Field of the invention
[0001] The present invention relates to cleaning compositions, especially to thickened liquid
cleaning compositions exhibiting effective cleaning performance and viscosity.
Background of the invention
[0002] Efficient cleaning performance and viscosity of the cleaning compositions are two
requirements which drive consumer acceptance of cleaning products. Effective cleaning
of surfaces is important, especially on greasy and oily soils and/or where the composition
is thereafter diluted. However viscosity is also a key factor in the preparation of
such a cleaning composition. The viscosity of the cleaning composition must be high
enough to enable the cleaning compositions to remain on the surface being cleansed
for a sufficiently long period of time to ensure effective cleaning. Such a requirement
is of particular utility in cleaning compositions intended to be applied "as is" to
non-horizontal structural surfaces such as walls, windows and sanitary fittings such
as sinks, baths, showers, wash basins and WCs. More particularly, viscosities of 10
cps to 4000 cps are suitable.
[0003] It is therefore an object of the present invention to provide cleaning compositions
having effective cleaning performance and viscosity.
[0004] Thickened cleaning compositions are known in the art. The most commonly used thickener
is a polycarboxylate polymer of high molecular weight i.e. in the range of 500 000
to 4 500 000. Furthermore for best results it is preferred that the polycarboxylate
polymer is cross-linked. EP 834 549 and EP 812 904 both describe cleaning compositions
comprising such polymeric thickeners. However the Applicant has found disadvantages
in the use of such a polymeric thickeners in that whilst the polymer provides adequate
increase in viscosity, the yield stress of the composition is also increased. The
effect of the increase in yield stress is that the composition can become too thick
such that it does not spread easily on the surface and is therefore difficult to use
and/or rinse. In addition it has been found that occasionally air bubbles may become
trapped in the composition during manufacture which are difficult to remove and not
consumer acceptable.
[0005] The Applicant has now found that the polymeric thickening system described herein
provides thickening of the composition without the disadvantages of the previously
used thickening systems as described above.
Summary of the invention
[0006] According to the present invention there is provided a cleaning composition comprising
a polymeric thickening system comprising a polycarboxylate homo or copolymer having
molecular weight in the range of from 500 000 to 4 500 000 and a polycarboxylate homo
or copolymer having a molecular weight of from 500 to 10 000.
[0007] In another aspect of the invention, there is provided a method for cleaning a hard
surface by applying on said surface an effective amount of a composition of the present
invention.
Detailed description of the invention
Polymeric Thickening System
[0008] The compositions of the present invention comprise a polymeric thickening system.
The benefits of using the polymers described herein versus others described in the
art for example cellulosic polymers such as guar gum or xanthum gum, are that they
are more stable in the presence of bleach (especially hypochlorite bleach), provide
better thickening efficiency and do not elevate the yield stress value to levels that
might cause flow problems.
[0009] The polymeric thickening system of the present invention comprises at least two polycarboxylate
polymers; a high molecular weight and a low polycarboxylate homo or copolymer. By
high molecular weight it is meant a polycarboxylate homo or copolymer having a molecular
weight in the range of from 500 000 to 4 500 000, more preferably from 1 000 000 to
4 000 000.
[0010] Most preferred high molecular weight polymers for use herein contain from 0.5% to
4% by weight of a cross-linking agent, wherein the cross-linking agent tends to interconnect
linear strands of the polymers to form the resulting cross-linked products. Suitable
cross-linking agents include the polyalkenyl polyethers. Preferred homo- polymers
include the polyacrylate polymers. Preferred copolymers comprise acrylic acid monomers
in combination with other monomers for maleic acid, maleic anhydride, nethacylic acid,
suucinic acid, vinyl ester and/or mixtures thereof. Preferred monomers of the homo
or copolymeric species contain a carboxylic group. The molecular weight of the carboxylate
group-containing monomers typically varies from 25 to 200, preferably from 50 to 150,
more preferably from 75 to 125. Further, other monomers may be present in the monomeric
mixture, if desired, such as ethylene and propylene, which act as diluents.
