Note: Descriptions are shown in the official language in which they were submitted.
~ CA 02083331 1998-04-07
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DETERGENT COMPOSITIONS
TECHNICAL FIELD
The present invention is concerned with particulate
detergent compositions that combine exceptionally good
cleaning performance with high bulk density and excellent
powder properties. The compositions contain a high
level of high-performance organic surfactant - selected
ethoxylated alcohol plus a minor amount of
alkyl sulphate - and zeolite detergency builder, and
are preferably prepared by an agglomeration process using
a high-speed mixer/granulator.
BACKGROUND
Recently the trend in detergent powders has been
towards increased bulk density, for example, above
600 g/l. These high-density or "concentrated" powders
have been prepared by various processes, some involving
post-densification of a spray-dried powder, and others
based on dry mixing, agglomeration or other wholly
non-tower processes.
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The move to higher densities, and thus inherently
less porous particles, has made the incorporation of high
levels of mobile organic ingredients without loss of
powder flow properties more difficult. However, it has
become highly desirable to improve detergency performance
by incorporating higher levels of surfactant, and by
using surfactants having the greatest possible
effectiveness against oily and fatty soils. One class
of such surfactants consists of ethoxylated alcohols
having a relatively low degree of ethoxylation, and those
are generally mobile liquids at ambient temperature.
In view of increasing environmental awareness, it
has also become desirable to use alkyl sulphates in
preference to the linear alkylbenzene sulphonates
traditionally used in laundry detergents. Alkyl
sulphates are readily biodegradable and can be obtained
from renewable sources such as coconut and palm oil.
However, they are generally more difficult to process
into high quality detergent powders than are alkylbenzene
sulphonates.
Nonionic surfactants, alkyl sulphates and mixtures
of the two have been found to provide highly efficient
detergency, but because of their mobility are difficult
to incorporate, even at moderate levels, into
free-flowing powders that will disperse in the wash
liquor. When higher proportions of these surfactants
are required in order to push detergency performance to
ever higher levels, these difficulties would be expected
to increase, and to be exacerbated even further in the
highly concentrated, dense powders currently favoured by
the consumer and the detergents industry.
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The present inventors, however, have succeeded in
formulating high bulk density free-flowing detergent
powders combining excellent performance with good powder
properties and dispersibility, despite their containing
relatively high levels of high-performance mobile
surfactants. The powders of the invention contain
relatively high levels of zeolite builder, and may be
prepared by a granulation process in a high-speed
mixer/granulator. Especially good powder properties may
be obtained by use of a novel zeolite P as the builder;
and especially good detergency may be obtained by use of
selected nonionic surfactants.
PRIOR ART
EP 265 203A (Unilever) discloses a surfactant blend
mobile at a temperature within the range of from 20 to
80~C, comprising from 20 to 80 wt% of alkylbenzene
sulphonate or alkyl sulphate, from 80 to 20 wt% of
ethoxylated nonionic surfactant and from 0-10 wt% water.
The surfactant blend may be sprayed on to an absorbent
particulate solid material, for example, spray-dried
polymer-modified Burkeite, to give free-flowing detergent
powder containing up to about 25 wt% of surfactant.
EP 436 240A (Unilever) discloses a similar mobile
surfactant blend additionally cont~;n;ng a fatty acid
soap. When sprayed onto an absorbent solid material,
this blend gives powders having improved flow and
dispensing properties.
GB 1 462 134 (Procter & Gamble/Collins) discloses
linear or predominantly linear ethoxylated primary
alcohols of closely defined chain length, chain length
distribution, ethylene oxide content, ethoxylation
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distribution and free alcohol content. These materials
give improved oily soil detergency as compared with
conventional commercially available materials.
EP 133 715A (Union Carbide) discloses an
alkoxylation product mixture having an especially highly
peaked distribution of alkoxylation species, in which a
single prevalent alkoxylation species constitutes 20 to
40 wt% and the amounts of species differing substantially
from the prevalent species are strictly limited.
EP 384 070A (Unilever) discloses the use as a
detergency builder of zeolite P having a silicon to
aluminium ratio not greater than 1.33 (zeolite MAP).
This zeolite has been found to be a more effective and
rapid binder of calcium ions than is conventional zeolite
4A.
EP 521 635A, discloses free-flowing particulate
detergent compositions based on zeolite MAP and
containing high levels of liquid, viscous-liquid, oily or
waxy components (for example, nonionic surfactants) while
displaying excellent flow properties.
Example K of that application discloses a high bulk
density powder consisting of 50 wt% zeolite 4A, 23.4 wt%
sodium carbonate, and 26.6 wt% of the nonionic surfactant
Synperonic A3 (synthetic C12 15 alcohol having an average
degree of ethoxylation of 3); and Example 7 discloses a
high bulk density powder consisting of 56.6 wt~ zeolite
MAP, 13.3 wt% sodium carbonate, and 30.1 wt% Synperonic
A3. These compositions are specifically disclaimed in
the present application.
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EP 544 365A (Unilever), claims a process for
preparing a granular detergent composition having a bulk
density of at least 650 g/l, which comprises treating a
particulate starting material in a high speed
mixer/densifier in the presence of a liquid surfactant
composition comprising an alkyl sulphate (20-80 wt%), an
ethoxylated nonionic surfactant (80-20 wt~) and water
(0-20 wt%).
