Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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FREE-(LOWING PARTICULATE DETERGENT COMPOSITIONS
Technical field
The present invention relates to built particulate laundry
detergent compositions containing especially high levels of
surfactant while retaining free-flowing properties.
Background
High levels of organic detergent surfactant (active) are
sometimes required in laundry detergent compositions,
particularly in compositions intended for washing by hand,
to give effective soil removal. However, it has been found
that problems of poor powder properties can be encountered
in high-active compositions, for example, powder stickiness
leading to agglomeration and poor flow.
Flow properties are improved by the presence of inorganic
materials having a good carrying capacity for mobile organic
surfactants, but the higher the intended surfactant level,
the less room there is in the formulation for inorganic
material.
Clearly it is preferable that the inorganic material
included for this purpose should also itself have
functionality, for example, as a detergency builder.
However, one of the most effective and popular detergency
builders, sodium tripolyphosphate, has a relatively poor
carrying capacity for surfactants unless spray-dried.
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In order to improve the liquid carrying capacity of
particulate detergent compositions to allow a high active
level, it is known in the art to include a relatively high
proportion of material, typically builder material, which
has a better carrying capacity than sodium tripolyphosphate.
For example, zeolite may be used in this role. However,
zeolite is insoluble and its presence may lead to residues
on washed fabrics. The present inventors have therefore
sought to provide particulate detergent compositions having
a high surfactant content, yet having acceptable or good
powder properties, without the need to incorporate
substantial quantities of zeolite.
Traditionally detergent powders contain a base powder,
prepared by spray-drying or granulation or a combination of
such processes, consisting of structured particles
containing all, or the major part of, the surfactant and
builder in the formulation. Other ingredients not suitable
for incorporation in the base powder, such as bleaches,
enzymes, heat-sensitive nonionic surfactants,
antiredeposition polymers, dye transfer inhibiting polymers,
foam control granules, and perfumes are subsequently sprayed
on to, or dry mixed with, the base powder.
The present inventors have discovered that free-flowing
powders having higher surfactant to builder ratios than have
previously been possible may be prepared, if the base powder
is partly or wholly replaced by, or supplemented with,
separate granular components in which certain ingredients
are concentrated, or segregated from one another.
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~~;B~vPCl " .
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Definition of the invention
The present invention accordingly provides a free-flowing
built particulate laundry detergent composition comprising:
(i) at least 27% by weight of non-soap organic detergent
surfactant,
(ii) one or more detergency builders, but not more than 7%
by weight of alkali metal aluminosilicate,
the weight ratio of surfactant (i) to builder (ii) being at
least 1.2:1,
the composition comprising at least two different granular
components selected from
(a) granules containing at least 60°s by weight of anionic
surfactant, and optionally from 0 to 40% by weight of
detergency builder,
(b) granules containing at least 20a by weight of nonionic
surfactant, and optionally from 0 to less than 10°s by weight
of anionic surfactant, on a water-soluble or water-insoluble
carrier material,
(c) builder granules, optionally containing from 0 to l0a
by weight of surfactant,
(d) a spray-dried or granulated detergent base powder
containing surfactant and builder.
(page 3a follows)
AMENDED SHS~~
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Detailed description of the invention
The compositions of the invention are characterised by good
flow properties despite the high surfactant content and high
ratio of surfactant to builder. This ratio is at least
1.2:1, and may be at least 1.5:1 or even higher.
The total content of non-soap surfactant in the compositions
of the invention is at least 27o by weight, preferably from
27 to 50o by weight. The surfactant content is preferably
at least 28% by weight, and more preferably at least 30% by
weight. Compositions having a surfactant content of 35o by
weight or more are of especial interest.
,~5 The surfactant (i) preferably comprises anionic surfactant,
nonionic surfactant or a combination of the two. If both
anionic and nonionic surfactants are present, the weight
(page 4 follows)
AMENDED SHEET
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ratio of anionic surfactant to nonionic surfactant is
preferably at least 1:1, and more preferably at least 1.5:1.
Formulations containing anionic surfactant only, or nonionic
surfactant only, are also of interest. Other surfactant
types, for example, cationic, amphoteric or zwitterionic,
may also be present. Examples of suitable surfactants are
listed below.
Soap, if present, should not be taken into account when
calculating the surfactant to builder ratio.
The builder (ii) may be any true detergency builder having a
significant calcium binding capacity, whether inorganic or
organic. The term builder as used herein specifically
excludes alkali metal carbonates and soluble alkali metal
silicates, both of which are sometimes referred to elsewhere
as builders. Those materials may of course be present, but
should not be taken into account when calculating the
surfactant to builder ratio.
Similarly, sequestrants present in minor amounts as bleach
stabilisers, for example aminophosphonates, should not be
taken into account when calculating the surfactant to
builder ratio.
Preferred inorganic builders are selected from alkali metal
phosphates and layered silicates. The preferred alkali
metal phosphate is sodium tripolyphosphate. Layered
silicate is available as SKS-6 from Hoechst.
