Note: Descriptions are shown in the official language in which they were submitted.
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PROCESS OF CLEANING A HARD SURFACE
WITH ZWITTERIONIC COPOLYMER
Field of the invention
The present invention relates to a process of cleaning a hard surface with a
composition
comprising a zwitterionic polymer of defined structure. More specifically it
relates to a process
of cleaning a hard surface in a so called dilute / no rinse application,
wherein a composition
comprising the zwitterionic polymer herein is applied onto said hard surface
in its diluted form
and is left to dry on said hard surface.
Background of the invention
Manufacturers of hard surface cleaning compositions are continuously searching
for new
components that will improve the effectiveness of the compositions. The
present invention
relates to a new ingredient for use in cleaning of hard surfaces such as
floors, tiles, work surfaces,
ceramic surfaces, windows, blinds, shades, mirrors, household appliances, etc.
in a so called
dilute / no rinse hard surface cleaning application.
In such a dilute / no rinse hard surface cleaning application wherein a hard
surface cleaning
composition is applied onto a hard surface in its diluted form an left to dry
on said hard surface
without rinsing said surface, the resulting appearance of the hard surface
after the dilute / no rinse
hard surface cleaning application is of high relevance. Indeed, such a dilute
/ no rinse hard
surface cleaning application has not only to provide a clean surface but the
hard surface should
also not show any visible filming and/or streaking. Furthermore, the hard
surface should have a
shiny appearance. In addition, providing the hard surface with soil repellency
properties,
meaning the prevention or at least reduction of deposition of soil after an
initial cleaning
operation, is a desired property. Moreover, providing a next time cleaning
benefit, wherein the
subsequent cleaning of an initially cleaned surface is facilitated, is a
desired feature in such a
dilute / no rinse hard surface cleaning application.
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It has been found that the performance with regard to filming and/or streaking
as well as to shine
of compositions used in dilute / no rinse hard surface cleaning application
may be improved.
Furthermore, it has been found that the performance with regard to soil
repellency and next time
cleaning of compositions used in dilute / no rinse hard surface cleaning
application may be
improved.
Thus, the objective of the present invention is to provide a process of
cleaning a hard surface
with a liquid composition exhibiting good filming and/or streaking
performance, good shine
performance, good soil repellency performance as well as good next time
cleaning benefit
performance.
It has now been found that this objective can be met by a process of cleaning
a hard surface with
a liquid composition as described herein.
Advantageously, the process as described herein provides good cleaning
performance.
A further advantage of the present invention is that the process herein may be
used to clean hard
surfaces made of a variety of materials like glazed and non-glazed ceramic
tiles, enamel, stainless
steel, Inox , Formica , vinyl, no-wax vinyl, linoleum, melamine, glass,
plastics and plastified
wood.
Summary of the Invention
The present invention relates to a process of cleaning a hard surface with a
liquid composition
comprising a water-soluble or water-dispersible copolymer as described herein
below, said
process comprises the steps of applying said composition onto said surface in
diluted form and
leaving said diluted composition to dry on said surface without rinsing said
surface.
In an alternative embodiment, the present invention also encompasses the use
of a water-soluble
or water-dispersible copolymer herein in a process of cleaning a hard surface
with a liquid
composition comprising the water-soluble or water-dispersible copolymer as
described herein
below wherein the process comprises the step of applying said composition in
its neat form onto
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said hard surface, wherein good filming and/or streaking performance as well
as good shine
performance is achieved.
Detailed Description of the Invention
The process of cleaning a hard surface
The present invention encompasses a process of cleaning a hard surface with a
liquid
composition as described herein. In particular, the present invention
encompasses a process of
cleaning a hard surface with a liquid composition comprising the water-soluble
or water-
dispersible copolymer as described herein, said process comprises the steps of
applying said
composition onto said surface in diluted form and leaving said diluted
composition to dry on said
surface without rinsing said surface.
By "hard surface", it is meant herein any kind of surface typically found in
houses like kitchens,
bathrooms, e.g., floors, walls, tiles, windows, cupboards, sinks, showers,
shower plastified
curtains, wash basins, WCs, dishes, fixtures and fittings and the like made of
different materials
like ceramic, vinyl, no-wax vinyl, linoleum, melamine, glass, Inox , Formica ,
any plastics,
plastified wood, metal or any painted or varnished or sealed surface and the
like. Hard-surfaces
also include household appliances including, but not limited to refrigerators,
freezers, washing
machines, automatic dryers, ovens, microwave ovens, dishwashers and so on.
In a preferred embodiment according to the present invention, the hard surface
to be cleaned in
the process herein is a floor. Preferably, the hard surface to be cleaned in
the process herein is
selected from the group consisting of ceramic surfaces.
The composition herein is applied in its diluted form.
By "diluted form", it is meant herein that said liquid composition is diluted
by the user with an
appropriate solvent, typically with water. The composition is diluted prior to
use to a typical
dilution level of 10 to 400 times its weight of water, preferably from 10 to
200 and more
preferably from 10 to 100. A usually recommended dilution level is a 1.2%
dilution of the
composition in water. Dilution may occur immediately prior to the application
of the composition
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herein onto the hard surface to be cleaned, e.g., in an appropriate receptacle
such as a bucket,
wherein an effective amount of liquid composition herein is mixed with water.
In a preferred
embodiment, the process herein comprises the additional step of diluting said
composition with
an appropriate solvent, preferably with water, before applying said
composition in diluted form
onto said hard surface.
In the process herein, said composition is applied onto said surface by
conventional means
known by the skilled person. Indeed, the composition, may be applied by
pouring or spraying
said composition onto said surface. Alternatively, said composition may be
applied using an
appropriate implement, such as a mop or a cloth, soaked in the diluted
composition herein.
Furthermore, once applied onto said surface said composition may be agitated
over said surface
using an appropriate implement. Indeed, said surface my be wiped using a mop
or a cloth. During
such a cleaning operation parts of the composition herein may be captured in
the cleaning
implement, if any, (preferably in combination with soil initially present on
the surface) and
transferred into a bucket or another suitable receptacle (squeezing of the mop
or cloth), another
part of the composition will be left on the surface after the cleaning
operation. Indeed, the
composition is, preferably at least partially, left on said surface at the end
of said process of
cleaning said hard surface, more preferably left on said surface until the
next cleaning operation
and still more preferably at least partially left on said surface until the
next cleaning operation.
However, in the process of cleaning a hard surface according to the present
invention, the
composition is applied onto said surface in diluted form without rinsing said
hard surface after
application. Indeed, the composition is (at least partially) left to dry on
said hard surface.
By "rinsing", it is meant herein contacting the hard surface cleaned with the
process according to
the present invention with substantial quantities of appropriate solvent,
typically water, directly
after the step of applying the liquid composition herein onto said hard
surface. By "substantial
quantities", it is meant herein between 0.01 lt. and 1 lt. of water per m2 of
hard surface, more
preferably between 0.1 lt. and 1 lt. of water per m2 of hard surface.
However, the hard surface cleaned with the process according to the present
invention may
eventually be rinsed during a subsequent cleaning process. Furthermore, due to
normal use of the
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hard surfaces cleaned by the process herein, said hard surfaces may eventually
be wetted, by for
example by spilling water or other liquids onto said surface. Such subsequent
cleaning processes
or the accidental wetting of the hard surface shall not be considered as
rinsing of the surface
within the meaning of the present invention. Moreover, the removal of parts of
the composition
5 applied onto the hard surface during the cleaning, e.g., be means of
squeezing soiled composition
out of a mop or cloth shall not be considered as rinsing of the surface within
the meaning of the
present invention.
The hard surfaces to be treated may be soiled with a variety of soils, e.g.,
greasy soils (e.g.,
greasy soap scum, body grease, kitchen grease or burnt/sticky food residues
typically found in a
kitchen and the like), particulate greasy soils or so called "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, 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).
Liquid Composition
The composition used in the process according to the present invention is
formulated as a liquid
composition.
Preferred compositions herein have a viscosity of 1 cps or greater, more
preferably of from 1 to
20000 cps, and still more preferably of from 1 to 500 cps at 20 C when
measured with a CSL2
100 Rheometer at 20 C with a 4 cm spindle (linear increment from 10 to 100
dyne/cm2 in 2
minutes).