DEFINITION OF THE INVENTION
The present invention provides a particulate
detergent composition having a bulk density of at least
650 g/l, preferably at least 700 g/l and advantageously
at least 800 g/l, comprising:
(a) from 15 to 50 wt% of a surfactant system consisting
essentially of:
~i) et~oxylated nonlonlc surfac~ant which i8 a
primary C8-C18 alcohol ha~ing an avera~e de~ree
of etho~ylation not exceedin~ 6.5 (from 60 to
95 wt~ of the ~urfactant ~yste~), and
~ii) primary C8-C18 alkyl ~lDhate ~from 5 to 40 wt%
of the surfactant 8y8tem)
(b) from 20 to 60 wt% of zeolite,
(c) optionally other detergent ingredients to 100 wt%.
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DETAILED DESCRIPTION OF THE INVENTION
The particulate detergent composition of the
invention is characterised by an especially high level of
a high-performance organic surfactant system. At least
15 wt% of the composition is constituted by the
surfactant, and as much as 50 wt% may be present.
Compositions may advantageously contain at least 20 wt%,
more advantageously at least 25 wt%, of the surfactant
system.
The surfactant system consists essentially of
ethoxylated alcohol having a relatively low degree of
ethoxylation, with a minor proportion (not
exceeding 40 wt% of the surfactant system) of primary
alkyl sulphate.
The proportion of primary alkyl sulphate preferably
does not exceed 35 wt% (of the surfactant system), and
more preferably does not exceed 30 wt% of the surfactant
system. Preferred proportions of alkyl sulphate in the
surfactant system are from 5 to 35 wt%,
and advantageously from 10 to 30 wt%.
Also preferred are surfactant systems in which the
proportion of alkyl sulphate does not exceed 15 wt%, for
example, from 0.1 to 15 wt%, preferably from 0.1 to
10 wt%.
The ethoxylated alcohol nonionic surfactant
The ethoxylated alcohol nonionic surfactant employed
in the detergent compositions of the present invention
has a relatively low degree of ethoxylation, not
exceeding 6.5.
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The ethoxylated alcohol preferably has an average
degree of ethoxylation within the range of from 3 to 6.5.
The preferred range for the average degree of
ethoxylation of the nonionic surfactant is within the
range of from 4 to 6.5, more preferably from 4 to 6 and
most preferably from 4 to 5.5.
A mixture of differently ethoxylated materials may
be used, provided that the overall degree of ethoxylation
meets the stated requirements.
The HLB value of the nonionic surfactant preferably
does not exceed 11.0, and more preferably does not exceed
10.5. Desirably the HLB value is within the range of
from 9.5 to 10.5.
The chain length of the ethoxylated alcohol may
generally range from C8 to C18, preferably from C12 to
C16; an average chain length of Cl2_l5 is preferred-
Especially preferred is ethoxylated alcohol consisting
wholly or predominantly of C12-C14 material.
The ethoxylated alcohol is preferably primary, but
secondary alcohol ethoxylates could in principle be used.
The alcohol is preferably wholly or predominantly
straight-chain. Suitable alcohols are
vegetable-derived, for example, coconut, which is the
most preferred material. Among the synthetic alcohols,
Ziegler alcohols are preferred to oxo-based alcohols.
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According to a preferred embodiment of the
invention, giving exceptionally good oily soil
detergency, the ethoxylated alcohol (which of course is
always a mixture of species having different numbers of
ethylene oxide units) is a "narrow range" material having
a distribution of ethoxylated species that is more highly
peaked about a single prevalent value than is the case in
conventional commercial nonionic surfactants. The
content of unethoxylated material is also generally
lo lower, and may be reduced further by so-called
"stripping".
"Narrow range" alkoxylates are described and
claimed, for example, in EP 133 715A (Union Carbide)
mentioned previously.
These are especially highly peaked mixtures having
an average alkoxylation number of at least 4, in which at
least one alkoxylation species (the "prevalent species")
constitutes about 20 to 40 wt% of the mixture; the
proportion of species having 3 or more alkoxylation units
above the mean is less than 12 wt%; and the species
having 1 more and 1 less alkoxylation unit that the mean
are each present in a weight ratio to the prevalent
species of 0.6:1 to 1:1. Preferred product mixtures
contain from 80 to 95 wt% of alkoxylation species having
alkoxylation numbers within plus or minus 2 of the mean.
However, the term "narrow range" as used in the
present specification also covers materials that are not
so highly peaked as to meet the requirements of the Union
Carbide patent claims, but yet are substantially more
peaked than, for example, the commercially available ICI
"Synperonic" (Trade Mark) ethoxylated alcohols.
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The term therefore is defined herein as covering any
ethoxylated alcohol product in which a single
ethoxylation species constitutes 13 wt% or more,
preerably 15 wt% or more, of the product. Conventional
ethoxylates contain no more than about 10 wt% of any one
ethoxylation species. The prevalent species preferably
contains 4 or 5 ethoxylation units.
Preferred "narrow range" ethoxylated alcohol used in
the compositions of the invention may have any one or
more of the following characteristics:
at least 20 wt% of the ethoxylated alcohol may be
constituted by a single ethoxylation species;
at least one ethoxylation species (hereinafter the
prevalent species) may constitute from 20 to 40 wt%
of the ethoxylated alcohol, the proportion of
species having 3 or more ethoxylation units above
the mean being less than 12 wt%, and the species
having 1 more and 1 less ethoxylation unit than the
mean each being present in a weight ratio to the
prevalent species of 0.6:1 to 1:1;
from 80 to 95 wt% of the ethoxylated alcohol may be
constituted by ethoxylation species having
ethoxylation numbers within plus or minus 2 of the
mean.
