Note: Descriptions are shown in the official language in which they were submitted.
~3[379~
DETERGENT COMPOSITIONS
.
The present invention relates to detergent compositions. In
particular, it relates ~o built laundry detergent co~positions
which are es6entially free of phosphate and have exc~llent
cleaning, whiteness maintenance and stain-removal performance
together with improved bleach stability and fabric-care
characteristics.
The role of phosphate detergency builders as adjuncts for
organic, water-soluble, synthetic detergents and their value in
improving the overall performance of such detergents are
well-known. In recent years, however, the use of high levels ~f
phosphate builders, such as the tripolyphosphates, has come under
scrutiny because of the su6picion that soluble phosph~te specLes
accelerate the eutrophication or ageing process of water bodies.
me need exists, therefore for a built laundry detergent
composition which is free of phosphate but which i~ comparable to
a conventional tripolyphosphate-built composition in overall
detergency effectiveness.
The mechanism whereby detergency builders function to improve
the detergency action of water-soluble organic detergent compounds
is not precisely known, but appears to depend on a combination of
such factors as water-softening action, soil su6pension and
anti-redeposition effects, clay swelling and peptization and pH
adjustment. However, present theory doe~ not allow the
prediction of which compound~ will serve as effective detergency
builders. Sodium alumino~ilicates, commonly known as zeolites
have been proposed for use as phosphate builder substitute6 since
they are able to soften water by removing calcium ions (see, for
example, BE-A-814,B74 and BE-A-813581). Zeolite6 are unable to
3~ duplicate the full range of builder functions demonstrated by
phosphates, however, and in practice, they have been restricted to
the role of a partial phosphate substitute.
"~.
~;~3~'79~7
One way of boosting the overall detergency of zero-phosphate
formulations is through the use of bleaching auxiliaries such as
the inorganic or organic peroxy bleaches and organic bleach
activators. Although careful rebalancing of builder and bleach
types and levels can indeed provide some improvement in
performance, such formulations remain fundamentally weak in
three areas, firstly bleach stability, secondly fabric damage
characteristics, and thirdly, greasy and particulate soil
removal especially at low wash temperatures.
Applicants have now found, however, that a zero phosphate
builder system having defined building capacity and defined
selectivity for magnesium versus calcium, in combination with
certain heavy-metal scavenging agents results in excellent
through-the-wash bleach stability a~d fabric damage
characteristics. Moreover, applicants have further discovered
that certain organic peroxy acid bleach precursors of defined--
chain length are operable in combination with the zero-phosphate
builder system to provide at least phosphate-equivalent cleaning
performance across the range of wash temperature-s with
particularly outstanding performance-on greasy and particulate
soils at low wash temperatures.
According to a first aspect of the invention, therefore,
there is provided a detergent composition comprising
a) from about 5% to about 60% of organic surfactant
selected from anionic, nonionic, zwitterionic,
ampholytic and cationic surfactants and mixtures
thereof,
b) from about 7% to about 80% of a detergency builder
essentially free of phoRphate having a calcium builder
3~ capacity at pH 10 and 25C of at least 1.5 moles/kg
and a magnesiumscalcium selectivity factor of at least
0.2 and comprising
(i)from 2% to 30% of polycarboxylate polymer selected
from compounds having the empiricai formula I
97
_ _
Rl - yp - ( X - CR3) R2
_ C02M n
wherein X is 0 or CH2, Y is a comonomer or mixture
oS comonomer~, Rl and R2 are bleach and
alkali-stable polymer-end group~, R3 i8 H, OH or
Cl_4 alkyl, M i8 ~, alkali metal, alkaline earth
metal, ammonium or substituted am~onium groups, p is
from O to 2, and n is at least 10, and mixtures
thereof
(ii)-from 5% to 50% of a water insoluble
ion-exchange material having the formula II
Mz[Al02)z (SiO2)y] xH20 II
wherein M i8 a calcium-exchange cation, z and y are
at least 6; the molar ratio of z to y is in the
range from about 1.0 to about 0.5; and x is from
about 10 to about 264; the aluminosilicate having a
calcium ion exchange capacity of at least 200
milligrams equivalent of CaC03/gram, a calcium ion
exchange rate of at least about 2 grains of
Ca2+/gallon/minute/gram/gallon, and a particle
size diameter of from about 0.1 microns to about 10
microns, and
c) a bleach system compri~ing
(i) from 5% to 35~ of inorganic or organic peroxy
bleaching agent,
(ii) from 0% to 10% of organic peroxy acid bleach
precursor, and
(iii) a heavy metal scavenging agent.
In another aspect o$ the invention there is provided a
detergent composition comprising
_ 4 ~ '7~7
a) ~rom about 5% to about 60~ of organic surfactant
selected fron anionic, nonionic, zwitterionic,
ampholytic and cationic surfacants and Lixtures
thereof,
b) from about 7% to about 80% of a detergency builder
essentially free of phosphate having a calcium
builder capacity at 25C of at least l.S moles/kg
and a magnesium:calcium selectivity factor of at
least 0.2, and
c) a bleach system comprising
(i) from S~ to 35~ of inorganic or organic peroxy
bleaching agent,
(ii) from 0.5~ to 10% of organic peroxy acid bleach
precursor having the general formula IV, and
A 1l
R~-C-L IV
wherein R4 is an alkyl group containing 6 to 12
carbon atoms wherein the longest linear alkyl chain
extending from and including the carboxyl carbon
contains from 5 to 10 carbon atoms and L is a
leaving group, the conjugate acid of which has a
PKa in the range from 6 to 13, and
(iii) a heavy metal ~cavenging agent.
The compositions of the invention contain an organic
surfactant, an essentially non-phosphate detergent builder
and a bleach system. The detergent builder has defined
calcium building capacity and defined magnesium;calcium
building eelectivity. The compositions can be liquid or
solid, granular
spray-dried compositions being preferred.
~23~ 7
- 5 -
The compositions of the invention contain from about 7% to
about 80%, preferably from about 10% to about 60%, more
preferably from about 15% to about 50% of a det0rgency builder
which i8 essentially free of phosphate, i.e. which contains less
than about 2%, preferably less than about 1/2% phosphate on a
compositional baB i 8 -
The detergency builder herein has a calcium buildingcapacity at pH 10 and 25C of at least 1.5, preferably at
least 2.0, more preferably at least 3.5 moles Ca2 /kg of
builder and a magnesium:calcium selectivi~y factor of at least
0.2, preferably at least 0.25, more preferably at least 0.3.
The building capacity and selectivity factor are measured as
follows.
