Note: Descriptions are shown in the official language in which they were submitted.
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WO 99/23194 PCTNS98/?3377 -
LIQUID ACIDIC LIMESCALE REMOVAL COMPOSITIONS PACKAGED iN
°A SPRAY-TYPE DISPENSER
Technical field of the Invention
The present invention relates to liquid acidic limescale removal
compositions packaged in a spray-type dispenser.
Back4round 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 hard-
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 limescale removal
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 good shine to the surfaces treated. However,
surface shine is often compromised because, when water comes in contact
with hard-surfaces it has the tendency to form droplets on the surface rather
than forming a thin film uniformly spread over the surface or to run off the
surface. This results, as water evaporates, in precipitation of poorly water
soluble inorganic salts such as calciumlmagnesium carbonate and/or
phosphate salts with consequent formation of watermarks on the surface
and, eventually limescale deposits, resulting in an anaesthetic aspect of the
surface.
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2
It is thus an object of the present invention to reduce the formation of
watermarks andlor fimescale deposits on a hard-surface that has been
treated with a liquid wacidic composition and hence to provide improved
shine to this surface. More particularly, it is an object of the present
invention to provide liquid acidic compositions delivering improved shine to
the surface treated while exhibiting excellent limescale removing
performance. It is yet another object of the present invention to provide such
liquid acid compositions in a convenient way so as to facilitate any hard-
surface descaling operation therewith by the consumer.
The present invention overcomes these problems by formulating liquid
acidic compositions comprising an acid, a polysaccharide polymer (0.001 %-
20%) and a vinylpyrrolidone homopolymer or copolymer (0.001 °/p-20%),
said
compositions being packaged in a spray type-dispenser. Indeed, it has been
found that the addition of a polysaccharide polymer, preferably xanthan
gum, together with a vinylpyrrolidone homopolymer or copolymer, 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.
Another advantage of the present invention is that the shine benefit
delivered to a hard-surface treated with the compositions of the present
invention persists even after several cycles of rinsing, thus providing long
lasting protection against formation of watermarks andlor even limescale
deposits on the surface, and hence long lasting shiny surfaces. In other
words, the house wife will have the advantage to delay the next descaling
operation. Advantageously, the shine benefits herein are obtained at very
low total levels of both a polysaccharide polymer and a vinylpyrrolidone
homopolymer or copolymer, in the acidic compositions of the present
invention.
Another advantage of the liquid acidic compositions of the present invention
is that the surfaces treated become smoother (this can be perceived by
touching said surfaces). This may also contribute to convey to consumer
perception of surface perfectly descaled.
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3
Also it has surprisingly been found that the compositions according to the
present invention deliver the benefits mentioned herein (e.g., reduction or
prevention of the formation of watermarks andlor even limescale deposits,
resulting in good shine benefit and even long lasting shine benefit), when
used to treat 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.
In a preferred embodiment of the present invention, the compositions herein
comprise malefic acid together with a second acid typically sulfamic acid.
These compositions have been found to be particularly safe to various types
of hard-surfaces treated therewith as well as milder to the skin.
Another benefit of the present invention is that the compositions herein are
easily applied to the surface to treat while using a minimum amount of said
composition, as compared to applying a liquid composition by directly
pouring it onto the surface to treat, instead of spraying it according to the
present invention. Also spraying the composition on the surface to treat
allows to treat a larger area with a give amount of product versus pouring
the liquid composition on the surface to treat. Furthermore, the risk of
spillage as well as the tendency of the liquid compositions to be messy
when applied onto the surface is reduced when said application is made by
using a spray-type dispenser.
Advantageously, the liquid acidic compositions of the present invention are
applied to the surfaces to treat by the means of a spray-type dispenser
while being safe both to the user and to the surfaces treated therewith.
Indeed, the acidic compositions herein may be sprayed onto the surfaces to
treat with minimal inhalation by the user of said acidic compositions and
thus by avoiding any potential health issue due to the presence of an acid in
said compositions.
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4
Background art
Limescale compositions comprising acids are known in the art. For example
EP-A- 666 305 discloses acidic limescate removing compositions
comprising malefic acid and a second acid like sulphamic acid. However, no
liquid acidic compositions as described in the present invention comprising
a polysaccharide polymer together with a vinylpyrrolidone homopolymer or
copolymer are disclosed therein.
EP-A-467 472 discloses a hard-surface liquid composition with anti-
staticlanti-soiling cationic quaternized polymers. Cationic quaternized
polymethacrylate include beta(trialkyl ammonium) ethylmethacrylates/
acrylates. However, no liquid acidic compositions as described in the
present invention comprising a polysaccharide polymer together with a
vinylpyrrolidone homopolymer or copolymer are disclosed therein.
WO 94126858 discloses acidic compositions (pH 2-8) comprising a nonionic
surfactant and an anionic polymer having an average molecular weight less
than 1 000 000 said polymer being free of quaternary nitrogen groups.
