with a m~kin~ arrangement to prevent egress of wetted,
undissolved, product, this arrangement typically comprising radially
extending walls extending from a central boss in a spoked wheel
configuration, or a ~imil~r structure in which the walls have a helical
form.
Alternatively, the dispensing device may be a flexible container, such as a
bag or pouch. The bag may be of fibrous construction coated with a
water impermeable protective material so as to retain the contents, such as
is disclosed in European published Patent Application No. 0018678.
Alternatively it may be formed of a water-insoluble synthetic polymeric
material provided with an edge seal or closure designed to rupture in
aqueous media as disclosed in European published Patent Application
Nos. 0011500, 0011501, 0011502, and 0011968. A convenient form of
water frangible closure comprises a water soluble adhesive disposed along
and sealing one edge of a pouch formed of a water impermeable
polymeric film such as polyethylene or polypropylene.
Pack~in~ for the compositions
Commercially marketed executions of the bleaching compositions can be
packaged in any suitable container including those constructed from
paper, cardboard, plastic materials and any suitable l~min~tes. A
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preferred pack~gin~ execution is described in European Application No.
94921505.7.
linity r~quirement and relative delay of ~ linity release
In the following Examples 1 to 9 an ~lk~linity system is provided. In each
example a means is provided for delaying the release to a wash solution of
the ~lk~linity system, relatively to the cationic ester surfactant. The means
for delaying the ~lk~linity release is such that the time to achieve a
concentration that is 50% of the ultimate concentration of the cationic
ester surfactant is at least 120 seconds less than the time to achieve a
concentration that is 50% of the ultimate concentration of the ~lk~linity
system, as described herein in the T50 test method.
Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications
have the following me~nin~:
LAS : Sodium linear C12 alkyl benzene sulfonate
TAS : Sodium tallow alkyl sulfate
C45AS : Sodium C14-C1s linear alkyl sulfate
CxyEzS : Sodium Clx-C1y branched alkyl sulfate
condensed with z moles of ethylene oxide
C45E7 : A C14 15 predomin~ntly linear primary alcohol
condensed with an average of 7 moles of
ethylene oxide
C25E3 : A C12 15 branched primary alcohol condensed
with an average of 3 moles of ethylene oxide
C25E5 : A C12 15 branched primary alcohol condensed
with an average of 5 moles of ethylene oxide
CEQI : R1COOCH2CH2.N+(CH3)3withR1 = C11-
cl3
CEQ II : R1COOCH2CH2CH2N + (CH3)3 with R
C 1 l-C13
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CEQ III : R1COO CH2 CH2 N +(CH3)2(CH2CH2OH)
with R1 =C11-C13
CEQ IV : R1 COOCH2CH2 N+ (CH3CH2)2(CH3) with
Rl =Cl l-C13
QAS : R2.N+(CH3)2(C2H4OH) with R2 = C12 - C14
Soap : Sodium linear alkyl carboxylate derived from an
80/20 mixture of tallow and coconut oils.
TFAA : C 16-c 18 alkyl N-methyl glucamide
TPKFA : C12-C14 topped whole cut fatty acids
STPP : Anhydrous sodium tripolyphosphate
Zeolite A : Hydrated Sodium Aluminosilicate of formula
Na12(A 1~2si~2) 12 - 27H20 having a primary
particle size in the range from 0.1 to 10
micrometers
NaSKS-6 : Crystalline layered silicate of formula
~ -Na2Si205
Citric acid : Anhydrous citric acid
Carbonate : Anhydrous sodium carbonate with a particle size
between 200~m and 900~m
Carbonate, : Amorphous sodium carbonate with a
amorphous particle size between 200~1m and 900~1m
Bicarbonate : Anhydrous sodium bicarbonate with a particle
size distribution between 400~m and 1200,um
Bicarbonate : Amorphous sodium bicarbonate with a
amorphous particle size distribution between 40011m and
1200~1m
Silicate : Amorphous Sodium Silicate (SiO2:Na2O; 2.0
ratio)
Sodium sulfate: Anhydrous sodium sulfate
Citrate : Tri-sodium citrate dihydrate of activity 86.4%
with a particle size distribution between 425~m
and 850 ~m
MA/AA : Copolymer of 1 :4 maleic/acrylic acid, average
- molecular weight about 70,000.
