Note: Descriptions are shown in the official language in which they were submitted.
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Use of Polysaccharide Polymer in a Liquid Acidic Composition
10 The present invention is related to acidic hard-surfaces compositions,
especially limescale removal compositions.
Background of the invention
Tap water contains a certain amount of solubilized ions which upon water
evaporation eventually deposit as salts such as calcium carbonate on
surfaces which are often in contact with water, resulting in an anaesthetic
aspect of the surfaces. This limescale formation and deposition
phenomenon is even more acute in places where water is particularly hard.
It is well-known in the art that limescale deposits can be chemically
removed with acidic solutions, and a great variety of acidic cleaning
compositions have been described for this purpose.
It is also desirable that such liquid acidic compositions should have, in
addition to the ability to effectively remove limescale deposits present on a
surface, the ability to provide improved shine to the surface treated. It has
now been observed that surface shine is often compromised by the low
affinity the hard surface has with water when it comes in contact with it.
indeed, water has the tendency to form droplets on the surface rather
than forming a thin film uniformly spread over the surface. This results as
water evaporates in precipitation of poorly water sotubfe inorganic salts
such as carbonate and/or phosphate salts with consequent formation of
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2
watermarks on the surface, and eventually limescale deposits, resulting in
an anaesthetic aspect of the surface.
It is thus an object of the present invention to reduce formation of
limescale deposits and/or of watermarks on a surface that has been
treated with an acidic composition, especially an acidic limescale removal
composition, and hence to provide improved shine to said surface.
The present invention overcomes these problems by the use of a
polysaccharide polymer, in a liquid acidic composition suitable for
descaling hard-surfaces. Indeed, it has been found that the addition of a
polysaccharide polymer, preferably xanthan gum, in a liquid acidic
composition, reduces or even prevents the formation of limescale deposits
on a surface having first been treated with such a composition. Also less
formation of watermarks are observed on a surface having been first
treated with the compositions as described herein and then contacted with
water, for example, during a rinse operation, thereby providing improved
shine to said surface.
Advantageously, the shine benefit delivered to a hard surface treated with
the compositions according to the present invention persists even after
several cycles of rinsing thus providing long lasting protection against
limescale re-deposition/formation and/or watermarks formation on said
surface, and hence long lasting shiny surfaces. In other words, the house
wife will have the advantage to delay the next descaling operation.
Another advantage of the use of the polysaccharide polymer according to
the present invention in a liquid acidic composition is that the surfaces
treated become smoother (this can be perceived by touching said
surfaces). This may also contribute to convey to consumers the perception
of surface perfectly descaled.
The compositions described herein may be used on a variety of surfaces
including metal surfaces such as aluminium, chromed steel, stainless steel,
synthetic materials like vinyl, linoleum, glazed or non-glazed ceramic tiles,
and/or enamel surfaces.
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3
Background art
Limescale compositions comprising polysaccharide polymers like xanthan
gum are known in the art. For example,, EP-A-758 017 discloses acidic
compositions with an acidic system and an acid-stable thickener, e.g.
xanthan gum. EP-A-758 017 fails to disclose that polysaccharide polymers
when added in a liquid acidic composition reduce the formation of
l0 watermarks and/or limescale deposits on a surface having been first
treated with said composition, and thus provide improved shine to the
surface.
Summary of the invention
The present invention encompasses the use of a polysaccharide polymer
or a mixture thereof, in a liquid acidic composition, to treat a hard-surface,
whereby after said hard-surface has first been treated with said
composition, the formation of iimescalE: deposits on said hard-surface
when it comes in contact with water is reduced.
The present invention further encompasses the use of a polysaccharide
polymer or a mixture thereof, in a liquid acidic composition, to treat a
hard-surface whereby improved shine is delivered to the surface treated
with said composition.
, 30 The present invention also encompasses the use of a polysaccharide
polymer or a mixture thereof, in a liquid acidic composition, to treat a
hard-surface whereby long lasting shine is delivered to the surface treated
with said composition.
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Yet, the present invention also encompasses the use of a polysaccharide
polymer or a mixture thereof, in a liquid acidic composition, for improved
skin mildness.
Detailed description of the invention
An essential feature of the present invention is a polysaccharide polymer
or a mixture thereof.
Suitable polysaccharide polymers to be used herein include substituted
cellulose materials like carboxymethylcellulose, ethyl cellulose,
hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethyl cellulose,
succinoglycan and naturally occurring polysaccharide polymers like
xanthan gum, guar gum, locust bean gum, tragacanth gum or derivatives
thereof, or mixtures thereof.
2 o Particularly polysaccharide polymers to be used herein are xanthan gum
and derivatives thereof. Xanthan gum and derivatives thereof may be
commercially available for instance from Kelco under the trade name
Keltrol RD~, Kelzan S~ or Kelzan T~.