A preferred composition herein is an aqueous composition and therefore,
preferably comprises
water more preferably in an amount of from 50% to 98%, even more preferably of
from 75% to
97% and most preferably 80% to 97% by weight of the total composition.
The pH of the liquid composition according to the present invention may
typically be from 0 to
14.
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In a preferred embodiment, the pH range is from 7 to 14, preferably from 7.1
to 14, more
preferably from 7.1 to 13, even more preferably from 7.1 to 12 and most
preferably from 8.0 to
10. Indeed, it has been surprisingly found that the greasy cleaning
performance is further
improved at these preferred alkaline to neutral pH ranges, preferably alkaline
pH ranges.
Accordingly, the compositions herein may further comprise an acid or base to
adjust pH as
appropriate.
A suitable acid for use herein is an organic and/or an inorganic acid. A
preferred organic acid for
use herein has a pKa of less than 6. A suitable organic acid is selected from
the group consisting
of citric acid, lactic acid, glycolic acid, succinic acid, glutaric acid and
adipic acid and a mixture
thereof. A mixture of said acids may be commercially available from BASF under
the trade name
Sokalan DCS. A suitable inorganic acid is selected from the group consisting
hydrochloric
acid, sulphuric acid, phosphoric acid and a mixture thereof.
A typical level of such an acid, when present, is of from 0.01% to 5.0%,
preferably from 0.04%
to 3.0% and more preferably from 0.05% to 1.5 % by weight of the total
composition.
A suitable base to be used herein is an organic and/or inorganic base.
Suitable bases for use
herein are the caustic alkalis, such as sodium hydroxide, potassium hydroxide
and/or lithium
hydroxide, and/or the alkali metal oxides such, as sodium and/or potassium
oxide or mixtures
thereof. A preferred base is a caustic alkali, more preferably sodium
hydroxide and/or potassium
hydroxide.
Other suitable bases include ammonia, ammonium carbonate, K2C03, Na2CO3 and
alkanolamines (as e.g. monoethanolamine).
Typical levels of such bases, when present, are of from 0.01% to 5.0%,
preferably from 0.05% to
3.0% and more preferably from 0.1% to 0.6 % by weight of the total
composition.
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Water-Soluble or Water-dispersible Copolymer
The water-soluble or water-dispersible copolymer herein is either a water-
soluble or water-
dispersible copolymer I as described herein below or a water-soluble or water-
dispersible
copolymer II as described herein below.
The water-soluble or water-dispersible copolymer I of the present invention
comprises, in the
form of polymerized units:
a) at least a monomer compound of general formula i:
Ri X- R2 X- R2 R4 X- (i)
I I I I
H2C=C-Z-[CH2]õ-N+[A- N+lm B- N+-Rs
I 1 1
R3 R3 R6
in which
Rl is a hydrogen atom, a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or
branched C1 -C6, alkyl,
hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10;
n is an integer from 1 to 6;
Z represents a--C(O)O- or --C(O)NH- group or an oxygen atom;
A represents a(CH2)p group, p being an integer from 1 to 6;
B represents a linear or branched C2 -C12, polymethylene chain optionally
interrupted by one or
more heteroatoms or heterogroups, and optionally substituted by one or more
hydroxyl or amino
groups;
X-, which are identical or different, represent counterions; and
(b) at least one hydrophilic monomer carrying a functional acidic group which
is
copolymerizable with (a) and which is capable of being ionized in the
application medium;
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(c) optionally at least one monomer compound with ethylenic unsaturation with
a neutral charge
which is copolymerizable with (a) and (b), preferably a hydrophilic monomer
compound with
ethylenic unsaturation with a neutral charge, carrying one or more hydrophilic
groups, which is
copolymerizable with (a) and (b).
The monomer (a) can be prepared, for example, according to the reaction
schemes shown in US
6,569,261 to Rhodia, column 2, line 40 to column 3, line 45 which is
incorporated herein by
reference.
The resulting water-soluble or water-dispersible copolymer herein has a
molecular mass of at
least 1000, advantageously of at least 10,000; it can range up to 20,000,000,
advantageously up
to 10,000,000. Except when otherwise indicated, when the term molecular mass
is used, it will
refer to the weight-average molecular mass, expressed in g/mol. The latter can
be determined by
aqueous gel permeation chromatography (GPC) or measurement of the intrinsic
viscosity in a 1N
NaNO3 solution at 30 C. The copolymer is preferably a random copolymer.
Preferably, in the general formula (i) of the monomer (a), Z represents C(O)O,
C(O)NH or 0,
very preferably C(O)NH; n is equal to 2 or 3, very particularly 3; m ranges
from 0 to 2 and is
preferably equal to 0 or 1, very particularly to 0; B represents -CH2-CH(OH)-
(CH2)q, with q
from 1 to 4, preferably equal to 1; Rl to R6, which are identical or
different, represent a methyl or
ethyl group.
A preferred monomer (a) is a diquat of following formula:
CH3 X- X-
I
C=CH2 CH3 OH CH3
I I I I
O=C-NH-[CH2]3-N+-CH2-CH-CH2-N+-CH3
I I
CH3 CH3
in which X- representing the chloride ion.
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Other particularly advantageous monomers (a) are:
CH3 X- X- X-
1
C=CH2 CH3 CH3 OH CH3
I I I I I
O=C-NH-[CH2]3-N+[CH2]p-N+-CH2-CH-CH2-N+-CH3
I I I I
CH3 CH3 CH3 CH3
wherein p=2 to 4.
The X anions are in particular a halogen, preferably chlorine, sulfonate,
sulfate, hydrogensulfate,
phosphate, phosphonate, citrate, formate and acetate anion.
The monomers (b) are advantageously C3 -C8 carboxylic, sulphonic, sulfuric,
phosphonic or
phosphoric acids with monoethylenic unsaturation, their anhydrides and their
salts which are
soluble in water and mixture thereof. Preferred monomers (b) are acrylic acid,
methacrylic acid,
a-ethacrylic acid, (3,(3-dimethylacrylic acid, methylenemalonic acid,
vinylacetic acid, allylacetic
acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic
acid, fumaric acid,
itaconic acid, citraconic acid, mesaconic acid, N-(methacroyl)alanine, N-
(acryloyl)hydroxyglycine, sulfopropyl acrylate, sulfoethyl acrylate,
sulfoethyl methacrylate,
styrenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, phosphoethyl
acrylate,
phophonoethyl acrylate, phosphopropyl acrylate, phophonopropyl acrylate,
phosphoethyl
methacrylate, phophonoethyl methacrylate, phosphopropyl methacrylate,
phophonopropyl
methacrylate and the alkali metal and ammonium salts thereof and mixtures
thereof.
Preferred optional monomers (c) include acrylamide, vinyl alcohol, Cl -C4
alkyl esters of acrylic
acid and of methacrylic acid, Cl -C4 hydroxyalkyl esters of acrylic acid and
of methacrylic acid,
in particular ethylene glycol and propylene glycol acrylate and methacrylate,
polyalkoxylated
esters of acrylic acid and of methacrylic acid, in particular the polyethylene
glycol and
polypropylene glycol esters, esters of acrylic acid or of methacrylic acid and
of polyethylene
glycol or polypropylene glycol Cl -C25 monoalkyl ethers, vinyl acetate,
vinylpyrrolidone or
methyl vinyl ether and mixtures thereof.
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The level of monomers (a) is advantageously between 3 and 80 mol %, preferably
10 to 70 mol
%.. The level of monomers (b) is advantageously between 10 and 95 mol %,
preferably 20 to 80
mol %. The level of monomers (c) is advantageously between 0 and 50%,
preferably 0 and 30%.
The molar ratio of cationic monomer to the anionic monomer (a)/(b) is
advantageously between
5 80/20 and 5/95, preferably between 60/40 and 20/80.
