Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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DISHWASHING COMPOSITION
Field of the invention
The present invention relates to cleaning compositions, to their preparation,
to
cleaning methods and to processes for enhancing the retention of cleaning
agents
into carriers. More specifically, the invention relates to cleaning
compositions for use
in hand dishwashing.
Background prior art
Liquid household cleaning products that provide thickening upon dilution are
known in
the art, as detailed in the following references:
US 5,922,664 describes a composition comprising a micellar dispersion of a
mixture
of at least two anionic surfactants having different resistance to
electrolytic salting out,
and alkali metal citrate. The attained viscosity upon dilution does not go
beyond 1,400
mPas.
EP 314,232 mentions a composition of: (a) a primary surfactant chosen from
amine,
amine oxide, betaine or quaternary ammonium compounds, preferably an amine
oxide, (b) a hydrotrope co-surfactant compound, e.g. ethanol, methanol or
triethanol-
amine, and (c) a water-ionisable non-surfactant compound, e.g. inorganic
acids,
neutral salts or alkali.
WO 96/32464 discloses a kit comprising a sponge and a water-thickening
surfactant
composition based on electrolyte concentration. This document also shows the
viscosity profile of the disclosed compositions, wherein the viscosity peak
reaches
1,685 mPas, which is only 2.7 times higher than the initial viscosity of 620
mPas.
In short, prior art documents teach simple compositions that can reach high
viscosities upon dilution, improving its use in situations similar to manual
dishwashing.
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In co-pending application PCT/EP2006/007038, a dilution thickening system is
disclosed, based on a surfactant mixture and electrolyte.
However, prior art compositions present technical and/or economical
bottlenecks that
are solved by the present invention, such as obtaining cleaning compositions
having
enhanced retention in a carrier and/or high viscosity upon dilution, even at
high
dilution rates. Enhanced retention in the carrier provides controlled release
of the
composition.
Thus it is an object to provide a cleaning composition with enhanced retention
of its
cleaning agents (such as surfactants) in a carrier when being diluted.
It is another object of the invention to provide a composition with a lower
consumption
rate in use, thus giving better yield, being more economical in use and being
environmentally friendly, than the compositions of the prior art.
It is a further object to provide enhanced retention of cleaning agent in a
carrier,
thereby decreasing the time spent in refilling the carrier, so that the
cleaning
compositions are faster and more efficient in use.
It is yet another object of the invention to allow a more rational use of
containers for
cleaning compositions.
It has now been surprisingly found that an improved and economical dilution
thickening system may be obtained by a dilution-thickening surfactant system.
Summary of the invention
Accordingly, the invention provides A dilution-thickening aqueous liquid
cleaning
composition comprising 5-50%w of dilution-thickening surfactant system
comprising:
- 40-85%w Alkyl ether sulphate (0-4 EO)
- 0.01-50%w Linear alkylbenzene sulphonate; and
- 0.01-55%w Betaine;
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The invention further provides a method to clean hard surfaces comprising the
steps
of:
- contacting a carrier with a composition according to the invention;
- treating the combination of carrier and composition with water; and
- performing a cleaning operation of a surface with the carrier.
The invention further provides a dilution-thickening surfactant system
comprising:
- 40-85%w Alkyl ether sulphate (0-4 EO)
- 0.01-50%w Linear alkylbenzene sulphonate
- 0.01 -55%w Betaine;
adding up to a 100%.
The invention also provides the use of the dilution thickening surfactant
system of the
invention in a dish washing composition.
These and other aspects, features and advantages will become apparent to those
of
ordinary skill in the art from a reading of the following detailed description
and the
appended claims. For the avoidance of doubt, any feature of one aspect of the
present invention may be utilised in any other aspect of the invention. It is
noted that
the examples given in the description below are intended to clarify the
invention and
are not intended to limit the invention to those examples per se. Similarly,
all
percentages are weight/weight percentages unless otherwise indicated.
Numerical
ranges expressed in the format "from x to y" are understood to include x and
y. When
for a specific feature multiple preferred ranges are described in the format
"from x to
y", it is understood that all ranges combining the different endpoints are
also
contemplated.
