Note: Descriptions are shown in the official language in which they were submitted.
PCT/EP94/01290
WO 94!26858
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HARD SURFACE CLEANING COMPOSITIONS COMPRISING POLYMERS
Technical Field
The present invention relates to general purpose,
particularly, hard surface, liquid cleaning compositions
comprising surfactants and polymeric components.
Background of the Invention
In traditional cleaning of hard surfaces such as wood,
glazed tiles, painted metal and the like, it is known to
follow soil removal using surfactant or solvent based
compositions with the application of a lacquer, wax or
polish as a separate operation so as to seal the surface
and reduce the rate of soil redeposition. This two-step
cleaning and sealing operation is time-consuming and
complex.
It is known to incorporate components into a surfactant-
based composition with the intention that deposition of
such components onto surfaces will provide a protective
layer in a one step cleaning operation.
US 3679592 (1972) discloses alkaline, cleaning and soil
preventative compositions which comprise surfactant and
1-l0~wt, particularly 4~, of a film forming component of
specified structure having a molecular weight in the range
500 to 100,000. In use, the compositions are said to
inhibit stain deposition and assist soil removal.
GB 1528592 (1978) discloses alkaline, floor cleaning
compositions which comprise an organic, polycarboxylic
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acid co-polymer having a molecular weight in the range
100,000-2,500,000 which is soluble in aqueous solutions
having a pH of 8.5 or above. These polymers are readily
available in commercial quantities.
GB 1534722 (1978) discloses granular hard surface cleaning
compositions which comprise surfactant and, as "a soil
removal improvement mixture", a polyvinyl alcohol or
pyrrolidone and a biopolysaccharide. These polymers have
molecular weights ranging from around 5000 to around
360,000 and are available in industrially useful
quantities. The compositions form alkaline solutions.
US 4252665 (1979) discloses aqueous, alkaline, hard
surface cleaning compositions of pH 9-12 which comprise a
'detergency-boosting' acrylic copolymer having a molecular
weight substantially in excess of 100,000 in combination
with anionic surfactants.
US 07/297807, as described in EP 0467472 A2 (Colgate
Palmolive) demonstrates that the incorporation of 2.3~ of
a 15-20~ aqueous solution of the cationic polymer poly-
[beta(methyl diethyl-ammonium) ethyl-methacrylate] in a
mixed nonionic surfactant system for hard surface cleaning
results in significant improvement of ease of subsequent
re-cleaning of previously soiled and cleaned ceramic
tiles. These cationic polymers are rather more expensive
than commonplace acrylic and methacrylic polymers and some
doubt has been cast upon the environmental acceptability
of cationic species containing quaternary nitrogen.
It is known for surfactant-based cleaning compositions to
contain structuring agents to aid in providing appropriate
rheological properties to enhance their distribution and
adherence of the composition to the hard surface to be
PCTIEP94/01290
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cleaned, particularly to provide enhanced cling on sloping
surfaces .
Known structuring agents include polymers such as poly-
saccharides, e.g. sodium carboxymethyl cellulose and other
chemically modified cellulose materials, xanthan gum and
other non-flocculating structuring agents such as
Biopolymer PS87 referred to in US Patent No. 4 329 448.
Polymers of acrylic acid cross-linked with a poly
functional agent, for example CARBOPOLR, are also used as
structuring agents. The amount of such structuring agents
can be as little as 0.001 but is more typically at least
0.01 by weight of the composition. A further function of
such structuring agents is to suspend particulate
components, such as abrasives.
It is also known to employ at least partially esterified
resins such as an at least partially esterified adduct of
rosin and an unsaturated dicarboxylic acid or anhydride,
or an at least partially esterified derivatives of co-
polymerisation products of mono-unsaturated aliphatic,
cycloaliphatic or aromatic monomers having no carboxy
groups and unsaturated dicarboxylic acids or anhydrides
thereof as additives. The purpose of such materials is to
modify the wetting properties of the composition so as to
produce a 'streak-free' finish after drying.
Typical examples of suitable copolymers of the latter type
are copolymers of ethylene, styrene and vinyl-methylether
with malefic acid, fumaric acid, itaconic acid, citraconic
acid and the like and the anhydrides thereof including the
styrene/maleic anhydride copolymers.
EP 0467472 A2 discloses that soil release promoting
polymers such as, but not limited to, the cationic poly-
[beta(methyl diethyl-ammonium ethyl-methacrylate] are
, . ) . . j '. : 1 1 ~ ) -
) -
C3529 . ,
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-a-
also effective in combination with anionic and cationic
surfactant . Iri that published application it is stated
that 'said adsorbed polymer forms a residual anti-soiling
hydrophilic layer of said soil release promoting polymer
on said surface, whereby removal of soils subsequently
deposited thereupon requires less work than in the absence
of said residual layer'. The molecular weight range of
the polymers falls into the range 4,000-100,000 although
the use of polymers having a molecular weight above 50,000
0 is discouraged for solubility reasons (see EP X67472, page
3 paragraph 3).
