Note: Descriptions are shown in the official language in which they were submitted.
2o~5~oz
LIQUID CLEANING PRODUCTS
The present invention relates to liquid non-aqueous
cleaning products, especially non-aqueous liquid
detergent compositions containing particulate solid
materials. Non-aqueous liquids are those containing
little or no water.
In liquid detergents in general, especially those for
the washing of fabrics, it is often desired to suspend
particulate solids which have beneficial auxiliary
effects in the wash, for example detergency builders
to counteract water hardness, as well as bleaches. To
keep the solids in suspension, generally some sort of
stabilising system is necessary.
Several different approaches have been used to provide
2o solid-suspending properties in non-aqueous liquids.
For example it has been proposed in GB 1 600 981 to
use dispersants, such as silica dispersants for the
stabilisation of heavy duty liquid detergent
compositions which contain builders dispersed in
substantially water-free non-ionic liquid surfactants.
Often, however, the use of silica dispersants for the
stabilisation of non-aqueous liquid detergents, leads
to the setting of the composition, possible resulting
in an unacceptable high viscosity.
FR-A-2 618 157 discloses non-aqueous liquid detergents
comprising solid particles, a low density compound and
an organophilic clay.
EP 30 096 discloses non-aqueous liquid detergent
compositions containing a dispersion of solids, which
are free from dispersants, in particular free from
silica containing dispersants. Applicants, however,
~pw~p~~! ?,
Vi=i S ..
~A~'5~0~
lb
have found that non-aqueous detergent compositions
which are free from dispersants, in particular silica
_ __ ,~.. :~~ .-.- .
WO 91/12312~~"~ ~~~, PCT/EP91/0(~~54
2
containing dispersants, sometimes suffer from physical
instability.
Surprisingly, it has now been found that the physical
stability of non-aqueous liquid detergent compositions
can be improved and the above described setting
problems can be minimised, if hydrophobically modified
dispersants are used.
Accordingly the present invention relates to a
substantially non-aqueous liquid cleaning product,
comprising a non-aqueous organic solvent, particles of
solid material dispersed in the solvent and a
dispersant, wherein the dispersant is a
hydrophobically modified material.
Preferably hydrophobically modified (HM) silica
containing dispersants are used. Preferred HM
dispersant materials have a weight average particle
size of from 0.005 to 5 micrometer, more preferred
0.01 to 3 micrometer, most preferred_from 0.02 to 0.5
micrometer. The level of the HM dispersant material is
preferably from 0.1 to 10 % by weight of the
composition, more preferred 0.3 to 5 %, most preferred
from 0.5 to 3 %.
PRODUCT FORM
All compositions according to the present invention
are liquid cleaning products. In the context of this
specification, all references to liquids refer to
materials which are liquid at 25°C at atmospheric
pressure.
WO 91/12312 ~, ~ ~ ~ PCT/EP91/00254
3
Preferably compositions of the invention have a
viscosity of less than 2,500 mPa.s at 21 S-l, more
preferred 100-2,000 mPa.s.
They may be formulated in a very wide range of
specific forms, according to the intended use. They
may be formulated as cleaners for hard surfaces (with
or without abrasive) or as agents for warewashing
(cleaning of dishes, cutlery etc) either by hand or
mechanical means, as well as in the form of
specialised cleaning products, such as for surgical
apparatus or artificial dentures. They may also be
formulated as agents for washing and/or conditioning
of fabrics.
Thus, the compositions will contain at least one agent
which promotes the cleaning and/or conditioning of the
articles) in question, selected according to the
intended application. Usually, this agent will be
selected from surfactants, enzymes, bleaches,
microbiocides, (for fabrics) fabric softening agents
and (in the case of hard surface cleaning) abrasives.
Of course in many cases, more than one of these agents
will be present, as well as other ingredients commonly
used in the relevant product form.