Xanthan gum or derivatives thereof are advantageously physically and
chemically stable in the acidic conditions of the compositions herein, this
even at very low pH typically below 1.5.
The acidic liquid compositions herein are chemically stable, i.e., there is
virtually no chemical changes of the different ingredients due to reaction
between different ingredients, and physically stable, i.e., that no phase
separation occurs when stored in rapid aging test (RAT) at 50 °C for 10
days.
According to the present invention the compositions comprise from
0.001 % to 10% by weight of the total composition of a polysaccharide
polymer, or a mixture thereof, preferably from 0.01 % to 3% by weight,
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more preferably from 0.01 % to 1 %, even more preferably from 0.05 % to
0.8% and most preferably from 0.05% to 0.6°~.
The polysaccharide polymers herein may act as a thickening agent,
5 accordingly the liquid acidic compositions herein have a viscosity of from
1 cps to 1500 cps at 20°C, preferably from 20 cps to 800 cps and more
preferably from 50 cps to 600 cps, when measured with a Carri-med
rheometer CLS 100~ at 5 N/m2.
l0 The liquid compositions according to the present invention are acidic
compositions. Accordingly, the compositions of the present invention are
formulated at a pH below 5, preferably k>elow 4, more preferably at a pH
between 0 and 3, even more preferably at a pH between 0.1 and 2.5,
even more preferably between 0.1 and 2, and most preferably at a pH
between 0.3 and 1.5.
The compositions according to the present invention are designed for
removing limescale deposits. Thus, they typically comprise an acid or a
mixture thereof. Typically, the acids to be used herein may be any
2 o inorganic or organic acid well-known to those skilled in the art, or a
mixture thereof. Suitable acids for use herein include malefic acid, citric
acid, adipic acid, sulfamic acid, phosphoric acid, nitric acid, malic acid,
sulfonic acid, sulphuric acid or their salts or mixtures thereof. Indeed,
such acids can be used in their acidic form or in the form of their salts
(mono-, di-, tri- salts? and in all their anhydrous and hydrated forms, or
mixtures thereof. Such acids may typically be used in the form of their
alkali metal salts (e.g. sodium salt, potassium salt, and then like) or their
alkali hydrogen acid salts. The compositions according to the present
invention comprise from 0.1 % to 70°~ by weight of the total
composition
of an acid or a mixture thereof.
In a preferred embodiment herein the compositions according to the
present invention comprise at least malefic acid. Accordingly, the
compositions according to the present invention comprise from 0.1 % to
45°~6 by weight of the total composition of malefic acid,
preferably from
1 % to 25% and more preferably from 8% to 20%. This percentage is
calculated on the basis of the molecular weight of the acid form, but
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malefic anhydride is equally convenient for use in the compositions
according to the present invention. Indeed, malefic anhydride is generally
cheaper and it is transformed into the acid form when incorporated in an
aqueous medium. In one embodiment herein malefic acid is used alone as
the acid of the acidic compositions according to the present invention.
In another embodiment of the present invention, a second acid is added on
top of said malefic acid. Said second acid is desired to strengthen the
limescale removal performance. Preferably the second acids to be used
herein which are particularly efficient to remove limescale on many
surfaces, have their first pKa not exceeding 5, more preferably not
exceeding 3, and most preferably not exceeding 2. According to the
present invention said acids can be organic or inorganic acids. Examples
of inorganic acids are sulphonic acid derivatives, sulphamic acid
(pKa =0.1 ), hydrochloric acid (pKa < 0), nitric acid (pKa < 0), phosphoric
acid (pKa =2.1 ) and sulphuric acid (pKa =0.4). An example of organic acid
is citric acid (pKa = 3.06).
Particularly suitable to be used herein is sulphamic acid. Indeed, the
2o addition of sulphamic acid to malefic acid-containing compositions
improves the skin safety profile of said compositions. The skin will be less
subject to become inflamed, red, sore and/or itchy when in contact with
those acidic compositions according to the present invention comprising
sulphamic acid on top of malefic acid, as compared to the same
compositions without said sulphamic acid.
Other suitable second acids are sulphonic acid derivatives including alkyl
sulphonic acids and aryl sulphonic acids.
Suitable alkyl sulphonic acids for use herein are C1-C6 linear or branched
alkylsulphonic acids or mixtures thereof, such as methanesulphonic acid
(pKa =1.9) commercially available for example from Aldrich, William
Blythe & Co. Ltd. or Elf. Atochem.
Suitable aryl sulphonic acids for use herein are according to the formula
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7
R,~ R5
R 1 ~ S03 H
R2 R3
wherein R1, R2, R3, R4 and R5 are each H or S03H, or linear or branched
C1-C4 alkyl chain; or mixtures thereof.