However, no liquid acidic compositions as described in the present
invention comprising a polysaccharide polymer together with a
vinylpyrrolidone homopolymer or copolymer are disclosed therein
Summary of the invention
The present invention relates to a liquid acidic composition suitable for
removing fimescale-containing stains from a hard-surface, comprising an
acid, from 0.001 % to 20% by weight of the total composition of a
polysaccharide polymer and from 0.001 % to 20% by weight of the total
composition of a vinylpyrrolidone homopolymer or copolymer, said
composition being packaged in a spray type-dispenser.
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The present invention also encompasses a process of treating hard-
surfaces wherein an acidic liquid composition according to the present
invention is applied onto said surfaces from a spray-type dispenser, then left
to act onto said surfaces and then removed by rinsing.
Detailed description of the invention
The liguid acidic compositions:
The liquid compositions of the present invention are acidic cbmpositions.
Accordingly, the compositions of the present invention are typically
formulated at a pH below 7, preferably below 5, more preferably below 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 liquid compositions according to the present invention are preferably
aqueous compositions. Therefore, they typically 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%.
The compositions according to the present invention are designed for
removing limescale deposits. Thus, they comprise as a first essential
ingredient an acid or a mixture thereof. Typically, the acids to be used
herein may be any 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. Said compositions comprise from 0.1 % to 70% by
weight of the total composition of an acid or a mixture thereof.
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6
Preferred herein the compositions of the present invention comprise at least
malefic acid. Accordingly, the compositions according to the present
invention comprise from 0.1 % to 45% by weight of the total composition of
malefic acid, preferably from 1 % to 25% and more preferably from 3% to
20%. This percentage is calculated on the basis of the molecular weight of
the acid form, but 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 of the present
invention malefic acid is used alone as the acid of the acidic compositions of
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 for use herein is sulphamic acid. Sulphamic acid may
be added in the compositions according to the present invention in its acid
form or as an alkali metal salts thereof. Thus sulphamic acid may be added
for example as sulphamate. Sulphamic acid is for example commercially
available under its chemical name from Albright & Wilson or Nissan
chemicals. Indeed, it has been found that the addition of sulphamic acid on
top of malefic acid in the compositions of the present invention improves the
skin mildness of said compositions. Indeed, less skin irritation is perceived
by the user when its skin comes into contact with these compositions as
compared to the same compositions but without sulphamic acid.
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7
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 methanesuiphonic 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
R~
S 03 H
R2 R3
wherein R1, R2, R3, R4 and RS 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
alkyl chain or only one. 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
the surface treated therewith. Particularly suitable arylsulphonic acids for
use herein are benzene sulphonic acid (pKa=0.7), toluene sulphonic acid
and cumene sulphonic 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.
Preferred acids having a first pKa not exceeding 5 for use herein are
sulphamic acid, sulphuric acid, aryl sulphonic acids, alkyl sulphonic acids,
citric acid, nitric acid, phosphoric acid, hydrochloric acid or mixtures
thereof,
more preferred are sulphamic acid, citric acid or mixtures thereof and highly
preferred is sufphamic acid.
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The compositions of 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°~.
The liquid acidic compositions of the present invention comprise as a
second essential ingredient a vinylpyrrolidone homopolymer or copolymer,
or a mixture thereof at a level of from 0.001 % to 20% by weight of the total
composition. Typically, the compositions of the present invention comprise
from 0.01 % to 5% by weight of the total composition of a vinylpyrroiidone
homopolymer or copolymer, or a mixture thereof, more preferably from
0.01 % to 3% and most preferably from 0.01 % to 1 %.
Suitable vinylpyrrolidone homopolymers for use herein are homopolymers of
N-vinylpyrrolidone having the following repeating monomer:
H
I
C-CH~
I
N
H~ C~ ~C=O
'I I
H~ C- CHI
n
wherein n (degree of polymerisation) is an integer of from 10 to 1,000,000,
preferably from 20 to 100,000, and more preferably from 20 to 10,000.
Accordingly, suitable vinylpyrrolidone homopolymers ("PVP") for use herein
have an average molecular weight of from 1,000 to 100,000,000, preferably
from 2,000 to 10,000,000, more preferably from 5,000 to 1,000,000, and
most preferably from 50,000 to 500,000.
Suitable vinylpyrrolidone homopolymers are commercially available from ISP
Corporation, New York, NY and Montreal, Canada under the product names
PVP K-15~ (viscosity molecular weight of 10,000), PVP K-30~ (average
molecular weight of 40,000), PVP K-60~ (average molecular weight of
CA 02308295 2004-03-24
9
160,000), and PVP K-90~ (average molecular weight of 360,000). Other
suitable vinylpyrroiidone homopolymers which are commercially available
from BASF Cooperation include Sokalan HP 165~, Sokaian HP 12~,
- Luviskol K30~, Luviskol K60~, Luviskol K80~, Luviskol K90~;
vinyipyrrolidone homopolymers known to persons skilled in the detergent
field (see for example EP-A-262,897 and EP-A-256,696).