HYDROPHOBICALLY MODIFIED MATERIAL
Compositions of the invention contain a
hydrophobically modified dispersant material. For the
purpose of the present invention, a dispersant
material is a material, of which the main purpose is
to stabilise the composition. Hydrophobically modified
dispersant materials are particulate materials, of
which the outer surface has chemically been treated to
reduce the hydrophilic nature thereof.
WO 91/12312 PCT/EP91/On?54
4
Pre~~ably the number of hydroxy- and/or acid- groups
at the surface of the particles is reduced by the
hydrophobing treatment. Suitable reactions include
esterification or etherification of the hydrophilic
groups. Preferably the hydrophobing treatment involves
at least 10 % of the hydrophilic groups at the surface
of the particle. more preferably from 40 to 95 %, most
preferably from 50 to 90 %. Partial hydrophobing is
preferred over complete hydrophobation.
Preferably HM silica containing dispersants are used.
The hydrophobation of the silica particles preferably
involves the substitution of the free hydroxy-groups
at the outer surface of the silica particles by less
hydrophilic groups. More preferably the surface
hydroxy-groups are substituted by short alkyl groups
e.g. by methyl groups.
SURFACTANT
Where surfactants are solids, they will usually be
dissolved or dispersed in the liquid phase. Where they
are liquids, they will usually constitute all or part
of the liquid phase. However, in some cases the
surfactants may undergo a phase change in the
composition.
In general, surfactants for use in the compositions of
the invention may be chosen from any of the classes,
sub-classes and specific materials described in
"Surface Active Agents" Vol. I, by Schwartz & Perry,
Interscience 1949 and "Surface Active Agents" Vol. II
by Schwartz, Perry & Berch (Interscience 1958), in the
current edition of "McCutcheon's Emulsifiers &
Detergents" published by the McCutcheon division of
WO 91/12312 PCT/EP91/00254
5~Q"~a~
Manufacturing Confectioners Company or in "Tensid-
Taschenbuch", H. Stache, 2nd Edn., Carl Hanser Verlag,
Miinchem & Wien, 1981.
In respect of all surfactant materials, but also with
reference to all ingredients described herein as
examples of components in compositions according to
the present invention, unless the context requires
otherwise, the term "alkyl" refers to a straight or
branched alkyl moiety having from 1 to 30 carbon
atoms, whereas lower alkyl refers to a straight or
branched alkyl moiety of from 1 to 4 carbon atoms.
These definitions apply to alkyl species however
incorporated (e. g. as part of an aralkyl species).
Alkenyl (olefin) and alkynyl (acetylene) species are
to be interpreted likewise (i.e. in terms of
configuration and number of carbon atoms) as are
equivalent alkylene, alkenylene and alkynylene
linkages. For the avoidance of doubt, any reference to
lower alkyl or C1_4 alkyl (unless the
context so forbids) is to be taken specifically as a
recitation of each species wherein the alkyl group is
(independent of any other alkyl group which may be
present in the same molecule) methyl, ethyl, iso-
propyl, n-propyl, n-butyl, iso-butyl and t-butyl, and
lower (or C1_4) alkylene is to be construed likewise.