The water-soluble or water-dispersible copolymer I herein can be obtained
according to known
techniques for the preparation of copolymers, in particular by polymerization
by the radical route
of the starting ethylenically unsaturated monomers, which are known compounds
or compounds
10 which can be easily obtained by a person skilled in the art by employing
conventional synthetic
processes of organic chemistry. Reference may in particular be made to the
processes disclosed
in US 4,387,017 and EP 156,646. The radical polymerization is preferably
carried out in an
environment which is devoid of oxygen, for example in the presence of an inert
gas (helium,
argon, and the like) or of nitrogen. The reaction is carried out in an inert
solvent, preferably
ethanol or methanol, and more preferably in water. The polymerization is
initiated by addition of
a polymerization initiator. The initiators used are the free radical
initiators commonly used in the
art. Examples comprise organic peresters (t-butylperoxy pivalate, t-amylperoxy
pivalate, t-
butylperoxy a-ethylhexanoate, and the like); organic compounds of azo type,
for example
azobisamidinopropane hydrochloride, azobisisobutyronitrile, azobis(2,4-
dimethylvaleronitrile),
and the like); inorganic and organic peroxides, for example hydrogen peroxide,
benzyl peroxide
and butyl peroxide, and the like; redox initiating systems, for example those
comprising
oxidizing agents, such as persulfates (in particular ammonium or alkali metal
persulfates, and the
like); chlorates and bromates (including inorganic or organic chlorates and/or
bromates);
reducing agents, such as sulfites and bisulfites (including inorganic and/or
organic sulfites or
bisulfites); oxalic acid and ascorbic acid, as well as the mixtures of two or
more of these
compounds. Preferred initiators are water-soluble initiators. Sodium
persulfate and
azobisamidinopropane hydrochloride are in particular preferred. In an
alternative form, the
polymerization can be initiated by irradiation using ultraviolet light. The
amount of initiators
used is generally an amount sufficient can produce initiation of the
polymerization. The initiators
are preferably present in an amount ranging from 0.001 to approximately 10% by
weight with
respect to the total weight of the monomers and are preferably in an amount of
less than 0.5% by
weight with respect to the total weight of the monomers, a preferred amount
being situated in the
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range from 0.005 to 0.5% by weight with respect to the total weight of the
monomers. The
initiator is added to the polymerization mixture either continuously or
noncontinuously. When it
is wished to obtain copolymers of high molecular mass, it is desirable to add
fresh initiator
during the polymerization reaction. The gradual or noncontinuous addition also
makes possible a
more efficient polymerization and a shorter reaction time. The polymerization
is carried out
under reaction conditions which are effective in polymerizing the monomers
(a), the monomers
(b) and optionally the monomers (c) under an atmosphere devoid of oxygen. The
reaction is
preferably carried out at a temperature ranging from approximately 30 to
approximately 100
and preferably between 60 and 90 C. The atmosphere which is devoid of oxygen
is maintained
throughout the duration of the reaction, for example by maintaining a nitrogen
flow throughout
the reaction.
A particularly preferred water-soluble or water-dispersible copolymer I herein
is the following:
:l3.: (F:.. ~.;L].._
I1x~. ~::...., .Ed _14 15 ~ki
with x having a mean value of 0 to 50 mol%, preferably of 0 to 30 mol%, y
having a mean value
of 10 to 95 mol%, preferably of 20 to 80 mol%, z having a mean value of 3 to
80 mol%,
preferably of 10 to 70 mol% and the y/z ratio preferably being of the order of
4/1 to 1/2, with
x+y+z=100%, x, y and z representing the mol % of units derived from
acrylamide, acrylic acid
(sodium salt) and from Diquat respectively.
Other preferred water-soluble or water-dispersible copolymer I herein chemical
structures are as
follows:
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r~-
~ .
C: ,.a
, r'rs
with x having a mean value of 0 to 50 mol%, preferably of 0 to 30 mol%, y
having a mean value
of 10 to 95 mol%, preferably of 20 to 80 mol%. z having a mean value of 3 to
80 mol%,
preferably of 10 to 70 mol% and the y:z ratio preferably being of the order of
4:1 to 1:2;
< =~., c:si-;. Fi
!~.
.....~. .pi;,......~.;i.a...:~~~.,.....f'',1:1~; (.'k:1_,....E'h.a......
1=~?~ 41N.';1`
wherein x has a mean value of 0 to 50 mol%, preferably of 0 to 30 mol%, y has
a mean value of
to 95 mol%, preferably of 20 to 80 mol%; z has a mean value of 3 to 80 mol%,
preferably of
10 10 to 70 mol%, and the y:z ratio preferably being of the order of 4:1 to
1:2;
X-
~~-
~Ef<.
~EJy\;3
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with x has a mean value of 0 to 50%, preferably of 0 to 30 mol%, y has a mean
value of 10 to 95
mol%, preferably of 20 to 80 mol%, z has a mean value of 3 to 80 mol%,
preferably of 10 to 70
mol%, and the y:z ratio preferably being of the order of 4:1 to 1:2;
. ~ . . I . ~
' .. .i'. ['.'v... .......,..
...... . .. . . ...
t..~\ =rv-~:.... ~ ~.:.. _.` _~......
v =. ~ ... . n I .. n '~ ..
N<
5
wherein x having a mean value of 0 to 50 mol%, preferably of 0 to 30 mol%, y
has a mean value
of 10 to 95 mol%, preferably of 20 to 80 mol%, z has a mean value of 3 to 80
mol%, preferably
of 10 to 70 mol%, and the y:z ratio preferably being of the order of 4:1 to
1:2;
. I.~ .
ffiC-N, C.Or;- [J------: Ft: -~;: fc t~ ~_ ~ktt
t`-
~~~~'~.^,-~,,f.~~ 'i:~-~ t~'~~.'t'.~;.=~~-.
wherein x has a mean value of 0 to 50 mol%, preferably of 0 to 30 mol%, y has
a mean value of
10 to 95 mol%, preferably of 20 to 80 mol%, z has a mean value of 3 to 80
mol%, preferably of
10 to 70 mol%, and the y:z ratio preferably being of the order of 4:1 to 1:2;
or
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~- +~. .. ...- ~-~,
+.;E a
.3.
wherein x has a mean value of 0 to 50 mol%, preferably of 0 to 30 mol%, y has
a mean value of
to 95 mol%, preferably of 20 to 80 mol%, z has a mean value of 3 to 80 mol%,
preferably of
10 to 70 mol%, and the y:z ratio preferably being of the order of 4:1 to 1:2.
5
The water-soluble or water-dispersible copolymer II of the present invention
comprises, in the
form of polymerized units:
d) at least a monomer compound of general formula ii:
Ri R2 R4 (ii)
10 I I I
H2C=C-[CH2]õ-N+-[CH2]m C = CH2 X-
I
R3
in which :
R1 and R4 independently represent H or a C1-6linear or branched alkyl group;
R2 and R3 independently represent a linear or branched C1-6 alkyl,
hydroxyalkyl or aminoalkyl
group, preferably a methyl group;
n and m are integers of between 1 and 3;
X-represents a counterion compatible with the water-soluble or water-
dispersible nature of the
polymer;
e) at least one hydrophilic monomer with an acid functionality that is
copolymerisable with
monomer d) and capable of ionizing in the medium in which it is used; and
f) optionally an ethylenically unsaturated hydrophilic monomer compound of
neutral charge
bearing one or several hydrophilic groups which is copolymerisable with
monomers d) and e);
the monomer d) to monomer e) ratio ranging from between 60:40 and 5:95.
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More preferably, Rl represents hydrogen, R2 represents methyl, R3 represents
methyl, R4
represents hydrogen, and m and n are equal to 1. The ion X- is preferably
chosen from halogen,
sulfate, hydrogen sulfate, phosphate, citrate, formate and acetate.
5 The monomer (e) and optionally the monomer (f) give the copolymer II
hydrophilic properties.
The copolymer II according to the invention advantageously has a molecular
mass of at least
1000, advantageously of at least 10,000; it can be up to 20,000,000,
advantageously up to
10,000,000. Except where otherwise indicated, when a molecular mass is
mentioned, this will be
the weight-average molecular mass, expressed in g/mol. This can be determined
by aqueous gel
10 permeation chromatography (GPC) or by measuring the intrinsic viscosity in
a 1N NaNO3
solution at 30 C. The copolymer II is preferably a random copolymer.
The monomer (d) preferably has the following structure:
CH3
15 I
H2C=CH-CH2-N+-CH2-CH = CH2 X-
I
CH3
wherein X- is defined above. One monomer (d) which is particularly preferred
is that of the
above formula in which X- represents Cl-, this monomer being known as diallyl
dimethyl
ammonium chloride (DADMAC).