Alkali metal aluminosilicates may also be present, but only
in an amount not exceeding 7% by weight. Preferred alkali
metal aluminosilicates are zeolite 4A, and zeolite MAP
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(maximum aluminium zeolite P, as described in EP 384 070B
(Unilever), available as Doucil (Trade Mark) A24 from
Crosfield.
Preferred organic builders are di- and tricarboxylic acid
salts, for example, citrates, more especially trisodium
citrate; and polycarboxylate polymers, for example,
acrylate and acrylate/maleate polymers, more especially
Sokolan (Trade Mark) CP5 from BASF.
The total level of detergency builder in the compositions of
the invention will generally be lower than in known
formulations, for example, it may be as low as 4% by
weight. However, it is preferably at least 10% by weight,
more preferably at least 20o by weight, provided that the
weight ratio of surfactant to builder is always at least
1.2:1.
The compositions of the present invention are in the form of
free-flowing particulates or powders. Preferred
compositions of the invention have a dynamic flow rate of at
least 100 ml/s, preferably at least 110 ml/s and ideally at
least 120 ml/s. A method for measuring dynamic flow rate is
given below. It has not previously been possible to prepare
compositions having such high surfactant levels and high
surfactant to builder ratios that are in the form of free-
flowing powders.
Compositions of the invention may have any bulk density
ranging from very low to very high.
Preferred compositions of the invention have bulk densities
within the range of from 300 to 1000 g/l, preferably from
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High bulk density compositions (600 g/1 and above) may be
prepared in accordance with the invention.
Granules and adjuncts
As previously indicated, in the compositions of the
invention the base powder is partly or wholly replaced by,
or supplemented with, separate granular components in which
l0 certain ingredients are concentrated and/or segregated from
one another. This approach has made possible the
preparation, in free-flowing powder form, of compositions
which, if prepared by known methods, could only be obtained
in the form of poorly flowing powders, doughs or sticky
pastes.
Examples of such granules include:
- granules containing a high level of anionic surfactant
20 ("anionic granules"),
- granules containing a high level of nonionic surfactant
("nonionic granules"), and
25 - builder granules containing little or no surfactant.
The compositions of the invention comprise at least two
granular components selected from
30 (a) granules containing at least 60% by weight of anionic
surfactant and optionally from O to 40% by weight of
detergency builder,
A+'~END~D SHEET
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lb) granules containing at least 20% by weight of nonionic
surfactant, and optionally from 0 to less than 10% by weight
of anionic surfactant, on a water-soluble or water-insoluble
carrier material,
(c) builder granules, optionally containing from 0 to 10%
by weight of surfactant.
Especially preferred compositions of the invention comprise
at least two different granular components selected from
granules (a), (b), (c) above and
(d) a spray-dried or granulated detergent base powder
containing surfactant and builder.
The anionic surfactant granules (a
The anionic surfactant granules preferably comprise from 60
to 99% by weight, more preferably from 65 to 96% by weight,
of anionic surfactant.
The anionic surfactant granules may also contain nonionic
surfactant. The anionic surfactant granules may also
contain minor ingredients such as water, sodium
carboxymethylcellulose, fluorescers, dyes, etc.
The anionic surfactant granules may optionally comprise from
0 to 40% by weight of detergency builder. The builder
material may comprise soluble builder such as salts
p,MENDED SHEET
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The anionic surfactant granules may optionally comprise from
0 to 40% by weight of detergency builder. The builder
material may comprise soluble builder such as salts
(preferably alkali metal salts, particularly preferably
sodium salts) of tripolyphosphate, carbonate, silicate,
sesquicarbonate, citrate or mixtures thereof, or burkeite (a
double salt of sodium sulphate and sodium carbonate), NTA,
polycarboxylic acid monomer, polycarboxylic acid polymer,
polycarboxylic acid/maleic acid copolymer or mixtures
thereof. Preferred builders have already been indicated
above.
The builder may comprise insoluble builder such as
aluminosilicate. The aluminosilicate may comprise zeolite,
in particular zeolite MAP, zeolite 4A, amorphous
aluminosilicate and mixtures thereof. It is particularly
preferred, however, that the quantity of aluminosilicate
builder is low, in order to keep within the overall limits
for aluminosilicate content in the whole composition.
Preferably, aluminosilicate builder provides less than 25%
by weight of the anionic surfactant particles, more
preferably less than 150.
The anionic surfactant granules may be manufactured by any
suitable process. Preferably, such granules are
manufactured by mixing the components in a high speed mixer
to agglomerate the components. Suitable mixers will be
discussed further below.
Processes for producing granules containing high quantities
of anionic surfactant are set out in WO 96/06916A and
WO 96/06917A (Unilever).
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The method of WO 97/32002A (Unilever) is particularly
preferred. In this method, a paste material comprising
water and an anionic surfactant, or a mixture of acid
surfactant precursor and alkaline neutralising agent, is fed
into a drying zone, the paste material being heated in the
drying zone to reduce the water content thereof and the
paste material being subsequently cooled in a cooling zone
to form detergent particles, a layering agent being
introduced into the cooling zone during the cooling step.