Calcium building capacity (CO) is measured using a Corning
calcium ion selective electrode (from Scientific Products,
Corning Medical, Corning Ltd., Halstead, Essex, England) with an
Orion Double Junction Reference Electrode Model 90-02 (Orion
Research Inc., Cambridge, Mass., U.S.A.) as reference. A
calcium ion solution (0.05 M) is titrated into a solution (0.4%)
containing the builder under test at pH 10 and 25C. The
free calcium ion concentration i8 detexmined as a function of
added calcium ions using the calcium electrode precalibrated
against a number of standard calcium solutions. The calciu~ ion
solution is added until free calcium reaches 5 x 10 3M.
Calcium building capacity is calculated graphically from the
molar quantity of added calcium ions corresponding to the
intercept at zero free calcium ion concentration of the gradient
~ through 5 x 10 3M and is reported in moles Ca2 /kg of
builder.
Magnesium2calcium ~electlvity factor i~ again determined
using the calcium ion selective electrode. In this case,
3~ h~wever, the hardness solution contains both calcium and
magnesium ion~ (0.03 M each) and the calcium building capacity
80 measured (Cl), or more accurately the reduction in calcium
building capacity (CO - Cl), correlates with the selectivity
of the builder for magnesium as compared with calcium. The
~electivity factor herein is defined by the quotient
( O Cl)/cO-
-- 6 --
The essentially zero-phoBphate detergency builder preferably -
co~prise~ a mixture of a polycarboxylate polymer and a
water-insoluble, ion-exchangeable aluminosilicate. The
polycarbo~ylate i8 pre~erably selected to have a magnesium
building capacity of at least 2.0 preferably at least 3.0, more
preferably at least 3.5 moles/kg as measured at both 25 C and
90C: in other words, the builder should have substantial
magnesium building capacity acro~s the range of wash
temperatures. Magneæium building capacity can be measured as
1~ for calcium building capacity above but using an Orion Divalent
Cation Electrode. Alternatively, magnesium building capacity
can be measured on the basis of a turbidity method as follows.
A solution o~ magnesium ions to.4M) is titrated into a solution
of the polycarboxylate (1~) at pH 10.3 and at the specified
temperature. The solution additionally contains 1.6:1 ratio
sodium silicate (0.5%) aq indicator. Precipitation of
magnesium silicate above the building limit of the
polycarboxylate is monitored using a Mettler phototitrator.
Magnesium building capacity is calculated from the molar
quantity of added magnesium corresponding to the point of
maximum change in gradient in the turbidity vs added magnesium
plot and is reported here in moles Mg2 /kg of polycarboxylate.
Preferred polycarboxylates fall into several categories. A
first category belongs to the class of copolymeric
polycarboxylates which, formally at least, are formed from an
unsaturated polycarboxylic acid such as maleic acid, citraconic
acid, itaconic acid and mesaconic acid as first monomer, and an
unsaturated monocarboxylic acid such as acrylic acid or an
alpha -Cl 4 alkyl acrylic acid as second monomer. Referring
to formula I, therefore, preferred polycarbQxylates of this type
are those in which X i~ CH2, R i~ H or Cl_4 alkyl,
especially methyl, p i9 from about 0.1 to about 1.9, preferably
from about 0.2 to about 1.5, n averages from about 10 to abo~t
1500, preferably from about 50 to about 1000, more preferably
from 100 to 800, especially from 120 to 400 and Y comprises
monomer units of formula III
~3~79~
-- 7 --
CH CH ----
C02M C~2M
A second category belongs to the class of poly
(alpha-hydroxyacrylates) in which, referring to formula I, X
is CH2, R3 is OH, p is from O to 0.1, prefexably O and n
averages from about 50 to 1500, preferably from about 100 to
1000. Y, if present, can be a polycarboxylic acid such as
III above, or an ethylene oxide moiety.
A third category belongæ to the cla~s of acetal
polycarboxylates in which, referring to formula I, X is O,
R3 is H, p is from O to 0.1, preferably O and n averages
from lO to 500. If present, Y again can be a polycarboxylic
acid such as III above or an ethyleneoxide moiety.
A fourth category belonys to the cla~s of homopolymeric
polyacrylates in which referring to formula I, X i~ CH2,
R is ~ or Cl 4 alkyl, p is O and n averageC from about
10 to 1500, preferably from about 500 to 1000.
A fifth category of polycarboxylate has the formula I in
which X is CH2, R3 is H or Cl_4 alkyi, especially
methyl, p i9 from 0.01 to 0.09, preferably from 0.02 to 0.06,
n averages from about 10 to about 1500, preferably from about
15 to about 300 and Y is a polycarboxylate formed from maleic
acid, citraconic acid, itaconic acid or mesaconic acid,
highly preferred being maleic acid-derived comonomers of
formula III above.
The alkali-stable polymer end groups in formula I
suitably include alkyl groups, oxyalkyl groups and alkyl
carboxylic acid groups and salts and ester~ thereof.
In the above, n, the degree of polymerization of the
polymer can be determined from the weight average polymer
molecular weight by dividing the latter by the average
monomer molecular weight. Thu~, for a maleic-acrylic
copolymer having a weight average molecular weight of 15,500
and comprising 30 mole ~ of maleic acid derived units, n is
182 (i.e. 15,500 / (116 x 0.3 ~ 72 x 0.7).
~'~3Q'7~7
-- 8
In case of doubt, weight-average polymer ~olecular --
weights can be determined herein by gel permeation
chromotography using Waters ~Porasil (RTM) GPC 60 A2
and ~ ondagel (RTM) E-125, E-500 and E-1000 in series,
temperature-controlled column~ at 40C against ~odium
polystyrene sulphonate polymer standards, available from
Poly~er Laboratories Ltd., Shropshire, UK, the polymer
standards being calibrated as their sodium salts, and the
eluant being 0.15M sodium dihydrogen phosphate and O.O~M
tetramethyl ammonium hydroxide at pH 7.0 in 80/20
water/acetonitrile.
Mixtures of polycarboxylates are also suitable herein,
especially mixtures comprising a high molecular weight
component having an n value of at least 100, preferably at
least 120, and a low molecular weight component having an n
value of less than 100, preferably from 10 to 90, more
preferably from 20 to 80. Such mixtures are optimum from the
viewpoint of providing excellent bleach stability and
anti-incrustation performance in the context of a
2~ zero-phosphate detergent formula.
In mixtures of this type, the weight ratio of high
~olecular weight component to low molecular weight component
is generally at least 1:1, preferably from about 1.1:1 to
about 20:1, more preferably from about 1.5:1 to about 10.1,
especially from about 2:1 to about 8:1. Preferred
polycarboxylates of the low molecular weight type are
polycarboxylates of the fourth category (homopolyacrylates)
listed above.