The monomers (e) are preferably those selected from the group consisting of
water-soluble C3-C8
carboxylic, sulfonic, sulfuric, phosphonic or phosphoric acids containing
monoethylenic
unsaturation, anhydrides thereof and water-soluble salts thereof. Among the
preferred
monomers (e) are those selected from the group consisting of acrylic acid,
methacrylic acid, a-
ethacrylic acid, (3,(3-dimethacrylic acid, methylenemalonic acid, vinylacetic
acid, allylacetic acid,
ethylideneacetic acid, propylideneacetic acid, crotonic acid, maleic acid,
fumaric acid, itaconic
acid, citraconic acid, mesaconic acid, N-meth-acryloylalanine, N-
acryloylhydroxyglycine,
sulfopropyl acrylate, sulfoethyl acrylate, sulfoethyl methacrylate, sulfoethyl
methacrylate,
styrenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, phosphoethyl
acrylate,
phosphonoethyl acrylate, phosphopropyl acrylate, phosphonopropyl acrylate,
phosphoethyl
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methacrylate, phosphonoethyl methacrylate, phosphopropyl methacrylate and
phosphonopropyl
methacrylate, and the ammonium and alkali metal salts of these acids and
mixtures thereof.
Among the monomers (f) are those selected from the group consisting of
acrylamide, vinyl
alcohol, Cl-C4 alkyl esters of acrylic acid and of methacrylic acid, Cl-C4
hydroxyalkyl esters of
acrylic acid and of methacrylic acid, in particular ethylene glycol and
propylene glycol acrylate
and methacrylate, polyalkoxylated esters of acrylic acid and of methacrylic
acid, in particular the
polyethylene glycol and polypropylene glycol esters.
The monomer (d) content is advantageously between 5 mol % and 60 mol %,
preferably 20 mol
% to 50 mol %. The monomer (e) content is advantageously between 10 mol % and
95 mol %,
preferably 20 mol % to 80 mol %. The monomer (f) content is advantageously
between 0 mol %
and 50 mol %, preferably 5 mol % to 30 mol %. The d:e molar ratio is
preferably between 50:50
and 10:90.
The copolymers II of the invention can be obtained according to the known
techniques for
preparing copolymers, in particular by radical-mediated polymerization of the
ethylenically
unsaturated starting monomers which are known compounds or which can readily
be obtained by
a person skilled in the art using conventional synthetic processes of organic
chemistry. Water-
soluble or water-dispersible copolymer II is preferably obtained by the
copolymerization of
monomers containing a quaternary ammonium function and two groups containing
ethylenic
unsaturation with monomers containing a group capable of ionizing in the
application medium to
form anionic units, with a ratio of the first monomers to the second monomers
which is within a
given range. The radical-mediated polymerization is described in detail
earlier with respect to
agglomerating copolymer I.
The following copolymers II are most particularly preferred: DADMAC/acrylic
acid/acrylamide
copolymer; DADMAC/maleic acid copolymer; DADMAC/sulfonic acid copolymer; the
DADMAC/acidic monomer molar ratio being between 60:40 and 5:95, preferably
between 50:50
and 10:90. DADMAC stands for diallyl dimethyl ammonium chloride. Preferred
copolymer II
are available from Rhodia; an alternative is available from Reckitt-Benckiser
under the
tradename Merquat 280. A particularly preferred copolymer II is
CA 02649246 2008-10-14
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17
~3
H3C N
H \
-+C C+ ~C C C C+-
Hz Hz H H H
C
NaO ~O
Preferred water-soluble or water-dispersible copolymer herein are available
from Rhodia. In the
composition of the present invention, the water-soluble or water-dispersible
copolymer herein is
preferably present at a level of from 0.001% to 10%, more preferably from
0.005% to 1%, most
preferably from 0.01% to 0.5% by weight of the composition.
It has been found that the presence of the specific water-soluble or water-
dispersible copolymer
herein in a liquid composition used to clean a hard surface in a dilute / no
rinse application allows
to provide improved filming and/or streaking performance as well as improved
shine
performance as compared to the use in the same dilute / no rinse hard surface
cleaning
application of a composition that are free of the specific water-soluble or
water-dispersible
copolymer herein. Furthermore, it has been found that the presence of the
specific water-soluble
or water-dispersible copolymer herein in a liquid composition used to clean a
hard surface in a
dilute / no rinse application allows to provide improved soil repellency
properties to the hard
surface after an initial cleaning operation with the compositions herein using
a process according
to the present invention. Moreover, it has been found that the presence of the
specific water-
soluble or water-dispersible copolymer herein in a liquid composition used to
clean a hard
surface in a dilute / no rinse application allows to provide improved next
time cleaning benefit
properties to the hard surface after an initial cleaning operation with the
compositions herein
using a process according to the present invention.
Due to its nature, after a dilute / no rinse hard surface cleaning application
residues are left on the
hard surface cleaned in such an application. Indeed, due to the fact that the
cleaning composition
applied onto the surface is not rinsed off the surface, the cleaning
composition along with a part
of the soil present on the hard surface is basically left on the surface
(another part of the soil is
captured in the implement (e.g., mop), if any, used in the dilute / no rinse
cleaning application).
Such residues often lead to visible films and/or streaks on the cleaned hard
surface and may
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18
impair the shine of the hard surface. Moreover, cleaned surfaces are prone to
re-soiling due to
their normal use. Indeed, marks, soils, stains and the like of various kinds
are deposited on hard
surface upon use (e.g., soil carried onto a floor sticking the bottom of
shoes).
It has surprisingly been found that the inclusion of said copolymer in a
liquid composition used
in a dilute / no rinse hard surface cleaning application provides a
composition that increases the
transparency of the residues (after drying) left on the hard surface after
cleaning. Such an
increase in transparency results in the residues being less or even not at all
visible, which in turns
significantly contributes to the fact that films and/or streaks are barely or
even not at all visible
on the cleaned hard surface and also to an improved shine of the cleaned hard
surface.
Furthermore, it has surprisingly been found that on a hard surface initially
cleaned with the
compositions herein using a process according to the present invention, soils
deposition is
reduced or even prevented. Indeed, so-called soil repellency properties are
observed. In addition,
it has surprisingly been found that on a hard surface initially cleaned with
the compositions
herein using a process according to the present invention, a next time
cleaning benefit is
observed. Indeed, subsequent cleaning operations of an initially cleaned
surface are facilitated.
In an alternative embodiment, the present invention also encompasses the use
of a water-soluble
or water-dispersible copolymer herein in a process of cleaning a hard surface
with a liquid
composition comprising the water-soluble or water-dispersible copolymer herein
wherein the
process comprises the step of applying said composition in its neat form onto
said hard surface,
wherein good filming and/or streaking performance as well as good shine
performance.
By "in its neat form", it is meant herein that said liquid composition is
applied directly onto the
surface to be treated without undergoing any dilution by the user
(immediately) prior to the
application, i.e., the liquid composition herein is applied onto the hard
surface as described
herein.
It has been found that the presence of the specific water-soluble or water-
dispersible copolymer
herein in a liquid composition used to clean a hard surface in neat
application allows to provide
improved filming and/or streaking performance as well as improved shine
performance as
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19
compared to the use in the same neat hard surface cleaning application of a
composition that are
free of the specific water-soluble or water-dispersible copolymer herein.
Due to its nature, after a neat hard surface cleaning application residues may
be left on the hard
surface cleaned in such an application. Indeed, after a neat cleaning
application the cleaned hard
surface may or may not be rinsed. Even if the hard surface is rinsed after the
neat cleaning
application, residues of the cleaning composition (though diluted) may still
remain on the hard
surface due to inefficient rinsing and due to the increased concentration that
was initially applied
onto the hard surface. Hence, the cleaning composition along with part of the
soil present on the
hard surface may be left on the surface. Such residues often lead to visible
films and/or streaks on
the cleaned hard surface and may impair he shine of the hard surface.
It has been surprisingly found that the inclusion of said copolymer in a
liquid composition used
in a neat hard surface cleaning application provides a composition that
increases the transparency
of the residues (after drying) left on the hard surface after cleaning. As
outlined above, such an
increase in transparency results in the residues being less or even not at all
visible, which in turns
significantly contributes to fact that films and/or streaks are barely or even
not at all visible on
the cleaned hard surface and also to an improved shine of the cleaned hard
surface.