Preferred arylsulphonic acids for use herein are those which comprise no
or only one alkyl chain. Indeed, such arylsulphonic acids are particularly
effective at removing limescale, which is not the case for their longer alkyl
chain homologues. Also, such arylsulphonic acids are particularly safe to
1 o the surface treated therewith. Particularly suitable arylsulphonic acids
for
use herein are benzene sulphonic acid (pKa=0.71, toluene sulphonic acid
and cumene sulphonic acid. Amongst these three, at equal weight %, the
shorter the alkyl chain, down to no chain at all, the better the limescale
removing performance.
20
Preferred acids having a first pKa not exceeding 5 for use herein are
sulphamic acid, sulphuric acid, aryl sulphonic acids, alkyl sulphonic acids,
or mixtures thereof, more preferred are sulphamic acid, sulphuric acid,
benzene sulphonic acid or mixtures thereof and highly preferred is
sulphamic acid.
The compositions according to the present invention comprise from 0.1
to 25% by weight of the total composition of a second acid which has a
first pKa not exceeding 5, or mixtures thereof, preferably from 0.1 % to
20°~, more preferably from 0.1 % to 10% and most preferably from 0.1
to 7%.
It has now surprisingly been found that the polysaccharide polymers
described herein when added into a liquid acidic composition typically
comprising an acid or a mixture thereof, preferably malefic acid and
sulphamic acid, reduce the formation of limescale deposits and/or
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8
watermarks on a surface that has been first treated with said composition,
when said surface comes into contact with water. This results in improved
shine to the surface so treated when it comes into contact with both hard
and/or soft water.
Although not wishing to be bound by theory, it has been observed that
hard surfaces often have low affinity with water. This means that, when
water gets in contact with hard-surfaces, its spreading, which is controlled
by the interfacial energy (i.e., solid/liquid surface tension), is very
limited.
l0 Indeed, it has been observed that the most stable configuration for the
water is grouping in spherical droplets rather than forming a thin film
uniformly spread over the surface. Then, as water droplets evaporate,
their content of salt progressively become higher and higher so that poorly
water soluble inorganic salts such as calcium/magnesium carbonate and/or
phosphate salts eventually precipitate, i.e. form limescale deposits
typically when water is hard and/or watermarks. The end result is a
reduction of surface shine. It has now been found that when the
polysaccharide polymers as described herein are added into a liquid acidic
composition an hydrophilic layer is left on a hard-surface treated with said
composition, said hydrophilic layer leaves the water coming in contact
with the surface that has been first treated with said composition (e.g.,
water which is used to rinse off the surfaces having been so treated)
uniformly spread over the surface ("sheeting effect") instead of forming
droplets. This way, the formation of limescale deposits and/or watermarks
upon drying is reduced or even prevented. This resulting in improved
shine.
Furthermore, it has surprisingly been found that the polysaccharide
polymers of the present invention have not only the ability to adhere on a
surface treated with the acidic compositions herein comprising the same
but to still remain adhered on the surface even after several cycles of
rinsing (e.g., when water comes into contact with this surface later on, for
example, during current household operation in a sink/, thus providing long
lasting protection against formation of limescale deposits/watermarks and,
hence, long lasting shiny surfaces.
Not to be bound by theory, it is believed that the polysaccharide polymers
also have the ability to form a film on the surface of the user skin, thereby
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9
providing improved skin mildness. In another embodiment the present
invention thus also encompasses the use of a polysaccharide polymer or a
mixture thereof, in a liquid acidic composition, for improved skin mildness.
An additional advantage related to the use of the polysaccharide polymers
of present invention is that, as they adhere on hard surface making them
more hydrophilic, the surfaces themselves become smoother (this can be
perceived by touching said surfaces) and this contribute to convey
perception of surface perfectly descaled.
The liquid compositions according to the present invention are preferably
aqueous compositions. Therefore, they comprise from 50% to 98% by
weight of the total composition of water, preferably from 60% to 95%
and more preferably from 70% to 90%.
Qntional ingredients
The compositions according to the present invention may further comprise
a variety of other ingredients including surfactants, colorants, bactericides,
thickeners, other polymers, dyes, chelants, pigments, solvents, stabilizers,
perfumes, corrosion inhibitors and the like.
A highly preferred optional ingredient suitable to be used in the
compositions according to the present invention is a surfactant or a
mixture thereof. Surfactants are desired herein as they contribute to the
cleaning benefits of the limescale removal compositions of the present
invention. Indeed, the presence of a surfactant allows to boost the greasy
soap scum cleaning of the compositions herein. More generally, the
presence of a surfactant in the liquid acidic compositions according to the
present invention allows to lower the surface tension and to improve the
wettability of the surfaces being treated with the liquid acidic compositions
of the present invention. The presence of a surfactant or a mixture thereof
in the liquid acidic compositions according to the present invention helps
to solubilize the soils.