Of all the above, highly preferred polycarboxylates
herein are those of the first category in which n averages
fro~ 100 to 800, preferably from 120 to 400 and mixtures
thereof with polycarboxylates of the fourth category in which
n averages from 10 to 90, preferably from 20 to 80.
According to a further aspect of the invention,
therefore, there is provided a detergent composition
co~prising
- g ~L23C~'7~37
a) from about 5~ to about 60% of organic surfactant
selected from anionic, nonionic, zwitterionic,
ampholytic and cationic surfacants and mixtures
thereof,
b) from about 7~ to about 80% of a detergency builder
essentially free of phosphate having a calcium
builder capacity at 25C of at least 1.5 moles/kg
and a magnesium:calcium selectivity factor of at
least 0.2, wherein the builder comprises from 24 to
30~ of a mixture of
(i) a copolymeric polycarboxylate having the general
formula I:
Rl ~ Y - ( X - CR3) ~ R2 I _
_ C02M n
wherein X is CH2, Y i8 a maleic-acid derived unit,
Rl and R2 are bleach and alkali stable
polymer-end groups, R3 is H, M i8 H, alkali metal,
alkaline earth metal, ammonium or substituted
ammonium, p i8 from about 0.1 to about 1.9 and n
. averages from 120 to 400, and
(ii) a homopolymeric polyacrylate having the general
I in which X, Rl, R2, R3 and M are each as
defined in (i) above, p is 0 and n averages ~rom 10
to 90, preferably from 20 to 80, the weight ratio o~
copolymeric polycarboxylate to homopolymeric
polyacrylate being at lea~t 1l1, and
c) a bleach system comprising
. (i) from 5% to 35% of inorganic or organic peroxy
bleaching agent,
(ii) from 0% to 10% of organic peroxy acid bleach
precursor, and
(iii) a heavy metal scavenging agent.
~3~ 3'7
-- 10 ~
The aluminosilicate ion-e~change materials herein are
preferably those having the unit cell formula
M [(A102)z (SiO2)y] xH20
wherein M i5 a calcium-exchange cation, z and y are at lea~t
6: the molar ratio of z to y i8 from about 1.0 to about 0.5
and x i8 at leaQt 5, preferably from about 7.5 to about 276,
more preferably from about 10 to about 2Ç4. The
aluminosilicate materials are in hydrated from and are
preferably crystalline containing from about 10% to about
28%, more preferably from about 18% to about 22% water.
The aluminosilicate ion exchange material~ are further
characterized by a particle size diameter of from about 0.1
micron to about 10 microns, preferably from about 0.2 micron
to about 4 microns. The term "particle ~ize diameter"
herein represents the average particle size diameter of a
given ion exchange material as determined by conventional
analytical techniques such as, for example, microscopic
determination utilizing a scanning electron microscope. The
aluminosilicate ion exchange materials herein are usually
further characterised by their calcium ion exchange capacity,
which is at least about 200 mg. equivalent of CaC03 water
hardness/g of aluminosilicate, calculated on an anhydrous
basis, and which generally is in the range of from about 300
mg e~./g to about 352 mg eq./g. The aluminosilicate ion
exchange materials herein are still further characterized by
their calcium ion exchange rate which is at least about 2
grains Ca++/gallon/minute/gram/gallon of aluminosllicate
(anhydroue basis), and generally lies within the range of
from about 2 grains/gallon/minute/gram/gallon to about 6
grains/gallon/minute/gram/gallon, based on calcium ion
hardness. Optimum aluminosilicates for builder purposes
exhibit a calcium ion exchange rate of at least about 4
grains/gallon/minute/gram/gallon.
3a~7
Alumino~ilicate ion exchange materials useful in the
practice of this invention are commerciall~ available and can
be naturally occurring aluminosilicates or synthetically
derived. A method for producing aluminosilicate ion exchange
materials is discussed in U.S.-A-3,985,669. Preferred
synthetic crystalline aluminosilicate ion exchange materials
useful herein are available under the designations Zeolite A,
Zeolite B, æeolite X, Zeolite HS and mixtures thereofO In an
especially preferred embodiment, the crystalline
aluminosilicate ion exchange material is Zeolite A and has
the formula
12[A12)12 (Si2)12] XH20
wherein x is from about 20 to about 30, especially about 27.
Zeolite X of formula Na86 [(A102)86~sio2)lo6] 276 H20
is also suitable, as well as Zeolite HS of formula
Na6 [(A102)6(sio2)6] 7-5 H20)-
The polycarboxylate and aluminosilicate components constitute
from about 2~ to about 30% and from about 5% to about 50% by weight
of composition respectively, more preferably from about 3% to about
10% and from about 10% to about 25% respectively. As a percentage
of the builder, polycarboxylate and aluminosilicate constitute from
about 5% to about 60% and from 20~ to 95% respectively, preferably
from about 10% to about 40% and from 25~ to 75% respectively.
Importantly, the selection of polycarboxylate and the relative
amounts of polycarboxylate and aluminosilicate should be such as to
meet the critical magnesium;calcium selectivity factor. Usually,
the weight ratio o~ polycarboxylatesaluminosilicate is from about
2sl to ls20, preferably from about 1:1 to ls5. Preferred mixtures
herein are such, however, that at a 1:1 ratio, the builder displays
3~ a magnesium:calcium selectivity factor of at lea~t about 0.3,
preferably at least about 0.35, more preferably at least about 0.4.
The polycarboxylate and aluminosilicate components of the
present compositions can be replaced at least in part by other
non-phosphate builder materials provided that the total builder
system meets the constraints of calcium builder capacity and
magnesium:calcium selectivity factor specified earlier.
- 12 - ~3~7
Specific example~ o~ non-phosphorus, inorganic builders are --
sodium and potassium carbonate, bicarbonate, ~esquicarbonate,
tetraborate decahydrate, and silicate having a molar ratio of
Si~2 to alkali metal oxide of from about 0.5 to about 4.0,
preferably from about 1~0 to about 3.2, more preferably from about
1.6 to about 2.4. "Seeded carbonate" builders as disclosed in
Be-A-798,856 are also suitable. Water-soluble, non-phosphorus
organic builders useful herein include the variou~ alkali metal,
ammonium and substituted ammonium carboxylates, monomeric
polycarboxylates, polyhydroxysulfonates and nitrilotriacetates.
