This invention relates to particulate silicone based
foam control agents, and especially those which are intended
for incorporation in powdered detergent compositions.
Foam control agents based on silicone antifoams and
foam control agents which are in particulate form are known
in the art. It is also known in the art that there is a
problem of diminishing foam control ability when a silicone
based foam control agent is stored in powder detergents for
prolonged periods of time.
Solutions to overcome the storage problem have been
suggested. They include the use of a variety of materials in
conjunction with the silicone antifoam. Examples of such
materials are given in the art. EP 013 028 suggests a non-ionic
surfactant such as ethoxylated aliphatic C12-20 alcohols
with 4 to 20 oxyethylene groups and ethoxylated
alkylphenols, fatty acids, amides of fatty acids, thio
alcohols and diols, all having 4 to 20 carbons atoms in the
hydrophobic part and 5 to 15 oxyethylene groups.
EP 142 910 discloses the use of a water soluble or
water dispersible organic carrier comprising a first organic
carrier component having a melting point of from 38 to 90°C
and a second organic carrier selected from ethoxylated non-ionic
surfactants having a HLB of from 9.5 to 13.5 and a
melting point from 5 to 36°C. Examples of the second
organic carrier materials include ethoxylated tallow
alcohol, fatty esters, amides and polyvinylpyrrolidone.
EP 206 522 describes the use of a material which is
impervious to oily antifoam active substances when in a dry
state, yet capable of disruption on contact with water.
Examples include materials with a waxy nature which form an
interrupted coating that allows water to pass through under
wet conditions.
EP 210 721 discloses a fatty acid or a fatty alcohol
having a carbon chain of from 12 to 20 carbon atoms and a
melting point from 45 to 80°C. Examples include stearic acid
or stearyl alcohol.
One theory as to why the above approaches overcome the
storage stability problem in silicone antifoams is that
encapsulation or binding of the antifoam counteracts the
spreading of the silicone polymers in the antifoam onto the
surrounding detergent powder. Such spreading reduces the
concentration of the silicone polymer in the foam control
agent and, in extreme cases, totally depletes the silicone
polymer. This depletion deactivates the foam control agent.
A carrier material is also often used to make the foam
control agents solid particles which are easier to handle
and which can be postblended as a powder with the rest of
the powder detergent composition.
Materials suggested in the prior art as useful for
carriers comprise water soluble, water insoluble and water
dispersible materials such as sulphates, carbonates,
phosphates, polyphosphates, silicas, silicates, clays,
starches, aluminosilicates.
If the carrier materials do not contribute to the
efficiency or activity of the powder detergents, however,
they are seen as additional components which will, in
effect, constitute an additional soil which has to be
removed during the laundering process. As a result, it is
preferred to use carriers which are standard components in
detergent powder compositions. Particularly preferred
carriers are those which generate a basic pH in water. They
include, for example, calcium carbonate, sodium
tripolyphosphate, silicate , aluminosilicate, sodium
citrate, sodium hydrogen carbonate and sodium carbonate.
It has been observed that the use of a carrier material
which generates a basic pH in water in combination with a
silicone antifoam in a detergent powder composition causes
the antifoam to lose its efficiency on storage. This is
particularly so when the silicone antifoam is based on
branched silicone polymers. It is believed that the carrier
contributes to the antifoam degradation and this degradation
increases with prolonged time of storage.
It is desirable to provide foam control agents which
have improved stability during storage in powder detergent
compositions, particularly where materials which provide a
basic pH in water are used as carrier materials.
The present invention provides in one of its aspects a
particulate foam control agent comprising a silicone
antifoam adsorbed on particles of a solid carrier which
generates a basic pH when contacted with water,
characterized in that the particulate foam control agent
also comprises an alkyl saccharide.
The silicone antifoams used herein are known materials
and many have been described in patent specifications.
These antifoams generally comprise a liquid
organopolysiloxane polymer and a filler particle, the
surface of which has been rendered hydrophobic.
The liquid organopolysiloxane polymers which are useful
in silicone antifoams are also known and have been described
in many patent specifications. Full description of all
options is, therefore, not included but can be found in many
publications including European application EP 0578424.