NON-IONIC SURFACTANTS
Nonionic detergent surfactants are well-known in the
art. They normally consist of a water-solubilizing
polyalkoxylene or a mono- or di-alkanolamide group in
chemical combination with an organic hydrophobic group
derived, for example, from alkylphenols in which the
alkyl group contains from about 6 to about 12 carbon
atoms, dialkylphenols in which each alkyl group
contains from 6 to 12 carbon atoms, primary, secondary
WO 91/12 ~~~'~ PCT/EP91/On~54
6
or tertiary aliphatic alcohols (or alkyl-capped
derivatives thereof), preferably having from 8 to 20
carbon atoms, monocarboxylic acids having from l0 to
about 24 carbon atoms in the alkyl group and
polyoxypropylenes. Also common are fatty acid mono-
and dialkanolamides in which the alkyl group of the
fatty acid radical contains from 10 to about 20 carbon
atoms and the alkyloyl group having from 1 to 3 carbon
atoms. In any of the mono- and di- alkanolamide
derivatives, optionally, there may be a
polyoxyalkylene moiety joining the latter groups and
the hydrophobic part of the molecule. In all
polyalkoxylene containing surfactants, the
polyalkoxylene moiety preferably consists of from 2 to
20 groups of ethylene oxide or of ethylene oxide and
propylene oxide groups. Amongst the latter class,
particularly preferred are those described in the
applicants' published European specification
EP-A-225,654, especially for use as all or part of the
liquid phase. Also preferred are those ethoxylated
nonionics which are the condensation products of fatty
alcohols with from 9 to 15 carbon atoms condensed with
from 3 to il moles of ethylene oxide. Examples of
these are the condensation products of C11-13 alcohols
with (say) 3 or 7 moles of ethylene oxide. These may
be used as the sole nonionic surfactants or in
combination with those of the described in the last-
mentioned European specification, especially as all or
part of the liquid phase.
Another class of suitable nonionics comprise the alkyl
polysaccharides (polyglycosides/oligosaccharides) such
as described in any of specifications US 3,640,998;
US 3,346,558; US 4,223,129; EP-A-92,355; EP-A-99,183;
EP 70,074, '75, '76, '77; EP 75,994, '95, '96.
p.
WO 91/12312 r
PGT/EP91/00254
7
Mixtures of different nonionic detergent surfactants
may also be used. Mixtures of nonionic detergent
surfactants with other detergent surfactants such as
anionic, cationic or ampholytic detergent surfactants
and soaps may also be used.
Preferably the level of nonionic surfactants is from
10-90% by weight of the composition, more preferably
20-70%, most preferably 35 to 50% by weight.
ANIONIC SURFACTANTS
Examples of suitable anionic detergent surfactants are
alkali metal, ammonium or alkylolamine salts of
alkylbenzene sulphonates having from 10 to 18 carbon
atoms in the alkyl group, alkyl and alkylether
sulphates having from 10 to 24 carbon atoms in the
alkyl group, the alkylether sulphates having from 1 to
5 ethylene oxide groups, and olefin sulphonates
prepared by sulphonation of Clo-24 alpha-olefins and
subsequent neutralization and hydrolysis of the
sulphonation reaction product.
All ingredients before incorporation will either be
liquid, in which case, in the composition they will
constitute all or part of the liquid phase, or they
will be solids, in which case, in the composition they
will either be dispersed in the liquid phase or they
will be dissolved therein. Thus as used herein, the
term "solids" is to be construed as referring to
materials in the solid phase which are added to the
composition and are dispersed therein in solid form,
those solids which dissolve in the liquid phase and
those in the liquid phase which solidify
(undergo a phase change) in the composition, wherein
they are then dispersed.
WO 91/12312 PCT/EP91/0~"~S4
,, ~~~ 8
THE NON-AQUEOUS ORGANIC SOLVENT
As a general rule, the most suitable liquids to choose
as the liquid phase are those organic materials having
polar molecules. In particular, those comprising a
relatively lipophilic part and a relatively
hydrophilic part, especially a hydrophilic part rich
in electron lone pairs, tend to be well suited. This
is completely in accordance with the observation that
liquid surfactants, especially polyalkoxylated
nonionics, are one preferred class of material for the
liquid phase.
Non-surfactants which are suitable for use as the
liquid phase include those having the preferred
molecular fonas referred to above although other kinds
may be used, especially if combined with those of the
former, more preferred types. In general, the non-
surfactant solvents can be used alone or with in
combination with liquid surfactants. Non-surfactant
solvents which have molecular structures which fall
into the former, more preferred category include
ethers, polyethers, alkylamines and fatty amines,
(especially di- and tri-alkyl- and/or fatty- N-
substituted amines), alkyl (or fatty) amides and mono-
and di- N-alkyl substituted derivatives thereof, alkyl
(or fatty) carboxylic acid lower alkyl esters,
ketones, aldehydes, and glycerides. Specific examples
include respectively, di-alkyl ethers, polyethylene
glycols, alkyl ketones (such as acetone)
and glyceryl trialkylcarboxylates (such as glyceryl
tri-acetate), glycerol, propylene glycol, and
sorbitol.