Examples of monomeric polycarboxylate builders are the sodium,
potassium, lithium, ammonium and substituted ammoniu~ salts of
oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids,
and citric acid.
Other useful builders hérein are ~odium and potassium
carboxymethyloxymalonate, carboxymethyloxysuccinate,
nitrilotriacetate, cis-cyclohexanehexacarboxylate,
cis-cyclopentanetetracarboxylate, and phloroglucinol
trisulfonate. Such additional non-phosphorus inorganic builders
2~ can be included in levels of from about 0.5~ to about 8%,
preferably from about 1% to about 4~ by weight of composition.
The detergent compositions herein contain from about 5% to
about 60% by weight of an organic surfactant selected from
anionic, nonionic, zwitterionic, ampholytic and cationic
surfactants, and mixtures thereof. The surfactant preferably
represents from about 8% to about 30%, more preferably from
about 10% to about 20~ by weight in the case of solid
compositions and from about 10% to about 50~, ~ore preferably
from about 15~ to about 40% in the case of liquid compositions.
Surfactants useful herein are listed in US-A-4,222,905 and
US-A-4,239,659.
The anionic surfactant can be any one or more of the
materials used conventionally in laundry detergents. Suitable
synthetic anionic surfactants are water-soluble salts of alkyl
benzene sulphonates, alkyl sulphate~, alkyl polyethoxy ether
sulphates, paraffin sulphonates, alpha-olefin sulphonates,
1~3~7
-- 13 --
- alpha-sulpho-carbo~ylate~ and their esters, alkyl glyceryl ether-
sulphonates, fatty acid monoglyceride sulphate~ and sulphonates,
alkyl phenol polyethoxy ethër sulphate~, 2-acyloxy
alkane-l-sulphonate, and beta-alkylo~y alkane sulphonate.
A particularly suitable class of anionic surfactants
includes water-soluble salts, particularly the alkali metal,
ammonium and alkanolammonium salts or organic sulphuric reaction
products having in their molecular structure an alkyl or alkaryl
group containing from about 8 to about 22, especially from about
10 to about 20 carbon atoms and a sulphonic acid or sulphuric
acid ester group. (Included in the term "alkyl" i8 the alkyl
portion of acyl groups). Examples of this group of synthetic
detergents which form part of the detergent compositions of the
present invention are the sodium and potassium alkyl sulphates,.
especially those obtained by sulphating the higher alcohols
(C8 18) carbon atoms produced by reducing the glycerides of
tallow or coconut oil and sodium and potassium alkyl benzene
sulphonates, in which the alkyl group contains from about 9 to
about 15, especially about 11 to about 13, carbon atoms, in
2~ straight chain or branched chain configuration, e.g. those of
the type described in U.S-A- 2,220,099 and U.S-A- 2,477,383 and
those prepared from alkylbenzenes obtained by alkylation with
straight chain chloroparaffins (using aluminium trichloride
catalysis) or straight chain olefins (using hydrogen fluoride
catalysis). Especially valuable are linear straight chain alkyl
benzene sulphonates in which the average of the alkyl group is
about 11.8 carbon atoms, abbreviated as Cll 8 LAS, and
C12-C15 methyl branched alkyl sulphates.
Other anionic detergent compounds herein include the sodium
3~ C10_18 alkyl glyceryl ether sulphonates, eapecially those
ethers of higher alcohols derlved from tallow and coconut oil;
sodium coconut oil fatty acid monoglyceride
sulphonates and sulphates; and sodium or potassium ~alts of
alkyl phenol ethylene oxide ether sulphate containing about 1 to
about 10 units of ethylene oxide per molecule and wherein the
alkyl groups contain about 8 to about 12 carbon atoms.
- 14 ~ 3!D'797
Other useful-anionic detergent compounds hersin include the -
water-soluble salts or esters of alpha-sulphonated fatty acids
containing from about 6 to 20 carbon atoms in the fatty acid
group and from about 1 to 10 carbon atoms in the e~ter group;
water-soluble salts of 2-acyloxy-alkane-1-sulphonic acids
containing from about 2 to 9 carbon atoms in the acyl group and
from about 9 to about 23 carbon atoms in the alkane moiety;
alkyl ether sulphates containing from about 10 to 18, especially
about 1~ to 16, carbon ato~s in the alkyl group and from about 1
to 12, especially 1 to 6, more especially 1 to 4 moles of
ethylene oxide; water-soluble salts of olefin sulphonates
containing from about 12 to 24, preferably aout 14 to 16, carbon
atoms, especially those made by reaction with sulphur trioxide
followed by neutralization under conditions such that any
sultones present are hydrolysed to the corresponding hydroxy
alXane sulphonates; water-soluble salts of paraffin sulphonates
containing from about 8 to 24, especially 14 to 18 carbon atoms,
and beta-alkyloxy alkane sulphonates containing from about 1 to
3 carbon atoms in the alkyl group and from about 8 to 20 carbon
atoms in the alkane moiety.
The alkane chains of the foregoing non-soap anionic
surfactants can be derived from natural sources such as coconut
oil or tallow, or can be made synthetically as for example using
the Ziegler or Oxo processes. Water solubility can be achieved
by using alkali metal, ammonium or alkanolammonium cations;
sodium is preferred. Suitable fatty acid soaps can be selected
from the ordinary alkali metal (sodium, potassium), ammonium,
and alkylolammonium salts of higher fatty acids containing from
about 8 to about 2~, preferably from about 10 to about 22 and
especially from about 16 to about 22 carbon atoms in the alkyl
chain. Suitable fatty acids can be obtained from natural
sources such as, for instance, from soybean oil, castor oil,
tallow, whale and fish oils, grease, lard and mixtures
thereof). me fatty acids also can be synthetically prepared
(e.g., by the oxidation of petroleum, or by hydrogenation of
carbon monoxide by the Fischer-Tropsch process). Resin acids
are suitable such as rosin and those resin acids in tall oil.
3'7~7
-- 15 --
Napthenic acids are also suitable. Sodium and potassium soaps
can be made by direct saponification of the fats and oils or by
the neutralization of the free fatty acids which are prepared in
a separate manufacturing process. Particularly useful are the
sodium and potassium salts of the mixtures of fatty acids
derived from tallow and hydrogenated fish oil.