CMC : Sodium carboxymethyl cellulose
-- ...................... . .
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Protease : Proteolytic enzyme of activity 4KNPU/g sold by
NOVO Industries A/S under the tradename
Savinase
Alcalase : Proteolytic enzyme of activity 3AU/g sold by
NOVO Industries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g sold
by NOVO Industries A/S under the tradename
Carezyme
Amylase : Amylolytic enzyme of activity 60KNU/g sold by
NOVO Industries A/S under the tradename
Termamyl 60T
Lipase : Lipolytic enzyme of activity 100kLU/g sold by
NOVO ~n~ stries A/S under the tradename
Lipolase
Endolase : Endoglunase enzyme of activity 3000 CEVU/g
sold by NOVO Industries A/S
PB4 : Sodium perborate tetrahydrate of nominal
formula NaBo2.3H2o.H2o2
PBl : Anhydrous sodium perborate bleach of
nominal formula NaBo2.H2o2
Percarbonate : Sodium Percarbonate of nominal formula
2Na2C03 ~3H2~2
Percarbonate : Anhydrous sodium percarbonate bleach coated
(slow release with a coating of sodium silicate (Si2O:Na2O
particle ratio = 2:1) at a weight ratio of percarbonate to
sodium silicate of 39:1
NOBS : Nonanoyloxybenzene sulfonate in the form of the
sodium salt.
TAED : Tetraacetylethylen~ min~
DTPMP : Diethylene tri~min~o penta (methylene
phosphonate), marketed by Monsanto under the
Trade name Dequest 2060
Photoactivated: Sulfonated Zinc Phthlocyanine encapsulated in
bleach dextrin soluble polymer
Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl
Brightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-
triazin-2-yl)amino) stilbene-2:2'-disulfonate.
, _
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HEDP ~ hydroxyethane diphosphonic acid
PVNO : Polyvinylpyridine N-oxide
PVPVI : Copolymer of polyvinylpyrolidone and
vinylimidazole
SRP 1 : Sulfobenzoyl end capped esters with oxyethylene
oxy and terephtaloyl backbone
SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate)
short block polymer
Silicone antifoam: Polydimethylsiloxane foam controller with
siloxane-oxyalkylene copolymer as dispersing
agent with a ratio of said foam controller to said
dispersing agent of 10:1 to 100:1.
In the following Examples all levels are quoted as % by weight of the
composition:
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Example 1
The following laundry detergent compositions A to F were prepared in
accord with the invention:
A B C D E F
LAS 8.0 8.0 8.0 8.0 8.0 8.0
C25E3 3.4 3.4 3.4 3.4 3.4 3.4
C E Q I - 0.8 - 2.0 - 0.7
C E Q II 6.0 0.5 - 0.7 2.0 0.8
Q AS - - 0.8 - - 0.8
Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1
Carbonate, 13.0 13.0 13.0 27.0 27.0 27.0
amorphous
Silicate 1.4 1.4 1.4 3.0 3.0 3.0
Sodium sulfate 26.1 26.1 26.1 26.1 26.1 26.1
PB4 5.0 5.0 6.0 6.0 4.0 4.0
Percarbonate 4.0 4.0 3.0 3.0 5.0 5.0
slow release
particle
T A E D 1.5 1.5. 1.5 1.5 1.5 1.5
D ETP M P 0.25 0.25 0.25 0.25 0.25 0.25
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HEDP 0.3 0.3 0 3 0 3 0 3 0 3
Protease 0.26 0.26 0.26 0.26 0.26 0.26
Amylase 0.1 0.1 0.1 0.1 0.1 0.1
MA/AA 0.3 0.3 0.3 0.3 0.3 0.3
C M C 0.2 0.2 0.2 0.2 0.2 0.2
Photoactivated 15 15 15 15 15 15
bleach (ppm) ppm ppm ppm ppm ppm ppm