Suitable copolymers of vinylpyrrolidone for use herein include copolymers of
N=vinylpyrrolidone and alkylenically unsaturated monomers or mixtures
thereof.
The alkylenically unsaturated monomers of the copolymers herein include
unsaturated dicarboxylic acids such as malefic acid, chloromaleic acid,
furnaric acid, itaconic acid, citraconic acid, phenylmaleic acid, aconitic
acid,
acrylic acid, N-vinylimidazole and vinyl acetate. Any of the anhydrides of the
unsaturated acids may be employed, for example acrylate, methacrylate,
Aromatic monomers like styrene, sulphonated styrene, alpha-methyl styrene,
vinyl toluene, t-butyl styrene and similar well known monomers may be used.
The molecular weight of the copolymer of vinylpyrrolidone is not especially
critical so long as the copolymer is water-soluble, has some surface activity
and is adsorbed to the hard-surface from the liquid composition comprising it
in such a manner as to increase the hydrophilicity of the surface. However,
the preferred copolymers of N-vinylpyrrolidone and alkylenically unsaturated
monomers or mixtures thereof, have a molecular weight of between 1,000
and 1,000,000, preferably between 10,000 and 500,000 and more preferably
between 10,000 and 200,000.
For example particularly suitable N-vinylimidazole N-vinylpyrrolidone
polymers for use herein have an average molecular weight range from 5,000
to 1,000,000, preferably from 5,000 to 500,000, and more preferably from
10,000 to 200,000. The average molecular weight range was determined by
light scattering as described in Barth H.G_ and Mays J.W. Chemical Analysis
Vol 113,"Modern Methods of Polymer Characterization". (whey 1991) .
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WO 99/23194 PCT/US98/23377 -
Such copolymers of N-vinylpyrrolidone and alkylenically unsaturated
monomers like PVP/vinyl acetate copolymers are commercially available
under the trade name ~uviskol~ series from BASF.
The copolymers of vinylpyrrolidone for use in the compositions of the
present invention also include quaternized or unquaternized
vinylpyrrolidoneldialkylaminoalkyl acrylate or methacrylate copolymers.
Such vinylpyrrolidoneldialkylaminoalkyl acrylate or methacrylate copolymers
(quaternised or unquaternised) suitable to be used in the compositions of
the present invention are according to the following formula:
N R~
C H H2-C
. ( m
(C-O'Y +
~'-Rz-N (R3)2Ra.X
in which n is between 20 and 99 and preferably between 40 and 90 mol%
and m is between 1 and 80 and preferably between 5 and 40 mol%; R1
represents H or CH3; y denotes 0 or 1; R2 is -CH2-CHOH-CH2- or CXH2x,
in which x=2 to 18; R3 represents a lower alkyl group of from 1 to 4 carbon
atoms, preferably methyl or ethyl, or
CHZ
R4 denotes a lower alkyl group of from 1 to 4 carbon atoms, preferably
methyl or ethyl; X- is chosen from the group consisting of C1, Br, I, 112S04,
HS04 and CH3S03. The polymers can be prepared by the process
described in French Pat. Nos. 2,077,143 and 2,393,573.
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The preferred quaternized or unquaternized
vinylpyrrolidoneldialkylaminoalkyl acrylate or methacrylate copolymers for
use herein have a molecular weight of between 1,000 and 1,000,000,
preferably between 10,000 and 500,000 and more preferably between
10, 000 and 100, 000.
Such vinyfpyrrolidoneldialkylaminoalkyl acrylate or methacrylate copolymers
are commercially available under the name copolymer 845~, Gafquat 734~,
or Gafquat 7550 from ISP Corporation, New York, NY and Montreal,
Canada or from BASF under the tradename Luviquat~.
Preferred second essential ingredient for use herein are the vinylpyrrolidone
homopolymers.
The liquid acidic compositions of the present invention comprise as a third
essential ingredient a polysaccharide polymer or a mixture thereof at a level
of from 0.001 % to 20% by weight of the total composition. Typically, the
compositions of the present invention comprise from 0.01 % to 10% by
weight of the total composition of a polysaccharide polymer or a mixture
thereof, more preferably from 0.01 % to 5% and most preferably from 0.01
to 2%.
Suitable polysaccharide polymers for use 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.
Particularly polysaccharide polymers for use 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~. Other suitable Xanthan gum are
commercially available by Rhone Poulenc under the trade name Rhodopol T
~ and Rhodigel X7470. Succinoglycan gum for use herein is commercially
available by Rhone Poulenc under the trade name Rheozan ~.