The liquid organopolysiloxane can be linear or branched
and can have a structure according to the general formula:
wherein R denotes a monovalent hydrocarbon group having from
1 to 8 carbon atoms , R
1 denotes a group R, a hydroxyl group
or a group
wherein R
2 denotes a divalent hydrocarbon, hydroxycarbonoxy
or siloxane group or oxygen and Y denotes a group R or a
hydroxyl group, R
3 denotes a C
9-35 alkyl group ,
a,
b,
c, and
d, have a value of 0 or an integer, provided that at least
one of
a and
b is an integer and the total of
a+b+c+d has a
value such that the viscosity of the organopolysiloxane
polymer is at least 50mm
2/s at 25°C, preferably at least
500mm
2/s.
The preferred linear organopolysiloxanes is one having
the above formula in which R1 denotes R or a hydroxyl group.
The preferred non-linear organopolysiloxanes are those
having branching in the siloxane chain and have the above
structure in which b has a value of at least 1 and R2 is
preferably a divalent siloxane group or an oxygen atom.
Particularly preferred siloxane groups R2 are small three-dimensional
siloxane resin particles which may have a number
of pendant siloxane polymer units.
Suitable branched siloxanes and methods for their
manufacture are known in the art and examples have been
described in a number of patent specifications such as
GB 639 673, EP 031 352, EP 217 501, EP 273 448, DE 38 05 661
and GB 2 257 709.
The most preferred liquid organopolysiloxanes are
branched siloxanes because they show an improved ability to
control foam in many aqueous surfactant solutions.
Filler particles which are useful in the antifoams of
the present invention are also well known and have been
described in many publications. They are finely divided
particulate materials including, for example, silica, fumed
TiO2, Al2O3, zinc oxide, magnesium oxide, salts of aliphatic
carboxylic acids, reaction products of isocyanates with
certain materials such as cyclohexylamine, alkyl amides such
as ethylene or methylene bis stearamide.
The most preferred fillers are silica particles with a
surface area of at least 50m2/g as measured by BET.
Suitable silica particles may be made according to any of
the standard manufacturing techniques, for example, thermal
decomposition of a silicon halide, decomposition and
precipitation of a metal salt of silicic acid, e.g. sodium
silicate and a gel formation method. Suitable silicas for
use in the antifoams include, therefore, fumed silica,
precipitated silica and gel formation silica.
The average particle size of the fillers in this
invention may range from 0.1 to 20 micrometers, but
preferably is from 0.5 to 2.5 micrometers.
If the filler particles are not hydrophobic by nature,
their surface is rendered hydrophobic to make the antifoam
sufficiently effective in aqueous systems. The surface of
the filler may be rendered hydrophobic either prior to or
after dispersing the filler particles in the liquid
organopolysiloxane.
To render the fillers hydrophobic, they are treated
with treating agents such as reactive silanes or siloxanes.
Examples of treating agents include dimethyldichlorosilane,
trimethylchlorosilane, hexamethyldisilazane, hydroxyl end-blocked
and methyl end-blocked polydimethylsiloxanes,
siloxane resins, fatty acids or a mixture of one or more of
these.
Fillers which have been treated with such treating
agents are commercially available from many companies e.g.
Sipernat® D10 from Degussa.
If the surface of the filler is to be rendered
hydrophobic in situ, i.e. after the filler has been
dispersed in the liquid organopolysiloxane component, it is
accomplished by adding the appropriate amount of treating
agent to the liquid organopolysiloxane prior to, during or
after the dispersion of the filler therein and heating the
mixture to a temperature above 40°C.
The quantity of treating agent to be employed will
depend, for example, on the nature of the agent and the
filler. This amount will be evident or ascertainable by
those skilled in the art. Sufficient should be employed to
endow the filler with at least a discernible degree of
hydrophobicity.
The filler particles are added to the
organopolysiloxane in an amount of from 1 to 25% by weight
of the antifoam, preferably from 1 to 20%, most preferably
from 2 to 8%.
Alkylsaccharides are known in the art. They comprise
an alkyl chain linked to a sugar through an ether group
according to the general formula Z -O -R4, where R4 is the
alkyl chain having from 8 to 20 carbon atoms and Z is the
sugar.