Filminz / streakinz and shine test method
The filming/streaking and shine performance of a diluted hard surface cleaning
composition is
evaluated using the following tests method :
The hard surface cleaning composition is diluted to a 1.2% level (detergent
solution) in normal
tap-water, if needed adjusted with CaC12 to achieve a particular water
hardness of interest, mostly
16 gpg. 19 g (+/- 0.2 g) of said detergent solution is applied on a Vileda
cloth (20 cm * 9 cm),
followed by wiping lightly covering a surface of four black glossy ceramic
tiles (20*25 cm each),
wherein approx. 1 g. (+/- 0.2 g) of detergent solution is left on the tile.
Afterwards the tile is left
to dry without rinsing at constant temperature (22 C) and constant humidity
(30-40% rH).
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The shine performance is evaluated by visual assessment of a tile being
cleaned with a wash
solution containing polymer, versus a tile being cleaned with the same wash
solution though not
containing the polymer.
5 The filming / streaking and/or shine performance of said composition can be
assessed by visual
grading. The visual grading may be performed by a group of expert panellists
using panel score
units (PSU). To assess the filming / streaking and/or shine performance of a
given composition a
PSU-scale ranging from 0, meaning a poor filming / streaking and/or shine
impression (i.e.,
visible filing /streaking; no shine) of the given composition, to 6, meaning a
good filming /
10 streaking and/or shine impression (i.e., no visible filing /streaking;
excellent shine) of the given
composition, can be applied.
The filming / streaking and shine performance of an undiluted hard surface
cleaning composition
is evaluated using the following tests method :
1 ml of hard surface cleaning composition is applied neat onto two black
glossy ceramic tiles
(20*25 cm each), followed by wiping lightly with a wet Vileda cloth (20 cm *
9 cm -
containing lOg of water). Afterwards the Vileda cloth is squeezed 10 times
under running tap
water. The tiles are rinsed twice with this squeezed/rinsed Vileda cloth
(containing lOg of
water), and left to dry at constant temperature (22 C) and constant humidity
(30-40% rH).
The filming / streaking and/or shine performance of said composition can be
assessed by visual
grading as described herein above.
Soil repellency and next time cleaning benefit test method
The next time cleaning / soil repellency performance of a diluted hard surface
cleaning
composition is evaluated using the following tests method :
A clean white ceramic tile (ex Villeroy & Bosch UTO1 Serie Unit 1 -
dimensions 7*25cm) is
pretreated with test and reference products to be assessed by using a "Wet
Abrasian Scrub Tester
- Ref. 903PG/SA/B, available from Sheen Instruments Limited), a straight-line
washability
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21
machine having 4 cleaning tracks and 4 sponge holders. Two cleaning tracks are
preconditioned
with a wet sponge (yellow cellulose sponge, Type 7 ex Spontex US - total
weight wet sponge =
22g +/- 2 g) to which 20m1 (+/-0.2 ml) of a 1.2% detergent solution (see above
for preparation) is
added, the two other cleaning tracks are preconditioned with a wet sponge
containing 20m1 (+/-
0.2 ml) of a 1.2% wash solution of a reference detergent solution. The tile is
pretreated over 20
cycles, followed by allowing the tile to dry at constant temperature (25 C)
and humidity (70%
rH) for at least 2 hours, preferably overnight.
A soil mix of polymerized oil and particulate soil is prepared and 0.085g of
the soil mix is
homogeneously distributed over the pretreated tile. After application, the
soiled tile is left to
condition for 3-5 hours, preferably overnight, at constant temperature (25 C)
and humidity (70%
rH).
To cross-evaluate the cleaning performance of the test versus reference
detergent solution, the
number of counts is recorded to fully clean the pretreated tile areas by a
sponge containing 20m1
(+/-0.2 ml) of the corresponding 1.2% detergent solution, using the "Wet
Abrasian Scrub Tester"
as mentioned above.
Optional Composition Ingredients
The liquid compositions according to the present invention may comprise a
variety of optional
ingredients depending on the technical benefit aimed for and the surface
treated.
Suitable optional ingredients for use herein include surfactants, builders,
chelants, polymers,
buffers, bactericides, preservatives, hydrotropes, colorants, stabilisers,
radical scavengers,
bleaches, bleach activators, enzymes, soil suspenders, dye transfer agents,
brighteners, anti
dusting agents, dispersants, dye transfer inhibitors, pigments, silicones,
perfumes and/or dyes.
Surfactants
The compositions herein may comprise a nonionic, anionic, zwitterionic and
amphoteric
surfactant or mixtures thereof. Said surfactant is preferably present at a
level of from 0.01% to
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22
20% of composition herein. Suitable surfactants are those selected from the
group consisting of
nonionic, anionic, zwitterionic and amphoteric surfactants, having hydrophobic
chains containing
from 8 to 18 carbon atoms. Examples of suitable surfactants are described in
McCutcheon's Vol.
1: Emulsifiers and Detergents, North American Ed., McCutcheon Division, MC
Publishing Co.,
2002.
Preferably, the aqueous compositions comprise from 0.01% to 20%, more
preferably from 0.5%
to 10%, and most preferably from 1% to 5% surfactants.
Non-ionic surfactants are highly preferred for use in the compositions of the
present invention.
Non-limiting examples of suitable non-ionic surfactants include alcohol
alkoxylates, alkyl
polysaccharides, amine oxides, block copolymers of ethylene oxide and
propylene oxide, fluoro
surfactants and silicon based surfactants. Preferably, the aqueous
compositions comprise from
0.01% to 20%, more preferably from 0.5% to 10%, and most preferably from 1% to
5% non-
ionic surfactants.
A preferred class of non-ionic surfactants suitable for the present invention
is alkyl ethoxylates.
The alkyl ethoxylates of the present invention are either linear or branched,
and contain from 8
carbon atoms to 16 carbon atoms in the hydrophobic tail, and from 3 ethylene
oxide units to 25
ethylene oxide units in the hydrophilic head group. Examples of alkyl
ethoxylates include Neodol
91-6 , Neodo191-8 supplied by the Shell Corporation (P.O. Box 2463, 1 Shell
Plaza, Houston,
Texas), and Alfonic 810-60 supplied by Condea Corporation, (900 Threadneedle
P.O. Box
19029, Houston, TX). More preferred alkyl ethoxylates comprise from 9 to 12
carbon atoms in
the hydrophobic tail, and from 4 to 9 oxide units in the hydrophilic head
group. A most preferred
alkyl ethoxylate is C9_ll E05, available from the Shell Chemical Company under
the tradename
Neodo191-5 . Non-ionic ethoxylates can also be derived from branched alcohols.
For example,
alcohols can be made from branched olefin feedstocks such as propylene or
butylene. In a
preferred embodiment, the branched alcohol is either a 2-propyl-l-heptyl
alcohol or 2-butyl-l-
octyl alcohol. A desirable branched alcohol ethoxylate is 2-propyl-l-heptyl
E07/A07,
manufactured and sold by BASF Corporation under the tradename Lutensol XP 79
/XL 79 .
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23
Another class of non-ionic surfactant suitable for the present invention is
alkyl polysaccharides.
Such surfactants are disclosed in U.S. Patent Nos. 4,565,647, 5,776,872,
5,883,062, and
5,906,973. Among alkyl polysaccharides, alkyl polyglycosides comprising five
and/or six carbon
sugar rings are preferred, those comprising six carbon sugar rings are more
preferred, and those
wherein the six carbon sugar ring is derived from glucose, i.e., alkyl
polyglucosides ("APG"), are
most preferred. The alkyl substituent in the APG chain length is preferably a
saturated or
unsaturated alkyl moiety containing from 8 to 16 carbon atoms, with an average
chain length of
carbon atoms. C8-C16 alkyl polyglucosides are commercially available from
several suppliers
(e.g., Simusol surfactants from Seppic Corporation, 75 Quai d'Orsay, 75321
Paris, Cedex 7,
10 France, and Glucopon 220 , Glucopon 225 , Glucopon 425 , Plantaren 2000 N ,
and
Plantaren 2000 N UP , from Cognis Corporation, Postfach 13 01 64, D 40551,
Dusseldorf,
Germany).