Mixtures of anionic surfactants are particularly suitable
herein, especially mixtures of sulfonate and sulfate ~urfactants
in a weight ratio of from about 5:1 to about 1:5, preferably
1~ from about 5:1 to about 1:1, more preferably from about 5:1 to
about 1.5:1. Especially preferred i-~ a mixture of an alkyl
benzene sulfonate having from 9 to 15, especially 11 to 13
carbon atoms in the alkyl radical, the cation being an alkali
metal, preferably sodium; and either an alkyl sulfate having
from 10 to 20, preferably 12 to 18 carbon atoms in the alkyl
radical or an ethoxy sulfate having from 10 to 20, preferably ~0
to 16 carbon atom-q in the alkyl radical and an average degree of
ethoxylation of 1 to 6, having an alkali metal cation,
preferably sodium.
The nonionic surfactants useful in the present invention are
condensates of ethylene oxide with a hydrophobic moiety to provide
a surfactant having an average hydrophilic-lipophilic balance
(HLB) in the range from about 8 to 17, preferably from about 9.5
to 13.5, more preferably from about 10 to about 12.5. The
hydrophobic moiety may be aliphatic or aromatic in nature and the
length of the polyoxyethylene group which is condensed with any
particular hydrophobic group can be readily adjusted to yield a
water-soluble compound having the desired degree of balance
b0tween hydrophilic and hydrophobic elements.
3~ Examples of suitable nonionic surfactants include:
1. The polyethylene oxide condensates of alkyl phenol,
e.g. the condensation products of alkyl phenols having an alkyl
group containing from 6 to 12 carbon atoms in either a straight
chain or branched chain configuration, with ethylene oxide, the
said ethylene oxide being present in amounts equal to 3 to 30,
preferably 5 to 14 moles of ethylene oxide per mole of alkyl
phenol. The alkyl ~ubstituent in such compounds may be derived,
- 16 - ~3~797
for example, from polymerised propylene, di-~30butylene, octene
and nonene. Other exa~ples include dodecylphenol condensed with 9
moles of ethylene oxide per mole of phenol; dinonylphenol
condensed with 11 moles of ethylene o~ide per mole of phenol;
nonylphenol and di-isooctylphenol condensed with 13 moles of
ethylene oxide.
2. The condensation product of primary or secondary aliphatic
alcohols having from 8 to 24 carbon atom~, in either straight
chain or branched chain configuration, with from 2 to about 40
mole~, preferably 2 to about 9 moles of ethylene oxide per mole of
alcohol. Preferably, the aliphatic alcohol comprises between 9
and 18 carbon atoms and i~ ethoxylated with between 2 and 9,
desirably between 3 and 8 moles of ethylene oxide per mole of
aliphatic alcohol. The preferred surfactants are prepared fro~
primary alcohols which are either linear (such as those derived
from natural fats or, prepared by the Ziegler process from
ethylene, e.g. myristyl, cetyl, stearyl alcohols), or partly
branched such a~ the Lutensols, Dobanols and Neodols which have
about 25% 2-methyl branching (Lutensol being a Trade Name of BASF,
Dobanol and Neodol being Trade Names of Shell), or Synperonics,
which are understood to have about 50~ 2-methyl branching
(Synperonic is a Trade Name of I.C.I.) or the primary alcohols
having more than 50% branched chain structure sold under the Trade
Name Lial by Liquichimica. Specific examples of nonionic
surfactants falling within the scope of the invention include
Dobanol 45-4, Dobanol 45-7, Dobanol 45-9, Dobanol 91-2.5, Dobanol
91-3, Dobanol 91-4, Dobanol 91-6, Dobanol 91-8, Dobanol 23-6.5,
Synperonic 6, Synperonic 14, the condensation products of coconut
alcohol with an average of between 5 and 12 moles of ethylene
oxide per mole of alcohol, the coconut alkyl portion having fro~
10 to 14 carbon atoms, and the condensation products of tallow
alcohol with an average of between 7 and 12 moles of ethylene
oxide per mole of alcohol, the tallow portion comprising
essentially between 16 and 22 carbon atoms. Secondary linear
alkyl ethoxylates are also suitable in the present compositions,
especially those ethoxylates of the Tergitol series having from
about 9 to 15 carbon atoms in the alkyl group and up to about 11,
especially from about 3 to 9, ethoxy residues per molecule.
- 17 - ~3~)~97
The compounds formed by condensing ethylene oxide with a
hydrophobic ba~e formed by the condensation of propylene oxide
with propylene glycol. The molecular weight of the hydrophobic
portion generally falls in the range of about lS00 to 1800. Such
synthetic nonionic detergents are available on the market under
the Trade Name of "Pluronic" supplied by Wyandotte Chemicalc
Corporation.
Especially preferred nonionic ~urfactants for use herein are
the Cg-Cl5 primary alcohol ethoxylates containing 3-8 mole~ of
ethylene oxide per mole of alcohol, particularly the C12-C15
primary alcohols containing 6-8 moles of ethylene oxide per mole
of alcohol.
Cationic surfactants suitable for use herein include
quaternary ammonium surfactants and surfactants of a semi-pola~
nature, for example amine oxides.
Suitable surfactants of the amine oxide class have the
general formula V
R6 R
R5 1+ (CH2)i 1 R6 V
O _ O
wherein R5 is a linear or branched alkyl or alkenyl group having
2~ 8 to 20 carbon atoms, each R6 is independently selected from
Cl_4 alkyl and -(CnH2nO)mH where i i8 an integer from 1 to
6, j is 0 or 1, n is 2 or 3 and m is from 1 to 7, the sum total of
CnH2nO groups in a molecule being no more than 7.
In a preferred embodiment R has from lO to 14 carbon atoms
and each R6 i8 independently selected from methyl and
-(CnH2nO)mH wherein m i8 from 1 to 3 and the sum total of
C~H2nO groups in a molecule is no more than 5, preferably no
more than 3. In a highly preferred embodiment, j i8 0 and each
R6 i8 methyl, and R i8 C12-C14 alkyl-
3~ Another suitable class of amine oxide species i9 represented
by bis-amine oxides having the following substituents.
~ 3~7~7
8 -
R : tallow C16-C18 alkyl: palmityl; oleyl: stearyl
R6: hydroxyethyl
i : 2 or 3
A ~pecific example of this preferred clas~ of bis-amine oxide~
N-hydrogenated C16-C18 tallow
alkyl-N,N',N'tri-~2-hydroxyethyl) -propylene-1,3-diamine oxide.
Suitable quaternary ammonium surfactants for use in the
present composition can be defined by the general formula VI:
R8 R8
R7 h+ - - (CH2)i R8 l _ R8 z VI
wherein R i6 a linear or branched alkyl, alkenyl or alkaryl
group having 8 to 16 carbon atoms and each R i6 Illdependently
selected from Cl_4 alkyl, Cl_4 alkaryl and -(CnH2nO)m
wherein i is an integer from 1 to S,-j i8 0 or 1, n is 2 or ~ and
m i8 from 1 to 7, the sum total of CnH2nO groups in a molecule
being no more than 7, and wherein Z represents counteranion in
number to give electrical neutrality.