Differently defined "narrow range" ethoxylates are
also described in GB 1 462 132 (Procter & Gamble/
Collins): these are materials having an average degree
of ethoxylation between 3.5 and 6.5, the amount of
material having a degree of ethoxylation within the 2-7EO
range being at least 63 wt%, and the amount of free
alcohol not exceeding 5 wt%. These materials are also
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suitable for use in the compositions of the present
nvention .
The following table shows the ethoxylation
distribution of some commercially available coconut-based
ethoxylates, both narrow-range (NRE7, NRE5 etc), and
broad-range (E7, E3), the figures indicating the nominal
average degree of ethoxylation in each case.
It is within the scope of the invention to achieve
the preferred value of 4 to 6.5 for the average degree of
ethoxylation by using a mixture of commercial materials,
eg a (nominal) 3EO ethoxylate and a (nominal) 7EO
ethoxylate, in appropriate proportions.
However, it is especially preferred to use a single
commercial material, and the materials designated NRE5,
NRE4.6 and NRE4.2 are especially preferred, NRE4.2 being
particularly favoured.
It is especially preferred, in accordance with the
invention, to use wholly or predominantly straight-chain
ethoxylated alcohol that is also "narrow range".
It may also be desirable to use a "narrow range"
ethoxylate having a narrower distribution of chain length
than do conventional commercial nonionic surfactants.
For example, the nonionic surfactants described in the
aforementioned GB 1 462 134 (Procter & Gamble/Collins)
are such that at least 65 wt% of the material has a chain
length within + 1 carbon atom of the mean value.
"Narrow range" ethoxylates are now commercially
available in Europe and North America, for example, from
Vista, Union Carbide and Hoechst.
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CA 02083331 1998-04-07
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The primary alkyl sulphate
The primary alcohol sulphate (PAS) may have a chain
length in the range of C8-C18, preferably C12-C16, with a
mean value preferably in the C1215 range. Especially
preferred is PAS consisting wholly or predominantly of
C12-C14 material.
If desired, mixtures of different chain lengths may
be used as described and claimed in EP 342 917A
(Unilever).
As for the ethoxylated alcohol, predominantly or
wholly straight-chain material, is preferred. PAS of
vegetable origin, and more especially PAS from coconut
oil (cocoPAS) is especially preferred. However, it is
also within the scope of the invention to use branched
PAS as described and claimed in EP 439 316A (Unilever).
The PAS is present in the form of the sodium or
potassium salt, the sodium salt generally being
preferred.
The zeolite deterqency builder
The amount of zeolite builder in the compositions of
the invention may range from 20 to 60 wt%, usually from
25 to 55 wt% and suitably, in a heavy duty detergent
composition, from 25 to 48 wt%.
Depending on the amount and composition of the
surfactant system, the zeolite may be the commercially
available zeolite 4A now widely used in laundry detergent
20~3:331
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powders. For example, the use of zeolite 4A can give
powders having satisfactory flow properties when 17 wt%
of surfactant consisting of 30 wt% PAS and 70 wt%
nonionic surfactant is present.
However, as the total surfactant loading and/or the
proportion of nonionic surfactant is or are ncreased,
the more difficult it is to obtain acceptable powder flow
properties. According to a preferred embodiment of the
invention, the zeolite builder incorporated in the
compositions of the invention is zeolite MAP as described
and claimed in EP 384 070A (Unilever Case T3047).
Zeolite MAP is defined as an alkali metal aluminosilicate
of the zeolite P type having a silicon to aluminium ratio
not exceeding 1.33, preferably within the range of from
0.90 to 1.33, and more preferably within the range of
from 0.90 to 1.20.
Especially preferred is zeolite MAP having a silicon
to aluminium ratio not excee~;ng 1.07. The calcium
binding capacity of zeolite MAP is generally at least
150 mg CaO per g of anhydrous material.
In the present invention, the use of zeolite MAP has
another advantage quite independent of its greater
building efficacy: it enables more higher total
surfactant levels, and more nonionic-rich surfactant
systems, to be used without loss of powder flow
properties.
Preferred zeolite MAP for use in the present
invention is especially finely divided and has a d50 (as
defined below) within the range of from 0.1 to 5.0
microns, more preferably from 0.4 to 2.0 microns and most
preferably from 0.4 to 1.0 microns. The quantity "d50"
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indicates that 50 wt% of the particles have a diameter
smaller than that figure, and there are corresponding
quantities "d80", ''dgo'l etc. Especially preferred
materials have a d90 below 3 microns as well as a d50
below 1 micron.
Sodium carbonate
lo The compositions in accordance with the invention
may contain sodium carbonate, to increase detergency and
to ease processing. Sodium carbonate may generally be
present in amounts ranging from 1 to 60 wt%, preferably
from 2 to 40 wt%, and most suitably from 2 to 13 wt%.
The optional powder structurant
Powder flow may be improved by the incorporation of
a small amount of a powder structurant, for example, a
fatty acid (or fatty acid soap), a sugar, an acrylate or
acrylate/maleate polymer, or sodium silicate.
The preferred powder structurant is fatty acid soap,
suitably present in an amount of from 1 to 5 wt%. As
will be discussed below in the context of processing,
this is preferably incorporated as the free acid and
neutralised in situ.