EP 0379256 discloses similar compositions to the above-
mentioned document, having up to 2%wt of an optional
quaternised, anti-static, polymer of molecular weight in
the range of 2,000 - 500,000, and being characterised by
an acidic pH of 2-4 and a 2-4%wt of a nonionic surfactant
system. Specific examples relate to compositions having a
pH of 2.5 and comprising 2.2%wt of a mixed nonionic system
and 0.07% of the specified cationic polymer. The modified
polymer is again said to function as a soil release agent.
In addition to the above it is known from US 4606842 to
use low molecular weight polyacrylic resins as a builder
in glass cleaning compositions of the spray-on, wipe-off
type. Baker et al in US 4690779 discloses the use of the
combination-of polymers-~f po-lyacrylic acid having a
molecular weight below 5000 with certain nonionic
surfactants in hard surface cleaning compositions. The
primary function of the polymer in these systems is as a
builder.
US 4678596 relates to a rinse aid formulation for hand
dishwash and machine dishwash of pH 7.5-10, which
comprises S-60% nonionic surfactant (examples are 15%),
and preferably 2%wt of anionic poly(meth)aczylic acid
n~ ~rrT
. .. , . . .: ~, o > > o
C3529 :,.v ~~~~~~~~ ' ,
- 4a -
polymer of molecular weight 1,000-50,000. Compositions
having a pH of 6.5 comprising relatively high levels of
polymer are said to be unstable.
US 4657690 relates to a washing and foaming composition
for hair and skin in the acid/neutral pH range (4.5-7.7)
which comprises nonionic surfactant (typically at around
5~) and poly(meth)acrylic acid to improve the primary
detergency of the surfactant wherein the weight ratio of
the polymer to the surfactant is no gxeater than 0.2:1.
From the above it can be seen that it is known to include
certain polymers in generally alkaline hard surface
cleaning compositions so as to obtain either a primary
cleaning benefit when the composition is first used on the
CA 02161324 2003-10-07
surface or a secondary cleaning benefit by modification of
the surface so as hinder soil deposition.or otherwise
facilitate repeated cleaning. As will be illustrated by
way of example hereafter, known compositions are generally
not efficient in both primary and secondary cleaning.
Brief Descrin,~ion of the Inve~r~.~'~,_or~
we have now determined that the use of certain, relatively
long chain, anionic water-soluble polymers in acidic or
neutral surfactant based composition brings a surprising
initial cleaning benefit in addition to the anti-soiling
benefit. Surprisingly, we have found that commonplace
acrylic, methacrylic and malefic anhydride derived polymers
exhibit this effect in acidic solutions of nonionic
surfactants to the same extent as expensive cationic
polymers.
Accordingly the invention provides a liquid hard-surface
cleaning composition of pH 3-6, comprising:
a) 1-30~wt nonionic surfactant,
b) 0.05-2~wt of a water soluble,. anionic polymer having
an average molecular weight less than 1,000,000 but greater than 100,000, said
-
polymer being free of quaternary nitrogen groups, wherein
the ratio of polymer: nonionic is 0.1:1 or less,
c) not more than 33%wt anionic detergent on
total detergent actives.
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Detailed Description of the Invention
Without wishing to be limited by any theory of operation,
it is believed that the cleaning benefit of the water-
soluble polymer arises from a phase separation of the
nonionic surfactant causing penetration into and/or
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deposition onto soil, resulting in a higher effective
surfactant concentration, than is found in compositions
which are free of polymer. An alternative explanation is
that deposition of surfactant at the soil surface may be
enhanced by the formation and deposition of a polymer
surfactant complex.
Polymers
The water soluble polymer of the above-mentioned size
range is an essential component of the compositions
according to the present invention.
Surprisingly, the preferred polymers in embodiments of the
present invention are those which are readily available in
the marketplace. These are polymers of acrylic or
methacrylic acid or malefic anhydride, or a co-polymer of
one or more of the same either together or with other
monomers.
Particularly suitable polymers include polyacrylic acid,
polymaleic anhydride and copolymers of either of the
aforementioned with ethylene, styrene and methyl vinyl
ether.
The most preferred polymers are malefic anhydride co-
polymers, preferably those formed with styrene, acrylic
acid, methyl vinyl ether and ethylene.
Preferably, the molecular weight of the polymer is at
least, 5000, more preferably at least 50,000 and most
preferably in excess of 100,000.
Typically, the surfactant based cleaning compositions
comprise at least 0.01wt~ polymer, on product.