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12
The polysaccharide polymers herein may act as a thickening agent,
accordingly the liquid acidic compositions herein have a viscosity of from 1
cps to 1500 cps, 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 NIm2 at 20°C.
The polysaccharide polymers, preferably xanthan gum or derivatives
thereof, and vinylpyrrolidone homopolymer or copolymers, 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.
It has now surprisingly been found that the polysaccharide polymers,
preferably xanthan gum or derivatives thereof, and vinylpyrrolidone
homopolymers or copolymers described herein, when added into a liquid
acidic composition packaged in spray-type dispenser deliver improved shine
while not compromising the limescale removal performance of said
composition.
The present invention is based on the finding that the polysaccharide
polymers and vinylpyrrolidone homopolymers or copolymers present in the
compositions of the present invention are able to modify the surface by
depositing on the surface itself treated therewith. Although not wishing to be
bound by theory, it has been observed that hard surfaces typically found in
a household are neither highly hydrophobic nor highly hydrophilic. 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. 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 or than running off the
surface. Then, as water droplets evaporate, their content of salt
progressively becomes higher and higher so that carbonate salts eventually
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~3
precipitate resulting in watermarks or even limescale deposits. 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 liquid acidic compositions a hydrophilic layer is left
on
a hard-surface treated therewith, especially low energy surfaces like
stainless steel, said hydrophilic layer leaves the water coming in contact
with the surface having first been so treated (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. It has further been
found that when the vinylpyrrolidone homopolymers or copolymers as
described herein are added into liquid acidic compositions a hydrophobic
layer is left on a hard-surface treated therewith, especially high energy
surfaces like ceramic, porcelain, glass and the like, said hydrophobic layer
causes the water coming in contact with the surface having first been so
treated (e.g., water which is used to rinse off the surfaces having been so
treated) to run off the surface instead of forming droplets. Thus by modifying
the surface features as indicated, the formation of watermarks andlor
limescale deposits upon drying is reduced or even eliminated. In other
words, the second and third essential ingredients of the composition of the
present invention act together to provide the benefits herein on all type of
hard-surfaces from low energy to high energy surfaces.
A definition to what is understood by low energy to high energy surfaces is
given in "Surfactant Science and Technology", 2"d Edition, by Drew Myers,
1992 VCH Publishers Inc. , on pages 268-272.
Furthermore, it has surprisingly been found that the polysaccharide
polymers and vinylpyrrofidone homopolymers or copolymers have not only
the ability to adhere on a surface treated with the liquid acidic compositions
of the present invention comprising the same and being packaged in a
spray-type dispenser, but to still remain adhered on the surface even after
several cycles of rinsing (e.g., when water comes onto this surface later on
for example in a sink during daily household operation), thus providing long
lasting protection against formation of watermarks and/or deposition of
(imescale deposits, hence, long lasting shiny surfaces.
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14
Not to be bound by theory, it is believed that the polysaccharide polymers,
and vinylpyrrolidone homopolymers or copolymers also have the ability to
form a film on the surface of the user skin thereby further contributing to
the
skin mildness characteristics delivered due to the presence of sulphamic
acid on top of malefic acid otherwise perceived to be more irritant to skin,
this in the preferred embodiment of the present invention where indeed
sulphamic acid is used on top of malefic acid.
An additional advantage related to the use of the polysaccharide polymers,
and vinylpyrrolidone homopolymers or copolymers in the acidic
compositions herein, 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 contributd to convey
perception of surface perfectly descaled.
Advantageously, these benefits are obtained at low levels the
polysaccharide polymers, preferably xanthan gum or derivatives thereof,
and vinylpyrrolidone homopolymers or copolymers described herein, thus it
is yet another advantage of the present invention to provide the desired
benefits at low cost. Typically, the liquid acidic compositions according to
the present invention comprise from 0.002% to 5% by weight of the total
composition of a polysaccharide polymer or mixture thereof together with a
vinylpyrrolidone homopolymer and/or copolymer, preferably from 0.005 % to
2%, more preferably from 0.01 % to 2% and most preferably from 0.01 % to
1 °~.
As a further essential feature, the liquid acidic compositions according to
the
present invention are packaged in a spray-type dispenser.
By "spray dispense', it is meant any spray dispenser known to those skilled
in the art including trigger spray dispensers or pump spray dispensers.
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.
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WO 99/23194 PCT/US98/23377 -
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 providing shocks to help atomise the liquid
composition, i.e. to help the formation of liquid droplets.
Preferred foam trigger-type dispensers for use herein have a cone as
impingement zone. The two most important dimensions determining the
foam character, size and distribution of pattern are orifice diameter and
spinner channel width. The interaction of these two factors also determine
amount of flow and velocity of that flow trough the nozzle.