Powder flow properties
The compositions of the invention are characterised
by excellent flow properties, despite the high content of
mobile high-performance organic surfactant.
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For the purposes of the present invention, powder
flow is defined in terms of the dynamic flow rate, in
ml/s, measured by means of the following procedure. The
apparatus used consists of a cylindrical glass tube
having an internal diameter of 35 mm and a length of 600
mm. The tube is securely clamped in a position such that
its longit~l~; n~ 1 axis is vertical. Its lower end is
terminated by means of a smooth cone of polyvinyl
chloride having an internal angle of 15~ and a lower
outlet orifice of diameter 225 mm. A first beam sensor
is positioned 150 mm above the outlet, and a second beam
sensor is positioned 250 mm above the first sensor.
To determine the dynamic flow rate of a powder
sample, the outlet orifice is temporarily closed, for
example, by covering with a piece of card, and powder is
poured through a funnel into the top of the cylinder
until the powder level is about 10 cm higher than the
upper sensor; a spacer between the funnel and the tube
ensures that filling is uniform. The outlet is then
opened and the time t (seconds) taken for the powder
level to fall from the upper sensor to the lower sensor
is measured electronically. The measurement is normally
repeated two or three times and an average value taken.
If V is the volume (ml) of the tube between the upper and
lower sensors, the dynamic flow rate DFR (ml/s) is given
by the following equation:
DFR = V ml/s
t
The averaging and calculation are carried out
electronically and a direct read-out of the DFR value
obtained.
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Compositions and components of the present invention
generally have dynamic flow rates of at least 90 ml/s,
preferably at least 100 ml/s.
Other optional ingredients
Fully formulated laundry detergent compositions in
accordance with the present invention may additionally
contain any suitable ingredients normally encountered,
for example, inorganic salts such as sodium silicate or
sodium sulphate; organic salts such as sodium citrate;
antiredeposition aids such as cellulose derivatives and
acrylate or acrylate/maleate polymers; fluorescers;
bleaches, bleach precursors and bleach stabilisers;
proteolytic and lipolytic enzymes; dyes; coloured
speckles; perfumes; foam controllers; fabric softening
compounds.
Preparation of the detergent compositions
The compositions of the invention may advantageously
be prepared by granulating the zeolite and surfactants in
a high-speed mixer/granulator. PAS may be incorporated
either in salt form (generally as an aqueous paste), or
as the free acid (for neutralisation in situ).
An especially preferred process includes the steps
of:
(i) preparing the surfactant system in the form of a
homogeneous mobile liquid blend, and
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(ii) agglomerating the mobile liquid surfactant blend
with the zeolite and other solids present in a high-speed
mixer/granulator.
The homogenous mobile liquid blend may be prepared
by mixing PAS paste with the nonionic surfactant.
Alternatively, the nonionic may be admixed during the
neutralisation of PAS acid by alkali, for example in a
loop reactor, as described and claimed in EP 507 402A
(Unilever) filed on 31 March 1992 and published on 7
October 1992.
-
The high-speed mixer/granulator, also known as a
high-speed mixer/densifier, may be a batch machine such
as the Fukae (Trade Mark) FS, or a continuous machine
such as the L~dige (Trade Mark) Recycler CB30.
The process is described in more detail, and
claimed, in our Canadian Patent Application No. 2,083,332
filed on 19 November 1992, from which the present
application claims priority.
The process allows the incorporation of high levels
of surfactant without loss of powder flow properties,
especially when the zeolite component of the composition
is zeolite MAP and/or when soap is present as a
structurant.
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If soap is to be included as a structurant, this is
preferably incorporated in the mobile surfactant blend,
either as such, or as the corresponding fatty acid
(together with a suitable amount of alkali) for
neutralisation in situ.
The other optional ingredients mentioned above may
be incorporated at any suitable stage in the process. In
accordance with normal detergent powder manufacturing
practice, bleach ingredients (bleaches, bleach precursors
and bleach stabilisers), proteolytic and lipolytic
enzymes, coloured speckles, perfumes and foam control
granules are most suitably admixed (postdosed) to the
dense granular product after it has left the high-speed
mixer/granulator.
Of course the compositions of the invention may also
be prepared by other processes, involving spray-drying or
non-tower technology or combinations of the two.
The invention is further illustrated by the
following non-limiting Examples, in which parts and
percentages are by weight unless otherwise stated.
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EXAMPLES
The abbreviations used in the Examples indicate the
following materials:
CocoPAS Linear C12_14 primary alcohol
sulphate (sodium salt) derived from
coconut oil, ex Philippine Refining
Co .
E7(s) C13 15 oxo alcohol 7EO, not "narrow
range": Synperonic (Trade Mark) A7 ex
ICI
E3(s) C13 15 oxo alcohol 3EO, not "narrow
range": Synperonic (Trade Mark) A3 ex
ICI
E7 Coconut alcohol 7E0, not "narrow
range"
E3 Coconut alcohol 3EO, not "narrow
range"
NRE7(s) C12 14 Ziegler linear "narrow range"
alcohol 7EO: Alfonic (Trade Mark) 7
ex Vista
NRE3(s) C12 14 Ziegler linear "narrow range"
alcohol 3EO: Alfonic (Trade Mark) 3
ex Vista
NRE7 Coconut alcohol 7E0, "narrow range"
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NRE5 Coconut alcohol 5E0, "narrow range"
NRE4.6 Coconut alcohol 4.6EO, "narrow range"
NRE4.2 Coconut alcohol 4.2EO, "narrow range"
NRE3 Coconut alcohol 3EO, "narrow range"
Zeolite 4A Wessalith (Trade Mark) P powder ex
Degussa
Zeolite MAP Zeolite MAP prepared by a method
similar to that described in Examples
1 to 3 of EP 384 070A (Unilever);
Si:Al ratio 1.07.