Description of the figure
Figure 1 shows a ternary diagram of the dilution-thickening surfactant system
of the
invention. The shaded area shows the preferred concentrations of the three
ingredients of the dilution-thickening surfactant system of the invention. The
dashed
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line in the ternary diagram shows the approximate boundary for structured
liquids on
the bottom/right side of the dashed line and non-structured liquids on the
top/left side
of the dashed line. The double headed arrow shows performance vs cost;
although
the dilution thickening effect is obtained everywhere in the shaded area, the
performance and cost increase towards the right side.
Detailed description of the invention
The invention provides a dilution-thickening surfactant system and cleaning
compositions using the same.
The most suitable cleaning compositions have a low viscosity in concentrated
form
(i.e. in the bottle), and a high viscosity when diluted on the application
device, such as
a sponge; eventual the composition is released by application to a surface.
Dilution-thickening surfactant system
The thickening surfactant provides a surfactant system that has a low
viscosity in
concentrated form, and increasing viscosity when diluting up to a maximum
viscosity
(or a viscosity peak) and a decreasing viscosity upon further dilution.
The dilution-thickening surfactant system comprises alkyl ether sulphate (AES)
optionally ethoxylated with 0-4 EO groups, linear alkyl benzene sulphonate
(LAS) and
betaine. Depending on the market a low-cost or premium dilution thickening
system
may be preferred as indicated herein below.
The dilution-thickening surfactant system is preferably not a structured
liquid. It is
also preferred that the composition is clear and transparent. Cloudy or hazy
compositions are not preferred.
Alkyl ether sulphate
The alkyl ether sulphates as defined herein are alkali metal, ammonium or
alkanolammonium salts of C8-C18 alkyl ether sulfates with 0 to 25 moles of
alkylene
oxide (thus also including C8-C18 alkyl sulfates). The alkyl ether sulphates
may be
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linear or branched. A common example of an alkyl ether sulphate is lauryl
ether
sulphate, preferably sodium lauryl ether sulphate (SLES).
The alkyl ether sulphate is present in the dilution-thickening surfactant
system in a
5 concentration of at least 40%, preferably at least 50%, more preferably at
least 55%
by weight, but not more than 85%, preferably not more than 70%.
Betaine
Betaines are a class of zwitterionic surfactants. The preferred betaines are
carboxybetaines such as (dodecyldimethylammonium)acetate (lauryl betaine),
(tetradecyldimethylammonium)acetate (myristyl betaine),
(cocodimethylammonium)acetate (coconut betaine), (oleyldimethylammonium)
acetate (oleyl betaine), (dodecyloxymethyldimethylammonium) acetate,
(cocoamido-
propyldimethylammonium)acetate (also known as cocoamido-propyl betaine or
CAPB); the sulfoniumbetaines such as (dodecyldimethylsulfonium) acetate and 3-
(cocodimethyl-sulfonium)-1-propane sulfonate and the phosphoniumbetaines such
as
4-(trimethylphosphonium)-1-hexadecane sulfonate, 3-
(dodecyldimethylphosphonium)-
1 -propanesulfonate, 2-(dodecyldimethylphosphonium)-1 -ethane sulfate and
mixtures
thereof.
The betaine is present in the dilution-thickening surfactant system in a
concentration
of at least 0.01 %, preferably at least 5%, and for premium dilution-tickening
compostions even at least 10%, but not more than 55%, preferably not more than
35%, or for low cost dilution-thickening compositions even not more than 20%.
LAS
The third ingredient of the dilution thickening is linear alkylbenzene
sulphonate (LAS).
LAS is present in the dilution-thickening surfactant system in a concentration
of 0.01-
50%w. In order to obtain the premium dilution-thickening effect, a LAS
concentration
of 0.1-35%w is preferred. In order to get an economical composition, with a
good
dilution thickening effect at lower cost, a concentration of 25-45%w is
preferred. A
balance between premium performance and cost is found at the intermediate
range of
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15-25%w of LAS.
Aqueous liquid cleaning composition
The aqueous liquid cleaning compositions according to the invention, comprise
the
dilution-thickening surfactant system of the invention in a concentration of 5
- 50%w,
preferably at least 10%w, more preferably at least 15%w, still more preferably
at least
20%w, most preferably 25%w, but preferably not more than 40%w, more preferably
not more than 35%w, most preferably not more than 30%w.
