Note: Descriptions are shown in the official language in which they were submitted.
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HARD SURFACE CLEANING COMPOSITION
Technical Field
The present invention relates to a composition for hard
surface cleaning.
Background to the Invention
There is a general need for compositions which assist in the
removal of 'soap scum' and limescales from bathroom and
kitchen fittings and tiles. Limescale mainly comprises
calcium and magnesium carbonates, and can contain lesser
amounts of soap scum, protein, particulates and other soils.
Limescale is formed on evaporation of water containing said
soils. While the deposit formed by evaporation is initially
paste-like, it hardens with time to form a recalcitrant
deposit. Conventional cleaning compositions are generally
buffered at alkaline pH so as to attack fatty soils.
Limescale is resistant to the action of alkali and
specialist cleaning compositions, of acid pH, are generally
used to remove it. 'Soap-scum' is a deposit formed by the
reaction of soaps with metal ions. Soap-scum differs from
limescale in that it is removed better under alkaline
conditions and acid cleaners are generally poor at removing
soap-scum.
Although such compositions have been in existence for some
years, it has recently become apparent that many
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formulations have the ability to cause surface damage
either through enamel etching by acidic formulations or via
stress cracking of plastics induced by components, such as
solvents and nonionic surfactants which are typically
present in the cleaning compositions. There is
consequently a need for cleaning compositions which are
effective for the removal of limescale and other related
soils but which do not suffer from the above-mentioned
disadvantages.
Brief Description of the Invention
We have now determined that a well-defined group of
solvents at relatively low levels are particularly
effective solvents for soil removal in the presence of a
sequestering agent in combination with anionic surfactants
and/or alkyl poly glycoside nonionic surfactants and at
non-acidic pH.
Accordingly, the present invention provides a hard surface
cleaning composition of pH 7-13 comprising:
a) a surfactant selected from the group comprising
anionic sulphate, anionic sulphonate, alkyl poly
glycoside and mixtures thereof,
b) a sequestering agent for Group II metals and
c) a solvent selected from the group consisting of
hexanol, methyl digol, methanol and mixtures thereof.
Without wishing to limit the scope of the invention by
reference to any theory of operation, it is believed that
improved cleaning is obtained for example with short chain
AIb~111D~D StfEET
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nonionic surfactants which give low contact angles on
surfaces such as perspex. It is believed that these low
contact angle surfactants can wet the soil and allow the
penetration of the sequestering agent into to soil such that
the sequestering agent can attack the calcium bridges which
bind the soil together and to the surface.
However, short chain nonionic materials which are known for
their low contact angles are believed to be particularly
damaging to surfaces. The anionic and glycoside surfactants
employed in the compositions of the present invention are
believed to be less damaging but have high contact angles
and consequently wet soils and surfaces poorly. In the
compositions of the invention, it is believed that either
wetting is improved by the addition of, for example, hexanol
as solvent or that overall desorption of the soil particles
is effected by the addition of, for example, methanol.
It should be noted that for the series of short chain
alcohols there is considerable variation in the effect on
soil removal which these materials have. Detachment of soil
particles slows dramatically if methanol is replaced by
ethanol, propanol or butanol with the effect becoming
progressively larger until with butanol the desorption of
soil is actually worse than with no solvent at all. At
longer chain lengths the effect appears to be one of
improved wetting and penetration into the soil of the
solvent, surfactant and sequesterant which causes a break-up
of the soil particle rather than a desorption of the
particle as a whole. It is therefore believed that there
are at least two different mechanisms acting in the removal
of these soils, both of which show reduced efficacy with
alcoholic solvents in the range ethanol to butanol.
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Detailed Description of the Invention
The invention is described in further detail below with
especial reference to preferred features including levels
and natures of components.
Surfactants:
Typically, the compositions of the invention comprise total
surfactant levels of 2-80 on product, preferably around 40
on product. In this specification all levels of components
are given as %wt on product unless stated as otherwise.