Polymer Acrylic/maleic copolymer:
Sokalan (Trade Mark) CP5 ex BASF
LAS Linear alkylbenzene sulphonate,
sodium salt
Perborate mono Sodium perborate monohydrate
TAED Tetraacetylethylenediamine, as 83 wt%
granules
EDTMP Ethylenediaminetetramethylene-
phosphonic acid, calcium salt:
Dequest (Trade Mark) 2041 or 2047 ex
Monsanto (34 wt% active)
Antifoam Antifoam granules in accordance with
EP 266 863B (Unilever)
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EXAMPLES 1 TO 9 - DETERGENCY
Examples 1 to 4
Detergent compositions were prepared to the
following general formulation:
parts %
Surfactant system (see below) 17 20.11
Zeolite 4A 32 37.86
Polymer 4 4.73
Carbonate 14.5 17.16
Silicate 0.5 0.59
lS Metaborate 16.5 19.53
84.50 100.00
The surfactant systems were made up as follows (wt%):
Example CocoPAS E7(s) E3(s) NRE7(s) NRE3(s)
1 30 30 40
2 30 - - 30 40
3 10 40 50
4 10 - - 40 50
Both mixtures of 30 parts of 7EO nonionic surfactant
and 40 parts of 3EO nonionic surfactant had an average E0
number of 4.7 and an HLB value of 10.1.
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The percentage of the predominant ethoxylation
species (4EO) in the NRE mix was estimated to be 14 wt%.
Detergencies (removal of radio-labelled triolein
soil from polyester) were compared in the tergotometer
using a 5 g/l product concDntration, 24~ (French) hard
water and a wash temperature o~ 23~C. The results were
as follows: ~
Example ~ triolein removal
1 42.2
2 47.4
3 59.8
4 61.6
Comparison of the results for Comparative Example A,
Example 1 and Example 3 shows how increasing the
proportion of nonionic surfactant at the expense of PAS
increases detergency: while comparison of the results
for Examples 1 and 2, and for Examples 3 and 4, shows the
detergency benefit obtained by changing to "narrow range"
ethoxylated alcohol. The outst~n~;ngly good result for
Example 4 shows the benefit of combining these two
measures.
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Examples 5 to 7
A further detergency comparison was carried out,
using test cloths carrying a number of different soils.
This experiment was carried out using a Miele (Trade
Mark) computer-controlled wA~h;ng machine, using a
product concentration of 5 g/l, and a 30-minute wash at
20~C in 26~ (French) hard water.
The compositions had the following general
formulation:
Parts %
Surfactant system (see below) 17.0 19.50
Zeolite 4A 30.5 35.00
Sodium carbonate 12.77 14.65
Sodium silicate 0.5 0.57
Sodium perborate monohydrate 16.25 18.65
TAED (83% granules) 7.25 8.32
EDTMP 0.37 0.42
Antifoam granules 2.50 2.87
87.14 100.00
The surfactant systems were made up as follows (wt%):
ExamPle CocoPAS E7(s) E3(s) NRE7(s) NRE3(s)
5 30 30 40
6 30 - - 30 40
7 10 - - 40 50
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The results (expressed as reflectance changes at 460
nm) were as follows:
Test cloth 1: kaolin and wool fat on polyester/cotton
(WFK lOC)
Reflectance change (delta R460)
Example 5 10.9
Example 6 11.8
Example 7 12.4
Test cloth 2: kaolin and wool fat on polyester (WFK 30C)
Reflectance change (delta R460)
Example 5 21.4
Example 6 24.5
Example 7 27.5
Test cloth 3: kaolin and sebum on cotton (WFK lOD)
Reflectance change (delta R460)
Example 5 16.5
Example 6 17.4
Example 7 18.8 .
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Test cloth 4: kaolin and sebum on polyester (WFK 3OD)
Reflectance change (delta R460)
Example 5 18.7
Example 6 21.5
Example 7 25.1
ExamPle 8
Using the same tergotometer procedure as in Examples
1 to 4, the detergencies of various surfactant mixtures
containing different ethoxylated coconut alcohols were
compared.
In each case the compositions were as given in
Example 1, and the surfactant systems consisted of 30 wt%
cocoPAS, and 70 wt% ethoxylated alcohol. The
ethoxylated alcohol component was made up
(i) by mixing E7 and E3 (broad range) in varying
proportions, or
(ii) by mixing NRE7 and NRE3 (narrow range) in varying
proportions, or
(iii) by use of a single narrow range ethoxylate.
The true degrees of ethoxylation will be recognised
from the Table given earlier in this specification.
- 20~333~
- 26 - C3431
Detergencies (% removal of radio-labelled triolein
from polyester) as a function of degree of ethoxylation
and starting ethoxylated alcohol are shown in the
following Table.