The sugar may be a mono-, oligo- or polysaccharide.
Monosaccharides are known in the art and include groups
comprising glucose, mannose, galactose, fructose.
Oligosaccharides comprise, for example, sucrose, maltose,
cellobiose, isomaltose, and lactose. Polysaccharides
comprise, for example, amylose, amylopectin and
polyglucamide.
Preferred alkylsaccharides are material made of pentose
or hexose units or a combination of both. The most
preferred alkylsaccharides are made of sucrose, for example,
alkylsucrose according to a general formula:
where R
5, R
6, R
7 are the same or different alkyl chains
having from 8 to 20 carbon atoms, preferably 8-18 or a
hydrogen.
The alkylsaccharides herein are preferably made of
glucose units according to the general formula:
where R
8 is an alkyl chain as already defined, preferably
having 8 to 18 carbon atoms, more preferably 12 to 18 carbon
atoms, most preferably 12 to 14 or 16 to 18 carbon atoms and
n= 1, 2 or 3.
Commercial alkylpolyglucoside can also include
geometrical isomers. Mixtures of alkylpolyglucoside with
n=1.1 to 3 are commonly available.
Preferred alkylpolyglucoside for use in the present
invention have preferably 2 glucose units according to the
general formula
where R
8 is as already defined.
The carriers herein are known in the art and many are
standard components in detergent powder compositions.
Particularly preferred carriers are those which generate a
basic pH in water. They include, for example, calcium
carbonate, sodium tripolyphosphate, silicate ,
aluminosilicate, sodium citrate, sodium hydrogen carbonate
and sodium carbonate
A foam control agent according to the invention
exhibits the advantages of high dispersibility in water and
good storage stability.
The invention provides in another of its aspects a
detergent composition in powder form comprising 100 parts by
weight of a detergent component and sufficient particulate
foam control agent described above to give 0.01 to 20 parts
by weight silicone antifoam in the detergent composition.
Suitable detergent components are well known in the art
and have been described in numerous publications. These
comprise active detergents, organic and/or inorganic builder
salts and other additives and diluents.
The active detergent may comprise organic detergent
surfactants of the anionic, cationic, non-ionic or
amphoteric type, or mixtures thereof. Suitable anionic
organic detergent surfactants include alkali metal soaps of
higher fatty acids, alkyl aryl sulphonates, for example
sodium dodecyl benzene sulphonate, long chain (fatty)
alcohol sulphates, olefine sulphates and sulphonates,
sulphated monoglycerides, sulphated esters,
sulphosuccinates, alkane sulphonates, phosphate esters,
alkyl isothionates, sucrose esters and fluoro-surfactants.
Suitable cationic organic detergent surfactants include
alkylamine salts, quaternary ammonium salts, sulphonium
salts and phosphonium salts.
Suitable non-ionic detergent surfactants include
condensates of ethylene oxide with a long chain (fatty)
alcohol or (fatty) acid, for example, C14-15 alcohol,
condensed with 7 moles of ethylene oxide (Dobanol® 45-7),
condensates of ethylene oxide with an amine or an amide,
condensation products of ethylene and propylene oxides,
fatty acid alkylol amide and fatty amine oxides.
Suitable amphoteric organic detergent surfactants
include imidazoline compounds, alkylaminoacid salts and
betaines.
Examples of inorganic components are phosphates,
polyphosphates, silicates, carbonates, sulphates, oxygen
releasing compounds such as sodium perborate and other
bleaching agents and alumino-silicates, e.g. zeolites.
Examples of organic components are anti-redeposition
agents such as carboxymethylcellulose (CMC), brighteners,
chelating agents such as ethylene diamine tetra-acetic acid
(EDTA) and nitrilotriacetic acid (NTA), enzymes and
bacteriostats.
Other optional components include colorants, dyes,
perfumes, softeners, and clays, some of which may be
encapsulated.
Materials suitable for the detergent component are well
known to the person skilled in the art and are described in
many text books as well as other publications.
There is also provided in a third aspect of the present
invention a method of making a particulate foam control
agent comprising a silicone antifoam absorbed on particles
of a solid carrier which generates a basic pH when contacted
with water, characterized in that the method comprises a
step of depositing an alkylsaccharide onto the carrier not
later than depositing the silicone antifoam onto the
carrier.