WO 94/26858
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PCT/EP94101290
Unexpectedly, it has been found that the positive benefit
of the presence of polymer can be identified even when
very low levels of polymer and surfactant are present.
This property of a low concentration threshold is
particularly advantageous in applications of the invention
where considerable dilution is expected.
Preferably the level of polymer is 0.05-5.Owt~ at which
level the anti-recoiling benefits become particularly
significant. More preferably 0.2-2.Owt~ of polymer is
present. We have determined that higher levels of polymer
do not give significant further advantage with common
dilution factors, while increasing the cost of
compositions. It is believed that high levels of polymer
increase the viscosity of the product and hinder product
wetting and penetration of the soil. However, for
concentrated products which are diluted prior to use, the
initial polymer level can be as high as 5$wt.
In the context of the present invention, anionic polymers
are those which carry a negative charge or similar
polymers in protonated form. Mixtures of polymers can be
employed.
As mentioned above, the molecular weight of the polymer is
below 1 000 000 Dalton. As the molecular weight increases
the cleaning benefit of the polymer was reduced.
Surfactants
It is essential that compositions according to the present
invention comprise at least one nonionic surfactant.
The composition according to the invention comprise
detergent actives which can be chosen from nonionic
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detergent actives. We have determined that an detrimental
effect occurs if the anionic polymers are used together
with anionic surfactant only or with mixtures of anionic
and nonionic surfactant which largely comprise anionic
surfactant.
Suitable nonionic detergent active compounds can be
broadly described as compounds produced by the
condensation of alkylene oxide groups, which are
hydrophilic in nature, with an organic hydrophobic
compound which may be aliphatic or alkyl aromatic in
nature.
The length of the hydrophilic or polyoxyalkylene radical
which is condensed with any particular hydrophobic group
can be readily adjusted to yield a water-soluble compound
having the desired degree of balance between hydrophilic
and hydrophobic elements.
Particular examples include the condensation product of
aliphatic alcohols having from 8 to 22 carbon atoms in
either straight or branched chain configuration with
ethylene oxide, such as a coconut oil ethylene oxide
condensate having from 2 to 15 moles of ethylene oxide per
mole of coconut alcohol; condensates of alkylphenols whose
alkyl group contains from 6 to 12 carbon atoms with 5 to
25 moles of ethylene oxide per mole of alkylphenol;
condensates of the reaction product of ethylenediamine and
propylene oxide with ethylene oxide, the condensates
containing from 40 to 80~ of polyoxyethylene radicals by
weight and having a molecular weight of from 5,000 to
11,000; tertiary amine oxides of structure R3N0, where one
group R is an alkyl group of 8 to 18 carbon atoms and the
others are each methyl, ethyl or hydroxy-ethyl groups, for
instance dimethyldodecylamine oxide; tertiary phosphine
oxides of structure R3P0, where one group R is an alkyl
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group of from 10 to 18 carbon atoms, and the others are
each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms,
for instance dimethyldodecylphosphine oxide; and dialkyl
sulphoxides of structure RzSO where the group R is an alkyl
group of from 10 to 18 carbon atoms and the other is
methyl or ethyl, for instance methyltetradecyl sulphoxide;
fatty acid alkylolamides; alkylene oxide condensates of
fatty acid alkylolamides and alkyl mercaptans.
The amount of nonionic detergent active to be employed in
the composition of the invention will generally be from 1
to 30~wt, preferably from 10 to 20~wt, and most preferably
from 12 to 20~wt. Levels of around 15~ active are
particularly preferred as little increase in neat-use
cleaning performance is found at higher levels, although
such higher levels can be employed in products intended to
be considerably diluted prior to use.
Optionally, anionic surfactant can be present in
relatively small proportions.
Suitable anionic detergent active compounds are water-
soluble salts of organic sulphuric reaction products
having in the molecular structure an alkyl radical
containing from 8 to 22 carbon atoms, and a radical chosen
from sulphonic acid or sulphur acid ester radicals and
mixtures thereof.
Examples of anionic detergents are sodium and potassium
alcohol sulphates, especially those obtained by sulphating
the higher alcohols produced by reducing the glycerides of
tallow or coconut oil; sodium and potassium alkyl benzene
sulphonates such as those in which the alkyl group
contains from 9 to 15 carbon atoms; sodium and potassium
secondary alkanesulphonates; sodium alkyl glyceryl ether
sulphates, especially those ethers of the higher alcohols
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derived from tallow and coconut oil; sodium coconut oil
fatty acid monoglyceride sulphates; sodium and potassium
salts of sulphuric acid esters of the reaction product of
one mole of a higher fatty alcohol and from 1 to 6 moles
5 of ethylene oxide; sodium and potassium salts of alkyl
phenol ethylene oxide ether sulphate with from 1 to 8
units of ethylene oxide molecule and in which the alkyl
radicals contain from 4 to 14 carbon atoms; the reaction
product of fatty acids esterified with isethionic acid and
10 neutralised with sodium hydroxide where, for example, the
fatty acids are derived from coconut oil and mixtures
thereof .