Suitable anionic surfactants for use in the compositions of
the invention include: secondary alkane sulphonates, fatty
acid ester sulphonates, dialkyl sulphosuccininates, alpha-
olefin sulphonates, primary alkyl sulphates, alkylbenzene
sulphonates and alkyl ether sulphates.
The most preferred anionic is primary alkyl sulphate (PAS)
and this preferably comprises the major part (i.e. 500 or
more) of the surfactant present. Preferably the PAS
comprises a mixture of materials of the general formulation:
ROSO~M
wherein R is a CQ to C1,~ primary alkyl group and M is an
equivalent ration. This class of surfactant is not only
particularly efficient in cleaning hard surfaces but is also
readily broken down in the environment and can be obtained
from natural sources. The ration M is preferably an alkali
metal or ammonium or substituted ammonium. Sodium is
preferred as ration.
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We have found that combinations of methanol and/or methyl
digol and PAS show a much more rapid removal of soil
particles by desorption than other anionic detergents. No
such benefit is seen with cationic or nonionic surfactants.
While it might be suspected that the solvents are acting a
hydrotropes this particular benefit is not seen with other
hydrotropes when these replace the solvent.
Preferred alkyl polyglycosides (APG's) have an alkyl chain
comprising C<>_l6and it is preferred that more than 50owt of
the APG present in the compositions of the invention
comprises a C~,_,~ alkyl APG. It is particularly preferred
that the APG as a chain length of around C8. The preferred
degree of polymerisation is 1.1-1.6, more preferably 1.3-
1.5. Suitable materials include GLUCOPON 225 and GLUCOPON
600 (both RTM ex HENKEL). It was noted that compositions
which comprise both the APG surfactant and hexanol spread
over surfaces with particular ease to give very thin surface
films.
Where mixtures of anionics and APG's are used it is
preferred that the weight ratio of APG to anionic lies in
the range 1:10-10:1 as anionic:APG.
It is preferred that the compositions of the invention are
free of ethoxylated alcohol nonionic surfactants.
Sequestering Agents:
The sequestering agents present in the composition of the
invention are preferably organic and include the di and
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tricarboxylic .acids such as adipate, glutarate, succlnate,
maleate and citrate.
It is particularly preferred to use a sequestering agent
with a pK~~>5. Suitable sequestering materials include
nitrillo triacetic acid (NTA), methylglycine diacetic acid
(MGDA) and ethylene diamine tetraacetic acid (EDTA).
Preferred sequesterants are of the general formula:
R-CH(COOH)-N-(CH2COOH)2
where R=CH3, CH2COOH or CH20H.
MGDA is particularly preferred.
Typical levels of the sequestering agent in the compositions
of the invention are 1-l0owt, more preferably 2-7%wt, most
preferably 2.5-6 or around 4%wt on product.
Solvents:
Hexanol is the preferred solvent at levels of 0.5-20, more
preferably 0.5-l0. At levels of hexanol above 2o surface
damage can occur and usage at this level should be avoided
for surfaces which are sensitive to this solvent.
When methanol and/or methyl digol are used, solvent levels
can be 1-5%, with levels of 1-3o being preferred. Care
should be taken when using methanol due to it's toxicity and
flammability.
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It is particularly preferred that the compositions of the
invention are free of solvents selected from the group
comprising propylene glycol n-butyl ether and 2-butoxy
ethanol.
Thickeners:
We have found it be advantageous to thicken the products of
the invention so as to prevent run-off from sloping or
vertical surfaces. Preferred final product viscosities are
in the range 6-15 centipoise with viscosities of 8-10
centipoise being particularly preferred.
Preferred thickeners are polymers giving the required
viscosity provided that they are compatible with the ionic
strength of the composition. Preferably the thickeners are
non-charged polymers or nonionic/anionic saccharide
polymers. These are preferably polysaccharrides and
particularly xanthan gums and/or nonionic guar gums.