A fourth aspect of the present invention is to provide
a use of alkylsaccharide as a stabilising additive in a
particulate foam control agent which comprises a silicone
antifoam absorbed on particles of a solid carrier which
generates a basic pH when contacted with water.
The foam control agents made according to the invention
are useful in any powdered surfactant composition where foam
levels need to be controlled, e.g. in laundry detergents and
in dishwasher detergents.
The foam control agent according to the invention has
effects on the detersive activity when added to the final
composition of a detergent powder. No spotting due to the
carrier on the laundered fabrics is observed.
There now follow a number of examples to illustrate the
invention in which all parts and percentages are given by
weight unless otherwise indicated.
EXAMPLES 1-15
1. Preparation of foam control agents.
Foam control agent FCA1 to FCA15 were prepared by
mixing x parts of sodium carbonate manufactured by Solvay
SODASOLV®L with a mixture of y parts of a silicone antifoam
A and z parts of ingredient Z .
Silicone antifoam A comprised a branched polydimethyl
siloxane polymer and 5% hydrophobic silica, and was prepared
according to the teaching of EP 217 501.
A mixture was prepared by pure mechanical mixing of the
silicone antifoam and ingredient Z and pouring the mixture
very slowly into a drum mixer in which the carbonate of
sodium was placed. The mixture was stirred continuously
until a particulate material was obtained. The particulate
material was subsequently passed through an Aeromatic® spray
granulator over a period of 20 minutes at 80°C.
Ingredient Z was selected from a polycarbonate
copolymer (maleic/acrylic acid) supplied as a 40% aqueous
solution under the name Sokalan® CP5 referred to as CP5, a
hydroxypropylcellulose prepared as a 20% aqueous solution,
and supplied under the name Klucel®, a polyvinylpyrrolidone
prepared as a 50% aqueous dispersion, called PVP below, a
secondary alkyl sulphonate supplied by Hoechst under the
name Hostopur® SAS60 referred to as SAS60, an
alkylpolyglucoside with a degree of polymerisation of from
1.1 to 3 and a C8-18 hydrocarbon tail supplied as a 50%
dispersion in water by Henkel under the name Glucopon® 600
CS UP referred to as Glucopon, a di-fatty acyloxyethyl
ammonium methosulphate sold as a 70% dispersion in water
under the name HOE S4039 and an alkyl amidodimethyl amine
betaine, supplied as a 30% dispersion in water under the
name Empigen BS/F.
Details of the foam control agents FCA1 to FCA15 are
given below in table 1.
Foam control agent composition |
FCA | Z | z | x | y |
FCA1 | --- | - | 90 | 10 |
FCA2 | CP5 | 14 | 76 | 10 |
FCA3 | PVP | 10 | 80 | 10 |
FCA4 | Klucel | 8 | 82 | 10 |
FCA5 | Hoe S4039 | 16 | 74 | 10 |
FCA6 | Empigen BS/F | 6.5 | 82.5 | 11 |
FCA7 | SAS60 | 13 | 77 | 10 |
FCA8 | Glucopon | 7 | 83 | 10 |
FCA9 | Glucopon | 11 | 79 | 10 |
FCA10 | Glucopon | 15 | 75 | 10 |
FCA11 | Glucopon | 11 | 70 | 10 |
CP5 | 9 |
FCA12 | SAS60 | 10 | 79 | 8 |
CP5 | 3 |
FCA13 | Glucopon | 3 | 84 | 10 |
CP5 | 3 |
FCA14 | Glucopon | 7 | 69 | 10 |
CP5 | 14 |
FCA15 | Glucopon | 9 | 81 | 9 |
Klucel | 1 |
2. Preparation of powder detergent composition.
A powder detergent composition was prepared by mixing
together 30 parts of zeolite Wessalith® CD, 20 parts of
sodium carbonate, 7.5 parts of sodium sulphate, 12.5 parts
of dodecyl benzene sulphonate, 10 parts of a non-ionic
surfactant made by the condensation of a C14-15 alcohol with 7
moles of ethylene oxyde and 20 parts of sodium perborate
monohydrate. To 100g lots of the detergent composition was
added sufficient foam control agent of examples 1 to 15 to
give 0.1 g of antifoam, thus forming Lot 1 to Lot 15.