Another class of non-ionic surfactant suitable for the present invention is
amine oxide. Amine
oxides, particularly those comprising from 10 carbon atoms to 16 carbon atoms
in the
hydrophobic tail, are beneficial because of their strong cleaning profile and
effectiveness even at
levels below 0.10%. Additionally Clo-16 amine oxides, especially C12-C14 amine
oxides are
excellent solubilizers of perfume. Alternative non-ionic detergent surfactants
for use herein are
alkoxylated alcohols generally comprising from 8 to 16 carbon atoms in the
hydrophobic alkyl
chain of the alcohol. Typical alkoxylation groups are propoxy groups or ethoxy
groups in
combination with propoxy groups, yielding alkyl ethoxy propoxylates. Such
compounds are
commercially available under the tradename Antarox available from Rhodia (40
Rue de la
Haie-Coq F-93306, Aubervilliers Cedex, France) and under the tradename Nonidet
available
from Shell Chemical.
Also suitable for use in the present invention are the fluorinated nonionic
surfactants. One
particularly suitable fluorinated nonionic surfactant is Fluorad F170 (3M
Corporation, 3M
Center, St. Paul, MN, USA). Fluorad F170 has the formula C8Fi7SO2N(CH2-
CH3)(CH2CH2O)X.
Also suitable for use in the present invention are silicon-based surfactants.
One example of these
types of surfactants is Silwet L7604 available from Dow Chemical (1691 N.
Swede Road,
Midland, Michigan, USA).
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24
The condensation products of ethylene oxide with a hydrophobic base formed by
the
condensation of propylene oxide with propylene glycol are also suitable for
use herein. The
hydrophobic portion of these compounds will preferably have a molecular weight
of from 1500
to 1800 and will exhibit water insolubility. The addition of polyoxyethylene
moieties to this
hydrophobic portion tends to increase the water solubility of the molecule as
a whole, and the
liquid character of the product is retained up to the point where the
polyoxyethylene content is
about 50% of the total weight of the condensation product, which corresponds
to condensation
with up to 40 moles of ethylene oxide. Examples of compounds of this type
include certain of the
commercially available Pluronic surfactants, marketed by BASF. Chemically,
such surfactants
have the structure (EO)X(PO)y(EO)z or (PO)X(EO)y(PO)z wherein x, y, and z are
from 1 to 100,
preferably 3 to 50. Pluronic surfactants known to be good wetting surfactants
are more
preferred. A description of the Pluronic surfactants, and properties thereof,
including wetting
properties, can be found in the brochure entitled "BASF Performance Chemicals
Plutonic &
Tetronic Surfactants", available from BASF.
Other suitable though not preferred non-ionic surfactants include the
polyethylene oxide
condensates of alkyl phenols, e.g., the condensation products of alkyl phenols
having an alkyl
group containing from 6 to 12 carbon atoms in either a straight chain or
branched chain
configuration, with ethylene oxide, the said ethylene oxide being present in
amounts equal to 5 to
25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in
such compounds
can be derived from oligomerized propylene, diisobutylene, or from other
sources of iso-octane
n-octane, iso-nonane or n-nonane. Other non-ionic surfactants that can be used
include those
derived from natural sources such as sugars and include C8-C16 N-alkyl glucose
amide
surfactants.
Suitable anionic surfactants for use herein are all those commonly known by
those skilled in the
art. Preferably, the anionic surfactants for use herein include alkyl
sulphonates, alkyl aryl
sulphonates, alkyl sulphates, alkyl alkoxylated sulphates, C6-C20 alkyl
alkoxylated linear or
branched diphenyl oxide disulphonates, or mixtures thereof.
Suitable alkyl sulphonates for use herein include water-soluble salts or acids
of the formula
RSO3M wherein R is a C6-C20 linear or branched, saturated or unsaturated alkyl
group,
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preferably a C g-C 1 g alkyl group and more preferably a C 10-C 16 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
5 quaternary ammonium cations derived from alkylamines such as ethylamine,
diethylamine,
triethylamine, and mixtures thereof, and the like).
Suitable alkyl aryl sulphonates for use herein include water-soluble salts or
acids of the formula
RSO3M wherein R is an aryl, preferably a benzyl, substituted by a C6-C20
linear or branched
10 saturated or unsaturated alkyl group, preferably a C8-C18 alkyl group and
more preferably a
C10-C16 alkyl group, and M is H or a cation, e.g., an alkali metal cation
(e.g., sodium,
potassium, lithium, calcium, magnesium and the like) 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
15 cations derived from alkylamines such as ethylamine, diethylamine,
triethylamine, and mixtures
thereof, and the like).
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..
20 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 R1S04M wherein
R1 represents a hydrocarbon group selected from the group consisting of
straight or branched
25 alkyl radicals containing from 6 to 20 carbon atoms and alkyl phenyl
radicals containing from 6
to 18 carbon atoms in the alkyl group. M is H or a cation, e.g., an alkali
metal cation (e.g.,
sodium, potassium, lithium, calcium, magnesium and the like) 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).
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26
Particularly preferred branched alkyl sulphates to be used herein are those
containing from 10 to
14 total carbon atoms like Isalchem 123 AS . Isalchem 123 AS commercially
available from
Enichem is a C12_13 surfactant which is 94% branched. This material can be
described as CH3-
(CH2)m-CH(CH2OSO3Na)-(CH2)õ-CH3 where n+m=8-9. Also preferred alkyl sulphates
are the
alkyl sulphates where the alkyl chain comprises a total of 12 carbon atoms,
i.e., sodium 2-butyl
octyl sulphate. Such alkyl sulphate is commercially available from Condea
under the trade name
Isofol 12S. Particularly suitable liner alkyl sulphonates include C12-C16
paraffin sulphonate like
Hostapur SAS commercially available from Hoechst.
Suitable alkyl alkoxylated sulphate surfactants for use herein are according
to the formula
RO(A)mSO3M wherein R is an unsubstituted C6-C20 alkyl or hydroxyalkyl group
having a C6-
C20 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more
preferably C12-C18
alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero,
typically between
0.5 and 6, more preferably between 0.5 and 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 C 12-C 1 g
alkyl polyethoxylate (1.0) sulfate (C12-C18E(1.0)SM), C12-C18 alkyl
polyethoxylate (2.25)
sulfate (C12-C18E(2.25)SM), C12-C18 alkyl polyethoxylate (3.0) sulfate (C12-
C18E(3.0)SM),
and C12-C18 alkyl polyethoxylate (4.0) sulfate (C12-C18E(4.0)SM), wherein M is
conveniently
selected from sodium and potassium.
Suitable C6-C20 alkyl alkoxylated linear or branched diphenyl oxide
disulphonate surfactants for
use herein are according to the following formula:
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WO 2007/119195 PCT/IB2007/051241
27
(7O~R
S03-X+ S03-X+
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 X+ is H or
a cation, e.g.,
an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium
and the like).
Particularly suitable C6-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, C8-C24 olefinsulfonates, sulphonated polycarboxylic acids prepared by
sulphonation of the
pyrolyzed product of alkaline earth metal citrates, e.g., as described in
British patent specification
No. 1,082,179, C8-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-C18
monoesters) diesters of sulfosuccinate (especially saturated and unsaturated
C6-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(CH2CH2O)kCH2COO-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). A variety of such
surfactants are also
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28
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.
Zwitterionic surfactants represent another class of preferred surfactants
within the context of the
present invention.
Zwitterionic surfactants contain both cationic and anionic groups on the same
molecule over a
wide pH range. The typical cationic group is a quaternary ammonium group,
although other
positively charged groups like sulfonium and phosphonium groups can also be
used. The typical
anionic groups are carboxylates and sulfonates, preferably sulfonates,
although other groups like
sulfates, phosphates and the like, can be used. Some common examples of these
detergents are
described in the patent literature: U.S. Patent Nos. 2,082,275, 2,702,279 and
2,255,082.