Alternatively, a paste material comprising water and an
anionic surfactant, or a mixture of acid surfactant
precursor and alkaline neutralising agent, are fed into a
drying zone, the material being heated in the drying zone to
reduce the water content thereof and the material being
subsequently cooled in a cooling zone to form detergent
particles, the material being treated in the cooling zone
with a stream of cooling gas. This process can provide
detergent particles comprising at least 60o by weight of the
particle of an anionic surfactant and not more than 5% by
weight of the particle of water. The particles are coated
with layering agent.
The detergent particles may comprise anionic surfactant in
an amount of at least 60o by weight of the particle, the
particles being coated with layering agent and having a
porosity of from 0 to 25% by volume of the particle and a
particle size distribution such that at least 800 of the
particles have a particle size of 180-1500 microns. The
layering agent may comprise an aluminosilicate, a silica or
a mixture thereof. The layering agent may be dosed into the
cooling zone at a weight ratio of from 1:5 to 1:20 relative
to the finished particles. The anionic surfactant may be
formed in situ by neutralisation of a free acid with
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neutralising agents such as sodium hydroxide solution or
sodium carbonate.
The nonionic surfactant granules (b)
The nonionic surfactant granules preferably comprise at
least 20% by weight of nonionic surfactant.
The quantity of aluminosilicate builder should be less than
10% by weight. This helps to avoid unfavourable generation
of residues and poor dispersing properties in wash water.
The nonionic surfactant particles preferably contain less
than 10% by weight of anionic surfactant, and preferably
substantially no anionic surfactant.
Nonionic surfactant particles suitable for use in the
present invention generally fall into one of two classes.
The first class comprises nonionic surfactant carried on
water-soluble carrier material. Suitable carrier materials
include burkeite, sodium sesquicarbonate, sodium carbonate,
sodium sulphate and mixtures thereof. A nonionic surfactant
granule comprising water-soluble carrier preferably
comprises from 20 to 50% by weight, preferably from 25 to
40% by weight, of nonionic surfactant.
The water-soluble carrier material is preferably present at
a level exceeding 40% by weight, preferably 60% by weight or
more.
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The second class of nonionic surfactant granule comprises
water-insoluble carrier material. The insoluble carrier
material may comprise silica or aluminosilicate, such as
zeolite. However, it is essential that, if aluminosilicate
is present, the quantity is less than 10% by weight. Where
an insoluble carrier material is used, the quantity of
nonionic surfactant may exceed 55~ by weight of the granule.
Structuring agents such as polyethylene/poly-propylene
glycol of average molecular weight in the region 4000-12000,
sodium soap, polyvinyl alcohol of average molecular weight
in the range 30 000-200 000, alkaline metal succinate etc.
may be present. The preferred quantity of structuring agent
is in the region of from 0.5 to 10o by weight.
Nonionic-surfactant-containing granules comprising 55o by
weight or more of nonionic surfactant, at least 5~ by weight
of silica of oil absorption capacity of 1.0 ml/g and less
than 10% by weight of aluminosilicate are disclosed in our
copending application of even date (reference C3777)
entitled "Detergent Compositions Containing Nonionic
Surfactant Granule". These granules can be manufactured by
mixing together components in a granulator (for example an
Eirich RV02 Granulator). Alternatively, 70 to 100 by
weight of the solid components and 70 to 95o by weight of
the nonionic surfactant can be mixed together in a first
step, the remainder of the solid components and nonionic
surfactant being added in a second step, preferably under
moderate shear. In the second process, the majority of the
structurant is preferably added in the second step.
As indicated previously, the nonionic surfactant granules
are preferably present in an amount of from 1 to 50~,
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preferably from 1 to 30%, by weight of the composition.
They may suitably provide 20% or more of the composition.
The builder granules (c)
Builder granules suitable for use in the compositions of the
invention may contain soluble builder such as sodium
tripolyphosphate, sodium carbonate, sodium silicate, NTA,
sodium sesquicarbonate, Burkeite, sodium citrate,
polycarboxylic acid monomer, polycarboxylic acid
polymer/copolymer or mixtures thereof.
The builder granules may also comprise aluminosilicate,
preferably crystalline aluminosilicate such as zeolite,
provided that the overall limits for zeolite content in the
formulation are not exceeded.
The most preferred builders for use in the compositions of
the present invention have already been indicated above.
The builder granule is preferably present in an amount of
from 5 to 80% by weight, and may suitably represent 15% by
weight or more of the composition, more preferably 28% by
weight or more.
The builder granule optionally contains additional nonionic
and/or anionic surfactant. The total quantity of surfactant
in the builder granule is preferably less than 10o by
weight.
The builder granule may also comprise layered silicate,
available, for example, as SKS-6 (Hoechst).
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Any suitable means may be used to prepare the builder
granules. For example, the builder granules may be
manufactured by spray drying a slurry of the components.
Alternatively, the components may be placed in a high speed
mixer/densifier and granulated in the presence of liquid
binder such as water or solution of polymer, such as builder
polymer, or solution of salt, such as silicate.
Detergent base powders (d)
The term "detergent base powder" as used herein is intended
to mean a homogeneous granulate consisting of structured
particles containing anionic and/or nonionic surfactant plus
detergency builder and other ingredients, but the
surfactants are not present at such high levels as in the
high-active granules discussed above, or at such low levels
as in the builder granules discussed above.