(i) (ii) (iii)
E0 E7 + E3 NRE7 + NRE3 Sinqle NRE
(average)
6.88 9.9 (E7)
5.96 14.1 (NRE7)
5.90 15.7
5.22 18.4
5.20 25.1 (NRE5)
5.17 21.0
4.94 21.2
4.86 30.7 (NRE4.6)
4.70 23.3
4.66 26.4
4.49 31.1
4.27 35.7 (NRE4.2)
3.96 27.3
3.75 35.5
3.01 36.4 (NRE3)
3.00 28.5 (E3)
These results illustrate the advantage of average
degrees of ethoxylation of 6 or below; the improvements
obtained by moving to narrow range ethoxylates; and the
especial benefits of using a single, narrow range
material, in particular NRE4.2.
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Example 9
The procedure of Example 8 was repeated using a
series of compositions having a more nonionic-rich
surfactant system: 10 wt% cocoPAS and 90 wt% ethoxylated
alcohol. The results are sho~l in the following Table.
(i) (ii) (iii)
EO E7 + E3 NRE7 + NRE3 Sinqle NRE
(average)
6.88 22.6 (E7)
5.96 34.3 (NRE7)
5.20 44.1 45.5 (NRE5)
5.17 35.3
4.94 35.5 51.5 (NRE4.6)
4.70 36.1
4.66 44.5
4.49 43.0
4.31 43.1
4.27 53.5 (NRE4.2)
3.75 44.1
3.01 35.4 (NRE3)
3.00 37.2 (E3)
Again the benefits of using narrow range
ethoxylates, especially single materials, are apparent.
CA 02083331 1998-04-07
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EXAMPLES 10 to 28 _ POWDER PRO~K~ S
Examples 10 and 11, Comparative Example A
Detergent base powders of high bulk density,
consisting of the surfactant system, zeolite and (in some
cases) sodium carbonate, were prepared by agglomeration
in a Fukae FS100 batch high-speed mixer/granulator.
These powders are not intended as fully formulated
detergent compositions, but are readily converted to such
compositions by admixture (postdosing) of other
components such as bleach ingredients, enzymes, lather
control granules and perfume.
The surfactant system was as follows:
30 wt% cocoPAS
30 wt% E7(s)
40 wt% E3(s)
The compositions, in parts by weight and
percentages, are shown below.
_ 10 11
Surfactant 17 (38.64) 17 (31.48) 17 (40.48)
Zeolite 4A 27 (61.36) 27 (50.00)
Zeolite MAP - - 25 (59.52)
Carbonate - 10 (18.52)
_- __ __
44 (100.00) 54 (100.00) 42 (100.00)
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A homogeneous liquid blend of the surfactants was
prepared by neutralising PAS acid with sodium hydroxide
solution in a loop reactor in the presence of the
nonionic surfactants. Zeolite and (where present)
sodium carbonate were dosed into the Fukae mixer, the
liquid surfactant blend added and the mixture granulated.
The granular product was then dried using a fluidised
bed.
In the case of Comparative Example A it proved
impossible to obtain a granular product; the mixture
formed a solid mass. The addition of 10 parts of sodium
carbonate (Example 10) enabled a granular product to be
prepared. With zeolite MAP (Example 11), at a slightly
lower level, the same amount (in parts - actually a
slightly higher percentage loading) of the surfactant
system could be incorporated without the need for sodium
carbonate, and a free-flowing granular product was
obtained.
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Comparative Examples B to E
Further attempts to prepare base powders containing
zeolite 4A with differing amounts of surfactant (the same
system as in Examples A, 10, and 11) and carbonate were
unsuccessful:
Compositions in Parts by weight
B C D E
Surfactant 13 15.3 17.2 18.5
Zeolite 4A 27 27 27 27
Carbonate - 5 10 15
__ __ __ __
47.3 54.2 60.5
Compositions in Percentages
B C D E
Surfactant 32.50 32.35 31.73 30.58
Zeolite 4A 67.50 57.08 49.82 44.63
Carbonate - 10.57 18.45 24.79
Composition B produced a solid mass, while
Compositions C, D and E initially produced free-flowing
powders which, however, lost their flow on drying.
CA 02083331 1998-04-07
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Examples 11 to 14
An experiment similar to that of Comparative
Examples B to E, but using zeolite MAP, gave powders
having good flow properties, even at substantially higher
surfactant contents. The compositions and powder
properties are shown below.
r 12 13 l4
Compositions in parts by weight
Surfactant 17 18.4 19.6 20.8
Zeolite MAP 25 25 25 25
Carbonate - 4.4 8.9 13.9
__ ____ ____ ____
42 47.8 53.5 59.7
Com~ositions in percentaqes
Surfactant 40.48 38.49 36.64 34.84
Zeolite MAP 59.52 52.30 46.73 41.88
Carbonate - 9.21 16.64 23.28
Powder properties
Bulk density (g/l) 794 817 829 867
DFR (ml/s) lOo 93 56 72
CA 02083331 1998-04-07
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Examples 15 and 16
Compositions similar to those of Comparative
Examples B to E were prepared, but this time fatty acid
soap was present.
The method of preparation of these powders was
slightly different from that used in previous Examples.
A homogeneous mobile blend was prepared by mixing PAS in
sodium salt form (70 wt%), fatty acid, sufficient sodium
hydroxide solution to neutralise the fatty acid, and the
nonionic surfactants. Ingredients were dosed into the
Fukae mixer in the order zeolite, carbonate, surfactant
blend, granulation/densification was carried out as in
previous Examples, and the products were finally dried
using a fluidised bed.
Powders having excellent flow properties were
obtained.