In a preferred embodiment, R7 has from 10 to 14 carbon
atoms and each R~ is independently selected from methyl and
(CnH2nO)mH wherein m is from 1 to 3 and the sum total of
2~ CnH2nO groups in a molecule is no more than 5, preferably no
more than 3. In a highly preferred embodiment j is O, R~ i6
selected from methyl, hydroxyethyl and hydroxypropyl and R7 i 9
C12-C14 alkyl. Particularly preferred surfactants of this
class include C12 alkyl trimethylammonium salts, C14
alkyltrimethylammonium salts, coconutalkyltrimethylammonium salts,
coconutalkyldimethyl-hydroxyethylammonium salts,
coconutalkyldimethylhydroxy-propylammonium salts, and C12
alkyldihydroxyethylmethyl ammonium salts.
- 19 ~.~3~'7~97
Another group of useful cationic compounds are the diammonium
salt~ of formula VI in which j is 1, R is C12-C14 alkyl,
each ~8 i~ methyl, hydroxyethyl or hydroxypropyl and i i~ 2 or
3. In a particularly preferred surfactant of this type, R i8
coconut alkyl, R8 i~ methyl and i is 3.
The detergent compositions of the invention al60 include a
bleach system comprising an inorganic or organic peroxy bleaching
agent, a heavy metal scavenging agent and in preferred
compositions, an organic peroxy acid bleach precursor.
Suitable inorganic peroxygen bleaches i~clude sodium
perborate mono- and tetrahydrate, sodium percarbonate, sodium
persilicate and urea-hydrogen peroxide addition products and the
clathrate 4Na2S04:2H202:1NaCl. Suitable orqanic bleaches
include peroxylauric acid, peroxyoctanoic acid, peroxynonanoic
acid, peroxydecanoic acid, diperoxydodecanedioic acid,
diperoxyazelaic acid, mono- and diperoxyphthalic acid and mono-
and diperoxyisophthalic acid. The bleaching agent is present-in
the compositions of the invention at a level of from about 5~ to
about 35% preferably from about 10% to about 25% by weight.
The heavy metal scavenging agent is preferably a
water-soluble chelating agent. Preferred are aminopolyacids
having four or more acidic protons per molecule. Suitable
chelating agents include aminocarboxylate chelating agents such as
ethylenediaminetetraacetic acid (EDTA),
hydroxyethylethylenediaminetriacetic acid ~HEEDTA),
dihydroxyethylethylenediaminediacetic acid ~DHEEDDA),
diethylenetriaminepentaacetic acid ~DETPA),
1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid (~CTA) and
water-soluble salts thereof, and aminopolyphosphonate chelating
agents such as ethylenediaminetetra~methylenepho~phonic acid)
~EDTMP), diethylenetriaminepenta~ethylenephOsphoniC acid)
~DETPMP), nitrilotri~methylenephosphonic acid) ~NTMP),
hexamethylenediaminetetramethylenephosphonic acid (HMTPM) and
water-soluble salts thereof. The above water-soluble sequestrants
are generally at a level of from about 0.05% to about 4%
preferably from about 0.1% to about 1.0% by weight. In any event
the total content of phosphorus in the present compositions is
preferably no more than about 1%, more preferably no more than
about 0.1% by weight of total composition.
- 20 ~ 97
The heavy metal scavenging agent herein can also be
represented by water-soluble smeCtite-type clay~ selected from
saponites, hectorites and sodium and calcium montmorillorites
(sodium and calcium here designating the principal inorganic
cation of the clay).
While any of the above smectite-type clays can be
incorporated in the compositions of the invention, particularly
preferred smectite-tyPe clays have ion-e~change capacities of at
least 50 meq/lOOg clay, more preferably at least 70 meq/lOOg
(meacured, for instance, as described in "The Chemistry and
Physics of Clays", p.p. 264-265, Interscience (1979)). Especially
preferred materials are as follows:-
Sodium Montmorillonite
Brock
Volclay BC
Gelwhite GP
Thixo-Jel
Ben-A-Gel
Imvite
Sodium Hectorite
Veegum F
Laponite SP
Sodium Saponite
Barasym NAS 100
Calcium Montmorillonite
Soft Clark
Gelwhite L
Lithium Hectorite
Barasym LIH 200
~3~
- 21 -
When pre~ent, the above clay~ are generally added at a level
of from about 1% to about 20~, more preferably from about 2% ~o
about 10% by weight of composition. Such clays also provide a
fabric softening benefit to the compo~ition~.
Another suitable heavy metal scavenging agent is
water-insoluble, preferably colloidal magne~ium silicate or a
water-soluble magnesium salt forming magnesium silicate in the
aqueous slurry crutcher mix prior to spray-drying. The magnesium
silicate or salt is generally added at a level in the range from
1~ about 0.015% to about 0.2%, preferably from about 0.03% to about
0.15%, more preferably from about 0.05% to about 0.12% by weight
(maqnesium basis). Suitable magne~ium salts include magnesium
sulfate, magnesium sulfate hepatydrate, magnesium chloride and
magnesium chloride hexahydrate.
The compositions of the invention preferably also contain_an
organic peroxy acid bleach precursor at a level of from about 0.5%
to about 10%, preferably from about 1~ to about 6% by weight.
Suitable bleach precursors are disclosed in UK-A-2040983, and
include for example, the peracetic acid bleach precursors such as
tetraacetylethylenediamine, tetraacetylmethylenediamine,
tetraacetylhexylenediamine, sodium p-acetoxybenzene sulphonate,
tetraacetylglycouril, pentaacetylglucose, octaacetyllactose, and
methyl o-acetoxy benzoate. Highly preferred bleach precursors,
however, have the general formula IV
R4-l-L IV
wherein R4 is an alkyl group containing from 6 to 12 carbon
atoms wherein the longest linear alkyl chain extending from and
including the carboxyl carbon contains from 5 to 10 carbon atoms
and L is a leaving group, the conjugate acid of which has a pK
3~ in the range from 6 to 13.
The alkyl group, R4, can be either linear or branched and,
in preferred embodiments, it contains from 7 to 9 carbon atoms.