Base powders may be manufactured by spray-drying or
agglomeration techniques, as are well-known in the art.
High bulk density base powders may be prepared by spray-
drying followed by densification, or by wholly non-tower
granulation or agglomeration routes.
A base powder suitable for use in the compositions of the
invention may suitable contain at least 5% by weight of
anionic surfactant, preferably from 10 to 30°s by weight.
Nonionic surfactant may also be present, typically in
amounts of from 5 to 30% by weight of the base powder.
The content of builder in the base powder may suitably be at
least 50~ by weight.
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Postdosed ingredients
The detergent composition of the present invention may
consist only of "base ingredients" such as the anionic
granule, the nonionic granule, the builder granule and the
detergent base powder described above.
However, other detergent ingredients may be added by
postdosing to provide additional detergent benefits.
Examples of ingredients which may be postdosed are bleach
ingredients, bleach precursors, bleach catalysts, bleach
stabilisers, photobleaches, alkali metal carbonate,
water-soluble crystalline or amorphous alkaline metal
silicates, layered silicates, anti-redeposition agents, soil
release polymers, dye transfer inhibitors, fluorescers,
inorganic salts, foam control agents, foam boosters,
proteolytic, lipolytic, amylitic and cellulytic enzymes,
dyes, speckles, perfume, fabric conditioning compounds and
mixtures thereof.
Preferably the detergent composition contains 40 to 85% by
weight, in total, of the "base ingredients", ie the totality
of granules selected from anionic surfactant granules,
nonionic surfactant granules, builder granules, detergent
base powder present; the balance, if any, being postdosed
ingredients.
The compositions of the invention may, if desired, contain
more than one type of anionic surfactant granule, and/or
more than one type of nonionic surfactant granule, and/or
more than one type of builder granule.
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In the present specification, the term "granule" is used to
denote a solid particle of size greater than 200
micrometers. Preferably, such granules will be the direct
product of a spray drying or agglomeration process.
Detergent ingredients
Some preferred ingredients of the compositions of the
invention have been discussed above. The following is a
more thorough, but not totally exhaustive, listing of
possible ingredients suitable for incorporation in the
compositions of the invention.
The detergent compositions of the invention will contain, as
essential ingredients, one or more detergent active
compounds (surfactants) which may be chosen from soap and
non-soap anionic, cationic, nonionic, amphoteric and
zwitterionic detergent active compounds, and mixtures
thereof.
Many suitable detergent active compounds are available and
are fully described in the literature, for example, in
"Surface-Active Agents and Detergents", Volumes I and II, by
Schwartz, Perry and Berch.
The preferred detergent active compounds that can be used
are soaps and synthetic non-soap anionic and nonionic
compounds.
Anionic surfactants are well-known to those skilled in the
art. Examples include alkylbenzene sulphonates,
particularly linear alkylbenzene sulphonates having an alkyl
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chain length of Ce-Cls; primary and secondary alkylsulphates,
particularly C8-Cls primary alkyl sulphates; alkyl ether
sulphates; olefin sulphonates; alkyl xylene sulphonates;
dialkyl sulphosuccinates; and fatty acid ester sulphonates.
Sodium salts are generally preferred.
Anionic surfactants may be produced by neutralising a liquid
acid precursor with alkali, such as sodium hydroxide
solution or solid sodium carbonate in situ in the
granulation process.
The liquid acid precursor of an anionic surfactant may be
selected from the acid precursors of linear alkyl benzene
sulphonate, alpha-olefin sulphonate, internal olefin
sulphonate, alkyl ether sulphate or fatty acid ether
sulphate and combinations thereof.
The anionic surfactants may be primary or secondary alcohol
sulphates. Linear or branched primary alcohol sulphates
having 10 to 20 carbon atoms are particularly preferred.
These surfactants can be obtained by sulphation of the
corresponding primary or secondary alcohols, of synthetic or
natural origin, followed by neutralisation. Because the
acid precursors of alcohol sulphates are chemically
unstable, they are not commercially available and they have
to be neutralised as quickly as possible after their
manufacture.
Nonionic surfactants that may be used include the primary
and secondary alcohol ethoxylates, especially the Cs-Cao
aliphatic alcohols ethoxylated with an average of from 1 to
20 moles of ethylene oxide per mole of alcohol, and more
especially the C1o-Cls primary and secondary aliphatic
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alcohols ethoxylated with an average of from 1 to 10 moles
of ethylene oxide per mole of alcohol. Non-ethoxylated
nonionic surfactants include alkylpolyglycosides, glycerol
monoethers, and polyhydroxyamides (glucamide).
Cationic surfactants that may be used include quaternary
ammonium salts of the general formula R1RZR3R4N' X- wherein
the R groups are long or short hydrocarbyl chains, typically
alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a
solubilising cation (for example, compounds in which R1 is a
C8_ZZ alkyl group, Rz is a methyl group, and R, and R9, which
may be the same or different, are methyl or hydroxyethyl
groups); and cationic esters (for example, choline esters).