Compositions
16
parts % Parts %
Surfactant 17 25.95 17 29.18
Zeolite 4A 32 48.85 32 54.94
Carbonate 14.5 22.14 7.25 12.45
Soap 2 3.05 2 3.43
____ _____ _____ ______
65.5 loo.oo 58.25 loo.oo
CA 02083331 1998-04-07
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Powder Properties
16
Bulk density (g/l) 918 872
DFR (ml/s) 122 143
These Examples, when compared to Comparative
Examples C to F, show that the inclusion of fatty acid
soap made it possible to produce good high density
powders from formulations unprocessable in its absence.
Examples 17 and 18
Compositions similar to those of Examples 15 and 16
were prepared, by the same method, but using zeolite MAP
instead of zeolite 4A.
Compositions
17 18
parts % parts %
Surfactant 17 25.95 17 29.18
Zeolite MAP 32 48.85 32 54.94
Carbonate 14.522 .14 7.25 12.45
Soap 2 3.05 2 3.43
65.5lO0.00 58.25 lOO.O0
CA 02083331 1998-04-07
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Powder proPerties
17 18
Bulk density (g/l) 980 959
DFR (ml/s) 131 143
Comparison of these Examples with Examples 11 to 14
shows that the inclusion of soap improved flow, but when
zeolite MAP was used it was not essential in order to
obtain acceptable powders.
CA 02083331 1998-04-07
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Examples 19 and 20, Com~arative Examples F and G
Detergent base powders generally as described in
Examples 10, 11 and A were prepared using a different
surfactant system:
lO wt% cocoPAS
40 wt% E7(s)
50 wt~ E3(s)
The surfactant system was prepared as a homogeneous
mobile blend by the method described in Examples 10, 11
and A, and the other process steps were also carried out
as in those Examples.
Compositions in parts by weight
F 19 G 20
Surfactant 17 17 17 17
Zeolite 4A 27 27
Zeolite MAP - - 25 25
Carbonate - 25 - 15
44 69 42 57
CA 02083331 1998-04-07
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_ 36 _ C3431
Compositions in percentaqes
F 19 G 20
Surfactant 38.64 24.64 40.48 29.82
Zeolite 4A 61.36 39.13
Zeolite MAP - - 5~.52 43.86
Carbonate - 36.23 - 26.32
In the case of Comparative Examples F and G it
proved impossible to obtain a granular product; both
mixture formed a solid mass. The addition of 25 parts
of sodium carbonate to the zeolite 4A-based composition
(Example 19) was required to enable a granular product to
be prepared. With zeolite MAP (Example 20), only 15
parts of sodium carbonate were required.
CA 02083331 1998-04-07
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Examples 21 and 22 , ComparatiVe Example H
Compositions similar to those of Examples 17 and 18
were prepared, but containing higher levels of.zeolite.
Compositions in ~arts by weight
H 21 22
Surfactant 17 17 17
Zeolite 4A 32 32
Zeolite MAP - - 32
Carbonate - 10
_ _ _ _ _ _
49 59 49
Compositions in percentages
H 21 22
Surfactant 34.69 28.81 34.69
Zeolite 4A 65.31 54.24
Zeolite MAP - - 65.31
Carbonate - 16.95
Composition H would not give a granular product: 10
parts of sodium carbonate were required to produce a
processable formulation. With zeolite MAP at this
level, however, no carbonate was required despite the
high percentage level of surfactant in this composition
(Example 22).
CA 02083331 1998-04-07
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Example 23, Comparative Examples J and K
Formulations based on zeolite 4A, with and without
soap, were prepared using the surfactant system of
Examples 19 to 21. The fatty acid soap was incorporated
by mixing fatty acid and an eguivalent amount of sodium
hydroxide solution into the surfactant blend (prepared as
described in Example 10) before addition of the blend to
the Fukae mixer.
J K 23
Com~ositions in ~arts bY weiqht
Surfactant 17 17 17
Zeolite 4A 32 32 32
Carbonate 14.5 14.5 14.5
Soap - 2 4
63.5 65.5 67.5
Compositions in percentaqes
Surfactant 26 . 77 25 . 95 25.19
Zeolite 4A 50. 39 48.85 47.41
Carbonate 22.8 3 22.14 21.48
Soap _ 3 05 5 93
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Composition J gave a non-flowing product both before
and after drying, while Composition K initially gave a
good product but lost its flow on drying. A larger
amount of soap (Example 23) gave an excellent powder
having a bulk density of 920 g/l and a dynamic flow rate
of 109 ml/s.
Examples 24 and 25
Compositions similar to those of Examples 23 and J
but cont~;n;ng zeolite MAP and a higher level of
surfactant were prepared.
Compositions
24 25
parts % parts %
Surfactant 20.5 30.60 20.5 29.71
Zeolite MAP 32 47.76 32 46.37
Carbonate 14.5 21.64 14.5 21.01
Soap - - 2 2.90
67.0 69.0
208333
-40- C3431
Powder properties
24 25
Bulk density (g/l) 928 898
DFR (ml/s) 115 114
Example26
A composition similar to that of Example 23 but
containing a different nonionic surfactant, NRE5, was
prepared. All solid components had a particle size
lower than 200 microns.
The method of preparation was substantially as
described in Example 10. The mean residence time of the
granular detergent composition in the batch high-speed
mixer/granulator was approximately 3 minutes.
Composition %
Surfactant: PAS 8.3
NRE5 19.5
Zeolite 4A 43.7
Carbonate 16.2
Water 12.3
100 . O
The granular detergent composition obtained had a
bulk density of about 770 g/l and a dynamic flow rate of
101 ml/s.