Preferred foam trigger spray type dispenser for use herein is the model
known as T8900~ commercially available by CSI. This foam spray-type
dispenser has a piston pump with an impingement tube that contacts the
spray cone causing turbulence and creating foam. Originally, this foam
spray dispenser has a orifice diameter of 0.028" (0.028 inches) and a two
spinner channels 0.0425" (0.0425 inches) width. Such a commercially
available spray may also undergone modifications to improve the spray
pattern and reduced the misting effect. For instance preferred configurations
are those with smaller spinner channels and larger orifices that will result
in
a foam spray with less misting. More preferred configuration has a diameter
orifice of 0.030" or 0.032" width and spinner channels of 0.0425" or 0.030"
width. Most preferred foam spray-type dispenser has 0.030" orifice and
0.0425" spinner channels.
The foam trigger spray dispensers mentioned in the present invention have
preferably a bayonet closure instead of a threaded closure, thereby
providing a child resistant device. Indeed, the bayonet package (having two
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16
or tour lugs) allows the spray-type dispenser to be fastened to the bottle in
a
safer way avoiding ease of opening by children and messiness in use.
An advantage of the present invention is that the acidic liquid compositions
of the present invention may be applied uniformly to a relatively large area
of a surface to be treated via a spray-type dispenser, thereby ensuring
excellent limescale removal performance while being particularly safe to the
surface treated and the user.
Another advantage of the present invention is that the liquid acidic
compositions of the present invention may be easily dispensed onto the
surfaces to treat.
A further advantage according to the present invention is that the surface
treatment is carried out in an economical way, i.e. no more product that what
is really necessary is used.
Optional ingredients
The compositions according to the present invention may further comprise a
variety of other ingredients including surfactants, colorants, bactericides,
thickeners, dyes, chelants, pigments, solvents, stabilizers, perfumes,
corrosion inhibitors and the like.
Surfactants
A highly preferred optional ingredient suitable for use in the compositions of
the present invention is a surfactant or a mixture thereof. Surfactants are
desired herein as they contribute to the cleaning benefits of the limescaie
removal compositions of the present invention. Indeed, the presence of a
surfactant contributes to 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 of the
present invention helps to solubilize the soils.
CA 02308295 2000-04-28
WO 99123194 PCT/US98/23377 -
17
Accordingly, the compositions according to the present invention 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 a surfactant or a mixture thereof, more preferably from
0.05°~
to 15%, even more 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 for use herein are zwitterionic surfactants.
Indeed, they have the ability when added in the acidic compositions of the
present invention to maintain the timescale removal performance of the
acidic system (i.e. similar limescale removing performance as compared to
the same acidic compositions but without any surfactant), white providing
excellent grease soap scum cleaning ability to the compositions of the
present invention.
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)(R3)R4X-
wherein R1 is a hydrophobic group; R2 is hydrogen, C1-Cg alkyl, hydroxy
alkyl or other substituted C1-Cg alkyl group; Rg is C1-Cg alkyl, hydroxy
alkyl or other substituted C1-C6 alkyl group which can also be joined to R2
to form ring structures with the N, or a C1-Cg carboxylic acid group or a C1-
CA 02308295 2000-04-28
WO 99/23194 PCT/US98/2337'7 -
18
C6 sulfonate group; R4 is a moiety joining the cationic nitrogen atom to the
hydrophilic group and is typically an alkylene, hydroxy alkylene, 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
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 containing from 8 up to 20 carbon
atoms, 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,
mare 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.
CA 02308295 2004-03-24
19
Some common examples of betainelsulphobetaine 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-(N-
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 dimethy) 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 BBIL~.
A further example of betaine is Lauryl-immino-dipropionate commercially
available from Rhone-Poulenc under the trade name Mirataine H2C-HA ~.
Particularly preferred zwitterionic surfactants for use in the acidic
compositions of the present invention are the sulfobetaine surfactants as
they deliver optimum limescale removal benefits and soap scum cleaning
benefits.
Examples of particularly suitable suffobetaine 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.
Further examples of amidobetaineslamidosuifobetaine 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~
sulfobetaine".
Suitable amine oxides for use herein are according to the following formula
R1 R2R3N0 wherein each of R1, R2 and R3 is independently a saturated or
unsaturated, substituted or unsubstituted, linear or branched alkyl group
containing from 1 to 30 carbon atoms, and preferably from 1 to 20 carbon
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atoms. Particularly preferred amine oxides to be used according to the
present invention are amine oxides having the following formula R1 R2R3N0
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 16, 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
commercially available from Hoechst, Stephan, AKZO (under the trade
name Aromox~) or FINA (under the trade name Radiamox~).
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
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 dimethyl amine, C12-C16 dimethyl amine. Said amines may be
commercially available from Hoechst under the trade name Genamin~,
AKZO under the trade name Aromox~ or Fina under the trade name
Radiamine~.