A specific example of a zwitterionic surfactant is 3-(N-dodecyl-N,N-dimethyl)-
2-
hydroxypropane-l-sulfonate (Lauryl hydroxyl sultaine) available from the
McIntyre Company
(24601 Governors Highway, University Park, Illinois 60466, USA) under the
tradename
Mackam LHS . Another specific zwitterionic surfactant is C12_14
acylamidopropylene
(hydroxypropylene) sulfobetaine that is available from McIntyre under the
tradename Mackam
50-SB . Other very useful zwitterionic surfactants include hydrocarbyl, e.g.,
fatty alkylene
betaines. A highly preferred zwitterionic surfactant is Empigen BB , a coco
dimethyl betaine
produced by Albright & Wilson. Another equally preferred zwitterionic
surfactant is Mackam
35HP , a coco amido propyl betaine produced by McIntyre.
Another class of preferred surfactants comprises the group consisting of
amphoteric surfactants.
One suitable amphoteric surfactant is a C8-C16 amido alkylene glycinate
surfactant ('ampho
glycinate'). Another suitable amphoteric surfactant is a C8-C16 amido alkylene
propionate
surfactant ('ampho propionate'). Other suitable, amphoteric surfactants are
represented by
surfactants such as dodecylbeta-alanine, N-alkyltaurines such as the one
prepared by reacting
dodecylamine with sodium isethionate according to the teaching of U.S. Patent
No. 2,658,072,
N-higher alkylaspartic acids such as those produced according to the teaching
of U.S. Patent No.
2,438,091, and the products sold under the trade name "Miranol ", and
described in U.S. Patent
No. 2,528,378.
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The weight ratio of water-soluble or water-dispersible copolymer herein to
nonionic, anionic,
amphoteric, zwitterionic surfactant or mixtures thereof is between 1:100 and
10: 1, more
preferably between 1: 50 and 1:1.
Chelating agents
One class of optional compounds for use herein includes chelating agents or
mixtures thereof.
Chelating agents can be incorporated in the compositions herein in amounts
ranging from 0.0%
to 10.0% by weight of the total composition, preferably 0.01% to 5.0%.
Suitable phosphonate chelating agents for use herein may include alkali metal
ethane 1-hydroxy
diphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as amino
phosphonate
compounds, including amino aminotri(methylene phosphonic acid) (ATMP), nitrilo
trimethylene
phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and
diethylene triamine
penta methylene phosphonates (DTPMP). The phosphonate compounds may be present
either in
their acid form or as salts of different cations on some or all of their acid
functionalities.
Preferred phosphonate chelating agents to be used herein are diethylene
triamine penta methylene
phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP). Such
phosphonate
chelating agents are commercially available from Monsanto under the trade name
DEQUEST =
Polyfunctionally-substituted aromatic chelating agents may also be useful in
the compositions
herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al.
Preferred compounds of
this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-
disulfobenzene.
A preferred biodegradable chelating agent for use herein is ethylene diamine
N,N'- disuccinic
acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium
salts thereof or
mixtures thereof. Ethylenediamine N,N'- disuccinic acids, especially the (S,S)
isomer have been
extensively described in US patent 4, 704, 233, November 3, 1987, to Hartman
and Perkins.
Ethylenediamine N,N'- disuccinic acids is, for instance, commercially
available under the
tradename ssEDDS from Palmer Research Laboratories.
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Suitable amino carboxylates for use herein include ethylene diamine tetra
acetates, diethylene
triamine pentaacetates, diethylene triamine pentaacetate (DTPA),N-
hydroxyethylethylenediamine triacetates, nitrilotri-acetates, ethylenediamine
tetrapropionates,
triethylenetetraaminehexa-acetates, ethanol-diglycines, propylene diamine
tetracetic acid (PDTA)
5 and methyl glycine di-acetic acid (MGDA), both in their acid form, or in
their alkali metal,
ammonium, and substituted ammonium salt forms. Particularly suitable amino
carboxylates to be
used herein are diethylene triamine penta acetic acid, propylene diamine
tetracetic acid (PDTA)
which is, for instance, commercially available from BASF under the trade name
Trilon FS and
methyl glycine di-acetic acid (MGDA).
Further carboxylate chelating agents for use herein include salicylic acid,
aspartic acid, glutamic
acid, glycine, malonic acid or mixtures thereof.
Fatty acid
The liquid compositions of the present invention may comprise a fatty acid, or
mixtures thereof
as an optional ingredient.
Suitable fatty acids for use herein are the alkali salts of a C8-C24 fatty
acid. Such alkali salts
include the metal fully saturated salts like sodium, potassium and/or lithium
salts as well as the
ammonium and/or alkylammonium salts of fatty acids, preferably the sodium
salt. Preferred fatty
acids for use herein contain from 8 to 22, preferably from 8 to 20 and more
preferably from 8 to
18 carbon atoms.
Suitable fatty acids may be selected from caprylic acid, capric acid, lauric
acid, myristic acid,
palmitic acid, stearic acid, oleic acid, and mixtures of fatty acids suitably
hardened, derived from
natural sources such as plant or animal esters (e.g., palm oil, olive oil,
coconut oil, soybean oil,
castor oil, tallow, ground oil, whale and fish oils and/or babassu oil.
For example Coconut Fatty Acid is commercially available from UNICHEMA under
the name
PRIFAC 5900 .
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Fatty acids are desired herein as they reduce the sudsing of the liquid
composition used in the
process according to the present invention.
Typically, the liquid composition herein may comprise up to 6%, preferably
from 0.1% to 2.0%,
more preferably from 0.1% to 1.0% and most preferably from 0.2% to 0.8% by
weight of the
total composition of said fatty acid.
Branched fatty alcohol
The liquid compositions of the present invention may comprise a branched fatty
alcohol, or
mixtures thereof as a highly preferred optional ingredient.
Such suitable compounds are commercially available, for instance, as the
Isofol series such as
Isofol 12 (2-butyl octanol) or Isofol 16 (2-hexyl decanol) commercially
available from
Condea.
Preferably said branched fatty alcohol is selected from the group consisting
of 2-butyl octanol,
2-hexyl decanol, and a mixture thereof. More preferably said 2-alkyl alkanol
is 2-butyl octanol.
Typically, the liquid composition herein may comprise up to 2%, preferably
from 0.10% to 1.0%,
more preferably from 0.1% to 0.8% and most preferably from 0.1% to 0.5% by
weight of the
total composition of said branched fatty alcohol.
Solvent
The liquid compositions of the present invention may comprise a solvent, or
mixtures thereof as
an optional ingredient.
Suitable solvent is selected from the group consisting of : ethers and
diethers having from 4 to 14
carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably from 8
to 10 carbon
atoms; glycols or alkoxylated glycols; alkoxylated aromatic alcohols; aromatic
alcohols;
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alkoxylated aliphatic alcohols; aliphatic alcohols; C8-C14 alkyl and
cycloalkyl hydrocarbons and
halohydrocarbons; C6-C16 glycol ethers; terpenes; and mixtures thereof.
Suitable glycols to be used herein are according to the formula HO-CRIR2-OH
wherein R1 and
R2 are independently H or a C2-C10 saturated or unsaturated aliphatic
hydrocarbon chain and/or
cyclic. Suitable glycols to be used herein are dodecaneglycol and/or
propanediol.
Suitable alkoxylated glycols to be used herein are according to the formula R-
(A)n-R1-OH
wherein R is H, OH, a linear or branched, saturated or unsaturated alkyl of
from 1 to 20 carbon
atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein R1 is
H or a linear
saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2
to 15 and more
preferably from 2 to 10, and A is an alkoxy group preferably ethoxy, methoxy,
and/or propoxy
and n is from 1 to 5, preferably 1 to 2. Suitable alkoxylated glycols to be
used herein are methoxy
octadecanol and/or ethoxyethoxyethanol.
Suitable alkoxylated aromatic alcohols to be used herein are according to the
formula R-(A)n-OH
wherein R is an alkyl substituted or non-alkyl substituted aryl group of from
1 to 20 carbon
atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein A is
an alkoxy group
preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5,
preferably 1 to 2.
Suitable alkoxylated aromatic alcohols are benzoxyethanol and/or
benzoxypropanol.
Suitable aromatic alcohols to be used herein are according to the formula R-OH
wherein R is an
alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon
atoms, preferably
from 1 to 15 and more preferably from 1 to 10. For example a suitable aromatic
alcohol to be
used herein is benzyl alcohol.
Suitable alkoxylated aliphatic alcohols to be used herein are according to the
formula R-(A)n-OH
wherein R is a linear or branched, saturated or unsaturated alkyl group of
from 1 to 20 carbon
atoms, preferably from 2 to 15 and more preferably from 3 to 12, wherein A is
an alkoxy group
preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5,
preferably 1 to 2.