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Accordingly, the compositions herein may comprise a surfactant or a
mixture thereof. The compositions according to the present invention may
comprise up to 40% by weight of the total composition of said surfactant
or a mixture thereof, more preferably from 0.05% to 15%, even more
5 preferably from 0.1 % to 10%, and most preferably from 0.1 % to 5%. All
types of surfactants may be used in the present invention including
nonionic, anionic, cationic, zwitterionic or amphoteric surfactants. It is
also
possible to use mixtures of such surfactants without departing from the
spirit of the present invention.
Highly preferred surfactants to be used herein are zwitterionic surfactants.
Suitable zwitterionic surfactants for use herein contain both basic and
acidic groups which form an inner salt giving both cationic and anionic
hydrophilic groups on the same molecule at a relatively wide range of
pH's. The typical cationic group is a quaternary ammonium group,
although other positively charged groups like phosphonium, imidazolium
and sulfonium groups can be used. The typical anionic hydrophilic groups
are carboxylates and sulfonates, although other groups like sulfates,
phosphonates, and the like can be used.
A generic formula for preferred zwitterionic surfactants for use herein (i.e.,
betaine and/or sulfobetaine) is
R1-N+(R2)(Rg)R4X_
wherein R1 is a hydrophobic group; R2 is hydrogen, C1-C6 alkyl, hydroxy
alkyl or other substituted C1-Cg alkyl group; R3 is C1-Cg alkyl, hydroxy
alkyl or other substituted C1-Cg alkyl group which can also be joined to
RZ to form ring structures with the N, or a C1-Cg carboxylic acid group or
a C1-Cg sulfonate group; R4 is a moiety joining the cationic nitrogen atom
to the hydrophilic group and is typically an alkylene, hydroxy alkyiene, or
polyalkoxy group containing from 1 to 10 carbon atoms; and X is the
hydrophilic group which is a carboxylate or sulfonate group, preferably
sulfonate group.
Preferred hydrophobic groups R1 are aliphatic or aromatic, saturated or
unsaturated, substituted or unsubstituted hydrocarbon chains that can
CA 02287969 2004-03-04
11
contain linking groups such as amido groups, ester groups. More preferred
R1 is an alkyl group containing from 1 to 24 carbon atoms, preferably
from 8 to 18, and more preferably from 10 to 16. These simple alkyl
groups are preferred for cost and stability reasons. However, the
hydrophobic group R1 can also be an amido radical of the formula Ra-
C(O)-NRb-(C(Rc)2)m, wherein Ra is an aliphatic or aromatic, saturated or
unsaturated, substituted or unsubstituted hydrocarbon chain, preferably an
alkyl group containing from 8 up to 20 carbon atoms, preferably up to 18,
more preferably up to 16, Rb is either a hydrogen a short chain alkyl or
substituted alkyl containing from 1 to 4 carbon atoms, preferably a group
selected from the group consisting of methyl, ethyl, propyl, hydroxy
substituted ethyl or propyl and mixtures thereof, more preferably methyl or
hydrogen, Rc is selected from the group consisting of hydrogen and
hydroxy groups, and m is from 1 to 4, preferably from 2 to 3, more
preferably 3, with no more than one hydroxy group in any (C(Rc)2)
moiety.
Preferred R2 is hydrogen, or an alkyl or substituted alkyl containing from 1
to 4 carbon atoms, preferably a group selected from the group consisting
of methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures
thereof, more preferably methyl. Preferred R3 is a C1-C4 carboxylic acid
group, a C1-C4 sulfonate group, or an alkyl or substituted alkyl containing
from 1 to 4 carbon atoms, preferably a group selected from the group
consisting of methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and
mixtures thereof, more preferably methyl. Preferred R4 is (CH2)n wherein
n is an integer from 1 to 10, preferably from 1 to 6, more preferably is
from 1 to 3.
Some common examples of betaineJsulphobetaine are described in U.S.
Pat. Nos. 2,082,275, 2,702,279 and 2,255,082.
Examples of particularly suitable alkyldimethyl betaines include coconut-
dimethyl betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2-fN-
decyl-N, N-dimethyl-ammonia)acetate, 2-(N-coco N, N-dimethylammonio)
acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, cetyl
dimethyl betaine, stearyl dimethyl betaine. For example Coconut dimethyl
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12
betaine is commercially available from Seppic under the trade name of
Amonyl 265~. Lauryl betaine is commercially available from Albright &
Wilson under the trade name Empigen BB/L~.
A further example of betaine is Lauryl-immino-dipropionate commercially
available from Rhone-Pouienc under the trade name Mirataine H2C-HA ~.
Examples of particularly suitable sulfobetaine surfactants include tallow
bis(hydroxyethyl) sulphobetaine, cocoamido propyl hydroxy sulfobetaines
which are commercially available from Rhone Poulenc and Witco, under
the trade name of Mirataine CBS~ and Rewoteric AM CAS 15~
respectively.