In the compositions of the invention, the total quantity of
detergent surfactant in the composition is at least 27o by
weight, preferably at least 28o by weight, more preferably
at least 30o by weight. The composition may comprise up to
50% by weight of detergent surfactant, preferably up to 500
by weight.
Preferably, the quantity of anionic surfactant is in the
range of from 5 to 50o by weight of the total composition.
More preferably, the quantity of anionic surfactant is in
the range of from 8 to 35o by weight.
Preferably, the quantity of nonionic surfactant is in the
range of from 5 to 25% by weight, more preferably from 5 to
20~ by weight.
The compositions of the present invention contain from 10 to
70~, preferably from 15 to 70o by weight, of detergency
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builder. Preferably, the quantity of builder is in the
range of from 15 to 50% by weight.
The detergent composition of the invention may contain a
S crystalline aluminosilicate, preferably an alkali metal
aluminosilicate, more preferably a sodium aluminosilicate.
The aluminosilicate may generally be incorporated in amounts
of up to 7o by weight (anhydrous basis). Aluminosilicates
are materials having the general formula:
0 . 8 -1 . 5 M20 . A12O3 . 0 . 8 - 6 S i02
where M is a monovalent cation, preferably sodium. These
materials contain some bound water and are required to have
a calcium ion exchange capacity of at least 50 mg Ca0/g.
The preferred sodium aluminosilicates contain 1.5-3.5 SiOz
units in the formula above. They can be prepared readily by
reaction between sodium silicate and sodium aluminate, as
2C amply described in the literature.
The zeolite used in the compositions of the present
invention may be the commercially available zeolite A
(zeolite 4A) now widely used in laundry detergent powders.
However, according to a preferred embodiment of the
invention, the zeolite incorporated in the compositions of
the invention is maximum aluminium zeolite P (zeolite MAP)
as described and claimed in EP 384 070B (Unilever), and
commercially available as Doucil (Trade Mark) A24 from
Crosfield Chemicals Ltd, UK.
AME(~DED SHEET
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Zeolite MAP is defined as an alkali metal aluminosilicate of
zeolite P type having a silicon to aluminium ratio not
exceeding 1.33, preferably within the range of from 0.90 to
1.33, preferably within the range of from 0.90 to 1.20.
especially preferred is zeolite MAP having a silicon to
aluminium ratio not exceeding 1.07, more preferably about
1.00. the calcium binding capacity of zeolite MAP is
generally at least 150 mg Ca0 per g of anhydrous material.
The detergent composition may contain crystalline or
amorphous water-soluble alkali metal silicate, preferably
sodium silicate having a Si0?:Na?O mole ratio within the
range of from 1.6:1 to 4:1, 2:1 to 3.3:1.
The water-soluble silicate may be present in an amount of
from 1 to 20 wt o, preferably 3 to 15 wt % and more
preferably 5 to 10 wt %, based on the total composition.
As well as the crystalline aluminosilicate builders already
mentioned, other inorganic or organic builders may be
present. Inorganic builders that may be present include
sodium carbonate, layered silicate, amorphous
aluminosilicates, and phosphate builders, for example,
sodium orthophosphate, pyrophosphate and tripolyphosphate.
Organic builders that may additionally be present include
polycarboxylate polymers such as polyacrylates and
acrylic/maleic copolymers; polyaspartates; monomeric
polycarboxylates such as citrates, gluconates,
oxydisuccinates, glycerol mono-di- and trisuccinates,
carboxymethyloxysuccinates, carboxy-methyloxymalonates,
dipicolinates, hydroxyethyliminodiac-etates, alkyl- and
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alkyenylmalonates and succinates; and sulphonated fatty acid
salts.
Especially preferred organic builders are citrates, suitably
used in amounts of from 5 to 30 wt o, preferably from 20 to
25 wt o; and acrylic polymers, more especially
acrylic/maleic copolymers, suitably used in amounts of from
0.5 to 15 wt a, preferably from 1 to 10 wt o.
Builders, both inorganic and organic, are preferably present
in alkali metal salt, especially sodium salt, form.
Detergent compositions according to the invention may also
suitably contain a bleach system. The compositions of the
invention may contain peroxy bleach compounds capable of
yielding hydrogen peroxide in aqueous solution, for example
inorganic or organic peroxyacids, and inorganic persalts
such as the alkali metal perborates, percarbonates,
perphosphates, persilicates and persulphates.
The sodium percarbonate may have a protective coating
against destabilisation by moisture. Sodium percarbonate
having a protective coating comprising sodium metaborate and
sodium silicate is disclosed in GB 2 123 044 (Kao).
The peroxy bleach compound, for example sodium percarbonate,
is suitably present in an amount of from 5 to 35 wt
preferably from 10 to 25 wt %.
The peroxy bleach compound, for example sodium percarbonate,
may be used in conjunction with a bleach activator (bleach
precursor) to improve bleaching action at low wash
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temperatures. The bleach precursor is suitably present in
an amount of from 1 to 8 wt %, preferably from 2 to 5 wt %.
Preferred bleach precursors are peroxycarboxylic acid
precursors, more especially peracetic acid precursors and
peroxybenzoic acid precursors; and peroxycarbonic acid
precursors. An especially preferred bleach precursor
suitable for use in the present invention is N, N, N', N'-
tetracetyl ethylenediamine (TAED).