3. Testing of the release in the washing cycle
A conventional automatic front-loading washing machine,
having a transparent loading door, was loaded with 3.5kg of
clean cotton fabric. A wash cycle with a main wash (90°C)
was carried out with each of the lots prepared above. The
door of the washing machine was indicated with four measures
at 25, 50, 75 and 100% of its height respectively indicated
below as 1, 2, 3 or 4, 0 indicating there is no foam
present, 5 indicating the drum is filled with foam and 6
that liquour escapes from the washing machine through an
opening at the top of the machine. The foam height during
the wash cycle was recorded when the rotation drum of the
washing machine was stationary. Higher values indicate a
higher foam level in the machine and thus worse performance
of the foam control agent.
Table 2 shows the foam levels for each of the lots for
the first 20 minutes of the washing cycle. Lower levels in
this part indicate better release of the antifoam in the
washing liquor.
test results |
Foam height at | 0 | 5 | 10 | 15 | 20 minutes |
Lot 1 | 0 | 2 | 2 | 3 | 3 |
Lot 2 | 2 | 2 | 2 | 2 | 2 |
Lot 3 | 2 | 2 | 2 | 2 | 2 |
Lot 4 | 2 | 2 | 2 | 2 | 2 |
Lot 5 | 0 | 2 | 2 | 2 | 2 |
Lot 6 | 0 | 0 | 0 | 1 | 1 |
Lot 7 | 0 | 2 | 2 | 2 | 2 |
Lot 8 | 0 | 2 | 2 | 2 | 2 |
Lot 9 | 0 | 2 | 2 | 2 | 2 |
Lot 10 | 0 | 2 | 2 | 2 | 3 |
Lot 11 | 0 | 2 | 4 | 6 | 5 |
Lot 12 | 2 | 2 | 2 | 2 | 2 |
Lot 13 | 0 | 2 | 2 | 2 | 2 |
Lot 14 | 0 | 2 | 2 | 2 | 2 |
Lot 15 | 0 | 0 | 0 | 1 | 1 |
It is evident from these results that there is a
benefit in the release of the antifoam during the initial
stages of the wash cycle when the foam control agent
according to the invention is used.
A detergent composition identical to lot 1-15 were also
stored at 40°C for 4 weeks prior to testing. Tests results
are given in Table 3.
Tests results after storage at 40°C |
Foam height at | 0 | 5 | 10 | 20 | 30 | 40 | 50 minutes |
Lot 1 | 0 | 6 | 6 | 6 | 6 | 6 | 6 |
Lot 2 | 6 | 6 | 6 | 6 | 6 | 6 | 6 |
Lot 3 | 0 | 5 | 6 | 4 | 5 | 5 | 6 |
Lot 4 | 0 | 2 | 6 | 6 | 6 | 6 | 6 |
Lot 5 | 0 | 2 | 4 | 6 | 6 | 6 | 6 |
Lot 6 | 0 | 3 | 3 | 3 | 4 | 4 | 4 |
Lot 7 | 0 | 2 | 4 | 6 | 6 | 6 | 6 |
Lot 8 | 0 | 2 | 2 | 2 | 2 | 2 | 3 |
Lot 9 | 0 | 2 | 2 | 2 | 2 | 2 | 2 |
Lot 10 | 0 | 2 | 2 | 3 | 3 | 3 | 2 |
Lot 11 | 0 | 2 | 2 | 2 | 3 | 3 | 3 |
Lot 12 | 0 | 2 | 6 | 6 | 6 | 6 | 6 |
Lot 13 | 0 | 2 | 2 | 2 | 3 | 2 | 3 |
Lot 14 | 0 | 2 | 3 | 3 | 3 | 3 | 3 |
Lot 15 | 0 | 1 | 2 | 2 | 2 | 2 | 3 |
It is clear from the results that the storage stability
of the foam control agent is improved by using alkyl
polyglucoside as surfactant in the FCA.
