TECHNICAL FIELD
[0001] The present invention relates to the use of compositions for the removal of limescale.
The compositions herein can be used on a variety of surfaces, ranging from bathrooms,
toilets, and kitchen surfaces to various appliances. The compositions herein can further
be used to remove limescale from dentures.
BACKGROUND
[0002] Tap water always contains a certain amount of solubilized ions which eventually deposit
as salts, on surfaces in contact with said water, as it evaporates. Such salts include
calcium carbonate, commonly referred to as limescale. This phenomenon of limescale
accumulation on surfaces which are often in contact with water may damage surfaces
and affect the functioning of taps or appliances. Also, the accumulation of limescale
in toilet bowls is aesthetically unpleasant and favors the deposition of further soil
and the growth of microorganisms. It is therefore important to control this limescale
accumulation phenomenon.
[0003] A variety of compositions have been proposed for this purpose, which typically comprise
various acids, such as hydrochloric acid. However, compositions of the art formulated
with said acids require a significant amount of acid to ensure effective removal of
limescale, and are thus potentially harmful to the user in case of contact with the
skin, or accidental ingestion. It is thus an object of the present invention to provide
limescale removing compositions which are particularly efficient in removing limescale,
yet which have a lower reserve of acidity than the compositions of the art, thus which
are less harmful.
[0004] It is also desirable to formulate compositions which comprise bleaches. Indeed, bleaches
possess many desirable properties, including disinfection properties. Furthermore,
such compounds as monopersulfuric acid are particularly effective as disinfectants
and in removing and or decolouring stains for household cleaning applications, see
EP 598 694. However, as said, bleaches in general raise compatibility issues in relation
with the acids used to remove limescale. In particular, persulfuric acid is not compatible
with the acids used in the art to remove limescale because persulfuric acid oxidizes
the limescale removing acid upon storage, resulting in a dramatic loss of available
oxygen. And by the time the product reaches the consumer, most of the available oxygen
is lost. Typical acids used in the art for removing limescale, namely maleic, citric,
hydrochloric and sulfamic acid are all oxidized by persulfuric acid in particular.
It is thus an object of the present invention to provide a limescale removing composition
which can be formulated with bleaches, in particular persulfuric acid, in a stable
manner.
[0005] In response to these objects, we have now found that such a limescale removing composition
could be formulated which comprises, as the acid, an arylsulfonic acid selected from
a specific group, or mixtures thereof.
[0006] EP 271 791 discloses compositions comprising short chain alkyl sulfonic acids for
cleaning and disinfecting in the food processing industry. European patent application
EP 656 417 discloses short chain alkylsulfonic acids for removing limescale. US 4,895,669
discloses hard surface cleaning compositions comprising long chain alkylarylsulfonic
acids and potassium peroxymonosulfate.
[0007] EP 265 979 relates to an aqueous composition incorporating low levels of quaternary
ammonium salts or amine oxide surfactant and an organic anionic sulphonate for cleaning
non horizontal surfaces.
[0008] EP 601 972 relates to a toilet cleaning composition comprising an acidic limesclae
removing agent, hydrogen peroxide, a buffer and a thickening agent.
SUMMARY OF THE INVENTION
[0009] The present invention encompasses the use of an arylsulfonic acid selected from the
specific group defined hereinafter, or mixtures thereof in an aqueous composition,
for removing limescale. In one embodiment of the invention, the compositions of the
present invention preferably comprise an acid-stable bleach compound. In another embodiment
of the invention, the compositions herein additionally comprise a small amount of
sulfamic acid.
DETAILED DESCRIPTION OF THE INVENTION
[0010] The compositions for use in the present invention are aqueous liquid compositions
comprising an arylsulfonic acid selected from the specific group defined hereinafter,
or mixtures thereof. Arylsulfonic acids suitable for use herein are selected from
the group of arylsulfonic acids according to the formula:

wherein R
1, R
2, R
3, R
4 and R
5 are each H or SO
3H, or linear or branched C
1-C
4 alkyl chain; or mixtures thereof.
[0011] Preferred for use herein are arylsulfonic acids which comprise no or only one alkyl
chain. Indeed, we have found that said arylsulfonic acids are particularly effective
at removing limescale, which is not the case for their longer alkyl chain homologues.