CA 02083331 1998-04-07
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Examples 27 and 28
Granular detergent compositions similar to that of
Example 26 were prepared using a continuous high-speed
mixer/granulator, the L~dige (Trade Mark) Recycler CB30.
The liquid surfactant mix included fatty acid in
combination with a stoichiometric amount of sodium
hydroxide, which during the course of the mixing and
lo densifying process formed soap.
The rotational speed was 1600 rpm and the mean
residence time of the granular mixture in the Recycler
was approximately 10 seconds.
The compositions of the granular materials leaving
the Recycler were as follows.
~ 27 28
Surfactant: PAS 8.5 8.3
NRE5 19.4 18.8
Zeolite 4A 52.6 47.1
Carbonate - 8.0
Soap 2.9 2.9
Water 16.4 14.9
100.0 100.O
Bulk densities were about 700 g/l, particle sizes
500-600 microns, and powder properties were good.
CA 02083331 1998-04-07
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Examples 29 to 31, Comparative ExamPle L
Fully formulated detergent powders were prepared to
the formulations given below.
L 29 30 31
Base powders
LAS 7.85
Coco PAS - 5.20 5.20 1.70
E7(S) 3.92 5.20
E3(s) 5.23 6.60
NRE7(s) - - 5.20 6.80
NRE3(s) - - 6.60 8.50
Soap 2.00 2.00 2.00 2.00
Zeolite 4A 32.00 32.00 32.00
Zeolite MAP - - - 32.00
Carbonate 11.52 11.52 11.52
Fluorescers 0.81 0.81 0.81 0.81
SCMC 0.60 0.60 0.60 0.60
Moisture 9.00 9.00 9.00 9.00
Postdosed
Carbonate - - - 11.52
Silicate 0.45 0.45 0.45 0.45
Perborate mono15.00 15.00 15.0015.00
TAED 7.75 7.75 7.75 7.75
EDTMP 0.37 0.37 0.37 0.37
Enzymes 1.00 1.00 1.00 1.00
Antifoam 2.50 2.50 2.50 2.50
Perfume 0.60 0.60 0.60 0.60
______ ______ ____________
lOO.oO 100.00 100.00100.00
CA 02083331 1998-04-07
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Comparative Composition L is a high-performance
concentrated powder based on a different surfactant
system (LAS with nonionic surfactants) similar to that
used in premium powders presently on sale in Europe.
Surfactant systems (wt%)
k 29 30
lo LAS 46
Coco PAS - 30 30 10
E7(s) 23 30
E3(s) 31 40
NRE7(s) - - 30 40
NRE3(s) - - 40 50
___ ___ ___ ___
100 100 100 100
The total amount of (non-soap) surfactant in each
formulation was 17 wt%.
All base powders were prepared in the Fukae FS100
batch high-speed mixer/granulator mentioned previously.
Composition L was prepared as follows. Zeolite and
carbonate (including an additional amount for
neutralisation of LAS acid) were dosed into the Fukae
mixer, followed by LAS acid, then a homogeneous
surfactant blend (nonionic surfactant), fatty acid and an
equivalent amount of sodium hydroxide solution). After
granulation, the powder was dried using a fluidised bed,
and the remaining ingredients postdosed.
CA 02083331 1998-04-07
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_ 44 _ C3431
Compositions 29 and 30 were prepared as follows.
Homogeneous surfactant blends were prepared by mixing PAS
paste (70%), nonionic surfactant, fatty acid and an
eguivalent amount of sodium hydroxide solution. Zeolite
and carbonate were dosed into the Fukae, followed by the
surfactant blend. After granulation, the powders were
dried using a fluidised bed, and the remaining
ingredients postdosed.
Composition 31 was prepared similarly except that no
carbonate was present during granulation.
Powder Properties
L 29 30 31
Bulk density 861 826 841 841
DFR 89 111 120 128
Deterqency results
2 5 Detergency was assessed in a Miele washing machine, in
the presence of a soiled load, using a product
concentration of 5 g/l, 26~ (French) hard water, and a
wash temperature of 30~C. The measure of detergency was
the change in reflectance (460 nm) of a polyester test
cloth soiled with kaolin and sebum (WFK 30D).
Delta R460 16.2 15.0 15. 7 17.2
CA 02083331 1998-04-07
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Examples 32 to 34
Further detergent powder formulations, containing
zeolite MAP and coconut nonionic surfactants, are shown
below.
32 33 34
Base powders
Coco PAS 5.20 1.70
E7 5.20 6.80 7.50
E3 6.60 8.50 9.50
Soap 2.00 2.00 2.00
Zeolite MAP 32.00 32.00 32.00
Fluorescers 0.81 0.81 0.81
SCMC 0.60 0.60 0.60
Moisture 9.00 9.00 9.00
Postdosed
Carbonate 11.52 11.52 11.52
Silicate 0.45 0.45 0.45
Perborate mono 15.00 15.00 15.00
TAED 7-75 7-75 7-75
EDTMP 0.37 0.37 0.37
Enzymes 1.00 1.00 1.00
Antifoam 2.50 2.50 2.50
Perfume 0.60 0.60 0.60
______ ______ ______
100.00 100.00 100.00
Similar compositions may be formulated containing
the narrow-range coconut nonionic surfactants NRE7 and
NRE3, instead of the broad range materials E7 and E3, in
the same proportions; or instead using one of the single
materials NRE5, NRE4.6 or NRE4.2.
** *