The preferred water-soluble synthetic anionic detergent
active compounds are the ammonium and substituted ammonium
(such as mono, di and triethanolamine), alkali metal (such
as sodium and potassium) and alkaline earth metal (such as
calcium and magnesium) salts of higher alkyl benzene
sulphonates and mixtures with olefinsulphonates and higher
alkyl sulphates, and the higher fatty acid monoglyceride
sulphates.
The most preferred anionic detergent active compounds are
higher alkyl aromatic sulphonates such as higher alkyl
benzene sulphonates containing from 6 to 20 carbon atoms
in the alkyl group in a straight or branched chain,
particular examples of which are sodium salts of higher
alkyl benzene sulphonates or of higher-alkyl toluene,
xylene or phenol sulphonates, alkyl naphthalene
sulphonates, ammonium diamyl naphthalene sulphonate, and
sodium dinonyl naphthalene sulphonate.
The amount of synthetic anionic detergent active to be
employed in the detergent composition of this invention
will generally be from 0.5 to 50~wt (on total active),
preferably less than 33~wt (on total active). For
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products containing around l5~wt of surfactant, the level
of anionic surfactant should preferably not exceed 5~wt on
product.
It is also possible optionally to include amphoteric,
cationic or zwitterionic detergent actives in the
compositions according to the invention.
Suitable amphoteric detergent-active compounds that
optionally can be employed are derivatives of aliphatic
secondary and tertiary amines containing an alkyl group of
8 to 18 carbon atoms and an aliphatic radical substituted
by an anionic water-solubilising group, for instance
sodium 3-dodecylamino-propionate, sodium 3-
dodecylaminopropane sulphonate and sodium
N-2-hydroxydodecyl-N-methyltaurate.
Suitable cationic detergent-active compounds are
quaternary ammonium salts having an aliphatic radical of
from 8 to 18 carbon atoms, for instance cetyltrimethyl
ammonium bromide.
Suitable zwitterionic detergent-active compounds that
optionally can be employed are derivatives of aliphatic
quaternary ammonium, sulphonium and phosphonium compounds
having an aliphatic radical of from 8 to 18 carbon atoms
and an aliphatic radical substituted by an anionic water-
solubilising group, for instance
3-(N,N-dimethyl-N-hexadecylammonium)propane-1-sulphonate
betaine, 3-(dodecylmethyl sulphonium) propane-1-sulphonate
betaine and 3-(cetylmethylphosphonium) ethane sulphonate
betaine.
Further examples of suitable detergent-active compounds
are compounds commonly used as surface-active agents given
in the well-known textbooks "Surface Active Agents",
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Vol. I by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry &
Berch, Interscience 1958.
The total amount of detergent active compound to be
employed in the detergent composition of the invention
will generally be from 1.5 to 30~, preferably from 2 to
20~ by weight, most preferably from 10-20wt~.
Minors
The composition according to the invention can contain
other ingredients which aid in their cleaning performance.
For example, the composition can contain detergent
builders other than the special water-soluble salts, as
defined herein, such as nitrilotriacetates,
polycarboxylates, citrates, dicarboxylic acids, water-
soluble phosphates especially polyphosphates, mixtures of
ortho-and pyrophosphate, zeolites and mixtures thereof.
Such builders can additionally function as abrasives if
present in an amount in excess of their solubility in
water as explained herein. In general, the builder, other
than the special water-soluble salts when employed, ''
preferably will form from 0.1 to 25~ by weight of the
composition.
Metal ion sequestrants such as
ethylenediaminetetraacetates, amino-polyphosphonates
(DEQUESTR) and phosphates and a wide variety of other poly-
functional organic acids and salts, can also optionally be
employed.
A further optional ingredient for compositions according
to the invention is a suds regulating material, which can
be employed in compositions according to the invention
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which have a tendency to produce excessive suds in use.
One example of a suds regulating material is soap. Soaps
are salts of fatty acids and include alkali metal soaps
such as the sodium, potassium, ammonium and alkanol
ammonium salts of higher fatty acids containing from about
8 to about 24 carbon atoms, and preferably from about 10
to about 20 carbon atoms. Particularly useful are the
sodium and potassium and mono-, di- and triethanolamine
salts of the mixtures of fatty acids derived from coconut
oil and ground nut oil. tnlhen employed, the amount of soap
can form at least 0.005, preferably 0.5~ to 2~ by weight
of the composition. A further example of a suds
regulating material is an organic solvent, hydrophobic
silica and a silicone oil or hydrocarbons.