WO 91/12312 ~ ~ ~ ~ ~ ~ ~ PGT/EP91/00254
9
Many light solvents with little or no hydrophilic
character are in most systems, unsuitable on their own
Examples of these are lower alcohols, such as ethanol,
or higher alcohols, such as dodecanol, as well as
alkanes and olefins. However, they can be combined
with other liquid materials.
LEVEL OF LIQUID PHASE
Preferably, the compositions of the invention contain
the liquid phase (whether or not comprising liquid
surfactant) in an amount of at least 10% by weight of
the total composition. The amount of the liquid phase
present in the composition may be as high as about
90%, but in most cases the practical amount will lie
between 20 and 70% and preferably between 35 and 50%
by weight of the composition.
SOLIDS CONTENT
In general, the solids content of the product may be
within a very wide range, for example from 10-90%,
usually from 30-80% and preferably from 50-65% by
weight of the final composition. The solid phase is
preferably in particulate form and preferably has a
weight average particle size of less than 300 microns,
preferably less than 200 microns, more preferably less
than 100 microns, especially less than 10 microns. The
particle size may even be of sub-micron size. The
proper particle size can be obtained by using
materials of the appropriate size or by milling the
total product in a suitable milling apparatus. In
order to control aggregation of the solid phase
leading to unredispersible settling or setting of the
composition, it is preferred to include a deflocculant
therein.
WO 91/12312 PCT/EP91/Or'S4
s~ '~~~ ..
OTHER~GREDIENTS
In addition to the components already discussed, there
are very many other ingredients which can be
5 incorporated in liquid cleaning products.
There is a very great range of such other ingredients
and these will be choosen according to the intended
use of the product. However, the greatest diversity is
10 found in products for fabrics washing and/or
conditioning. Many ingredients intended for that
purpose will also find application in products for
other applications (e.g. in hard surface cleaners and
warewashing liquids).
METAL OXIDES
For reducing the clear layer separation of liquid
detergent compositions of the invention, surprisingly
it has been found that the combined use of HM
particles and particulate metal oxides is especially
advantageous. Preferred suspended metal oxides have a
bulk density of 200 to 1,000 g/1, more preferred 250
to 800 g/1, especially preferably 300 to 700 g/1, most
preferably from 400 to 650 g/1.
Preferably the metal oxide is selected from calcium
oxide, magnesium oxide and aluminium oxide, most
preferably magnesium oxide is used.
The weight average particle size of the metal oxide is
preferably from 0.1 to 200 micrometer, more preferably
from 0.5 to 100 micrometer, most preferred from 2 to
70 micrometer. The level of metal oxide is preferably
from 0.1 to 7 % by weight of the composition, more
preferred from 0.5 to 5 %, most preferred from 1 to
4 %.
WO 91/12312 PCT/EP91/00254
11
DETERGENCY BUILDERS
The detergency builders are those materials which
counteract the effects of calcium, or other ion, water
hardness, either by precipitation or by an ion
sequestering effect. They comprise both inorganic and
organic builders. They may also be sub-divided into
the phosphorus-containing and non-phosphorus types,
the latter being preferred when environmental
considerations are important.
In general, the inorganic builders comprise the
various phosphate-, carbonate-, silicate-, borate- and
aluminosilicates-type materials, particularly the
alkali-metal salt forms. Mixtures of these may also be
used.
Examples of phosphorus-containing inorganic builders,
when present, include the water-soluble salts,
especially alkali metal pyrophosphates,
orthophosphates, polyphosphates and phosphonates.