Preferred leaving groups L have a PKa in the range from about 7
to about 11, more preferably from about 8 to about 10. Examples
of leaving groups are those having the formula
~;~3~
-- 22 --
a ) ~ 2 ) xY
0~
and b)
-N-C-R4
~2
wherein Z is ~, R or halogen, R is an alkyl group having
from 1 to 4 carbon atoms, x is O or an integer of from 1 to 4 and
Y is selected from SO3M, OSO3M, C02M, N (R )3Q and
N (R )2- wherein M i8 H, alkali metal, al~aline earth
metal, ammonium or substituted ammonium, and Q is halide or
methosulfate.
The preferred leaving group L has the formula (a) in which Z
1~ is H, x is O and Y is sulfonate, carboxylate or dimethylamine
oxide radicai. Highly preferred materials are sodium
3,5,5,-trimethylhexanoyloxybenzene sulfonate, sodium
3,5,5-trimethylhexanoyloxybenzoate, sodium 2-ethylhexanoyl
oxybenzenesulfonate, sodium nonanoyl oxybenzene sulfonate and
sodium octanoyl oxybenzene9ulfonate, the acyloxy group in each
instance pref~rably being p-substituted.
The bleach activator herein will normally be added in the
form of particles comprising ~inely-divided bleach activator and a
binder The binder is generally selected from nonionic
2~ surfactants such as the ethoxylated tallow alcohols, polyethylene
glycols, anionic surfactants, film forming polymers, fatty acids
and mixtures thereof. Highly preferred are nonionic surfactant
binders, the bleach activator being admixed with the binder and
extruded in the form of elongated particles through a radial
extruder as described in European Patent Application No. 62523,
published October 13, 1982.
i~,
,.~ , .
~ '~3 C9'797
The compositiona of the invention can be supplemented by all
manner of detergent and laundering components, inclusive of suds
suppres~ors, enzymes, fluorescers, photoactivators, bleach
catalysts, soil suspending agents, anti-caking agents, pigment~,
perfumes, fabric conditioning agents etc.
Suds suppressors are represented by materials of the
silicone, wax, vegetable and hydrocarbon oil and phosphate ester
varieties. Suitable silicone suds controlling agents~lnclude
polydimethylsiloxanes having a molecular weight in the ranga from
1~ about 200 to about 200,000 and a kinematic viscosity in the range
from about 20 to about 2,000,000 mm /8, preferably from about
3000 to about 30,000 ~m2/s, and mixtures of siloxanes and
hydrophobic silanated (preferably trimethylsilanated) silica
having a particle size in the range from about 10 millimicron~ to
about 20 millimicrons and a specific surface area above about 50
m2/g. Suitable waxes include microcrystalline waxes having a
melting point in the range from about 65 C to about 100C, a
molecular weight in the range from about 400-1000, and a
penetration value of at lea~t 6, measured at 77 F by ASTM-D1321,
2~ and also paraffin waxes, synthetic waxes and natural waxes.
Suitable phosphate esters include mono- and/or di-C16-C22
alXyl or alkenyl phosphate esters, and the corresponding mono-
and/or di alkyl or alkenyl ether phosphates containing up to 6
ethoxy groups per molecule.
Enzymes suitable 40r use herein include those discussed in
US-A-3,519,570 and US-A-3,533,139 to McCarty and McCarty et al
issued July 7, 1970 and Januar~ 5, 1971, respectlvely. Suitable
fluorescers include Blan~opho~ aBH ~Bayer AG) and Tinopal~CBS and
EM ~ ~Ciba Gelgy). Photoactlvators are discu8~ed in EP-A-57088,
3~ published August 4, 1982, highly preferred materials being z.lnc phthalocya-
nine tri- and tetra-sulfonates. Suitable fabric conditioning agents
i.nclude di-C12-C24 alkyl or aLkenyl amines and ammonium and quaternary
an ~ nium salts. Suitable bleach catalysts are discussed in European
Patent Application No. 72166, published February 16, 19~3 and Europear- ;
Patent Appli.cation No. 124,341, published November 7, 1984.
3~
- 24 -
Antiredeposition and 80il suspen~ion agents suitable herein
include cellulose derivatives such as methylcellulose,
carboxymethylcellulose and hydroxyethylcellulose.
Liquid detergent compositions of the invention can
additionally be supplemented by pH regulators such as potassium
hydroxide, potassium carbonate, potassium bicarbonate, sodium
hydroxide, sodium carbonate, sodium bicarbonate, and mono-, di-
and triethanolamine; solventS such as ethyl alcohol, i~sopropanol,
propylene glycol, propane-l, 2-diol, hexyleneglycol; ànd
1~ hydrotopes such as urea.
Granular detergent compositions of the invention are
preferably prepared by spray-drying an aqueous slurry comprising
the anionic surfactant and detergency builder. The aqueous slurry
is mixed at a temperature in the range from about 70-90C and
the water-content of the slurry adjusted to a range of about 25%
Spray drying is undertaken with a drying gas inlet temperature of
from about 250-350C, preferably about 275-330C, providing a
final moisture content in the range of from about 8~ to 14~ by
weight.
2~ In the Examples which follow, the abbreviations used have the
following designations:-
C12LAS Sodium linear C12 benzene sulphonate
TAS : Sodium tallow alcohol sulphate
C12/14As : C12/l4 alcohol sulphate, sodium salt
TAEn : Hardened tallow ~lcohol ethoxylated with
n moles o~ ethylene oxide per mole of
alcohol
3~ Cl2TMAB : C12 alkyl trimethyl ammonium bromide
Dobanol 45E7 : A C14_15 primary alcohol condensed
with 7 moles o~ ethylene oxide.
TAED : Tetraacetyl ethylene diamine
PAG : Penta acetyl glucose
AO~S : Sodium p-acetoxy benzene sulphonate
- 25 - ~ ~307~7
NOBS : Sodium nonanoyl oxybenzenesulphonate
INOBS : Sodium 3,5,5 trimethyl hexanoyl
oxybenzene sulphonate
INOBA : Sodium 3,5,5 trimethyl hexanoyl
oxybenzoic acid
EHOBS : Sodium 2-ethyl hexanoyl oxybenzene
sulphonate
Silicate : Sodium silicate having an
SiO2:Na20 ratio of 1.6
Sulphate : Anhydrous sodium sulphate
Carbonate : Anhydrous sodium carbonate
CMC : Sodium carboxymethyl cellulose
Silicone : Comprising 0.14 part6 by weight of an
85:15 by weight mixture of silanated
silica and silicone, granulated with
1.3 parts of sodium tripolyphosphate,
and 0.56 parts of tallow alcohol
condensed with 25 molar proportions
of ethylene oxide
2~ NTA : Sodium nitrllotriacetate
PCl : Copolymer of 3:7 maleic/acrylic acid,
average molecular weight about 70,000, as
sodium salt
PC2 : Copolymer of 1:20 maleic/acrylic acid,
average molecular weight about 12,000, as
sodium salt
PC3 : Polyacrylic acid, molecular weight
about 70,000, as sodium salt
PC4 : Copolymer o~ 3s7 maleic/acrylic acid,
3~ ave~ag~ molecular weight about 15,500 as
sodium salt
PC5 : Polyacrylic acid, average molecular
weight about 4,500, as sodium salt
Perborate : Sodium perborate tetrahydrate of
nominal formula NaB02.3H20.H202
Enzyme : Protease
EDTA : Sodium ethylene diamine tetra acetate
~30'7~'7
-- ~6 --
.