[0011] Preferred high molecular weight polycarboxylate polymers for use herein are the polyacrylate
polymers. Especially preferred polymers are those of the polyacrylate type including
those sold under the trade names Carbopol® (especially Carbopol ®ETD 2691 available
form Goodrich), Acrysol® ICS-1, Polygel®, and Sokalan®. Preferred polyacrylate copolymers
are those containing acrylic acid and alkyl (C
5-C
10) acrylate as monomers, (commercially available under the tradename Carbopol® 1623,
Carbopol® 695 from BF Goodrich). Most preferred are copolymers of acrylic acid and
maleic anhydride, (commercially available under the tradename Polygel® DB, Polygel®
DV, Polygel® DA) and copolymers of acrylic acid and vinyl ester (commercially available
under the tradename Polygel® DR from 3V Sigma)..
[0012] Mixtures of any of the high molecular weight polycarboxylate polymers, herein before
described, may also be used.
[0013] The second component of the polymeric thickening system is a low molecular weight
polycarboxylate homo or copolymer. By low molecular weight it is meant a polycarboxylate
polymer having a molecular weight of from 500 to 10 000, more preferably from 800
to 6000, most preferably from 1000 to 4000.
[0014] Preferred low molecular weight homo-polymers are not cross-linked and are most preferably
polyacrylates. Most preferred copolymers comprise acrylic acid in combination with
at least one other type of monomer. An especially preferred low molecular weight polymer
is Polygel® W30 available from 3V sigma.
[0015] The ratio of high molecular weight to low molecular weight polymer is preferably
from 50:1 to 1: 10, more preferably from 30:1 to 1:1, most preferably from 10:1 to
5:1.
[0016] The compositions of the present invention are shear thinning, meaning viscosity is
lowered with increasing shear rates. Viscosity is measured using any currently available,
suitable viscosity measuring equipment. Viscosity of the composition is preferably
in the range of from 10 cps to 4000 cps, more preferably from 50 to 1000cps, most
preferably from 100 to 550cps when measured using a Carrimed Rheometer at 25 °C and
a shear rate of from 10 to 100 s
-1.
[0017] The polymeric thickening system is preferably present at a level of from 0.1% to
10%, more preferably from 0.5% to 5% and most preferably from 0.7 to 2%.
Surfactant
[0018] A highly preferred, but optional component of the cleaning composition described
herein is a surfactant. The surfactant may be selected from anionic, non-ionic, cationic,
amphoteric, zwiterionic surfactants or mixtures thereof.
[0019] In a preferred aspect of the present invention, the cleaning composition comprises
an anionic surfactant system as described in more detail in the Applicants copending
patent application. The anionic surfactant system consists of at least one linear
short-chain and one branched long chain anionic surfactant. The anionic surfactants
are selected from sulphates, sulphonates, alkoxylated sulphates (preferably propoxylated,
more preferably ethoxylated), phosphates or mixtures thereof. The short chain surfactants
has from 5 to 9 carbon atoms whereas the long chain surfactant has from 10 to 16 carbon
atoms.
[0020] A preferred short-chain surfactant is C7-9 Empimin available from Albright and Wilson.
A preferred long-chain surfactant is C12-13 branched sulphate based on Isalchem 123
available from Albright and Wilson.
[0021] In another preferred aspect, the surfactant system additionally comprises a branched
short-chain anionic surfactant. A suitable such anionic surfactant is 2 ethyl hexyl
sulphate avaialble from Albright and Wilson under the tradename Empicol 0585/A.
Optional components
[0022] The compositions according to the present invention may comprise a number of optional
ingredients such as bleaching agents, fatty acids, radical scavengers, antimicrobial
compounds, builders, chelants, buffers, bactericides, solvents, enzymes, hydrotropes,
colorants, bleach activators, soil suspenders, dye transfer agents, brighteners, anti
dusting agents, dispersants, dye transfer inhibitors, pigments, perfumes and dyes.
[0023] A highly preferred optional ingredient according to the present invention is a hypochlorite
bleaching agent, preferably an alkali metal hypochlorite. Advantageously, the compositions
of the invention are stable in the presence of this bleaching agent. Although alkali
metal hypochlorites are preferred other hypochlorite compounds may also be used herein
and can be selected from calcium and magnesium hypochlorite. A preferred alkali metal
hypochlorite for use herein is sodium hypochlorite. Compositions according to the
present invention may comprise hypochlorite bleaching agents such that the content
of active chlorine in the compositions is from 0.1% to 4%, preferably from 0.5% to
2% by weight.