Specific examples of inorganic phosphate builders
include sodium and potassium tripolyphosphates,
phosphates and hexametaphosphates.
Examples of non-phosphorus-containing inorganic
builders, when present, include water-soluble alkali
metal carbonates, bicarbonates, borates, silicates,
metasilicates, and crystalline and amorphous
aluminosilicates. Specific examples include sodium
carbonate (with or without calcite seeds), potassium
carbonate, sodium and potassium bicarbonates,
silicates and zeolites.
WO 91/12312 ~ ~~~ PGT/EP91/0''S4
12
Examples of organic builders include the alkali metal,
ammoniwn and substituted ammonium, citrates,
succinates, malonates, fatty acid sulphonates,
carboxymethoxy succinates, ammonium polyacetates,
carboxylates, polycarboxylates, aminopolycarboxylates,
polyacetyl carboxylates and polyhydroxsulphonates.
Specific examples include sodium, potassium, lithium,
ammonium and substituted ammonium salts of
ethylenediaminetetraacetic acid, nitrilotriacetic
acid, oxydisuccinic acid, melitic acid, benzene
polycarboxylic acids and citric acid. Other examples
are organic phosphonate type sequestering agents such
as those sold by Monsanto under the tradename of the
bequest range and alkanehydroxy phosphonates.
Other suitable organic builders include the higher
molecular weight polymers and co-polymers known to
have builder properties, for example appropriate
polyacrylic acid, polymaleic acid and polyacrylic/
polymaleic acid co-polymers and their salts, such as
those sold by BASF under the Sokalan Trade Mark.
Preferably the level of builder materials is from 0-
75% by weight of the composition, more preferred 5-
50%, most preferred 10-40%.
THE DEFLOCCULANT
Preferably compositions of the invention also comprise
a deflocculant material. In principle, any material
may be used as a deflocculant provided it fulfils the
deflocculation test described in European Patent
Specification EP-A-266199 (Unilever). The capability
of a substance to act as a deflocculant will partly
depend on the solids/liquid phase combination.
However, especially preferred are acids.
WO 91/12312 13 ~ ~ ~ ~ ~ ~ ~ PCT/EP91/00254
Some typical examples of deflocculants include the
alkanoic acids such as acetic, propionic and stearic
and their halogenated counterparts such as
trichloracetic and trifluoracetic as well as the alkyl
(e. g. methane) sulphonic acids and aralkyl (e. g.
paratoluene) sulphonic acids.
Examples of suitable inorganic mineral acids and their
salts are hydrochloric, carbonic, sulphurous,
sulphuric and phosphoric acids; potassium monohydrogen
sulphate, sodium monohydrogen sulphate, potassium
monohydrogen phosphate, potassium dihydrogen
phosphate, sodium monohydrogen phosphate, potassium
dihydrogen pyrophosphate, tetrasodium monohydrogen
triphosphate.
Other organic acids may also be used as deflocculants,
for example formic, lactic, amino acetic, benzoic,
salicylic, phthalic, nicotinic, ascorbic,
ethylenediamine tetraacetic, and aminophosphonic
acids, as well as longer chain fatty carboxylates and
triglycerides, such as oleic, stearic, lauric acid and
the like. Peracids such as percarboxylic and
persulphonic acids may also be used.
The class of acid deflocculants further extends to the
Lewis acids, including the anhydrides of inorganic and
organic acids. Examples of these are acetic anhydride,
malefic anhydride, phthalic anhydride and succinic
anhydride, sulphur-trioxide, diphosphorous pentoxide,
boron trifluoride, antimony pentachloride.