Particularly suitable for use herein are benzene sulfonic acid, toluene sulfonic acid
and cumene sulfonic acid. Amongst these three, at equal weight %, we have found that
the shorter the alkyl chain, down to no chain at all, the better the limescale removing
performance.
[0012] The compositions herein preferably comprise from 1% to 50% by weight of the total
composition of said arylsulfonic acid or mixtures thereof, more preferably from 1%
to 30%, most preferably 1% to 10%.
[0013] We have also observed that mixtures of the arylsulfonic acids herein provided a poorer
limescale removing performance than single species. Accordingly, compositions herein
preferably contain only one arylsulfonic acid as defined hereinabove.
[0014] The compositions according to the present invention are less harsh than the compositions
of the art in that, at parity limescale removal performance, the reserve of acidity
is much less than the compositions in the art. Thus in this respect, in case of contact
with the user's skin or in case of ingestion, the composition of the present invention
will be less harmful.
[0015] The compositions herein are acidic. Accordingly, the pH of the compositions according
to the present invention may range from 0 to 4, preferably 0 to 2, and is essentially
determined by the type and amount of arylsulfonic acid used.
[0016] In one embodiment of the present invention, the composition herein may comprise an
acid-stable bleach, i.e. an oxidant compound. By acid-stable, it is meant herein a
compound which is stable in the acidic environment of the compositions herein. This
criterion is to be assessed on a case by case basis, depending on the specifics of
given formulations. It is essential that the bleach/oxidant chosen be stable at the
pH of the formulation being considered. By stable, it is meant herein that the oxidant
should preferably not undergo more than 30% loss of available oxygen in 2 months at
room temperature (25°C). A wide variety of oxidants have been described in the art
which are suitable for use herein. Suitable acid-stable oxidant compounds for use
herein include inorganic and organic peroxides. Examples of inorganic peroxides are:
hydrogen peroxide and sources thereof (e.g. perborate, percarbonate), persulfate salts
(i.e. dipersulfate and monopersulfate salts), persulfuric acid and mixtures thereof.
Examples of organic peroxides are: benzoyl peroxide, organic percarboxylic acids (i.e.
peracetic acid) and mixtures thereof. Percarboxylic acids and, in general, organic
or inorganic peroxides can be either solubilized in the formula or dispersed in the
form of suspended solids or emulsified liquids. Particularly preferred for use herein
are hydrogen peroxide or sources thereof, and persulfuric acid or salts thereof because
of their excellent stain removal performance and stability in acidic matrices, and
mixtures thereof.
[0017] Preferred salts of persulfuric acid for use herein are monopersulfate salts, commercially
available as Curox ® from Interox, Caroat from Degussa and Oxone from Du Pont. The
compositions herein may comprise from 0.1% to 50% by weight of the total compositions
of said acid-stable bleach/oxidant compound or mixtures thereof, preferably from 1%
to 30%, most preferably from 1% to 20%.
[0018] In another embodiment of the present invention, the compositions herein may comprise
a small amount of sulfamic acid. Indeed, we have found that the combination of the
arylsulfonic acids herein together with sulfamic acid act in synergy in removing limescale.
This property is particularly interesting as it allows the formulation of compositions
which are particularly effective in removing limescale, while they comprise only minor
amounts of sulfamic acid, thereby reducing harshness. Accordingly, the compositions
herein may comprise from 0.1% to 25% by weight of the total composition of sulfamic
acid, preferably from 0.1% to 20%, most preferably from 0.2% to 15%. The synergistic
effect observed depends to some extent on the ratio of sulfamic acid to arylsulfonic
acid. In this embodiment where sulfamic acid is incorporated in the compositions herein,
it is preferred to formulate the compositions without monopersulfuric acid and similar
oxidants, since monopersulfuric acid oxidizes sulfamic acid, thereby resulting in
loss of available oxygen.
[0019] The compositions herein may further comprise surfactants since they are often used
on items or surfaces which have soils or stains which do not comprise limescale, and
which require the presence of surfactants in the compositions of the present invention,
in order to be removed from said surfaces. Also, surfactant systems can be used to
provide viscosity to the compositions herein, and that is desirable since the compositions
herein are likely to be used on inclined surfaces such as bath tubs, sinks or toilet
bowls. Thickened compositions have a better cling onto inclined surfaces, thus a longer
residence time for the composition to remove limescale.