A bleach stabiliser (heavy metal sequestrant) may also be
present. Suitable bleach stabilisers include
ethylenediamine tetraacetate (EDTA), ethylenediamine
disuccinate (EDDS), and the aminopolyphosphonates such as
ethylenediamine tetramethylene phosphonate (EDTMP) and
diethylenetriamine pentamethylene phosphonate (DETPMP).
The compositions of the present invention may also include a
bleach catalyst, such as manganese cyclononane derivative.
The compositions of the present invention may also contain
soil release polymers, for example sulphonated and
unsulphonated PET/POET polymers, both end-capped and non-
end-capped, and polyethylene glycol/polyvinyl alcohol graft
copolymers such as Sokolan (Trade Mark) HP22.
The compositions of the invention may also contain dye
transfer inhibiting polymers, for example, polyvinyl
pyrrolidone (PVP), vinyl pyrrolidone copolymers such as
PVP/PVI, polyamine-N-oxides, PVP-NO etc.
A powder structurant, for example, a fatty acid (or fatty
acid soap), a sugar, an acrylate or acrylate/maleate polymer
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may be included in the granular components. A preferred
powder structurant is fatty acid soap, suitably present in
an amount of from 1 to 5 wt o.
Other materials that may be present in detergent
compositions of the invention include antiredeposition
agents such as cellulosic polymers; fluorescers;
photobleaches; inorganic salts such as sodium sulphate;
foam control agents or foam boosters as appropriate; enzymes
(proteases, lipases, amylases, cellulases); dyes; coloured
speckles; perfumes; and fabric conditioning compounds.
Ingredients which are normally but not exclusively
postdosed, may include bleach ingredients, bleach precursor,
bleach catalyst, bleach stabiliser, photobleaches, alkali
metal carbonate, water-soluble crystalline or amorphous
alkaline metal silicate, layered silicates,
anti-redeposition agents, soil release polymers, dye
transfer inhibitors, fluorescers, inorganic salts, foam
control agents, foam boosters, proteolytic, lipolytic,
amylitic and cellulytic enzymes, dyes, speckles, perfume,
fabric conditioning compounds and mixtures thereof.
It is particularly preferred to include sodium carbonate.
This has the advantage that it helps to structure the
granule, can act to control the pH of the detergent
composition when dissolved and acts as a builder.
Preferably 5-30% by weight sodium carbonate are present.
Minor ingredients such as layering agents (for example
zeolite, Alusil (trade mark) or clay) may be present at a
level 0.1-100.
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F'Y21MDT.~'C
The invention will be further illustrated by the following
non-limiting Examples, in which parts and percentages are by
weight unless otherwise stated.
Measurement of dynamic flow rate
The dynamic flow-rate or DFR is measured by the following
method.
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 champed in a position such that its
longitudinal 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
22.5 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 noxmally repeated two or three times and an
average value taken. If V is the volume (ml) of the tube
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between the upper and lower sensors, the dynamic flow rate
DFR !ml/s) is given by the following equation:
DFR=V/t
The averaging and calculation are carried out electronically
and a direct read-out of the DFR value obtained.
In the Examples, the abbreviation "NDOM" stands for "non-
detergent organic matter", ie minor organic impurities.
,a~J~~'3C~FD SHEET
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~VTMDT.G' 'I
Example 1, Comparative Example A
This Example shows how a formulation containing a very high
surfactant level and excellent powder properties can be
prepared by "topping up" a base powder having a medium
surfactant level with a high-active granule, without loss of
powder properties.
Base powder F1 was prepared by spray-drying to the following
formulation:
Component F
NaLAS 37.29
STP 22.99
Sodium sulphate 17.05
Silicate 10.85
SCMC 0.58
Water 10.22
Miscellaneous 1.03
BD [g/1] 315
I
DFR [ml/s] 84
An anionic granule A1 containing a high level of anionic
surfactant were prepared by a non-spray-drying process as
follows. Sodium linear alkyl benzene sulphonate particles
(NaLAS) were produced by neutralising LAS acid with sodium
carbonate. Furthermore, zeolite MAP was dosed as a layering
agent and optionally sodium sulphate was dosed as well. A
2.0 m2 VRV flash-drier machine was used having three equal
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jacket sections. Dosing ports for liquids and powders were
situated just prior to the first hot section, with mid-
jacket dosing ports available in the final two sections.
Zeolite was added via this port in the final section. An
electrically-powered oil heater provided the heating to the
first two jacket sections. Ambient process water at 15°C was
used for cooling the jacket in the final section. Make-up
air flow through the reactor was controlled between 10 and
50 m3/kg hr by opening a bypass on the exhaust vapour
extraction fan. All experiments were carried out with the
motor at full-speed giving a tip speed of about 30 m/s.
Screw-feeders were calibrated to dose sodium carbonate,
zeolite 4A, and zeolite MAP for layering. The sodium
carbonate, zeolite 4A and liquids were added just prior to
the first hot section and zeolite MAP for layering was added
into the third section which was cold. The minimum level of
zeolite MAP was added to give free-flowing granules leaving
the drier.