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21
Suitable quaternary ammonium surfactants for use herein are according to
the formula R~ R2R3R4N+ 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 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-C1g hydrocarbon chain, most preferably
C12, C1~,, or C16, and R2, R3 and R4 are all three methyl, and X is
halogen, preferably bromide or chloride, most preferably bromide.
Examples of quaternary ammonium surfactants are myristyl
trimethylammonium methyl sulphate, cetyl trimethylammoniurn 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~.
In a preferred embodiment, the surfactant used in the acidic compositions of
the present invention is a surfactant system comprising a zwitterionic
surfactant with a second surfactant, e.g. an amine oxide and/or amine
and/or a quaternary ammonium surfactant as described herein at a weight
ratio of the zwitterionic surfactant to the second surfactant of at least 1:1,
preferably at least 2:1. This surfactant system provides to the acidic
compositions according to the present invention both optimum limescale
removing performance (i.e, comparable to the limescale removing
performance of the same compositions without any surfactant) as well as
optimum greasy soap scum cleaning performance.
Suitable nonionic surfactants for use herein 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 andlor propoxylated alcohols is also
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22
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, a 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 15, preferably from 5 to 12. Such
suitable nonionic surfactants are commercially available from Shell, for
instance, under the trade name Dobanol~ or from BASF 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 C6-C20 linear or branched, saturated
or unsaturated alkyl group, preferably a C12-C18 alkyl group and more
preferably a C14-C16 alkyl group, and M is H or a cation, e.g., an alkali
metal cation (e.g., sodium, potassium, lithium), 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 aryl sufphonates for use herein include water- soluble salts or
acids of the formula RS03M wherein R is an aryl, preferably a benzyl,
substituted by a C6-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 canon, e.g., an alkali metal cation (e.g.,
sodium,
potassium, lithium, calcium, magnesium and the like) or ammonium or
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23
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 sulphonate from Su.Ma. Particularly preferred alkyl aryl
sulphonates are alkyl benzene sulphonates commercially available under
trade name Nansa~ available from Albright8~Wilson.
Suitable alkyl sulphate surfactants for use herein are according to the
formula R1 S04M 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 ration
(e.g.,
sodium, potassium, lithium, calcium, magnesium and the like) or ammonium
or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium
rations and quaternary ammonium rations, such as tetramethyi-ammonium
and dimethyl piperdinium rations and quaternary ammonium rations 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-C2p alkyl or
hydroxyalkyl group having a Cg-C20 alkyl component, preferably a C12-C20
alkyl or hydroxyalkyl, more preferably C12-C1g 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 ration which can be, for example, a metal ration (e.g., sodium, potassium,
lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium
CA 02308295 2004-03-24
29
ration, Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are
contemplated herein. Specific examples of substituted ammonium rations
include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium
rations, such as tetramethyl-ammonium, dimethyl piperdinium and rations
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-C1$E(1.0)M), C12-C1g alkyl
polyethoxylate (2.25) sulfate, C12-C18E(2.25)M), C12-C1g alkyl
polyethoxylate (3.0) sulfate C12-C18E(3.0), and C12-C1g alkyl
polyethoxylate (4.0) sulfate C12-ClgE(4_0)M), wherein M is conveniently
selected from sodium and potassium.
Suitable Cg-C20 alkyl alkoxylated linear or branched Biphenyl oxide
disulphonate surfactants for use herein are according to the following
formula:
0 ~ / -R
S03-X+ S03-X+
wherein R is a C6-C20 linear or branched, saturated or unsaturated alkyl
group, preferably a C12-C1g alkyl group and more preferably a C14-C16
alkyl group, and X+ is H or a ration, e.g., an alkali metal ration (e.g.,
sodium, potassium, lithium, calcium, magnesium and the like). Particularly
suifable Cg-C2p alkyl alkoxylated linear or branched Biphenyl 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 olefinsutfonates,
sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed
product of alkaline earth metal citrates, e.g.,
Cg-C2~ alkylpolyglycolethersulfates (containing
CA 02308295 2004-03-24
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 Cg-C14 diesters), acyl sarcosinates, sulfates of
alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic
nonsulfated compounds being described below), alkyl polyethoxy
carboxylates such as those of the formula RO(CH2CH20)kCH2CO0-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 II
by Schwartz, Perry and Berch, Krieger PubI.Comp., New York, 1977). 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.
Preferred anionic surfactants herein include the primary and secondary Cg-
C2i~ alkyl suplonates and the primary and secondary Cg-C20 alkyl aryl
sulphonates or a mixture thereof.
Dyes
Thc: liquid compositions according to the present invention may be coloured.
Accordingly, they may comprise a dye or a mixture thereof. Suitable dyes for
use 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 for use herein
include a or (i metal phthalocyanines andlor 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, (CgH4)C2N, linked by four nitrogen atoms to form a
conjugated chain. Their general structure is the following:
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26
X ~ /~ ~ (./~- X
N
,. ,
N - N..Me~N N
~N~ /
I
X X
where the substituent X may be one of the following groups : H, , CI, HS03,
COO-M+, Br, N02, OCH3 or a C1 to C10 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.