When used in the cleaning composition, the dilution-thickening surfactant
system
provides a viscosity profile of the cleaning composition showing low viscosity
at high
concentration (towards 100%) as well as low viscosity on high dilution
(towards 0%),
but a viscosity peak somewhere in between. The profile normally has the shape
of a
bell-curve.
The dilution-thickening surfactant system of the invention provides the shape
of the
curve, and is very suitable for use in a liquid cleaning composition. However,
to
improve the versatility of the composition, it is preferred to be able to
influence the
position of the peak, dependent on the concentration. In other words, it is
preferred to
be able to influence the position of the peak on the concentration scale.
Preferably the
peak viscosity of the diluted composition is reached at a concentration of
surfactant
system in diluent (such as water) between 30% and 70%, more preferably between
30% and 50% surfactant system in diluent. Furthermore, it is preferred that
the peak
viscosity is at least 5 times the initial viscosity, preferably at least 10
times.
Thus, the aqueous liquid cleaning composition may further comprise viscosity
modulating agents. The low viscosity in concentrated form helps the
composition to
easily penetrate a carrier, such as a sponge. Preferably, the undiluted
composition
has a viscosity below 1500mPas, more preferably 800-1250 mPas. Wherein the
viscosity is determined at 25 C, using a Haake VT550/VT500 viscometer at 21 s-
'
with an MVII spindle.
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Electrolyte
In order to influence the position of the peak on the concentration scale,
i.e. to move
the peak between high and low concentration, the cleaning composition of the
invention may comprise an electrolyte.
Electrolytes are water-soluble organic and inorganic salts (other than anionic
surfactants), wherein the cation is chosen from alkali metals, alkaline earth
metals,
ammonium and mixture thereof and the anion is chosen from chloride, sulfate,
phosphate, acetate, nitrate and mixtures thereof. Particularly useful are
Magnesium,
potassium, sodium and ammonium chloride and/or sulphate.
Preferably, the electrolyte is present in the cleaning composition in a
concentration of
0-7.5%, more preferably 2.5-5%, still more preferably 3-4% by weight.
Viscosity modifying agent
In order to influence the viscosity of the cleaning composition, without
moving the
position of the peak on the concentration scale, a viscosity modifying agent
may be
added.
One suitable class of viscosity modifying agents is the class of nonionic
surfactants.
Nonionic surfactants reduce the viscosity of the concentrated cleaning
composition,
without moving the peak on the concentration scale.
The nonionics of the invention preferably have a HLB value (the
hydrophilic/lipophilic
balance) of at least 8, preferably at least 10, more preferably at least 12,
but
preferably not more than 16.
Suitable nonionic surfactants include the condensation products of hydrophobic
alkyl,
alkenyl, or alkyl aromatic compounds bearing functional groups having free
reactive
hydrogen available for condensation with hydrophilic alkylene oxide, such as
ethylene
oxide, propylene oxide, butylene oxide, polyethylene oxide or polyethylene
glycol to
form nonionic surfactants. Examples of such functional groups include hydroxy,
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carboxy, mercapto, amino or amido groups.
Examples of useful hydrophobes of commercial nonionic surfactants include C$-
C1$
alkyl fatty alcohols, C$-C14 alkyl phenols, C$-C1$ alkyl fatty acids, C$-C1$
alkyl
mercaptans, C$-C1$ alkyl fatty amines, C$-C1$ alkyl amides and C$-C1$ alkyl
fatty
alkanolamides. The polyoxyalkylene condensation products of such materials may
comprise from 1 to 30 alkylene oxide groups, preferably from 5 to about 20
alkylene
oxide groups, even more preferably from 8 to about 12 alkylene oxide groups.
Accordingly, suitable ethoxylated fatty alcohols may be chosen from
ethoxylated cetyl
alcohol, ethoxylated ketostearyl alcohol, ethoxylated isotridecyl alcohol,
ethoxylated
lauric alcohol, ethoxylated oleyl alcohol and mixtures thereof.
Alternatively compounds from the group of propylene glycols, ethoxylated
glycerols,
and/or ethanol may be used as viscosity modifying agent. The most preferred
propylene glycol is MPG (mono propylene glycol). The preferred ethoxylated
glycerols
have 3-15 ethylene oxide (EO) groups, more preferably 5-10 ethylene oxide
groups.