Example of amidobetaines include cocoamidoethylbetaine,
cocoamidopropyl betaine or C10-C14 fatty
acylamidopropylene(hydropropylene)sulfobetaine. For example C10-C14
fatty acylamidopropylene(hydropropylene)sulfobetaine is commercially
available from Sherex Company under the trade name "Varion CAS~
sutfobetaine".
Suitable amine oxides for use herein are according to the following formula
R1R2R3N0 wherein each of R1, R2 and R3 is independently a saturated or
unsaturated, substituted or unsubstituted, linear or branched alkyl groups
containing from 1 to 30 carbon atoms, and preferably from 1 to 20 carbon
atoms. Particularly preferred amine oxides to be used according to the
present invention are amine oxides having the following formula
R1R2R3N0 wherein R1 is a saturated or unsaturated, substituted or
unsubstituted, linear or branched alkyl group containing from 1 to 30
carbon atoms, preferably from 8 to 20 carbon atoms, more preferably
from 6 to 1 fi, most preferably from 8 to 14, and wherein R2 and R3 are
independently substituted or unsubstituted, linear or branched alkyl groups
containing from 1 to 4 carbon atoms, preferably from 1 to 3 carbon
atoms, and more preferably are methyl groups, or mixtures thereof.
Suitable amine oxides for use herein are for instance coconut dimethyl
amine oxides, C12-C16 dimethyl amine oxides. Said amine oxides may be
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commercially available from Hoechst, Stephan, AKZO (under the trade
name Aromox~) or FINA sunder the trade name Radiamox~1.
Suitable amines for use herein are according to the following formula
RR'R"N wherein R is a saturated or unsaturated, substituted or
unsubstituted, linear or branched alkyl groups containing from 1 to 30
carbon atoms, and preferably from 1 to 20 carbon atoms and wherein R'
and R" are independently saturated or unsaturated, substituted or
unsubstituted, linear or branched alkyl groups containing from 1 to 30
carbon atoms or hydrogen. Particularly preferred amines to be used
according to the present invention are amines having the following formula
RR'R"N wherein R is a saturated or unsaturated, linear or branched alkyl
group containing from 1 to 30 carbon atoms, preferably from 8 to 20
carbon atoms, more preferably from 6 to 16, most preferably from 8 to 14
and wherein R' and R" are independently substituted or unsubstituted,
linear or branched alkyl groups containing from 1 to 4 carbon atoms,
preferably from 1 to 3 carbon atoms, and more preferably are methyl
groups, or mixtures thereof.
Suitable amines for use herein are for instance C12 dimethyl amine,
coconut dimethyt amine, C12-C16 dimethyl amine. Said amines may be
commercially available from Hoechst under the trade name Genamin~,
AKZO under the trade name AromoxU~ or Fina under the trade name
Radiamox~.
Suitable quaternary ammonium surfactants for use herein are according to
the formula R1R2R3R4N+ X-, wherein X is a counteranion such as
halogen, methyl sulphate, methyl sulphonate, or hydroxide, R1 is a
saturated or unsaturated, substituted or unsubstituted, linear or branched
3 o alkyl group containing from 1 to 30 carbon atoms, preferably from 12 to
20, more preferably from 8 to 20 and R2, R3 and R4 are independently
hydrogen, or saturated or unsaturated, substituted or unsubstituted, linear
or branched alkyl groups containing from 1 to 4 carbon atoms, preferably
from 1 to 3 and more preferably methyl. In highly preferred quaternary
ammonium surfactants herein R1 is a C10-C1 g hydrocarbon chain, most
preferably C12, C14,, or C16, and R2, R3 and R4 are all three methyl,
and X is halogen, preferably bromide or chloride, most preferably bromide.
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Examples of quaternary ammonium surfactants are myristyl
trimethylammonium methyl sulphate, cetyl trimethylammonium methyl
sulphate, lauryl trimethyl ammonium bromide, stearyl trimethyl ammonium
bromide (STAB), cetyl trimethyl ammonium bromide (CTAB) and myristyl
trimethyl ammonium bromide (MTAB). Highly preferred herein are lauryl
trimethyl ammonium salts. Such trimethyl quaternary ammonium
surfactants may be commercially available from Hoechst, or from Albright
& Wilson under the trade name Empigen CM~.
Suitable nonionic surfactants for use in the compositions according to the
present invention are alkoxylated alcohol nonionic surfactants which can
be readily made by condensation processes which are well-known in the
art. However, a great variety of such alkoxylated alcohols, especially
ethoxylated and/or propoxylated alcohols is also conveniently
commercially available. Surfactants catalogs are available which list a
number of surfactants, including nonionics.