Examples of such a copper phthalocyanine dyes to be used herein are
copper phthalocyanine (X = H, blue colour) commercially available under
the name UNISPERSE Blue 8-E~ from Ciba-Geigy, or Cosmenyl blue A2R
~ from Hoechst, or Pigmasol blue 6900~ from BASF, or chlorinated copper
phthalocyanine (X = C1, green colour) commercially available under the
name Pigmasol 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
~.
Also suitable dyes for use herein are polymeric liquid colours such as the
liquid polymer-blue supplied by Milliken Company under the name Liquitint~
Blue 65, Liquitinf~ Patent Blue and Liquitint~ Bright Blue.
Typically, the compositions of 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%.
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27
Radical scavengers:
The compositions of the present invention may comprise a radical scavenger
or a mixture thereof. w
Suitable radical scavengers for use herein include the well-known substituted
mono and dihydroxy benzenes and their analogs, alkyl and aryl carboxylates
and mixtures thereof. Preferred such radical scavengers for use herein
include di-tert-butyl hydroxy toluene (BHT), hydroquinone, di-tert-butt'!
hydroquinone, mono-tert-butyl hydroquinone, tert-butyl-hydroxy anysole,
benzoic acid, toluic acid, catechol, t-butyl catechol, benzylamine, 1,1,3-
tris(2-
methyl-4-hydroxy-5-t-butylphenyl) butane, n-propyl-gallate or mixtures thereof
and highly preferred is di-tert-butyl hydroxy toluene. Such radical scavengers
like N-propyl-gallate may be commercially available from Nipa Laboratories
under the trade name Nipanox S1 ~.
Radical scavengers when used, are typically present herein in amounts up to
10% by weight of the total composition and preferably from 0.001 % to 0.5%
by weight.
The presence of radical scavengers may contribute to the chemical stability
of the acidic compositions of the present invention.
Process for treating surfaces:
The compositions according ~ to the present invention are particularly
suitable for treating hard-surfaces soiled by limescale-containing stains. By
"limescale-containing stains" it is meant herein any pure limescale stains,
i.e., any stains composed essentially of mineral deposits as well as
limescale-containing stains typically found, for example, in a kitchen or in a
bathroom, i.e., stains which contain not only mineral deposits like calcium
and/or magnesium carbonate but also soap scum (e.g., calcium stearate)
and other grease (e.g. body grease). Actually, the compositions of the
present invention exhibit excellent limescale removing performance when
used to treat any types of surfaces soiled by limescale-containing stains
comprising not only pure limescaie deposits but also at least 10°~ by
weight
of the total stain of organic deposits tike soap scum and grease, preferably
more than 30%. Such surfaces can be found in bathrooms, kitchens, but
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28
also in appliances including large appliances such as automatic dish
washers and/or washing machines.
Accordingly, the present invention encompasses a process of treating hard-
surfaces soiled by limescale-containing stains wherein an aqueous acidic
liquid composition according to the present invention is applied onto said
surfaces from a spray-type dispenser, then left to act onto said surfaces and
then removed by rinsing.
The expression "treating" includes removing limescale deposits while being
safe to the surfaces treated and optionally cleaning greasy soap scum
stains especially when surfactants are present.
Limescale removal performance test method:
The limescale removal capacity of a composition according to the present
invention may be evaluated spraying the composition on encrusted ceramic
tiles prepared using the auto dish washing machine. Black glazed ceramic
tiles (typically 20 cm x 20 cm) are poured into the auto dish washing
machine and treated with 7 complete washing cycles. Each cycle is
performed using 15 g of Sodium Carbonate (instead of the detergent) at
temperature of 80 °C and rinsing water at 70 °C. The resulting
tiles will have
an homogeneous thin layer of limescale (calcium carbonate precipitated
during the washing cycle). Then, two vertical encrusted tiles are sprayed
three times (equivalent at about 5 g of product) with a composition
according to the present invention and a reference composition, e.g. the
same composition but without the polymers as described herein. The
compositions are sprayed using the T8900~ foamer spray dispenser
(having orifice diameter modified at 0.030" width and spinner channels
0.0425" width). Surfaces are rinsed after 30 seconds with water (until all
residues of product are removed) and then 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 limescale removal
difference. Performance evaluation may be generally done by applying the
Panel Score Unit (PSU).
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WO 99/23194 PCT/US98,'23377
29
Greasv soap scum cleaning performance test method:
In this test method enamel white tiles (typically 24 cm * 4 cm) are covered
with typical greasy soap scum soils mainly based on calcium stearate and
artificial body soils commercially available (e.g. 0.3 grams with a sprayer).
The soiled tiles are then dried in an oven at a temperature of 140 °C
for 30
minutes and then aged overnight at room temperature (around 15°C-
20°C).