Alternatively, this viscosity reducing effect may be obtained by the addition
of other
short chain organic alcohols. These solvents would have the same viscosity
reducing
effect as the nonionic surfactant, but are not preferred because they are
considered
"volatile organic compounds". Volatile organic compounds are not preferred in
the
context of the present invention.
Thus, nonionic surfactants are preferred in the cleaning compositions of the
inventions, as they also have detergent properties.
Another commonly used ingredient in cleaning compositions are hydrotropes.
Hydrotropes reduce the dilution thickening effect according to the invention.
It is
preferred to avoid hydroptropes such as sodium cumene sulphonate (SCS), sodium
xylene sulphonate (SXS), anionic hydroptropes and polyethylene glycols.
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Generally, the viscosity modifying agent reduces the viscosity of the
composition over
the entire concentration scale. The viscosity modifying agent is optionally
present in
the cleaning composition in a concentration of 0-5%, preferably 0.1-2%, more
preferably 0.5-1.5%.
Further surfactants
The compositions my further comprise surfactants. However, such surfactant may
have no or limited influence on the dilution thickening behaviour of the
composition.
Preferably said further surfactants do not move the peak more than 10% on the
concentration scale and do not reduce or increase the peak viscosity by more
than
20%. The cleaning compositions of this invention may further comprise selected
from
anionic, amphoteric, zwitterionic and nonionic surfactants and combinations
thereof.
Cationic surfactants are not preferred.
Suitable further surfactants are described in "Surface Active Agents" Vol. 1,
by
Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch,
Interscience
1958, in the current edition of "McCutcheon's Emulsifiers and Detergents"
published
by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache,
2nd Edn., Carl Hauser Verlag, 1981.
Optional Ingredients
The compositions of the invention optionally comprise other ingredients, such
as
fragrances, preservatives and colorants. Particularly colorants are useful to
indicate
the presence of the compositions in an absorbent carrier. Examples of useful
colorants are: Blue FDC (CI:42090); Patent blue (CI:42051); Blue ABL 80
(CI:61585);
Red punzo No 7(CI:16255), Red Puricolor Are 14 (CI: 14720), Yellow Tartrazine
CI
14190, Quinoline Yellow 47005, Brillant Black 28440,Sunset yellow Cl 15985,
and
mixtures thereof.
The present invention also discloses a method for cleaning domestic surfaces,
particularly hard surfaces, using the cleaning compositions according to the
invention.
The cleaning method of the invention has several advantages over known
methods.
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In one aspect, it provides less consumption of cleaning composition and is
therefore
more economical and environmentally friendly.
The cleaning method of the invention comprises the steps of:
5 i) contacting a carrier with the composition of the invention;
ii) treating the combination of carrier and composition with water; and
iii) performing a cleaning operation of a surface with the carrier.
In an alternative, but less preferred variation, water can be added to the
absorbent
10 carrier before the composition is added to it.
A cleaning operation is typically represented by pressing the absorbent
carrier to the
surface and scrubbing it with circular movements, or in any other way, to aid
in the
removal of soil, grease or dirt from the surface. Dish surfaces and crockery
are
particular examples of household surfaces that can be cleaned with the
composition
of the invention.
Useful absorbent or porous carriers are known, particularly the ones
comprising voids
where liquid can be stored, for instance, sponges (natural, polymeric, steel,
etc),
scouring pads, cloths. The composition is particularly suitable to be applied
onto
sponges in the cleaning method.
The ratio between the amount of water and the amount of cleaning composition
to be
used in the cleaning method according to the invention is preferably from
about 0.5 to
about 5, more preferably about 0.5-4, most preferably up to about 3.5.
The invention further provides a process for enhancing the retention of
cleaning
agents into a carrier comprising the steps of:
a) providing a solution of surfactants;
b) providing a solution of viscosity modulating agent;
c) mixing the solution of surfactants with the solution of viscosity
modulating
agent.