"Fatty" anions are very suitable deflocculants, and a
particularly preferred class of deflocculants
comprises anionic surfactants. Although anionics which
are salts of alkali or other metals may be used,
r o '~~
WO 91/123~~~ ~ ~~ PCT/EP91/0' - ~4
14
particularly preferred are the free acid forms of
these surfactants (wherein the metal cation is
replaced by an H+ cation, i.e. proton). These anionic
surfactants include all those classes, sub-classes and
specific forms described in the aforementioned general
references on surfactants, viz, Schwartz & Perry,
Schwartz Perry and Berch, McCutcheon's, Tensid-
Taschenbuch; and the free acid forms thereof. Many
anionic surfactants have already been described
hereinbefore. In the role of deflocculants, the free
acid forms of these are generally preferred.
In particular, some preferred sub-classes and examples
are the C1o-C22 fatty acids and dimers thereof, the
Cs-C18 alkylbenzene sulphonic acids, the C1o-Cls alkyl-
or alkylether sulphuric acid monoesters, the C12-Cis
paraffin sulphonic acids, the fatty acid sulphonic
acids, the benzene-, toluene-, xylene- and cumene
sulphonic acids and so on. Particularly are the linear
Ci2-Cis alkylbenzene sulphonic acids.
As well as anionic surfactants, zwitterionic-types can
also be used as deflocculants. These may be any
described in the aforementioned general surfactant
references. One example is lecithin.
The level of the deflocculant material in the
composition can be optimised by the means described in
the aforementioned EP-A-266199, but in very many cases
is at least 0.01%, usually 0.1% and preferably at
least 1% by weight, and may be as high as 15% by
weight. For most practical purposes, the amount ranges
from 2-12%, preferably from 4-10% by weight, based on
the final composition.
2~~.'_~~~~
WO 91/12312 PCT/EP91/00254
THE BLEACH SYSTEM
Bleaches include the halogen, particularly chlorine
5 bleaches such as are provided in the form of
alkalimetal hypohalites, e.g. hypochlorites. In the
application of fabrics washing, the oxygen bleaches
are preferred, for example in the form of an inorganic
persalt, preferably with a bleach precursor, or as a
10 peroxy acid compound.
In the case of the inorganic persalt bleaches, the
activator makes the bleaching more effective at lower
temperatures, i.e. in the range from ambient
15 temperature to about 60°C, so that such bleach systems
are commonly known as low-temperature bleach systems
and are well-known in the art. The inorganic persalt
such as sodium perborate, both the monohydrate and the
tetrahydrate, acts to release active oxygen in
solution, and the activator is usually an organic
compound having one or more reactive acyl residues,
which cause the formation of peracids, the latter
providing for a more effective bleaching action at
lower temperatures than the peroxybleach compound
alone.
The ratio by weight of the peroxybleach compound to
the activator is preferably from about 20:1 to about
1:1, preferably from about 10:1 to about 2:1, most
preferably 5:1 to 3.5:1. Whilst the amount of the
bleach system, i.e. peroxybleach compound and
activator, may be varied between about 5% and about
35% by weight of the total liquid, it is preferred to
use from about 6% to about 30% of the ingredients
forming the bleach system. Thus, the preferred level
of the peroxybleach compound in the composition is
between about 5.5% and about 27% by weight, while the
WO 91/12312 ~~ PGT/EP91/P ''54
16
preferred level of the activator is between about 0.5%
and about 14%, most preferably between about 1% and
about 5% by weight.
Typical examples of the suitable peroxybleach
compounds are alkalimetal perborates, both
tetrahydrates and monohydrates, alkali metal
percarbonates, persilicates and perphosphates, of
which sodium perborate and sodium percarbonate are
pref erred .
It is particularly preferred to include in the
compositions, a stabiliser for the bleach or bleach
system, for example ethylene diamine tetramethylene
phosphonate and diethylene triamine pentamethylene
phosphonate or other appropriate organic phosphonate
or salt thereof, such as the bequest range
hereinbefore described. These stabilisers can be used
in acid or salt form, such as the calcium, magnesium,
zinc or aluminium salt form. The stabiliser may be
present at a level of up to about 1% by weight,
preferably between about 0.1% and about 0.5% by
weight.