[0020] Thus, the compositions according to the present invention can comprise any surfactant,
cationic, anionic, nonionic and zwitterionic, in amounts ranging up to 50% by weight
of the total composition, preferably from 1% to 30%.
[0021] Suitable anionic surfactants include alkyl or alkylene sulfates or sulfonates, alkyl
or alkylene ether sulfates or sulfonates, linear alkyl benzene sulfonate. Suitable
cationic surfactants include quaternary ammonium salts. Suitable nonionic surfactants
for use herein include ethoxylated carboxylic acids, amine oxides and fatty alcohol
ethoxylates. Emulsions of nonionic surfactants, such as in co-pending European patent
application EP 598 692 are also suitable to provide pseudoplastic and thixotropic
compositions, which allow excellent spreading and clinging characteristics on dry
surfaces.
[0022] Another suitable thickening surfactant system that leads to excellent spreading and
clinging on wet surface for use herein is constituted by mixtures of amine oxides
and quaternary ammonium compounds. In particular, amine oxides according to the formula
R1R2R3NO where R1 is a C6-C10 alkyl chain and R2 and R3 are C1-C4 alkyl chains, in
combination with quaternary ammonium salts allow to build viscosity at a lower total
level than if quaternary ammonium salts were used alone. Preferred amine oxides in
such a system are those where R1 is C8-C10 alkyl, and R2 and R3 are C1-C3 alkyl chains,
preferably methyl. Suitable quaternary ammonium compounds in such a system have one
or two long alkyl chains, i.e. 6 to 30, preferably 12 to 20 carbon atoms linked to
the nitrogen atom, and the other alkyl chains linked to the nitrogen atom are shorter,
i.e. they have 1 to 4, preferably 1 carbon atom. Such a system can be used in total
amounts, i.e. amine oxide plus quaternary ammonium compound, of up to 20% by weight
of the total composition, but amounts as low as from 1% to 6% can be sufficient to
build the desired viscosity. Suitable weight ratios of amine oxide to quaternary ammonium
compound range from 1:2 to 1:100, preferably 1:4 to 1:30, most preferably 1:10 to
1:20. Desired viscosity herein ranges from 250 cps and up, preferably 250 cps to 1500
cps, more preferably 250 cps to 900 cps (at 50 dynes/cm2, at 20°C). Such a system
is particularly suitable herein since the viscosity it provides is not affected by
the presence of the bleach
[0023] The present invention can further comprise a multitude of optionals such as solvents,
colorants, dyes, perfumes, stabilizers, radical scavengers and the like.
EXAMPLES
[0024] The following compositions are made which comprise the following ingredients in the
following proportions (total weight %)
Example 1
[0025]
Dobanol ® 91-10 |
2.1 |
Dobanol ® 91-2.5 |
4.9 |
Curox ® |
6 |
Cumenesulfonic acid |
5 |
water and minors (e.g. dye, perfume, radical scavengers) up to 100% |
pH = 0.9 |
Example 2
[0026]
Dobanol ® 91-10 |
2.1 |
Dobanol ® 91-2.5 |
4.9 |
Curox ® |
6 |
Toluenesulfonic acid |
5 |
water and minors (e.g. dye, perfume, radical scavengers) up to 100% |
pH = 0.7 |
Example 3
[0027]
Dobanol ® 91-10 |
2.1 |
Dobanol ® 91-2.5 |
4.9 |
Benzenesulfonic acid |
5 |
water and minors (e.g. perfume, dye, radical scavengers) up to 100% |
pH = 0.7 |
Example 4
[0028]
C16 trimethyl ammonium methylsulfate |
4 |
C8/C10 amineoxide |
0.2 |
Benzenesulfonic acid |
10 |
water and minors (e.g. perfume, dye, radical scavengers) up to 100% |
pH = 0.6 |
Example 5
[0029]
C16 trimethyl ammonium methylsulfate |
4 |
C8/C10 amineoxide |
0.2 |
Toluenesulfonic acid |
15 |
water and minors (e.g. perfume, dye, radical scavengers) up to 100% |
pH = 0.6 |
Example 6
[0030]
C12/C14 Amineoxide |
3 |
Dobanol ® 91-2.5 |
3 |
Benzenesulfonic acid |
10 |
water and minors (e.g. perfume, dye, radical scavengers) up to 100% pH = 0.8 |
Example 7
[0031]
Sulfamic acid |
5 |
water and minors up to 100% |
pH = 0.7 |
Example 8
[0032]
Benzenesulfonic acid |
5 |
water and minors up to 100% |
pH = 0.7 |
Example 9
[0033]
Benzenesulfonic acid |
10 |
water and minor up to 100% |
pH = 0.5 |
Example 10
[0034]
Benzenesulfonic acid |
5 |
Sulfamic acid |
5 |
water and minor up to 100% |
pH = 0.7 |
[0035] The limescale removal efficiency of samples is evaluated by putting a block of 6
g of calcium carbonate in 50 mis of the sample to be evaluated for a period of 30
minutes. The block is weighed dry before and after the experiment. The bigger the
difference, the more efficient the composition.