Materials sold under the tradename KELZAN are especially
suitable, as are materials sold under the tradename TYLOSE,
such as TYLOSE H4000P. Charged thickener species are less
preferred as these can salt out of solution, however it is
envisaged that charged polymers, for example polyacrylates
could be used when low levels of MGDA are present.
Typical levels of polymer are 0.05-0.50, preferably around
0.10. Polymer was found to be particularly effective in
maintaining a stiff foam in the products of the invention
which also contained APG.
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Minors:
Hydrotrope can be present in the compositions as required
to improve the low temperature stability of the
composition. Suitable hydrotropes include the aromatic
sulphonates, particularly benzene, toluene and cumene
sulphonates at preferred levels of 0-6%wt, more preferably
1-2° .
pH regulants can be present to bring the compositions to
the preferred pH of 9-12, more preferably to around pH 10.
This can however be achieved without buffering systems in
the presence of a sequesterant. The alkaline pH is
particularly preferred in the presence of the sequestering
agents with a pK~a>5 as these are believed to be most
effective in a fully ionised form and generally ionise at
markedly alkaline pH.
The preferred delivery form for the compositions of the
invention is in the form of a clinging foam or other slow-
draining product form, preferably delivered to the surface
being cleaned in the form of a spray.
Particularly preferred compositions comprise:
a) 2-80 of a surfactant selected from the group
comprising anionic sulphate, anionic sulphonate, alkyl
poly glycoside and mixtures thereof,
b) 2-10% of a sequestering agent for Group II metals and
c) 1-So of a solvent selected from the group consisting
of hexanol, methyl digol, methanol and mixtures
thereof, provided that the hexanol level is less than
20 on product.
A~AENDED SHEET
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In order that the present invention can be better understood
it will be described hereinafter with reference to the
following non-limiting examples.
Examples:
The following materials were used in the examples, the
formulations of which are given in Tables 1 and 2, and the
identities of which is listed below.
Surfactants:
P Empicol LX 28 [TM] Sodium C12-14 primary alkyl
25 sulphate (PAS): ex Albright &
Wilson;
G Glucopon 225 CS UP [TM] C8-10 alkyl glycoside with a
DP of 1.6: ex. Henkel;
I Imbentin 92-35 OFA [TM] C20 E5 nonionic surfactant: ex
Dr W Kolb AG;
D Dehydol 04[TM] C8 E4 nonionic surfactant: ex
Henkel
Sequesterants:
M Trilon ES 9964 [TM) Methylglycinediacetic acid
(MGDA): ex BASF;
C Citric acid;
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Solvents:
MeOH Methanol
HEX Hexanol
O Octanol
IP Isopropanol
IMS Industrial Methylated (denatured ethanol)
Spirits
AMP 2-amino-2-methyl-1- propanol
NB n-butanol
TB t-butanol
DG Diethylene glycol H-(- O-CH~CH~)~-OH: ex
Dow;
PnB Dowanol PnB [TM] C~H<,- O-CH (CH-.,) -CH.-OH:
ex
Dow;
MD Methyl Digol [TM] CHI- ( -O-CH~CHl ) 2-OH
: ex.
Hopkin and
Williams;
Minors:
K Clear Kelzan [TM] Xanthan Gum: ex Kelco
International;
scs Eltesol SC 40[TM] Sodium cumene sulphonate: ex
Albright and Wilson;
Compositions were made up by simple mixing of the components
in the levels indicated in Tables 1A, 1B, 1C and 2A & 2B
below, in water. Tables 1A, 1B & 1C show comparative
examples while Tables 2A & B show compositions according to
the present invention.
In Tables 1A, 1B, 1C and 2A & B 'Al' is the level of
surfactant present and 'A2' the level of any further main
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surfactant species. The type and level of sequesterant is
identified in the column headed 'Seq' and the solvent type
and level is given for each formulation. 'C' is a cleaning
score further described below; 'V' the viscosity of the
product and 'Per' and 'Ena' the contact angles on perspex
and enamel respectively as described below. The tables also
provide observations which include the time to soil
deflocculation or break-up as seen under the microscope.