EXAMPLES 16-26 use sodium hydrogen carbonate as the solid
carrier
1. Preparation of foam control agents.
Foam control agent FCA16 to FCA26 were prepared by
mixing x parts of sodium hydrogen carbonate manufactured by
Solvay with a mixture of y parts of a silicone antifoam A
and z parts of one of the ingredient Z.
The mixture was prepared as in examples 1-15 except
that carbonate of sodium is replaced by sodium hydrogen
carbonate.
The ingredient Z is as described above for examples 1-15.
Details of the foam control agents FCA16 to FCA26 are
given below in table 4.
FCA | Z | z | x | y |
FCA1 6 | --- | - | 90 | 10 |
FCA17 | PVP | 6 | 88 | 6 |
FCA18 | Klucel | 2 | 92 | 6 |
FCA19 | Hoe S4039 | 10 | 84 | 6 |
FCA20 | Empigen BS/F | 4 | 90 | 6 |
FCA21 | SAS60 | 7 | 87 | 6 |
FCA22 | Glucopon | 5 | 90 | 5 |
FCA23 | SAS60 | 6 | 88 | 5 |
CP5 | 1 |
FCA24 | Glucopon | 4.5 | 89 | 4.5 |
CP5 | 2 |
FCA25 | Glucopon | 5 | 89 | 5 |
Klucel | 1 |
FCA26 | Glucopon | 4.5 | 90 | 4.5 |
CP5 | 1 |
2. Preparation of powder detergent composition.
A powder detergent composition was prepared as in
Examples 1-15, giving Lot 16 to Lot 26.
3. Testing of the release in the washing cycle
Table 5 shows the foam levels for each of the lots for
the first 20 minutes of the washing cycle. Lower levels in
this part indicate better release of the antifoam in the
washing liquor.
test results |
Foam height at | 0 | 5 | 10 | 15 | 20 minutes |
Lot 16 | 0 | 2 | 2 | 2 | 2 |
Lot 17 | 0 | 2 | 2 | 2 | 2 |
Lot 18 | 0 | 2 | 2 | 2 | 2 |
Lot 19 | 0 | 2 | 2 | 2 | 2 |
Lot 20 | 0 | 0 | 1 | 1 | 2 |
Lot 21 | 0 | 2 | 2 | 2 | 2 |
Lot 22 | 0 | 1 | 1 | 2 | 2 |
Lot 23 | 0 | 2 | 2 | 2 | 2 |
Lot 24 | 0 | 2 | 2 | 2 | 2 |
Lot 25 | 0 | 2 | 2 | 2 | 2 |
Lot 26 | 0 | 2 | 2 | 2 | 2 |
It is evident from these results that there is an
improvement in the release of the antifoam during the
initial stages of the wash cycle when the foam control
agent is used with alkylpolyglucoside only (Lot 22).
Detergent compositions identical to Lots 16-26 were
also stored at 40°C for 4 weeks prior to testing. Tests
results are given in Table 6.
tests results after storage at 40°C |
Foam height at | 0 | 5 | 10 | 20 | 30 | 40 | 50 |
Lot 16 | 0 | 4 | 6 | 6 | 6 | 6 | 6 |
Lot 17 | 0 | 4 | 6 | 6 | 6 | 6 | 6 |
Lot 18 | 0 | 4 | 6 | 6 | 6 | 6 | 6 |
Lot 19 | 0 | 3 | 4 | 5 | 3 | 5 | 3 |
Lot 20 | 2 | 2 | 3 | 4 | 4 | 4 | 6 |
Lot 21 | 0 | 6 | 6 | 6 | 6 | 6 | 6 |
Lot 22 | 0 | 1 | 1 | 2 | 2 | 3 | 3 |
Lot 23 | 0 | 6 | 6 | 6 | 6 | 6 | 6 |
Lot 24 | 0 | 2 | 2 | 2 | 2 | 2 | 3 |
Lot 25 | 0 | 2 | 3 | 3 | 3 | 3 | 3 |
Lot 26 | 0 | 2 | 2 | 2 | 3 | 3 | 3 |
It is clear that the storage stability of the foam
control agent is improved by using alkyl polyglucoside as
the surfactant in the FCA.