Compositions according to the invention can also contain,
in addition to the ingredients already mentioned, various
other optional ingredients such as pH regulants,
colourants, optical brighteners, soil suspending agents,
detersive enzymes, compatible bleaching agents, gel-
control agents, freeze-thaw stabilisers, bactericides,
preservatives, solvents, fungicides, insect repellents,
detergent hydrotropes perfumes and opacifiers.
It is preferable that the compositions of the present
invention are essentially free of abrasive particles.
Experiments have shown that the presence of abrasive
reduces the cleaning benefit due to the polymer although
abrasive would in itself provide a separate cleaning
benefit. It is believed that the abrasive, surfactant and
polymer form a complex which reduces the effective
concentration of the surfactant at the surface being
cleaned.
As mentioned above, the pH of the compositions according
to the present invention is acidic or neutral. We have
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C3529 : , , . , , . ~ ;
., _
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determined that improved cleaning and/or anti-recoiling
benefit is obtained at these pH's. The preferred pH of.
the products is in the range 3-6. A pH of 4-6 is
particularly preferred so as to provide a balance between
the hazards of acid compositions and the advantages of
acids for removing limescale.
Particularly preferred compositions according to the
present invention are mobile aqueous liquids, having a pH
of 3-6 which comprise:
a) 10-20%wt of a alkoxylated alcohol, nonionic
surfactant,
b) less than 3%wt of anionic surfactants,
c) 0.2-2%wt of a water soluble, anionic polymer having
an average molecular weight less than 1,000,000, said
polymer being a homo or hetero polymer of at least
one of acrylic acid, methacrylic acid or malefic
anhydride, with at least one of acrylic acid,
methacrylic acid, malefic anhydride, ethylene, styrene
and methyl vinyl ether, and said polymer being
essentially free of quaternary nitrogen groups.
In order that the present invention may be further
understood it will-be described hereafter by way of
example and with reference to the accompanying figures
wherein:
Figure 1: is a graph showing the effect of polymer
concentration on cleaning effort and anti-recoiling
benefit, and,
pMEND~D SHEET
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Figure 2: is a graph showing the relation of primary
and secondary cleaning benefits for a range of
polymer types.
EXAMPLES
Examples 1-8 use materials as mentioned below:
Sokolan series (TM) ex. BASF
Gantrez series (TM) ex. GAF
Scripset 520 (TM) ex Monsanto
EMA 31 T"~ ex Monsanto
SCMC (Courlose A600)T"~ ex Courtaulds
6047 polyacryamides ex. Allied Colloids
FRS 3966T"' ex Allied Colloids
Jaguar C162T"" ex Meyhall
Polyethylene Oxide (WSRN 80)T"' Union Carbide
ex
Polyvinyl Pyrollidone ex PolySciences
The polyvinyl pyrollidone had a molecular weight of circa.
386000 Dalton.
EXAMPLE 1a-c
Comparison with cationic polymers
0.25mg/cm2 (based on non-volatiles) of soil were deposited
on an 'A4' sized area of 'DECAMEL' (RTM ex Formica) test
surface by spraying. The soil comprised 1~ glycerol
tripalmitate, 0.5~ glycerol trioleate, 0.5$ kaolin, 0.2~
liquid paraffin, 0.1~ palmitic acid, 0.02 carbon black in
methylated spirits. The soil was allowed to age for 24
hours at room temperature prior to cleaning.
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The effort used to remove the soil from the test surface
using a cellulosic spongecloth was measured.
Formulations comprised nonionic surfactant and water with
and without polymer. The surfactant employed was
Imbentin 91-35 OFA (TM) (C9-C11 alkyl, 3-5 EO alkyl
ethoxylate ex. KOLB). The polymers illustrative of the
present invention were a polyacrylic acid (ex BDH) which
had an average molecular weight of 230,000 Daltons. The
cationic polymer used in the comparative examples was
Polymer JR-400 (TM: ex. Union Carbide) and had an average
molecular weight of 400,000 Daltons. The formulations are
given in Table 1 below, together the effort required in
the cleaning operation.
Results given are geometric means of eight replicate
experiments. In order to remove day to day variability,
arising from differences in soil level data is normalised
such that the ef fort required to clean a DECAMELT"~ tile with
the same polymer-free composition is constant.
From the results given under 'initial' it can be seen that
the compositions according to the present invention show
an improved cleaning performance over the comparative
example 1a, where no polymer was present. This
improvement is statistically significant at the 95~
confidence level.
In order to investigate the re-soiling performance, the
DECAMEL sheets were re-soiled and cleaned again using the
same soil and the same cleaning protocol. Cleaning
results for the first and second re-cleaning cycles are
given under 'same(2)' and 'same(3)'.
These results show the significant benefit of the presence
of the polymer. For compositions which did not contain
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polymer (see example 1a) the effort required in the
subsequent cleaning cycles remains essentially constant.