Cleaning data were obtained by soiling Perspex (TM] tiles
with an 'Artificial Sebum' soil made up of:
Glycerol trioleate 4008 19.950
Oleyl oleate 2468 12.3%
Squalene 1808 8.970
Oleic acid 1848 9.180
Linoleic acid 208 0.99%
Glycerol tripalmitate 4008 19.950
Tetracosane 248 1.19%
Steryl stearate 2468 12.27%
Cholesterol 848 4.19
n-Eicosane 258 1.250
Lauric acid 8g 0.4%
Myristic acid 488 2.4%
Palmitic acid 1128 5.6%
Stearic acid 238 1.15%
Total 20058
To prepare this soil one weighs out glycerol trioleate, puts
this into 4 litre beaker which is placed on a steam bath,
weighs out oleyl oleate and adds this to the beaker. Keeping
mixture at medium meat, one continues to add ingredients
ensuring that any powders are dissolved before adding more.
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Before adding n-eicosane, it was heated on a water bath to
melt. When all have been added and dissolved, one removes
the beaker from the bath and allows it to cool. One then
pours the cooled sebum into a polythene bag inserted into a
2.5 litre container and puts this into a refrigerator to
solidify.
The Perspex substrates used are 10 x 10 cm black Perspex
[TM] (ex. ICI) tiles and are prepared in the following way:
1. The protective backing film is first removed from the
tiles.
2. The tiles are then placed on the WIRA (Wool Industries
Research Abrasion Tester) machine for uniform
scratching. The total pressure applied is 252.5g.cm' on
a 3.8cm~ head (this equates to a total assembly mass of
959.6g applied to an area of 3.8cm'). A piece of P600
grade wet and dry abrasive paper is fitted to the head
and the tiles are scratched for 34 cycles on each side
of the tiles.
3. After the scratching, the tiles are then numbered for
identification purposes.
4. The tiles are then cleaned with either 10% nonionic or
hand dishwash liquid to remove perspex residues and
grease. The tiles are then rinsed and finally cleaned
in methylated spirits to ensure that they are
absolutely clean.
5. Tiles can be cleaned and reused. To do this the tiles
must be washed in washing up liquid and then soaked in
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ethanolic potassium hydroxide for one hour or more.
The tiles are then rinsed and washed in methylated
spirits before being allowed to dry.
Soil is applied to the Perspex tiles as follows: for each
set of ten tiles:
i. 5g coco soap (commercial 'Shield' (TM) soap was used),
0.75g 'Artificial Sebum' and 70-80g (normally 75g)
distilled water are all placed in a 250cm~ beaker.
ii. Ingredients are then stirred using a Heidolph (TM)
stirrer at full speed (approx. 2000RPM) for 5 minutes
at room temperature. A thick foam or mousse should be
produced.
iii. The prepared soil is then added to 7.5 litres of tap
water (approximately 10"FH see note below) and quickly
stirred in until large amounts of foam have subsided
and a scum is produced.
iv. The tiles are then dipped in the soil whilst being
suspended from a rack. The soiled tiles are then left
in racks overnight (approx 15 hours) at room
temperature to dry and age.
Cleaning is spray on/rinse off only. No mechanical effort is
applied. Formulations can be delivered to both vertical
surfaces or horizontal surfaces, as differences are seen due
to drainage rates and viscosity effects.
1. Each of the formulations is applied by a manually
operated spray pack, in this case a finger pump type
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spray with about 3 to 8 sprays given per soiled
surface (back and front). The typical amount of
formulation delivered is 0.12-0.158 per spray.
2. The formulation is left in contact with the tiles for
either 30 seconds or 1 minute.
3. The tile is rinsed under the tap until it is as clean
as possible, in all cases the same flow rate of water
is used and the rinsing process is carried out at the
same distance from the tap.