Brightener : Disodium 4,4'-bis(2-morpholino-4-
anilino-s-triazin-6-ylamino)
stilbene-2:2'-disulphonate.
DETPMP : Diethylene triamine penta(methylene
phosphonic acid), marketed by Monsanto
under the Trade name Dequest 2060
~DTMP : Ethylenediamine tetra ~methylene
phosphonic acid), marketed by Monsanto,
under the Trade name Dequest 2041
Clay : Sodium montmorillonite
Examples I to VIII
Granular detergent compositions are prepared as follows. A
base powder composition is first prepared by mixing all components
except DobanoI 45E7, bleach, bleach activator, enzyme and suds
suppressor in a crutcher a~ an aqueous ~lurry at a temperature of
about 80C and containing about 35~ water. The slurry i8 then
spray dried at a gas inlet temperature of about 300~C to form baæe
powder granules. The bleach activator, where present, i~ then
admixed with TAE80 as binder and extruded in the form of
elongate particles through a radial extruder as described in
European Patent Application Number 62523. The bleach activator
noodle-~, bleach, enzyme and suds suppressor are then dry-mixed
with the base powder composition and finally Dobanol 45E7 is
sprayed into the final mixture.
EXAMPLES
I II III IV V VI VII VIII
C12LAS 5 4 8 8 9 4 3 5
TAS - - 3 ~ 3
C12/14As 5 3 8 - 4 1 4
TAE80 0 5 0.6 0.8 0.3 0.5 0.8 0.2
TAEll - 0.6 - - 1 - _ 1
Dobanol 45E7 2 6 4 2 - 8 10 5
Cl2TMAB 2 - - - 3 2 2
NOBS 3
INOBS - 4 - - - _ _ _
- 27 -
EXAMPLES (Contd)
I~OBA - - . 5 _ _ _ _ _
EHOBS - - - 2
TAED - - - - 3
PAG - - _ _ _ 4 _ _
AOBS
Perborate 25 18 10 24 20 18 24 28
EDTMP - 0.4 0.3 - - - 1.0
DETPMP 0.4 - - - 0.5 - - 0.1
EDTA 0.2 0.2 0.2 0.1 0.3 0.1 0.2 0.3
Clay - 6 - 4
Magnesium (ppm) - - 750 - - - - ~00
PCl 1.5 4 2 - 1 7 1 2
PC2 5 9 - 10 4 - 15 8
PC3 - - 12 5
Zeolite A* 9 16 12 6 13 24 9 14
Soap 1 3 - 2 - 3 3 2
Carbonate 8 12 10 8 7 13 6 11
Silicate 6 4 7 3 7 5 8 3
Silicone 0.2 0.2 0.3 0.2 0.2 0.4 0.5 0.2
Enzyme 0.1 0.5 0.4 0.3 0.4 0.5 0.7 1.0
Brightener 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Sulphate,
Moisture &
Miscellaneous -----------------To 100-------------------------
* Zeolite A of 4 A pore size.
The above compogitiong are zero phosphate detergent
compositions displaying excellent bleach stability, fabric care
and detergency performance across the range of wash temperatures
with particularly outstanding performance in the case of Example~
I to IV on greasy and particulate soils at low wash temperatures.
~3ai7~
- 28 -
Examples IX to XII
The following granular detergent compo~itions are prepared as
described in Examples I to VIII above.
IX X XI XII
C12LAS 5 8 4 8
TAS - 3 2
C12/14As 8
AE80 0.8 0.3 0.3
Dobanol 45E7 2 4 6 2
C12TMAB 2
NOBS - - - 3
INOBS 2 - - -
I~OBA - 5 - - _-
TAED 0.5 - 2.5
PAG
AOBS - - - 0.8
Perborate 25 10 17 24
EDT M - 0.3 0.3
DETPMP 0.4 - _ 0.4
EDTA - 0.2 0.2 0.2 0.1
Clay - - - 6
Magnesium (ppm) - 800 750
PC4 7 5 8 5
PC5 2 1 1 0.5
Zeolite A (4 A pore size) 11 16 13 5
Zeolite X ~10 A pore size) - ~ - 15
Soap 1 - - 2
Carbonate 8 10 12 12
Silicate 6 5 4 8
Silicone 0.2 0.5 0.3 0.2
Enzyme 0.1 0.3 0.4 0.3
Brightener 0.2 0.2 0.2 0.2
Sulphate,
Moisture &
Miscellaneous ----------To 100---~
~3~
The above compo8ltion8 are zero pho8phate detergent
compositions displaying excellent bleach stability, fabric care
and detergency performance across the range of wash
temperatures with outstanding whiteness maintenance performance
and low wash temperature detergency performance on greasy and
particulate 80ils.
ExampIes XIII to XV
The following granular detergent ~omposition~ are prepared as
described in Examples I to VIII above.
1Q XIII XIV XV
C12LAS 4 8 14
C12/14As 4 a
TAS
AE80 0.3 0.3 0 4
Dobanol 45E7 6 2
INOBS 3 3 4
TAED 0.5 - - 2
Perborate 18 10 6
EDTMP 0.3
DETPMP - 0.4
EDTA 0.2 0.2 0.2
Magnesium (ppm) 1000
PCl 2 0.5
PC4 5 4 8
PC5 1 0.5
Zeolite A (4 A pore size~ 16 25 15
Carbonate 18 8 10
Silicate 1 6 5
NTA 4 3 7
Silicone 0.2 0.5 0.3
Enzyme 0.1 0.3 0.4
Brightener 0.2 0.2 0.2
Sulphate,
Moi~ture &
Miscellaneous -----------To 100-----------
- 30 -
97
. . .
The above compositions are zero phosphate detergent
compositions displaying excellent bleach ~tability, fabric care
and detergency performance across the range of wash
temperatures with outstanding whiteness maintenance performance
and low wash temperature detergency performance on greasy and
particulate soils.