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Application methods and use
For hand dishwashing application of the cleaning compositions, such
compositions
preferably have a low viscosity initially and only increase in viscosity after
addition of
a certain amount of diluent. This allows penetration of the composition
through the
pores of a porous carrier (e.g. a sponge), while at the same time keeping the
composition within the carrier for a longer period. The selective way by which
the
composition of the invention behaves provides an advantageous balance between
low initial viscosity, maximum viscosity and final viscosity, as well as
provides an
advantageous balance between viscosity increasing ratio (between minimum and
maximum viscosity) and viscosity decreasing ratio (between maximum and final
viscosity).
In a preferred embodiment, the cleaning compositions of the invention comprise
a
dilution-thickening surfactant system and viscosity modulating agents and
other
optional ingredients and provide:
- low initial viscosity so as to easily penetrate into a carrier;
- viscosity increase upon dilution after penetrating into said carrier, so
that the
cleaning compositions stay longer within the carrier, thus providing enhanced
performance even after repeatedly rinsing;
- on dilution the cleaning composition becomes a stable and transparent gel;
and
- controlled and sustained release of surfactants.
In another aspect there is provided a cleaning method for surfaces,
particularly hard
surfaces, which is more efficient and economic than the previously known
cleaning
methods.
In yet another aspect there is provided a process for enhancing the retention
of
cleaning agents into carriers such as sponges and the like.
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The invention provides dilution-thickening aqueous liquid cleaning
compositions
comprising:
- one or more surfactants;
- one or more viscosity modulating agents.
More specifically, the invention provides dilution-thickening aqueous liquid
cleaning
compositions comprising:
- one or more surfactants;
- at least one electrolyte as a viscosity modulating agent.
The invention will now be illustrated by means of the following non limiting
examples.
Examples
These examples show the performance the compositions of the invention vis-a-
vis the
prior art.
Example 1
In example 1, the controlled release of the composition according to the
invention is
compared to commercially available products.
The composition according to the invention is given in the table below
Ingredient Trade name Supplier %w
Sodium lauryl ether sulphate C12-C13 2 EO Texapon S 70 Cognis 15.5
(Ex Neodol 23)
Fatty Alcohol Ethoxylated (C12-C13 8E0) Neodol 91-8 Shell 1
Coco Amido Propyl Betaine Empigen BS/FE Huntsman 3
LAS (acid form) in HOME 8.5
Magnesium Sulphate MgSO4.7HZO K&S 4.5
Minors 3
Demin Water 64.5
pH 5.5
Viscosity (as is, mPa.s @20s 1000
~) Minors are pH adjustment materials, perfume, dye and preservative
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The commercial products tested are Dixan (ex Henkel, purchased in Italy 27
February
2006), Fairy (ex Procter&Gamble, purchased in UK 1 September 2005) Sole (ex
Reckitt Benckizer, purchased in Italy 12 April 2006) and Last (ex Bolton
Manitoba,
purchased in Italy 20 April 2006), see table below for an analysis of the
compositions.
Ingredient (%w) Dixan gel Fairy Sole Last
Linear alkylbenzone sulphonate 5.0 9.6
Secondary alkane sulphate 2.2
C12-14 PAS 7.8
Alkyl ether sulphate (C12-13, 1 EO) 9.8 15.8 5.0 2.0
Alkyl amido-propyl betaine 2.0
C12-16 Alkyl dimethyl amine oxide 5.6 0.1
Alcohol ethoxylate (C9-C11, 8E0) 3.0
Sodium chloride 2.0 1.1 1.6 1.3
Sodium sulphate 0.2 0.1 0.1 0.12
Magnesium sulphate 0.07
Minors rest rest rest rest
Water 83.4 62.3 87.6 86.3
pH (as is) 4.9 8.2 7.7 7.4
Viscosity (as is, mPa.s @20s ) 345 475 312 234
Chain lengths and degree of ethoxylation are estimated; Minors include dye,
perfume, solvents, preservatives etc
To determine the active dosing of the material 1 g of one of the compositions
was
applied directly onto a wet sponge suitable for cleaning dishes. The sponge
was then
rinsed with 50 ml demin water aliquots, by method of adding 50 ml of water to
the
sponge, squeezing the sponge and collecting the water. This was repeated with
several aliquots of 50 ml water until no more detergent was released from the
sponge.