It can be seen that significantly less effort is required
where surfaces are cleaned using a polymer containing
composition and are subsequently recleaned using the same
composition.
Results given under 'normal(4)' are results obtained by
subsequently cleaning the test surfaces used in examples
1a-a with the composition used in example 1a (i.e.
surfactant alone). This indicates that the benefit of the
present invention persisted when the test surfaces were
cleaned with a conventional surfactant-only composition.
It will be noted that the initial cleaning benefits of the
polymers according to the invention (examples 1c and 1e)
are comparable, if not directionally slightly better than
those attained with the quaternised polymer (as used in
comparative examples 1b and 1d).
WO 94126858 PCTlEP94/01290
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TABLE 1
la lb I is id 1e
Imbentin 10~ 10~ 10~ 10~ 10~
Polymer JR - 25~ - 1~
Polyacrylic Acid - - 25$ - 1~
(mol wt 230kD)
Water to 100
ph 4.2 4.4 3.7 4.6 3.3
Initial 1 .29 .24 .36 .25
Same(2) 1 .11 .15 .12 .14
Same(3) 1 .05 .06 .06 .06
Normal 1 .18 .18 .17 .21
EXAMPLE 2 d-cT
Effect of polvmer levels
Example 1 was repeated using the formulations given in
Table 2 below: except that the polyacrylacid used was
VERSICOL E11 (RTM) (ex. Allied Colloids: mol wt 250kD).
Effort to clean the DECAMEL (RTM) tiles is expressed in
terms of the logarithm (base 10) of the effort required.
Examples were repeated both with and without polymer and
at differing concentrations of surfactant. The values
given are the means of four replicates.
'Initial' results were obtained using the compositions
specified with polymer. 'Normal(1)' results were obtained
PCTIEP94101290
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by cleaning using the compositions as specified but
without polymer.
'Same(2)' values were obtained by re-cleaning the tiles
originally cleaned with the polymer-containing
composition, to obtain the results given at 'Initial(1)'
using the same composition in the same manner as the tiles
had initially been cleaned. 'Normal(2)' values were
obtained by cleaning the re-soiled tiles from 'Normal(1)'
with a polymer free composition having the same surfactant
level.
Normal(3-5) values were obtained by cleaning the tiles
originally cleaned by a polymer-containing composition (to
obtain the 'Same(2)' results) with a polymer-free
composition. In all the recleanings in the Normal(3-5)
series the same level of surfactant (7$wt: IMBENTIN) was
used.
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TABLE 2
2d 2e 2f 2Q
Imbentin 16~ 8~ 4$ 2~
Polyacrylic Acid 1~ 0.5~ 0.25 0.15
(mol wt 250kD)
Water to 100
Log initial effort
Required
Initial(1) 2.36 2.38 2.69 3.35
Normal(1) 2.37 3.04 3.43 ****
Same(2) 2.18 2.14 2.18 2.80
Normal(2) no significant
reduction
from
Normal(1)
Recleaning of 'Same(2)'
without polymer
Normal(3) 2.17 1.98 1.99 2.02
Normal(4) 2.86 2.92 2.90 2.83
Normal(5) 3.02 3.04 2.99 3.03
From the results it can be seen that the presence of
polymer has a primary cleaning benefit,: i.e. less
cleaning effort is required in the presence of polymer
than in its absence (compare the 'Normal(1)' results with
the 'Initial(1)' results. The magnitude of this effect
increases markedly at lower surfactant concentrations.
This is believed to be due to the excellent primary
cleaning expected at high surfactant levels masking the
effect of the polymer. In example 2g it proved impossible
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to clean the tile using reasonable efforts using a low
level of surfactant in the absence of polymer.
It can also be seen that the effect of polymer persists in
subsequent cleaning cycles but the effect is reduced as
the number of cycles is increased.
Significantly, low levels of polymer and surfactant show
slight improvement in secondary cleaning performance over
higher levels. Thus, compositions comprising the low
levels of surfactant and polymer clean at least as well as
the compositions containing higher levels of these
components: compare 2d with 2f in which four times the
levels of surfactant and polymer are present yet the same
effort was required to clean the tile. Compositions which
contain no polymer do not clean when only low levels of
surfactant are present. It was also determined that
compositions which contain no polymer show no reduction in
effort required on repeated use.
EXAMPLES 2h-1
Com arison with commercial hard surface cleaners
Examples 2h-21 compare the effort required using very
dilute solutions of the products listed in Table 2c. The
compositions are diluted to typical floor-cleaning
dilutions as recommended by the manufacturers
(approximately 3g/1).
The formulation of the embodiment of the invention is: 28~
IMBENTIN, 2~ polyacrylic acid (250kD: VERSICOL E11 (RTM),
ex Allied Colloids). The formulation of the comparative
example using nonionic alone omitted the polymer.