A jacket temperature of 145°C was used in the first two
sections, with an estimated throughput of components 60 to
100 kg/hr. A degree of neutralisation of alkyl benzene
sulphonate of greater than 95 was achieved.
The composition of the granules is shown below.
Ingredient (wta) A1
Na LAS 70
Zeolite 4A 20
Zeolite MAP 5
Water,Salts, NDOM 5
Base powder F1 was mixed with other granular components as
set out below and exhibited properties as specified:
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Ingredients [wt %] A 1
'Base powder F1 63.95 63.95
Anionic granule A1 21.70
Sodium carbonate 17.50 14.35
Sodium sulphate 18.55
Surfactant level (% wt) 23.8 39.0
Builder level (% wt~ 14.7 14.7
Zeolite level (% wt) 0 6.5
Surfactant: builder ratio 1.62 1.84
BD [g/1] 475 443
DFR [ml/s] 103 126
Comparative Example A was prepared by using the relatively
high-active base powder F1, and postdosing inorganic salts.
This powder which has a surfactant level lower than 27% has
a flow rate only just above 100 ml/s
However, Composition 1 which was similar to composition A
but containing a very large quantity of anionic surfactant,
has substantially better flow properties despite its very
high surfactant level of 39%.
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wrar~r ~
Base powder F2 was prepared by making a slurry containing
water, NaLAS, STP, silicate, sodium sulphate, SCMC and
fluorescer. This slurry was spray-dried in a countercurrent
spray-drying tower, resulting in the following composition:
Ingredients F2 (wto)
NaLAS 37.9
STP 23.3
Silicate 11.0
Sodium sulphate 17.3
Moisture, minors 10.5
Builder granule Bl was prepared by continuously dosing
sodium tripolyphosphate (STP) in a Schugi Flexomix, while
spraying on a 10% alkaline silicate solution. The resulting
powder was cooled in a fluid bed and collected. The
following powder was obtained:
Ingredients Builder granule
B1
[ wt o ]
STP 89.3
Silicate 1.8
Moisture, minors 8.9
etc
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Nonionic granule N1 was prepared by a process route
consisting of a Lodige CB30, followed by a Niro fluid bed
and a Mogensen sieve. The Lodige CB30 was operated at 1500
rpm. Water was used to cool the CB30 jacket during the
process. The air flow in the Niro fluid bed was 900-1000
m3/hr. The total flow of powder exiting the process was in
the order of 600 kg/h.
Silica (Sorbosil (Trade Mark) TC15 ex Crosfield) was
continously dosed into the CB30, into which also a mixture
of nonionic surfactant (Lutensol A07 ex BASF) and fatty acid
(Pristerene 4916 ex Unichema) was dosed via dosing pipes. At
the same time 50% NaOH was dosed to neutralise the fatty
acid. This set of solid and liquid materials was mixed and
granulated in the CB30 after which the resulting powder was
entered in the fluid bed and cooled with ambient air. Fines
were filtered from the air stream with a cyclone and filter
bags. Coarse particles (>1400um) were separated from the
product by the Mogensen sieve.
Composition [wt%] ~ N1
Sorbosil TC15 30.0
Lutensol A07 55.0
Soap 13.1
Water 1.9
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With these ingredients the following powder having very high
surfactant contents and excellent flow properties was
assembled:
Formulation 2
F2 60.2
B1 12.2
N1 27.6
Total surfactant (% wt) 38
Builder (o wt) 25
zeolite (% wt) 0
Surfactant: builder ratio 1.52
Anionic:nonionic ratio 1.5
BD (g/1] 353
DFR [ml/s] 122
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EXAMPLES 3 TO 5
Builder granule B2 was produced by continuously dosing
zeolite MAP, granular trisodium citrate and 40% Sokolan CP5
solution into a Lodige CB30 recycler. The CB30 was operated
at 1500 rpm. The exiting powder was led through a Lodige
KM300 ploughshare (120 rpm), in which densification took
place. The resulting powder was dried in a fluid bed with an
air temperature of 110 °C. The composition of the resulting
builder granule was:
Ingredients [wto] B2
Zeolite MAP (anh) 41.6
Trisodiurn citrate 31.3
Sokolan CP5 12.2
Water etc. 14.9
Nonionic granules N2 were produced by first spray-drying a
mixture of carbonate, bicarbonate, citrate and Sokolan CPS.
The spray-dried material was dosed into a Lodige FM300 D
after which nonionic was sprayed on. The Lodige was operated
at a speed of 120 rpm with the choppers switched off. Spray
on was carried out for 12 minutes. The final composition was
as follows:
Ingredients N2
Synperonic A7 25.4
i
NaHC03 31.
8
NazC03 31 .