The collected water was analysed to determine the concentration of released
detergent product. And the amount of remaining active was calculated by
deducting
the measured amount of detergent product in each rinse from the starting
amount and
calculating the remain amount on the sponge. The results are given in the
table
below.
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% active on sponge
rinsing step water (ml) Comp 1 Dixan Fairy Sole Last
0 0 100 100 100 100 100
1 50 90 37 74 42 8
2 100 83 19 56 13 2
3 150 75 8 38 4 2
4 200 66 3 27 2 1
250 54 1 19 1 1
6 300 42 1 12 0 1
7 350 31 1 7 0 0
8 400 23 1 5 0 0
9 450 16 0 3 0 0
500 10 0 2 0 0
11 550 8 0 1 0 0
12 600 6 0 1 0 0
13 650 4 0 0 0 0
14 700 2 0 0 0 0
750 1 0 0 0 0
As can be clearly seen from the results table above, the composition of the
invention
gives a much more controlled release of active during a greater number of
rinse
5 steps.
Example 2
In example 2, the viscosity profile of a number of compositions according to
the
invention is demonstrated.
The compositions of this example are given in the table below.
Product Ingredients
LAS LES Betaine NI MgS04.7H20
total actives % % % % %
Comp 2 32% 10.5 16.5 3 2 2
Comp 3 31% 10.5 16.5 3 1 2
Comp 4 32% 10.5 16.5 3 2 3
Comp 5 28.5% 9.15 15.4 3 0.95 2.5
Comp 6 25% 7.67 13.8 2.68 0.85 3
Comp 7 24.9% 8.75 13.75 2 0.4 4.5
*) Coco amidopropyl betaine
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In the table below, the viscosity of the product is given at different
dilutions. In this
table, 100% represents the neat undiluted product, while the other percentages
represent the percentage of product in water.
Viscosities un dilution mPa.s @20 s'
Composition 30% 40% 50% 60% 70% 100%
Comp 2 50 300 2880 5350 4350 1030
Comp 3 350 1750 4800 6150 4850 1150
Comp 4 100 420 2600 4650 2650 1090
Comp 5 100 560 3600 6100 6250 1000
Comp 6 100 640 3223 5390 4950 997
Comp 7 220 1730 5560 8350 6350 1130
5
The results clearly show that the viscosity of the product is relatively low
in undiluted
form and also low when diluted down to about 30%, but that the viscosity
between the
neat composition and the highly dilution form of the composition is very high.
10 Example 3
In example 3, the effect of an additional viscosity modifying agent (MPG,
composition
10) on the controlled release of the composition is demonstrated and compared
with a
similar composition without the additional viscosity modifying agent
(composition 9)
and a commercially available hand dish washing liquid (Lux Lemon). The
15 compositions are given in the table below.
Chemical name Comp 8 Comp 9 Comp 10
[%] [%] [%]
Sodium lauryl ether sulphate C12-C14 1E0 15.4 20
Sodium lauryl ether sulphate C12-C14 2E0 12
acid LAS ( MW 321) 20.7 8.56 8
alcohol ethoxylate 8 EO 0.95
alcohol ethoxylate 10 EO (Lialet 111-10EO) 1
Coco Amido Propyl Betaine 0.75 3 5
Sodium Hydroxide 2.2 1.3 0.95
MPG (mono propylene glycol) 5
Ethanol 4.3
Magnesium sulphate '7HZ0 4.5 5
Water 57 66.3 54.8
Minors (dye, perfume, preservative, etc) rest rest rest
pH (as is) 5.5 5.5 5.5
Viscosity (as is, mPa.s 20s Ca 1000 1000 1150
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The product release was tested with the method as given in example 1. The
release
results are given in the table below
rinsing step water (ml) Comp 8 Comp 9 Comp 10
0 0 100 100 100
1 50 73 90 96
2 100 49 83 92
3 150 30 75 87
4 200 19 66 80
250 11 54 73
6 300 8 42 65
7 350 6 31 58
8 400 4 23 49
9 450 2 16 39
500 2 10 31
11 550 1 8 24
12 600 1 6 17
13 650 1 4 11
14 700 0 2 5
750 0 1 0
5
As can be clearly seen from the results in the table above, the composition
with the
additional viscosity modifying agent gives an even more controlled release of
active
during a greater number of rinse steps.