Accordingly, preferred alkoxylated alcohols for use herein are nonionic
surfactants according to the formula RO(E)e(P)pH where R is a
hydrocarbon chain of from 2 to 24 carbon atoms, E is ethylene oxide and
P is propylene oxide, and a and p which represent the average degree of,
respectively ethoxylation and propoxylation, are of from 0 to 24. The
hydrophobic moiety of the nonionic compound can be a primary or
secondary, straight or branched alcohol having from 8 to 24 carbon
atoms. Preferred nonionic surfactants for use in the compositions
according to the invention are the condensation products of ethylene oxide
with alcohols having a straight alkyl chain, having from 6 to 22 carbon
atoms, wherein the degree of ethoxylation is from 1 to 7 5, preferably from
5 to 12. Such suitable nonionic surfactants are commercially available
from Shell, for instance, under the trade name Dobanol~ or from Shell
under the trade name Lutensol~~ These nonionics are preferred because
they have been found to allow the formulation of a stable product without
requiring the addition of stabilisers or hydrotopes.
Suitable alkyl sulphonates for use herein include water-soluble salts or
acids of the formula RS03M wherein R is a Cg-C20 linear or branched,
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saturated or unsaturated alkyl group, preferably a C12-C1 g alkyl group and
more preferably a C14-C1g alkyl group, and M is H or a ration, e.g., an
alkali metal ration (e.g., sodium, potassium, lithium), or ammonium or
substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium
5 rations and quaternary ammonium rations, such as tetramethyt-ammonium
and dimethyl piperdinium rations and quaternary ammonium rations
derived from alkylamines such as ethylamine, diethylamine, triethylamine,
and mixtures thereof, and the like).
10 Suitable alkyl aryl sulphonates for use herein include water- soluble salts
or
acids of the formula RS03M wherein R is an aryl, preferably a benzyl,
substituted by a CS-C20 linear or branched saturated or unsaturated alkyl
group, preferably a C12-C1g alkyl group and more preferably a C14-C16
alkyl group, and M is H or a ration, e.g., an alkali metal ration (e.g.,
15 sodium, potassium, lithium, calcium, magnesium etc) or ammonium or
substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium
rations and quaternary ammonium rations, such as tetramethyl-ammonium
and dimethyl piperdinium rations and quaternary ammonium rations
derived from alkylamines such as ethylamine, diethylamine, triethylamine,
and mixtures thereof, and the like).
By "secondary C6-C20 alkyl or C6-C20 alkyl aryl sulphonates", it is meant
herein that in the formula as defined above, the S03M or aryl-S03M group
is linked to a carbon atom of the alkyl chain being placed between two
other carbons of the said alkyl chain (secondary carbon atom).
An example of a C14-C16 alkyl sulphonate is Hostapur ~ SAS available
from Hoechst. An example of commercially available alkyl aryl sulphonate
is Lauryl aryl suiphonate. Particularly preferred alkyl aryl
sulphonates are alkyl benzene sulphonates commercially available under
trade name Nansa~ available from Albright&Wilson.
Suitable alkyl sulphate surfactants for use herein are according to the
formula R1SO~M wherein R1 represents a hydrocarbon group selected
from the group consisting of straight or branched alkyl radicals containing
from 6 to 20 carbon atoms and alkyl phenyl radicals containing from 6 to
15 carbon atoms in the alkyl group. M is H or a ration, e.g., an alkali metal
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16
cation (e.g., sodium, potassium, lithium, calcium, magnesium etc) or
ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and
trimethyl ammonium cations and quaternary ammonium cations, such as
tetramethyl-ammonium and dimethyl piperdinium cations and quaternary
ammonium cations derived from alkylamines such as ethylamine,
diethylamine, triethylamine, and mixtures thereof, and the like).
Suitable alkyl alkoxylated sulphate surfactants for use herein are according
to the formula RO(A)mS03M wherein R is an unsubstituted Cg-C20 alkyl
or hydroxyalkyl group having a Cg-C20 alkyl component, preferably a C12-
C2p alkyl or ~hydroxyalkyl, more preferably C12-C1 g alkyl or hydroxyalkyl,
A is an ethoxy or propoxy unit, m is greater than zero, typically between
about 0.5 and about 6, more preferably between about 0.5 and about 3,
and M is H or a cation which can be, for example, a metal cation (e.g.,
sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or
substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl
propoxylated sulfates are contemplated herein. Specific examples of
substituted ammonium cations include methyl-, dimethyl-, trimethyl-
ammonium and quaternary ammonium cations, such as tetramethyl-
ammonium, dimethyl piperdinium and cations derived from alkanolamines
such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the
like. Exemplary surfactants are C12-C1 g alkyl polyethoxylate (1.0) sulfate,
C12-C1gE11.0)M), C12-C1g alkyl polyethoxylate (2.25) sulfate, C12-
C1 gEf2.25)M), C12-C1 g alkyl polyethoxylate (3.0) sulfate C12-C1 gE(3.0),
and C12-C1g alkyl polyethoxylate (4.0) sulfate C12-CIgE(4.01M), wherein
M is conveniently selected from sodium and potassium.