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Results for percentage soil removal on a hydrophobic
surface, determined by a standard colourimetric method,
after 40 cleaning strokes, were obtained using an in-line
linear scrubber of the SHEEN (RTM) type using an applied
pressure of 80g/cm2. The surface was DECAMEL (RTM) and
pre-soiled with 0.061mg/cm2 (based on non-volatiles) of
soil. Cleaning was performed with a cellulosic sponge
pre-impregnated with the appropriate cleaning solution.
Results for percentage soil removal on a hydrophilic
surface were determined using the same soil applied to
ceramic floor tiles, under identical conditions but with a
single cleaning stroke.
Both sets of experiments were performed in three series
with soil types of:
a) 1~ glycerol tripalmitate, 0.5~ glycerol trioleate,
0.5~ kaolin, 0.2~ liquid paraffin, 0.1~ palmitic
acid, 0.02 carbon black in methylated spirits, (i.e.
80:20 fat :particulate)
b) as (a) with 50:50 fat particulate, and,
c) as (a) with 20:80 fat particulate.
The use of these three different model soil types and two
surfaces illustrates the performance of the compositions
in practice. Three replicates were performed with each of
the three soil type and the mean values over all nine
measurements, as expressed in the table, are taken as
indicative of the performance, in practice, of the
compositions on the surface indicated.
PCTIEP94/01290
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TABLE 3:
I~ Ex. Solution DECAMEL ceramic
2h Embodiment 65~ 47~
2i Nonionic alone 58~ 35~
2j AJAX COMPACT (RTM) 45$ 30$
2k FLASH ULTRA (RTM) 40$ 12$
21 FLASH LIQUID (RTM) 28$ 8~
From these results it can be seen that the embodiment of
the invention significantly outperforms the comparative
examples under the above-mentioned conditions.
In further experiments it was determined that the
embodiment used in example 2h gave less residues and
enhanced shine (as determined by gloss readings) than the
comparative formulations of examples 2i-21 on black
ceramic tiles.
EXAMPLE 3
Anionic Surfactant/Anionic Polymer (Comparative example)
Example 1 was repeated using simplified formulations
consisting of anionic surfactant only in water with and
without anionic or cationic polymer. The surfactant
employed was a magnesium salt of PAS. The anionic polymer
was polyacrylic acid as used in example 1. The cationic
polymer was Polymer JR as used in example 1. The
formulations are given in Table 4 below, together the
effort required in the cleaning operation as mentioned in
example 1. Figures given are geometric means of eight
replicate experiments, normalised to represent the data as
WO 94/26858 PCTIEP94/01290
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if compositions free of polymer always require the same
cleaning effort.
Initial cleaning performance data is presented at
'Initial(1)'. It can be seen that the polymer containing
compositions (3b-3e) have no significant primary cleaning
benefits, but rather that it is generally more difficult
to clean a surface with the anionic surfactant
compositions containing anionic or cationic polymer than
similar compositions without the polymer: e.g. in example
3c it can be seen that for polymer containing compositions
around two-and-a-half times the effort was required for
initial cleaning as compared with polymer free
compositions.
In order to investigate the re-soiling performance, the
DECAMEL sheets were re-soiled and cleaned again using the
same protocol. Cleaning results for the first and second
re-cleaning cycles are given under 'Same(2)' and
'Same(3)'. These results show a generally negative
benefit believed to be due to the presence of an anionic
polymer and a surfactant system of the same charge type.
Results given under 'Normal(4)' are results obtained by
subsequently cleaning the test surfaces used in examples
3a-a with the composition used in example 3a, i.e.
cleaning with surfactant only (an essentially conventional
composition) in the absence of polymer. This indicates
that the negative benefit of anionic polymers persisted
when the test surfaces were cleaned with a conventional
surfactant-only composition. These results also show that
cationic polymers exhibit a secondary cleaning benefit
which is not seen with anionic polymers in the presence of
anionic surfactant.
PCTIEP94/01290
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TABLE 4
3a 3b 3c 38 3~
Magnesium-PAS 5~ 5~ 5$ 5~ 5~
Polymer JR - 0.25 - 1~ -
Polyacrylic acid - - 0.25 - 1~
Water to 100
Ph 6.5 5.5 3.4 5.3 3.0
Initial(1) 1 1.18 2.42 1 1.18
Same(2) 1 0.20 2.10 0.18 1.10
Same(3) 1 0.15 2.01 0.16 0.90
Normal(4) 1 0.22 1.47 0.22 1.26
Similar experiments were performed with the cationic
polymer (Polymer JR) and cationic surfactant (Tetradecyl
trimethyl ammonium hydrogen sulphate). No benefits were
discerned. It is believed that this lack of benefit was
due to the surfactant and the polymer having the same
charge and the consequent inability of the surfactant and
the polymer to form a complex.