8
Sokolan CP5 8.OI
Water, minors etc. 3.0
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PAS granules A2 were produced by drying a primary alcohol
sulphate (PAS) paste containing 70% neutralised cocoPAS and
30~ water in a dryer/granulator supplied by VRV SpA, Italy,
as follows. The temperature of the material fed into the
drying zone was set at 60°C and a small negative pressure
was applied to the drying zone. A throughput in the flash
drier of 120 kg/hr of paste was used. The temperature of
the wall of the drying zone was initially 140°C. The heat
transfer area of the drying and cooling zones was 10 m' and
5mz respectively. The temperature of the wall of the drying
zone was raised in steps to 170°C. Correspondingly, the
throughput was increased in steps to 430 kg/hr at 170°C.
The particles then passed to a cooling zone operated at a
temperature of 30°C.
The formulations of the PAS granules (weight %) were as
follows:
A2
CocoPAS 90
water, NDOM etc 5
LAS granules A1 were produced as described in earlier
Examples.
These granules were mixed with other post dose materials to
make products according to the invention:
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Formulation 3 4 5
B2 5 10
N1 80 29
N2 38.6
A1 26
A2 17.8
Granular citrate 7.6
Dense carbonate 15 1.8 2
Percarbonate 19.0019.00
TAED 5 5
EAG adjunct 1.7 1.7
SCMC 0.6 0.6
Fluorescer adjunct 1.3 1.3
Nabion 15 5 5
bequest 2047 1 1
Total surfactant (o) 44.0 28.0 32.0
Builder (wt~) 4.26 9.59 15.35
Zeolite (wt%) 2.1 6.5 4.2
Surfactant/builder 10.342.92 2.08
Anionic/nonionic 0 1.86 1.00
BD [g/1] 646 750 682
DFR [ml/s] 137 118 134
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EXAMPLES 6 AND 7
Two particulate detergent compositions as shown in the table
below were manufactured as follows.
Base powder F3 was prepared by dosing the listed components
into a high-speed Fukae batch granulator and granulating.
The sodium LAS in the base powder was prepared by in situ
neutralisation of LAS acid with sodium carbonate. The
materials were granulated until powder with good particle
size was obtained. If necessary, the powder was layered with
zeolite.
LAS granules A3 were prepared by a method similar to that
described in Example 1, to the following formulation:
Ingredient (wt%) A3
Na LAS 81
Zeolite 4A 10
Sodium carbonate 5
Water 2
~ S a 1 t s , NDOM 3
The LAS granules A3 were dry-mixed in a low shear mixer with
the base powders produced in the Fukae granulator to provide
detergent compositions having the bulk densities indicated.
Good DFR values were obtained, indicating low stickiness in
the products.
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As can be seen below, compositions having very high active
(total surfactant) levels, and very high quantities of
sodium tripolyphosphate, can be prepared as free-flowing
powders. These compositions have good flow rates in spite
of the presence of little or no zeolite.
Example 6 7
Base powder F3
STP 29.0 29.0
Sodium Carbonate 17.1 17.1
NaLAS 18.3 18.3
SCMC 1.0 1.0
Water, minors 1.0 1.0
Postdosed
Granular sodium carbonate 4.8
Enzymes, speckles, etc 2.0 0.6
LAS granules A3 26.8 33.0
Final Properties
Total surfactant level 40 45
(wt%)
Builder level (wt%) 31.7 32.3
Zeolite level (wto) 2.7 3.3
Surfactant: builder ratio 1.26 1.39
Bulk Density [g/1] 895 896
DFR [ml/s] 135 135
Trade Mark: acrylic/maleic copolymer ex BASF
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EXAMPLES 8 AND 9
AOS granules A4 were produced by drying an AOS paste
containing 70~ neutralised AOS and 30o water in a
dryer/granulator supplied by VRV SpA, Italy. The temperature
of the material fed into the drying zone was set at 60°C and
a small negative pressure was applied to the drying zone.
The temperature of the wall of the drying zone was initially
140°C. The heat transfer areas of the drying and cooling
zones were 0.8 mz and 0.4 m' respectively. The temperature
of the wall of the drying zone was raised in steps to 155°C.
The particles then passed to a cooling zone operated at a
temperature of 30°C and were collected as free flowing
granules.
The AOS granules had the following composition:
AOS granules A4
Na AOS 96
Water
Sodium sulphate, 2
NDOM
Base powders F4 and F5 were prepared as described in
Examples 6 and 7, using a Fukae batch granulator. These
were mixed with PAS granules A2 as described in earlier
Examples, or with AOS granules A4 as described above, to
give full formulations within the invention.
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Ingredients wto] F4 F5
STP 43.7 41.0
Zeolite MAP 5.6
NaLAS 27.6 14.7
NaLESI (as 1000 7.1
Sodium carbonate 25.8 26.0
Moisture, NDOM etc 3.0 5.6
lsodium alkyl ether sulphate: Empicol (Trade Mark) 0251-70
ex Albright & fnlilson, supplied as 70% paste
Formulation 8 ~ 9
Base powder F4 65.3
Base powder F5 69
AOS granules A4 30
PAS granules A2 27.7
Granular sodium carbonate 4.7 3.3
Total surfactant (wt%) 46.8 40.0
Builder (wto) 29.3 33.3
Zeolite (wto) 0 3.9
Surfactant:builder ratio 1.6 1.2
Bulk density [g/1] 863 749
Dynamic flow rate (ml/s) 100 100