Suitable Cg-C20 alkyl alkoxylated linear or branched diphenyl oxide
disulphonate surfactants for use herein are according to the following
formula:
O \ / R
S03-X+ S03-X+
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wherein R is a Cg-C20 linear or branched, saturated or unsaturated alkyl
group, preferably a C12-C1g alkyl group and more preferably a Clq,-C16
alkyl group, and X+ is H or a cation, e.g., an alkali metal cation (e.g.,
sodium, potassium, lithium, calcium, magnesium etc). Particularly suitable
Cg-C20 alkyl alkoxylated linear or branched diphenyl oxide disulphonate
surfactants to be used herein are the C12 branched di phenyl oxide
disulphonic acid and C16 linear di phenyl oxide disulphonate sodium salt
respectively commercially available by DOW under the trade name Dowfax
2A1~ and Dowfax 8390~.
Other anionic surfactants useful herein include salts (including, for
example, sodium, potassium, ammonium, and substituted ammonium salts
such as mono-, di- and triethanolamine salts) of soap, Cg-C24
olefinsulfonates, sulfonated polycarboxylic acids prepared by sultonation of
the pyrolyzed product of alkaline earth metal citrates, e.g., as described in
British patent specification No. 1,082,179, Cg-C24
alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide);
alkyl ester sulfonates such as C14-16 methyl ester. sulfonates; acyl
glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene
oxide ether sulfates, alkyl phosphates, isethionates such as the acyl
isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates,
monoesters of sulfosuccinate !especially saturated and unsaturated C12-
C1g monoesters) diesters of sulfosuccinate (especially saturated and
unsaturated C6-Clq, diesters), acyl sarcosinates, sulfates of
2 5 alkylpolysaccharides such as the sulfates of alkylpoiyglucoside (the
nonionic nonsulfated compounds being described below), alkyl polyethoxy
carboxylates such as those of the formula ROICH2CH20)kCH2C00-M+
wherein R is a C8-C22 alkyl, k is an integer from 0 to 10, and M is a
soluble salt-forming cation. Resin acids and hydrogenated resin acids are
also suitable, such as rosin, hydrogenated rosin, and resin acids and
hydrogenated resin acids present in or derived from tall oil. Further
examples are given in "Surface Active Agents and Detergents" (Vol. I and
fl by Schwartz, Perry and Berch). A variety of such surfactants are also
generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975
to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
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Preferred anionic surfactants for use herein include the primary and
secondary Cg-C2p alkyl suplonates and the primary and secondary Cg-
C2p alkyl aryl sulphonates or a mixture thereof.
Iyes
The liquid compositions according to the present invention may be
colored. Accordingly, they may comprise a dye or a mixture thereof.
Suitable dyes to be used herein are acid-stable dyes. By "acid-stable", it is
meant herein a compound which is chemically and physically stable in the
acidic environment of the compositions herein. Suitable dyes to be used
herein include a or (3 metal phthalocyanines and/or trimethyl methane
dyes.
The a or (3 metal phthalocyanine dyes suitable to be used in the
compositions of the present invention are light-fast organic pigments with
four isoindole groups, (C6H4)C2N, linked by four nitrogen atoms to form a
conjugated chain. Their general structure is the following:
X X
\ /
I / iN \ I
Nw .NI~
N .Me~ N
-~ N
\ ~N /
/ \
X X
where the substituent X may be one of the following groups : H, Cl,
HS03, COO-M+, Br, N02, OCH3 or a C~ to Cep alkyl group and where
Me is copper, chromium, vanadium, magnesium, nickel, platinum,
aluminium, cobalt, lead, barium or zinc. Preferred a or ~ metal
phthalocyanine dyes to be used herein are a or ~i copper phthalocyanine
dyes.
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Examples of such a copper phthalocyanine dyes to be used herein are
copper phthalocyanine (X = H, blue colour) commercially available under
the name UNlSPERSE Blue B-E~ from Ciba-Geigy, or Cosmenyi blue A2R~
from Hoechst, or Pigmosoi blue 6900~ from BASF, or chlorinated copper
phthalocyanine (X = CI, green colourl commercially available under the
name Pigmosoi Green 8730 ~ from BASF.
Examples of trimethyl methane dyes are commercially available from
Hoescht under the name Vitasyn~ or from BASF under the name Acid Blue
l0
Typically, the compositions according to the present invention may
comprise up to 0.2% by weight of the total composition of a dye or a
mixture thereof, preferably from 0.0001 % to 0.015% and more preferably
from 0.001 % to 0.010%.