Preferred activator materials are TAED and glycerol
triacetate. The applicants have also found that liquid
bleach activator, such as glycerol triacetate and
ethylidene heptanoate acetate, isopropenyl acetate and
the like, also function suitably as a material for the
liquid phase, thus obviating or reducing any need of
additional relatively volatile solvents, such as the
lower alkanols, paraffins, glycols and glycolethers
and the like, e.g. for viscosity control.
~(~'~~8~~
WO 91/12312 PCT/EP91/00254
17
MISCELLANEOUS OTHER INGREDIENTS
Other ingredients comprise those remaining ingredients
which may be used in liquid cleaning products, such as
fabric conditioning agents, enzymes, perfumes
(including deoperfumes), micro-biocides, colouring
agents, fluorescers, soil-suspending agents (anti-
redeposition agents), corrosion inhibitors, enzyme
l0 stabilising agents, and lather depressants.
Amongst the fabric conditioning agents which may be
used, either in fabric washing liquids or in rinse
conditioners, are fabric softening materials such as
fabric softening clays, quaternary ammonium salts,
imidazolinium salts, fatty amines and cellulases.
Enzymes which can be used in liquids according to the
present invention include proteolytic enzymes,
amylolytic enzymes and lipolytic enzymes (lipases).
Various types of proteolytic enzymes and amylolytic
enzymes are known in the art and are commercially
available. They may be incorporated as "prills" or
"marumes", suspensions etc.
The fluorescent agents which can be used in the liquid
cleaning products according to the invention are well
known and many such fluorescent agents are available
commercially. Usually, these fluorescent agents are
supplied and used in the form of their alkali metal
salts, for example, the sodium salts. The total amount
of the fluorescent agent or agents used in a detergent
composition is generally from 0.02-2% by weight.
When it is desired to include anti-redeposition agents
in the liquid cleaning products, the amount thereof is
normally from about 0.1% to about 5% by weight,
~~Q~
WO 91/12312 PCT/EP91/P~~54
18
preferably from about 0.2% to about 2.5% by weight of
the total liquid composition. Preferred
anti-redeposition agents include carboxy derivatives
of sugars and celluloses, e.g. sodium carboxymethyl
cellulose, anionic poly-electrolytes, especially
polymeric aliphatic carboxylates, or organic
phosphonates.
WATER LEVEL
The compositions are substantially non-aqueous, i.e.
they contain little or no free water, preferably no
more than 5%, preferably less than 3%, especially less
than 1% by weight of the total composition. It has
been found that the higher the water content, the more
likely it is for the viscosity to be too high, or even
for setting to occur.
USE
Composition in accordance with the present invention
may be used for several detergency purposes, for
example the cleaning of surfaces and the washing of
fabrics. For the washing of fabrics, preferably an
aqueous liquor containing 0.05 to 10 %, more
preferably 0.1 to 2%, of the non-aqueous detergent
composition of the invention is used.
PROCESSING
During manufacture, it is preferred that all raw
materials should be dry and (in the case of hydratable
salts) in a low hydration state, e.g. anhydrous
phosphate builder, sodium perborate monohydrate and
dry calcite abrasive, where these are employed in the
composition. In a preferred process, the dry,
substantially anhydrous solids are blended with the
WO 91/12312 ~ ~ ~ _~ ~ ~ ~ PCT/EP91/00254
19
liquid phase in a dry vessel. If deflocculant
materials are used, these should preferably -at least
partly- be mixed with the liquid phase, prior to the
addition of the solids. In order to minimise the
rate of sedimentation of the solids, this blend is
passed through a grinding mill or a combination of
mills, e.g. a colloid mill, a corundum disc mill, a
horizontal or vertical agitated ball mill, to achieve
a particle size of 0.1 to 10o microns, preferably 0.5
to 50 microns, ideally 1 to 10 microns. A preferred
combination of such mills is a colloid mill followed
by a horizontal ball mill since these can be operated
under the conditions required to provide a narrow size
distribution in the final product. Of course
particulate material already having the desired
particle size need not be subjected to this procedure
and if desired, can be incorporated during a later
stage of processing.