Then the soiled tiles are cleaned using 3 ml of the liquid acidic composition
of the present invention poured directly on a Spontex~ sponge. The ability
of the composition to remove greasy soap scum is measured through the
number ofi strokes needed to perfectly clean the surface. The lower the
number of strokes, the higher the greasy soap scum cleaning ability of the
composition. I
Shine test method:
Obtaining a good shine end result results from a good spreading of a liquid
composition over the surface when the surface is treated therewith and from
the reduced formation of watermarks and reduced precipitation of poorly
water soluble salts 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 (10 cm x 4 cm) of a sink
(made of either stainless steel or ceramic) are sprayed twice (equivalent at
about 3 grams of product) with a composition according to the present
invention and a reference composition, e.g. the same composition but
without the polymers as described herein. Each surface is 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. Items are observed during the
drying phase in a way to evaluate water spreading/slipping on the treated
surface. 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 difference. Evaluation may be generally done by applying
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WO 99/23194 PCTNS98/23377 -
the Panel Score Unit (PSU). Shine result is expressed reporting whether the
effect of water spreadinglslipping is present and the final PSU evaluation.
Jn 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.
Examples
These compositions were made comprising the listed ingredients in the
listed proportions (weight %).
Ingredients: I It III IV V VI
(% by weight)
Malefic acid 10 10 10 10 6 10
Sulphamic acid 2 2 - - 2 2
Citric acid - - 2 - - 2
Dobanol ~ 91-8 2.2 - - 2.0 2.2
Mirataine CBS~ - 2 2 - - 2.0
Aromox ~ C 12-C - - - - - 0.5
14
Kelzan T ~ 0.35 0.35 0.30 0.40 0.35 0.30
PVP ~ K60 0.05 0.05 0.05 0.03 0.05 0.04
W 100
& M t
aters up
inors o
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31
Ingredients: VII VIII IX X XI XII
(% by weight)
Malefic acid 8 10 12 10 12 12
Sulphamic acid 2 2 2 - - -
Citric acid - 1 - 2 2 -
Dobanol 91-100 - 3 - 1 4 -
Rewoteric AM CAS 2 - 2 1 - 2.2
15~
Rhodopol ~ T 0.30 0.30 0.32 0.35 0.35 0.25
Luviskoi ~ K30 0.03 0.05 0.05 0.06 0.05 0.05
Waters 8 ---- - ----- u
Minors to 100
~ p
Ingredients: XIII XIV XV XVI XVII XVlII
(% by weight)
Malefic acid - 10 12 - 10 12
Sulphamic acid 2 2 - 2 - 2
Citric acid - - - 6 2 -
Lutensol TO 6~ - 0.4 2 - 0.5 1.5
Empigen BB/L~. 1 1 - 2 - 1
Rheozan ~ 1 0.5 0.8 0.3 0.25 0.4
BHT 0.05 0.05 0.03 0.05 0.05 0.05
Gafquat 7550 0.05 0.01 0.05 0.1 0.2 0.05
Waters & Minors --- o 100
up
t
Mirataine CBS~ and Rewoteric AM CAS~ 15 are cocoamidopropyl hydroxy
sulphobetaines supplied respectively by Rhone-Poulenc and Witco.
Dobanol ~ 91-8 and Lutensol TO 6~ are ethoxylated alcohol nonionic
surfactants supplied respectively by Shell (and having a alkyl chain length
of C9-C11 and a degree of ethoxylation of 8) and BASF (and having a alkyl
chain length of C13 and a degree of ethoxylation of 3).
Aromox ~ C12-C14 is an amineoxide having an alkyl chain length of C12 -
C14 supplied by AKZO.
CA 02308295 2000-04-28
WO 99/23194 PCT/US98/23377 -
32
Kelzan T~ and Rhodopol T~ are Xanthan gum supplied respectively by
Kelco and Rhone Poulenc.
Rheozan~ is a succinoglycan gum supplied by Rhone Poulenc.
PVP K60~ and Luviskol K30~ are polyvinylpyrrolidone homopolymer
supplied respectively by ISP and BASF.
Gafquat 755~ is a vinylpyrrolidoneldialkylaminoalkyl methacryiate
copolymers supplied by ISP.
BHT is tert-butyl hydroxy toluene.
The above compositions were packaged in a spray-type dispenser, for
example the model T8900~ (Continental Spray International) modified with
orifice diameter 0.030" (0.030 inches) width and spinner channels 0.0425"
(0.0425 inches) width. They all exhibit excellent immediate and tong fasting
shine benefits on the surface treated while providing excellent limescale
removal performance. Also the redeposition of limescale deposits on a hard-
surface that has been first treated with one of the compositions exemplified
above, is reduced or even prevented, when said surface comes again in
contact with water, upon prolonged period of time, this both when used neat
or in diluted form.