EXAMPLE 4
Comparison with other polymers
A further series of experiments were performed using the
materials mentioned in table 5 below. Simplified
formulations consisting of nonionic surfactant (l0wt~) and
water with and without polymer. The surfactant employed
was Imbentin 91-35 OFA (C9-C11 alkyl, 3-5 EO alkyl
WO 94126858 PCT/EP94101290
26
ethoxylate). The polymers are as listed in the table and
were present at a level of 0.5wt$.
Results were normalised such that the initial cleaning
effort required with the surfactant alone was 100. The
recleaning benefit was assessed by cleaning the surfaces
with a 7.5wt$ aqueous solution of nonionic surfactant
alone and measuring the effort required: results again
being normalised assuming 100 cleaning effort for
surfactant alone.
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TABLE 5
Initial Re-cleaning
Malefic Anhydride Copolymers
Acrylic acid
4a Sokolan CP12 (TM) 24 10
4b Sokolan CP13 (TM) 32 17
Methyl vinyl ether
4c Gantrez AN119 (TM) 25 8
4d Gantrez AN169 (TM) 34 12
Styrene
4e Scripset 520 (TM) 29
Ethylene
4f EMA 31 22 11
Carboxylate Polymer
4g SCMC 48 22
Cationic Polymers
Polyacrylamides
4h 6047A 34 21
4i 6047B 42 26
4j 6047C 47 23
4k 6047D 82 16
41 FRS 3966 80 24
Modified Guar
Jaguar C162 54 22
Nonionic Polymers
4n Polyethylene Oxide 29 49
4o Polyvinyl Pyrollidone 37 43
These results are presented in graphical form in figure 2.
In that figure, primary (initial) and secondary (re-
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cleaning) performance are plotted on separate axes.
Reference to the data in figure 2 is by means of the co-
ordinates.
Examples of nonionic polymers,las mentioned in GB 1534722
such as the coating agents PO (at 49,29) and PVP (at
43,37), show particularly poor recleaning benefits
although the primary cleaning performance is good.
The cationic polymers show some benefits both in primary
and secondary cleaning, although the trend indicates that
the two factors have an inverse relationship, that is,
better cleaning in one situation is generally associated
with worse performance in the other: compare
polyacrylamide at (82,16) and polyacrylamide at (42,26).
It is clear from figure 2 that more significant benefits
are obtained with the anionic polymers of the present
invention, and in particular with the malefic anhydride co-
polymers, preferably those formed with styrene, acrylic
acid, methyl vinyl ether and ethylene. The results show
that with the exception of carboxy methyl cellulose
(22,48) and the Sokolan CP13 (TM) (17,32) the anionic
polymers showed generally improved performance over all
the comparative examples as regards both primary and
secondary cleaning.
EXAMPLE 5
Effect of Polymer Concentration
Turning to figure 1 there is shown a graph of the effect
of polymer concentration (230kD, ex BDH) on cleaning
effort and anti-resoiling benefit. All compositions were
at the natural pH of 4, and comprised surfactant (Imbentin
91-35 OFA: C9-C11 alkyl, 3-5 EO alkyl ethoxylate) at a
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level of l0~wt. The cleaning and anti-recoiling benefits
were assessed as in Example 4.
The figure illustrates that with the compositions of the
present invention the initial (primary) cleaning benefit
becomes significant even at very low levels of polymer and
persists as the level of polymer increases. The anti-
resoiling benefits become apparent at levels of around
0.2~ polymer and again persist. This is in agreement with
the results obtained in example 2d-g.
EXAMPLE 6
Effect of pH
Table 6 shows the effect of pH for compositions of the
present invention comprising 0.5~ of a polyaczylic acid
polymer (230kD, ex BDH) and comparative compositions which
do not contain polymer. All compositions comprised
surfactant (Imbentin 91-35 OFA: C9-C11 alkyl, 3-5 EO alkyl
ethoxylate) at a level of l0~wt. pH was modified by the
presence of NaOH. The cleaning and anti-recoiling
benefits were assessed as in Example 4. Cleaning effort
is expressed as the logarithm (base 10) of the effort
required.
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TABLE 6
Primary Secondary
8ffort 8ffort
pH with without with without
polymer polymer polymer polymer
5
6a 3.5 2.25 2.45 2.25 2.72
6b 5.0 2.30 2.45 2.30 2.72
6c 7.0 2.50 2.45 2.85 2.72
6d 9.0 2.70 2.45 2.72 2.72
It can be seen that at low pH's, particularly below pH 7.0
there is a marked reduction in both the primary and
secondary cleaning effort requirements of polymer
containing systems over compositions comprising nonionic
only.