Once the tiles have dried, the performance of the cleaners
can then be assessed by means of subjective visual
examination. This is done by assigning a cleaning score to
each tile on a scale of 1 to 5 as follows:
0 - No effect/Heavy soiling
1 - Very poor
2 - Poor
3 - Average
4 - Good
5 - Very Good
6 - Completely clean/No soil remaining
Relative cleaning performance between experiments can be
measured and the use of a control or controls between
experiments has shown that the assessments are consistent
and reproducible. JIF BATHROOM (TM) was used as such a
control. All results are given as normalised results using
a score for JIF BATHROOM of 2.66 which was the average of
many trials. As noted above these scores are recorded in
the tables in column 'C'.
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It has been established that the water hardness of the bulk
7.5 litres that the soap/sebum mousse is added to, has a
major effect on the soil and the subsequent cleaning
performance of formulations. The water hardness is
therefore best maintained at 10°FH. Small variations either
higher or lower than this value make the soil much easier to
remove and hence discrimination between formulations is
reduced.
Contact angle measurements were performed using the Kruss
Goniometer (at room temperature) and either a perspex or a
calcium stearate on enamel substrate. In either case, a
small volume of the test liquor (10 uL or less) is applied
to the surface and the contact angle was measured at both 30
and 120 seconds. Contact angles are recorded in the tables
under 'Per' for perspex and 'Ena' for calcium stearate on
enamel. The enamel tiles used were white titanium enamelled
l0cm x l0cm (ex. Enamel Signs Co. Smethwick, West Midlands,
England, United Kingdom). The enamel tile preparation
method is as follows:
1. Tiles are washed and scrubbed with Jif LAC [TM] (a
liquid abrasive cleaner) and hot water. They are then
rinsed.
2. Tiles are then cleaned with hand dishwash liquid and
rinsed.
3. A heaped spatula (approximately 5g) of fine calcite
powder is placed on the tiles and they are then
scrubbed with a damp cloth.
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4. The tiles are then rinsed with demineralised water.
The tiles are deemed to be clean if the surface is
completely hydrophillic (ie: the water forms a constant
film and does not bead).
5. The tiles are dried and then wiped with a paper tissue
before use.
For coating with calcium stearate the treatment solution
contains 12.90 Calcium Stearate ( ex.. Fisons, Technical
Grade Reagent; made up to 100% with isopropyl alcohol. This
mixture is mixed using a Silverson stirrer/homogeniser at
full speed for 5 minutes. The soil is sprayed on to the
tiles to give a nominal coverage of 2.28mg/cm2 ( without
solvent ). This gives a coverage of 0.0176g/cm2 when
spraying the tile ( i.e. with solvent present ). The coated
tiles are placed in an oven at 180 degrees Celsius for 35
minutes. The tiles are then allowed to cool to room
temperature before use.
Viscosity was measured so as to give only a guide and a
relative measure of viscosity. A U-tube Viscometer was
employed and used in accordance with International Standards
ISO 3104-1976 and 3105-1976. All measurements were made at
25°C.
Optical microscopy observations were obtained on transparent
(unscratched) Perspex slides (occasionally glass slides)
which were soiled according to the method described earlier
for dipped soap/sebum (1:0.15). 10u1 of each formulation was
applied to the soil. The interaction of test liquors with
larger flocculated soil particles were examined under a X20
lens (and recorded on video) where the particles were remote
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from the edge of the liquid droplet to avoid
evaporation/triple interface effects. Attempts to examine
soil/surfactant interactions on enamel were unsuccessful as
the soil could not be viewed in light reflection mode when
immersed in cleaning fluid.
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WO 98/50510 PCT/EP98/02575
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CA 02288303 1999-10-25
WO 98/50510 PCT/EP98/02575
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- 23 -
From the results in Tables 1A, 1B, 1C and 2A & 2B it can be
seen that the formulations according to the present
invention show rapid release of soil from surfaces and give
acceptable cleaning performance.