Brightener 1 0.09 0.09 0.09 0.09 0.09 0 09
Perfume 0.3 0.3 0.3 0.3 0.3 0.3
Silicone antifoam 0.5 0.5 0.5 0.5 0.5 0.5
Misc/minors to
- 100 %
Density ing/litre 850 850 850 850 850 850
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Example 2
The following granular laundry detergent compositions G to I of bulk
density 750 g/litre were prepared in accord with the invention:
G H
LAS 5.25 5.61 4.76
TAS 1.25 1.86 1.57
C45AS - 2.24 3.89
C25AE3S - 0.76 1.18
C45E7 3.25 - 5.0
C25E3 - 5.5
CEQ II 0.8 - 2.8
CEQ III 0.4 2.0 0.5
STPP 19.7
Zeolite A - 19.5 19.5
NaSKS-6/citric acid - 10.6 10.6
(79:21)
Carbonate, amorphous 6.1 21.4 21.4
Bicarbonate, amorphous - 2.0 2.0
Silicate 6.8
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Sodium sulfate 39. 8 - 14.3
Percarbonate slow release 5.0 12.7 8.0
particle
TAED 0.5 3.1
DETPMP 0.25 0.2 0.2
HEDP - 0.3 0.3
Protease 0.26 0.85 0.85
Lipase 0.15 0.15 0.15
Cellulase 0.28 0.28 0.28
Amylase 0.1 0.1 0.1
MA/AA 0.8 1.6 1.6
C M C 0.2 0.4 0.4
Photoactivated bleach 15 ppm27 ppm 27 ppm
(ppm)
Brightener 1 0.08 0.19 0.19
Brightener 2 - 0.04 0.04
Perfume 0.3 0.3 0.3
Silicone antifoam 0.5 2.4 2.4
Minors/misc to 100%
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Example 3
The following detergent formulations, according to the present invention
were prepared, where J is a phosphorus-cont~inin~ detergent composition,
K is a zeolite-cont~ining detergent composition and L is a compact
detergent composition:
J K L
Blown Powder
S T PP 24.0 - 24.0
Zeolite A - 24.0
C45AS 9.0 6.0 13.0
MA/AA 2.0 4.0 2.0
LAS 6.0 8.0 11.0
TAS 2.0
CEQ I - 2.0
CEQ II - - 2.0
CEQ III 2.0
Silicate 7.0 3.0 3.0
CMC 1.0 1.0 0.5
Brightener 2 0.2 0.2 0.2
Soap 1.0 1.0 1.0
DTPMP 0.4 0.4 0.2
Spray On
C45E7 2.5 2.5 2.0
C25E3 2.5 2.5 2.0
Silicone antifoam 0.3 0.3 0.3
Perfume 0.3 0.3 0.3
Dry additives
Carbonate, amorphous 6.0 13.0 15.0
Percarbonate slow 18.0 18.0 10.0
release particle
PBl 4.0 4.0 0
TAED 3.0 3.0 1.0
Photoactivated bleach 0.02 0.02 0.02
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
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Amylase 0.25 0.30 0.15
Dry mixed sodium 3.0 3.0 5.0
sulfate
Balance (Moisture & 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 630 670 670
Example 4
The following nil bleach-cont~inin~ detergent formulations of particular
use in the washing of colored clothing, according to the present invention
were prepared:
M N O
Blown Powder
CEQII 0.5 0.5 0.5
CEQ III 1.0 1.5 0.5
CEQ IV 0.5 1.5 2.0
Zeolite A 15.0 15.0
Sodium sulfate 0.0 5.0
LAS 3.0 3.0
DTPMP 0.4 0.5
CMC 0.4 0.4
MA/AA 4.0 4.0
Agglomerates
C45AS - - 11.0
LAS 6.0 5.0
TAS 3.0 2.0
Silicate 4.0 4.0
Zeolite A 10.0 15.0 13.0
CMC - - 0.5
MA/AA - - 2.0
Carbonate 9.0 7.0 7.0
- Spray On
Perfume 0.3 0.3 0.5
C45E7 4.0 4.0 4.0
C25E3 2.0 2.0 2.0
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Dry additives
MA/AA - 3.0
NaSKS-6 - - 12.0
Citrate 10.0 - 8.0
Bicarbonate, amorphous 7.0 3.0 5.0
Carbonate, amorphous 8.0 5.0 7.0
PVPVI/PVNO 0.5 0.5 0.5
Alcalase 0.5 0.3 0.9
Lipase 0.4 0.4 0.4
Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 9.0 0.0
nre (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 700 700 700