The liquid acidic compositions according to the present invention may be
packaged in a variety of suitable detergent packaging known to those
skilled in the art. Indeed they may be easily dispensed onto the surface to
be treated via a spray-type dispenser such as for instance a trigger-
sprayer. Suitable spray-type dispensers to be used according to the
present invention include manually operated foam trigger-type dispensers
sold for example by Specialty Packaging Products, Inc. or Continental
Sprayers, Inc. These types of dispensers are disclosed, for instance, in
US-4,701,311 to Dunnining et al. and US-4,646,973 and US-4,538,745
both to Focarracci. Particularly preferred to be used herein are spray-type
dispensers such as T 8500 or T 8900~ commercially available from
Continental Spray International or T 8100~ commercially available from
Canyon, Northen Ireland. In such a dispenser the liquid composition is
divided in fine liquid droplets resulting in a spray that is directed onto the
surface to be treated. Indeed, in such a spray-type dispenser the
. composition contained in the body of said dispenser is directed through
the spray-type dispenser head via energy communicated to a pumping
mechanism by the user as said user activates said pumping mechanism.
More particularly, in said spray-type dispenser head the composition is
forced against an obstacle, e.g. a grid or a cone or the like, thereby
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providing shocks to help atomise the liquid composition, i.e. to help the
formation of liquid droplets.
5 Limescale removal performance test method'
The limescale removal capacity of an acidic composition may be evaluated
by soaking a marble block (marble blocks are chemically speaking very
similar to limescale, i.e. they are essentially made of calcium carbonate)
l0 into 20 g of this composition. The marble is weighed before and after the
experiment, and the performance is expressed in grams of marble block
dissolved over time. Alternatively, limescale removal performance can also
be evaluated by detecting the release of C02.
Shine test method:
Obtaining a good shine end result results from a good spreading of the
liquid acidic composition over the surface when the surface is treated
therewith and from the reduced formation of watermarks and even
reduced precipitation of poorly water soluble salts that otherwise typically
occurs in presence of hard water, when water evaporates. The ability of a
composition to provide "shine" to the surface refers to the composition's
ability to leave no watermarks after evaporation of water. This can be
evaluated by human visual grading.
In a suitable test method two rectangular areas (l0cmx4cm) of a sink
(made of either stainless steel or ceramic) are treated with a composition
according to the present invention and a reference composition, e.g. the
same composition but without said polysaccharide polymer. 3 grams of
composition is first poured onto each surfaces to be treated and, then
wiped ( 10 strokes) by using a Spontex~ sponge. Then each treated
surface is rinsed with 200 grams of tap water and left to dry. After the
surfaces treated with the compositions according to the present invention
and those treated with the reference composition get dried, they are
compared side by side and evaluated by visual grading to evaluate shine
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difference. Evaluation may be generally done by applying the Panel Score
Unit (PSU).
In a long lasting shine test method the test method as mentioned above
may be carried out, but the rinsing and drying cycle are repeated several
times. Each time, after both the surfaces get dried they are compared side
by side and evaluated by visual grading to see shine difference. Evaluation
is generally done by applying the Panel Score Unit (PSU).
The present invention is further illustrated by the following examples.
Exam I~es
These compositions were made comprising the listed ingredients in the
listed proportions (weight %1.
25
Composition
Ingredients: I II III IV V VI
( ~ by weight)
Malefic acid 10 10 1 ~. - 10 12
Sulphamic acid 2 2 - 2 - 2
Citric acid - - - 2 2 2
Mirataine CBS~ 2.0 2.0 - 2.0 - 2.0
HLAS - - - - 0.50 -
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Xanthan Gum 0.2 0.1 0.1 0.3 0.4 0.5
Waters & Minors ---------------------- up to 100 --------------------
Ingredients: VII VIII IX X XI XII
(% by weight)
Malefic acid 10 10 10 8 6 -
Sulphamic acid 2 2 2 - - 2
Citric acid - 1 - 2 4 8
Dobanol~ 91.8 2 2 - 1 - -
Mirataine CBS~ - - 2 - - 2.2
Xanthan Gum - - 0.05 - 0.50 0.1
Succinoglycan 0.05 0.1 - 0.05 0.05 -
Waters & Minors ----------------------
up to 100 --------------------
Mirataine CBS~ is cocoamidopropyl hydroxy sulphobetaine supplied by
l0 Rhone-Poulenc.
HLAS is Linear alkyl benzene sulphonate in acid form.
Dobanol~ 91.8 is a nonionic surfactant supplied by Shell.
All the compositions of the above examples exhibit excellent immediate
and long lasting shine benefits on the surface treated while providing
excellent limescaie removal performance. Also good greasy soap scum
cleaning performance have been obtained when these compositions are
used to treat limescale-containing stains found in a kitchen and in a
bathroom, this both when used neat or in diluted form.