[0036] The weight decrease measured with composition 1 was 0.40; for composition 2 it was
0.50, and for composition 3 it was 0.60. This indicates that the shorter the alkyl
chain (i.e., hydrogen for composition 3) in the arylsulfonic acid, the better the
limescale removal performance. This is verified comparing composition 4 (alkyl=H)
which provided a weight decrease of 0.5, with composition 5 (alkyl=C1) which required
a higher amount of acid to achieve the same performance. The synergistic effect of
sulfamic acid used together with benzenesulfonic acid can be seen comparing the weight
decrease of composition 7 (0.73) and 8 (0.57) and 9 (1.02) vs. composition 10 (1.55).
[0037] In terms of bleach stability, the available oxygen was monitored in composition 1.
The available oxygen is measured in the fresh composition , and in the same composition
after one week storage at room temperature (25°C). Persulfate concentration can be
measured by titration with potassium permanganate after reduction with a solution
containing ammonium ferrous sulfate. This test method is well known and reported for
instance in on the technical information sheet of Curox®, commercially available from
Interox. Another suitable method is disclosed in Gas-Liquid Chromatography Method
for the Determination of Peracids, Analyst, Vol 113, May 1988, pp 793-795. We have
measured that there was no loss of available oxygen with composition 1 whereas, in
the same composition where cumenesulfonic acid was replaced respectively by the same
amount (weight) of sulfamic or hydrochloric acid, the loss of available oxygen in
the same period ranges between 66% and 98%. Thus the compositions according to the
present invention allow for much more bleach stability.
1. The use of an arylsulfonic acid selected from the group of arylsulfonic acids according
to the formula:

wherein R
1, R
2, R
3, R
4 and R
5 are each H or SO
3H, or linear or branched C
1-C
4 alkyl chain; or mixtures thereof in an aqueous composition for removing limescale.
2. The use according to claim 1, wherein the composition comprises from 1% to 50% by
weight of the total composition of said acid.
3. Use according to the preceding claims, wherein said composition has a pH of from 0
to 4, preferably 0 to 2.
4. Use according to the preceding claims, which comprises form 1% to 30% of said arylsulfonic
acid, preferably from 1% to 10%, by weight of the total composition.
5. Use according to the preceding claims wherein said composition further comprises an
acid-stable oxidant compound, or mixtures thereof.
6. Use according to claim 5 wherein said oxidant is hydrogen peroxide or a salt of persulfuric
acid, preferably a monopersulfate salt.
7. Use according to the preceding claims wherein said composition further comprises up
to 50% by weight of the total composition of a surfactant, preferably a mixture of
amine oxide and quaternary ammonium compound.
8. Use according to claims 1-4 which further comprises sulfamic acid, in amounts of from
0.1% to 25% by weight of the total composition, preferably from 0.1% to 20%, most
preferably from 0.2% to 15%.
9. Use according to the preceding claims wherein said arylsulfonic acid is selected from
the group consisting of benzenesulfonic acid, cumene sulfonic acid or toluene sulfonic
acid, or mixtures thereof.
10. Use according to the preceding claims, where said composition comprises a single said
arylsulfonic acid.