During this milling procedure, the energy input
results in a temperature rise in the product and the
liberation of air entrapped in or between the
particles of the solid ingredients. It is therefore
highly desirable to mix any heat sensitive ingredients
into the product after the milling stage and a
subsequent cooling step. It may also be desirable to
de-aerate the product before addition of these
(usually minor) ingredients and optionally, at any
other stage of the process. Typical ingredients which
might be added at this stage are perfumes and enzymes,
but might also include highly temperature sensitive
bleach components or volatile solvent components which
may be desirable in the final composition. However, it
is especially preferred that volatile material be
introduced after any step of de-aeration. Suitable
equipment for cooling (e.g. heat exchangers) and de-
aeration will be known to those skilled in the art.
WO 91/12312 r ,,~'~t PCT/EP91/Q~'~~~.4
It follows that all equipment used in this process
should preferably be completely dry, special care
being taken after any cleaning operations. The same is
true for subsequent storage and packing equipment.
5
The invention will further be illustrated in the
examples.
21 C 7226 (R)
EXAMPLE I Z O ~ ~ ~ O
The following compositions (percent by weight) were
prepared by mixing the ingredients in the order
listed. The ingredients were milled after mixing to a
mean particle size of 5~m. The tendency for the
composition to give clear layer formation was
determined by filling a 10 cm tall measuring cylinder
and leaving it to stand for 4 weeks at 37°C or 8 weeks
at 20°C and then measuring the height of the upper
layer. The initial viscosity of each composition is
also given.
COMPOSITION (~ wt ) A B C D
Nonionic 1? <-----------39.6------------->
Glycerol triacetate <----------- 5.0------------->
ABS-acid <___________ g.0_____________>
Na Carbonate <-----------18.0------------->
Na bicarbonate 4.2 3.2 2.2 1.2
Calcite <__________- g.0_____________>
Na perborate monohydrate<-----------10.5------------->
TAED <-_-________ 3.0-____________>
~
Sipernat D 1 0.0 1.0 2.0 3.0
2>
Minors <-------- balance------------>
Viscosity(mPas 21 s-1) 1150 1175 1440 1970
Clear layer separation
8 weeks 20 °C (mm) 7 4 2 1
4 weeks 37 °C (mm) 10 5 3 2
This example clearly shows that the use of
hydrophobically modified dispersants increases the
stability of non-aqueous liquid detergent
compositions, without an unacceptable rise in
viscosity.
V~~'J~~~~~~ ~!~ ~ ~~.
S
~A ~5~ ~ ~
22 C 7226 (R)
1) A C11 alcohol ethoxylated with an average of 6.5 EO
groups.
2) HM silica (Degussa).
EXAMPLE II
The following formulations were prepared as in Example
I.
Ingredient (% wt) E F
Nonionic 1~ 31.996
Nonionic 2~ 42.9
GTA 15.0 6.1
ABS-acid 6.0 3.4
Na carbonate 18.0 15.8
Calcite (Sokal U3) 7.0 7.6
Mg03> 1.0 1.7
Silica (Sipernat D1~ 2.0 3.4
Perborate mono 10.5 11.0
TAED 3.0 3.4
SCMC 1.0
Fluorescer 0.3
Versa TL3 polymer 0.5 -
Methylhydroxyethyl
cellulose 0.5 -
Silicones 2.0 2.0
Protease 0.4 0.4
Lipolase 0.3 0.3
Perfume 0.5 0.5
Colour 0.004 0.1
Other minors ----------ba lance---------
Both compositions were of surprisingly good stability
and did show no or only little phase separation upon
storage.
WO 91/12312 PCT/EP91/00254
23
1) NRE nonionic material ex Vista
2) C10-12 6~5 EO
3) Mg0-170 having a bulk density of about 560 g/1,
particle size 2-25~m.