Suitable alkoxylated aliphatic linear or branched alcohols are butoxy propoxy
propanol (n-BPP),
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butoxyethanol, butoxypropanol (n-BP), ethoxyethanol, 1 -methylpropoxyethanol,
2-
methylbutoxyethanol, or mixtures thereof. Butoxy propoxy propanol is
commercially available
under the trade name n-BPP from Dow chemical. Butoxypropanol is commercially
available
from Dow chemical.
Suitable aliphatic alcohols to be used herein are according to the formula R-
OH wherein R is a
linear or branched, saturated or unsaturated alkyl group of from 1 to 20
carbon atoms, preferably
from 2 to 15 and more preferably from 5 to 12. With the proviso that said
aliphatic branched
alcohols is not a 2-alkyl alkanol as described herein above. Suitable
aliphatic alcohols are
methanol, ethanol, propanol, isopropanol or mixtures thereof.
Suitable terpenes to be used herein monocyclic terpenes, dicyclic terpenes
and/or acyclic
terpenes. Suitable terpenes are : D-limonene; pinene; pine oil; terpinene;
terpene derivatives as
menthol, terpineol, geraniol, thymol; and the citronella or citronellol types
of ingredients.
Other suitable solvents include butyl diglycol ether (BDGE), hexandiols,
butyltriglycol ether, ter
amilic alcohol and the like. BDGE is commercially available from Union Carbide
or from BASF
under the trade name Butyl CARBITOL .
Preferably said solvent is selected from the group consisting of butoxy
propoxy propanol, butyl
diglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol,
isopropanol, hexandiols and
mixtures thereof. More preferably said solvent is selected from the group
consisting of butoxy
propoxy propanol, butyl diglycol ether, benzyl alcohol, butoxypropanol,
ethanol, methanol,
isopropanol and mixtures thereof. Even more preferably said solvent is
selected from the group
consisting of butyl diglycol ether, butoxypropanol, ethanol and mixtures
thereof.
Typically, the liquid composition herein may comprise up to 30%, preferably
from 1% to 25%,
more preferably from 1% to 20% and most preferably from 2% to 10% by weight of
the total
composition of said solvent or mixture thereof.
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In a preferred embodiment the solvent comprised in the liquid composition
according to the
present invention is a volatile solvent or a mixture thereof, preferably a
volatile solvent or a
mixture thereof in combination with another solvent or a mixture thereof.
Perfumes
The liquid compositions of the present invention may comprise a perfume or a
mixture thereof as
a highly preferred optional ingredient.
Suitable perfumes for use herein include materials which provide an olfactory
aesthetic benefit
and/or cover any "chemical" odor that the product may have.
The compositions herein may comprise a perfume or a mixture thereof, in
amounts up to 5.0%,
preferably in amounts of 0.01% to 2.0%, more preferably in amounts of 0.05% to
1.5%, even
more preferably in amounts of 0.1% to 1.0%, by weight of the total
composition.
Builders
The liquid compositions of the present invention may also comprise a builder
or a mixture
thereof, as an optional ingredient.
Suitable builders for use herein include polycarboxylates and polyphosphates,
and salts thereof.
Typically, the compositions of the present invention comprise up to 20.0 % by
weight of the total
composition of a builder or mixtures thereof, preferably from 0.1% to 10.0%,
and more
preferably from 0.5% to 5.0%.
Radical scavenwr
The compositions of the present invention may comprise a radical scavenger.
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.
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Preferred such radical scavengers for use herein include di-tert-butyl hydroxy
toluene (BHT),
hydroquinone, di-tert-butyl 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-
5 tert-butyl hydroxy toluene. Such radical scavengers like N-propyl-gallate
may be commercially
available from Nipa Laboratories under the trade name Nipanox S 1 .
Radical scavengers when used, are typically present herein in amounts up to
10% and preferably
from 0.001% to 0.5% by weight of the total composition.
The presence of radical scavengers may contribute to the chemical stability of
the compositions
of the present invention.
Other Adjuvants
Non-limiting examples of other adjuncts are: enzymes such as proteases,
hydrotropes such as
sodium toluene sulfonate, sodium cumene sulfonate and potassium xylene
sulfonate, and
aesthetic-enhancing ingredients such as colorants, providing they do not
adversely impact on
filming/streaking. The compositions can also comprise one or more colored dyes
or pigments.
Dyes, pigments and disappearing dyes, if present, will constitute from 0.1 ppm
to 50 ppm by
weight of the aqueous composition.
Packaging form of the compositions
The compositions herein may be packaged in a variety of suitable detergent
packaging known to
those skilled in the art. The liquid compositions are preferably packaged in
conventional
detergent plastic bottles.
Examples
The following examples are meant to exemplify compositions used in a process
according to the
present invention but are not intended to limit the scope of the present
invention. The liquid
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compositions below are made by combining the listed ingredients in the order
given using the
listed proportions to form homogenous mixtures (solution % is by weight of
active material).
A B C D E F G
Alkoxylated
nonionic
surfactants
C 9-11 E05 4.5 - 9.0 4.0 3.0 - -
C 12,14 E05 1.5 - - 6.0 0.5 0.7 -
C10A07 - 3.5 - - - - 3.0
C 12,14 E021 - - - 2.0 - - -
Anionic
surfactants 0.5 0.2 0.4 1.5 0.2 - 0.5
NaLAS 0.4
Isalchem AS 1.5 0.7 1.7 3.0 1.4 0.8 0.8
NaCS
Neutralizing co-
surfactants 0.2 - - - 0.1 0.5 -
C12-14 AO
Polymers 0.1 - - 0.15 - 0.075 -
Copolymer I - 0.1 0.15 - 0.05 - 0.1
Copolymer II
Chelants 0.1 0.1 0.2 - 0.15 - 0.1
DTPMP
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Buffer
Na2C03 0.2 0.4 1.0 1.0 0.6 - 0.5
Citric 1.0 - 0.8 0.7 0.5 1.0 -
Caustic 0.8 - 0.3 0.4 0.3 0.7 -
Suds control
Fatty Acid 0.8 0.3 0.3 0.2 0.2 0.3 0.2
Isofo112 - - - 0.5 - - -
Solvents
EtOH - - - - - - 1.0
n-BP - - - - - 5.5 3.0
MEA - - - - - 0.7 -
Minors and water ------ ------ up to 100 ----- ------
pH 9.5 9.5 9.5 9.5 10.0 11.0 9.5
Copolymer I derived from Diquat and acrylic acid molar ratio 33/67 prepared by
Rhodia
Copolymer II derived from DADMAC and acrylic acid, molar ratio 40/60 prepared
by Rhodia
C 9-11 E05 is a C 9-11 E05 nonionic surfactant commercially available from ICI
or Shell.
C12,14 E05 is a C12, 14 E05 nonionic surfactant commercially available from
Huls, A&W or
Hoechst.
C10 A07 is an alkoxylated non-ionic surfactant commercially available from
BASF under the
tradename Lutensol XL 70 .
C12,14 E021 is a C12-14 E021 nonionic surfactant.
NaLAS is Sodium Linear Alkylbenzene sulphonate commercially available from
A&W.
NaCS is Sodium Cumene sulphonate commercially available from A&W.
Isalchem AS is a C12-13 sulphate surfactant commercially available from
Enichem.
C12-14 AO is a C12-14 amine oxide surfactant.
DTPMP is diethylenetriaminepentamethylphosponic acid commercially available
from Solutia.
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Isofol 12 is 2-butyl octanol commercially available from Condea.
n-BP is normal butoxy propanol commercially available from Dow Chemicals.
Ethanol is commercially available from Condea.
MEA is mono-ethanolamine commercially available from Condea.
These liquid compositions are used in a process as disclosed herein and
provide good filming
and/or streaking performance as well as good shine performance, when used in a
dilute / no rinse
hard surface cleaning application. In addition, when used in a dilute / no
rinse hard surface
cleaning application these liquid compositions provide good soil repellency
performance as well
as good next time cleaning benefit performance.
Furthermore, when used in a neat hard surface cleaning application, these
liquid compositions
provide good filming and/or streaking performance as well as good shine
performance.