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Example 5
The following detergent formulations, according to the present invention
were prepared:
P Q R S
CEQ III 0.4 - 3.5 1.5
CEQ IV 1.5 2.4 - 1.5
LAS 20.0 14.0 24.0 22.0
QAS 0.7 1.0 - 0.7
TFAA - 1.0
C25E5/C45E7 - 2.0 - 0.5
C45E3S - 2.5
STPP 30.0 18.0 30.0 22.0
Silicate 9.0 5.0 10.0 8.0
Carbonate, 13.0 7.5 - 5.0
amorphous
Bicarbonate - 7.5
DTPMP 0.7 1.0
SRP 1 0.3 0.2 - 0.1
MA/AA 2.0 1.5 2.0 1.0
CMC 0.8 0.4 0.4 0.2
Protease 0.8 1.0 0.5 0.5
Amylase 0. 8 0.4 - 0.25
Lipase 0.2 0.1 0.2 0.1
Cellulase 0.15 0.05
Photoactivated 70ppm 45ppm - 10ppm
bleach (ppm)
Brightener 1 0.2 0.2 0.08 0.2
Percarbonate 6.0 2.0
slow release
particle
PB1 - - 2.0 3.0
NOBS 2.0 1.0
B~l~nr.e 100 100 100 100
(Moisture and
Miscellaneous)
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Example 6
The following detergent formulations, according to the present invention
were prepared:
T U V
Blown Powder
Zeolite A 30.0 22.0 6.0
Sodium sulfate 19.0 5.0 7.0
MA/AA 3.0 3.0 6.0
LAS 14.0 12.0 22.0
C45AS 8.0 7.0 7.0
CEQ II - 0.4 2.5
CEQ IV 1.5 1.5 0.5
Silicate - 1.0 5.0
Soap - - 2.0
Brightener 1 0.2 0.2 0.2
Carbonate, 8.0 16.0 20.0
amorphous
DTPMP - 0.4 0.4
Spray On
C45E7 1.0 1.0 1.0
Dry additives
PVPVI/PVNO 0.5 0.5 0.5
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.1 0.1 0.1
Cellulase 0.1 0.1 0.1
NOBS - 6.1 4.5
PB1 1.0 5.0 6.0
Sodium sulfate - 6.0
Balance (Moisture 100 100 100
and Miscellaneous)
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Example 7
The following high density and bleach-cont~inin~ detergent forrnulations,
according to the present invention were prepared:
W X Y
Blown Powder
ZeoliteA 15.0 15.0 15.0
Sodim sulfate 0.0 5.0 0.0
LAS 3.0 3.0 3.0
QAS - 1.5 1.5
CEQ II 0.5 0.5
CEQ III 0.9 1.2 2.5
DTPMP 0.4 0.4 0.4
CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
Agglomerates
LAS 5.0 5.0 5.0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
Spray On
Perfume 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0 - -
Dry additives
Citrate 5.0 - 2.0
Bicarbonate, amorphous - 3.0
Carbonate, amorphous 8.0 15.0 10.0
TAED 6.0 2.0 5.0
PB1 7.0 3.5 5.0
Polyethylene oxide of MW - - 0.2
5,000,000
Bentonite clay - - 10.0
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
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Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
Percarbonate slow release 7.0 3.5 5.0
particle
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 850 850 850
-
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Example 8
The following high density detergent formulations, according to the
present invention were prepared:
Z AA
Agglomerate
C45AS 11.0 14.0
CEQ IV 0.8 2.2
Zeolite A 15 .0 6.0
Carbonate, amorphous 4.0 8.0
MA/AA 4.0 2.0
CMC 0.5 0.5
DTPMP 0.4 0.4
Spray On
C25E5 5.0 5.0
Perfume 0.5 0.5
Dry Adds
HEDP 0.5 0.3
SKS6 13.0 10.0
Citrate 3.0 1.0
TAED 5.0 7.0
Percarbonate 10.0 10.0
Percarbonate slow release 10.0 10.0
particle
SRP 1 0.3 0.3
Protease 1.4 1.4
Lipase 0.4 0.4
Cellulase 0.6 0.6
Amylase 0.6 0.6
Silicone antifoam 5.0 5.0
Brightener 1 0.2 0.2
~ Brightener 2 0.2
Balance (Moisture and 100 100
Miscellaneous)
Density (g/litre) 850 850