[0024] Another optional component of the present invention is an alkali metal salt of a
C
8-C
18 fatty acid. Said fatty acids are used as suds suppressors. Suitable fatty acids for
use herein can be any C
8-C
18 fatty acid, preferably fully saturated, preferably a sodium, potassium or lithium
salt, more preferably the sodium salt. Suitable fatty acids may be selected from caprylic
acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and mixtures
of fatty acids suitably hardened, derived from natural sources such as tallow, coconut
oil, ground oil and babassu oil. Other suitable suds suppressors include C10-18 alkoxylated
capped alcohols. Most preferably however the suds suppressor consists of a mixture
of fatty acid, preferably coconut fatty acid (e.g. Prifac 5900 available from Unichem)
and alkoxylated capped alcohol, preferably C12-14 ethoxy butoxy methyl ether (e.g.
Plurafac LF231 available from BASF). Compositions according to the present invention
comprise from 0.1% to 2%, preferably less than 0.6% by weight of the composition of
fatty acids.
[0025] A further optional component of the present invention is a radical scavenger. Said
radical scavengers are used as stabilisers. A suitable radical scavenger for use herein
is the aromatic molecule containing a carboxylic group ring substitution. Suitable
examples of radical scavengers for use herein include the meta and para-chlorobenzoic
acid, benzoic acid, meta- ortho- and para-methoxybenzoic acid, meta nitrobenzoic acid,
para bromobenzoic acid, salicylic acid, 5-sulphosalicylic acid, 3,5-dimethyl salicylic
acid and paratoluic acid. Of the above materials, ortho-methoxybenzoic acid is preferred.
Compositions according to the present invention comprise from 0.01% to 1.5% by weight,
preferably from 0.1% to 0.8% by weight and more preferably from 0.2% to 0.5% by weight
of the composition of radical scavengers.
[0026] An optional requirement of the compositions according to the present invention is
that the pH is greater than 10, preferably greater than 11, more preferably greater
than 12. This is achieved by the addition of from 0.4% to 2% of a caustic alkali.
Suitable caustic alkalis for use herein include sodium and potassium hydroxide. Compositions
according to the present invention comprising hypochlorite preferably have a pH greater
than 12 for hypochlorite stability.
[0027] The compositions according to the present invention are preferably aqueous and preferably
comprise from 80% to 95%, more preferably from 85% to 90% of water.
[0028] The compositions according to the present invention are prepared by methods well
known in the art such as the methods described in GB 1 329 086 with the exception
of the polymer being pre-dispersed in an acidic water solution of pH 3 and then neutralised
up to pH 7 before starting adding the other components. The compositions according
to the present invention can then be prepared by mixing all of the ingredients in
a non-metallic apparatus at room temperature or in warm water. If fatty acid is used,
it is melted before being added to the mixture. Preferably, the surfactant blend is
first prepared by adding the short chain surfactant to the long chain surfactants.
Other optionals such as perfume and the alkali metal hypochlorite are then added whilst
stirring. Colourants, if present, are added after all the other ingredients have been
mixed.
[0029] The compositions according to the present invention preferably have a viscosity of
from 10 cps to 4000 cps, more preferably from 50 cps to 2000 cps, most preferably
from 150 cps to 1000 cps measured with a Carrimed Rheometer at a temperature of 25°C
and a shear rate of 15-100 s
-1. Where the composition is in a sprayed form, the viscosity of said spraying compositions
is preferably of from 15 cps to 40 cps.
[0030] The compositions of the present invention may be used for a variety of cleaning purposes
such as cleaning hard surfaces whereby said compositions thickened nature results
in longer adhesion to the surface than non-thickened compositions. By "hard surface"
it is meant herein any surface like bathroom, sanitary fittings such as sinks, showers,
wash basins and WCs, kitchen, sinks, cooker tops, table tops, refrigerators, walls,
windows and the like.
Packaging form of the compositions
[0031] The compositions herein may be packaged in a variety of suitable detergent packaging
known to those skilled in the art. The liquid compositions herein may desirably be
packaged in manually operated spray dispensing containers, which are usually made
of synthetic organic polymeric plastic materials. Accordingly, the present invention
also encompasses liquid cleaning compositions of the invention packaged in a spray
dispenser, preferably in a trigger spray dispenser. Indeed, said spray-type dispensers
allow to uniformly apply to a relatively large area of a surface to be cleaned the
liquid cleaning compositions suitable for use according to the present invention;
thereby contributing to the cleaning properties of said compositions. Such spray-type
dispensers are particularly suitable to clean vertical surfaces. Surprisingly, the
spraying of a liquid composition containing a polycarboxylate polymer, contrary to
compositions which do not contain the polycarboxylate polymer, has been seen beneficial
for preventing or reducing inhalation of the composition by the user as said composition
is sprayed.
[0032] The present advantage is preferably observed where the cleaning composition is as
defined hereinbefore. Accordingly, the use of a polycarboxylate polymer in a liquid
cleaning composition is provided, said composition being in a sprayed form, for preventing
or reducing inhalation of said composition by the user as said composition is sprayed.
Preferably, the liquid cleaning composition is as defined hereinbefore.
[0033] Suitable spray-type dispensers to be used according to the present invention include
manually operated foam trigger-type dispensers sold for example by Specialty Packaging
Products, Inc. or Continental Sprayers, Inc. These types of dispensers are disclosed,
for instance, in US-4,701,311 to Dunnining et al. and US-4,646,973 and US-4,538,745
both to Focarracci. Particularly preferred to be used herein are spray-type dispensers
such as T 8500® or T 8900® commercially available from Continental Spray International
or T 8100® commercially available from Canyon, Northern Ireland. In such a dispenser
the liquid composition is divided in fine liquid droplets resulting in a spray that
is directed onto the surface to be treated. Indeed, in such a spray-type dispenser
the composition contained in the body of said dispenser is directed through the spray-type
dispenser head via energy communicated to a pumping mechanism by the user as said
user activates said pumping mechanism. More particularly, in said spray-type dispenser
head the composition is forced against an obstacle, e.g. a grid or a cone or the like,
thereby providing shocks to help atomise the liquid composition, i.e. to help the
formation of liquid droplets.
[0034] The present invention further encompasses a method for cleaning a hard surface by
applying on said surface an effective amount of a composition of the invention. The
said composition may be applied in its neat form or after having been diluted with
water. Preferably said composition is diluted up to 200 times its weight of water,
preferably into 50 to 150 times its weight of water and more preferably 75 to 95,
before it is applied to said surface. When the composition is diluted prior to use
(to reach a total active level in the order of 1.2%), the composition will still advantageously
provide effective cleaning performance. In the preferred embodiment of the method
of the present invention wherein said composition is applied to a hard-surface to
be cleaned in its diluted form, it may not be necessary to rinse the surface after
the composition has been applied.
Examples
[0035] The examples provided below are not intended to be limiting and merely provide an
example of the sort of formulation that is envisaged by the Applicant. All amounts
are listed in % weight of the total composition.
|
A % w/w |
B % w/w |
C % w/w |
High MW polymer #1 |
1.0 |
- |
1.0 |
Low MW polymer |
0.1 |
0.1 |
0.1 |
High MW polymer #2 |
- |
1.5 |
- |
Heptyl-nonyl sulfate (Empimin LN from A&W) |
1.5 |
1.5 |
3.0 |
Capped nonionic alcohol (Plurafac LF231 from BASF) |
- |
- |
0.1 |
Coconut fatty acid (Prifac 5900 from Unichema) |
- |
- |
0.1 |
2 ethyl-hexyl sulfate (Empicol 0585/A from A&W) |
1.5 |
1.5 |
- |
C12-C13 branched sulfate (based on Isalchem123) |
1.0 |
1.0 |
1.0 |
Citrus Bleach PCMF perfume |
0.3 |
0.3 |
0.2 |
Hypochlorite |
1.0 |
1.0 |
1.0 |
Caustic |
1.0 |
1.0 |
1.0 |
Green dye |
0.0058 |
0.0058 |
0.0058 |
Periodic acid |
0.01 |
0.01 |
0.01 |
Sodium silicate |
0.4 |
0.4 |
0.4 |
Demineralized water |
Balance |
Balance |
Balance |
High MW polymer #1 is Polygel DR from 3Vsigma
High MW polymer #2 is Carbopol ETD2691 from Goodrich
Low MW polymer is Polygel W30 from 3Vsigma |