Note: Descriptions are shown in the official language in which they were submitted.
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I~lCjLllC~ cleaning compositions
FIELD OF THE INVENTION
The present invention relates to liquid cleaning compositions
comprising antioxidants and peroxides and to a process for
cleaning hard surfaces using these compositions.
BACKGROUND TO THE INVENTION
Household surfaces are normally cleaned using compositions
which contain one or more ingredients which assist removal of
fatty/oily/greasy soil and/or any visible staining such as from
associated solid debris or coloured material. Such compositions
may be applied neat or in dilute solution, by pouring or as a
spray, such as from a trigger spray dispenser or other aerosol
applicator, and rubbed with a cloth or other wipe, optionally
followed by rinsing.
JP-A-07/228,892 discloses hard surface cleansing compositions
comprising anionic and amphoteric surfactants, a mono- or
polyhydric alcohol and from O.lo to 7o by weight of a tea leaf
extract. Tannins are commonly known to be an ingredient of tea,
but tannic acid (an antioxidant) is present only in very small
quantities in such extracts. Tannins are said to generally
adversely affect cleaning, especially of oily soil.
Other disclosures of using extracts of tea or other leaves in
hard surface cleaning and/or disinfecting products are in JP-A
07/228,890 and '891, JP-A-08/104,893, JP-A-10/273,698, JP-A-
11/100,596, JP-A-06/340,897, JP-A-63/196,693, JP-A-62/167,400,
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JP-A-59/-047,300 and US 4,220,676, although the products
disclosed in the latter two contain no surfactant.
US 5,965,514 discloses mildly acidic hard surface cleaning
compositions containing amine oxide surfactant, quaternary
disinfectant and a nitrogen-containing chelating agent.
Ascorbic acid is mentioned among a large number of possible
acids to provide acidity, but not among the preferred ones.
Tannic acid is mentioned as one of a large number of optional
possible acids useful as surface tension reducing agents.
An antifogging agent for glass is described in JP-A-49/113,811.
This comprises by weight, 3o dialkyl sulfosuccinate anionic
surfactant, 4o higher secondary alkoxyethyl sulfate anionic
surfactant, to tannic acid, 10o propylene glycol, 5o isopropyl
alcohol and 77o water.
US 5,602,090 discloses cleaning compositions containing easily
oxidisable terpenes such as limonene and hydrogen peroxide. The
example formulations contain 0.020 butylated hydroxyanisole as
an antioxidant.
EP 209228, WO 97/02331, EP 844302, EP 1069178 and disclose
fabric bleaching compositions comprising a surfactant, a
peroxide bleach such as hydrogen peroxide and various radical
scavengers. Propyl gallate, butyl-hydroxy anisole and partially
hindered substituted hydroxybenaenes have been mentioned.
Ascorbic acid and ascorbyl esters have been mentioned as
additional components. US 6,110,883 discloses similar
compositions having a pH above 8.
In US 6,296,880 farmaceutical skin cleansing compositions are
disclosed for treating various skin conditions. The
compositions contain an acidic compound like tannic acid,
preferably in an amount of at least 1o, a certain amount of
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hydrogen peroxide and an antimicrobial agent in an amount
sufficient to reduce microorganisms on the skin. The
compositions may further include antioxidants.
However, it is nowhere disclosed in the prior art that the
treatment of a surface with an antioxidant would have any
positive effect on the subsequent removal of oily soil
thereafter deposited on that surface.
EP 447553 disclosed bleaching compositions for cleaning hard
surfaces comprising hydrogen peroxide or a precursor thereof, a
peracid precursor that produces peracid with the hydrogen
peroxide and optionally a surfactant. The peracid precursor is
an alkoxylated aliphatic or araliphatic carboxylic acid. The
peracid is produced immediately prior to use of the composition
by mixing the hydrogen peroxide (or precursor) with the peracid
precursor at pH of 5-13. Thus the hydrogen peroxide and the
peracid precursor must be stored separately. An antioxidant is
optionally added to the peracid precursor to prevent premature
oxidation.
While it is known that hydrogen peroxide can be used for
bleaching of coloured soil and stains on hard surfaces, it has
been surprisingly found that hydrogen peroxide also generally
assists in the removal of soil (whether coloured or not) from
hard surfaces.
It has also been surprisingly found that certain antioxidants
when present on,a hard surface prevent oily soil later
deposited on that surface from adhering thereto and thus
facilitate subsequent removal of the oily soil.
Even more surprisingly it has been found that when hydrogen
peroxide and these antioxidants are present together in a one-
liquid cleaning composition both activities are retained
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independently without the hydrogen peroxide interfering with
the activity of the antioxidant and vice versa. Also, the
compositions are stable on storage without loss of hydrogen
peroxide or antioxidant activity during storage.
Furthermore, there is a preference among consumers for mild
ingredients in cleaning compositions, and natural ingredients,
more particularly natural antioxidants, are generally perceived
as being mild.
Brief description of the invention
Thus, in one aspect the present invention provides a process
for removing fatty soil from a hard surface, the process
comprising the steps, in sequence, of:
(a) treating the hard surface with a liquid cleaning
composition comprising a radical scavenging antioxidant
and hydrogen peroxide;
(b) allowing the fatty soil to deposit; and
(c) cleaning the surface to remove the fatty soil.
A second aspect of the present invention provides liquid
cleaning compositions comprising hydrogen peroxide and a
natural radical scavenging antioxidant.
A third aspect of the invention provides the use of a radical
scavenging antioxidant and hydrogen peroxide together for
removing fatty soil from a hard surface.
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Detailed description of the invention
Whilst not being bound by any particular theory or explanation,
it is believed that the radical scavenging antioxidant exerts
5 its effect by being retained on the surface in step (a), so
that fatty soil subsequently deposited on the surface in step
(b) does not toughen or polymerise, thereby allowing easier
removal of the soil in step (c). Therefore, one embodiment of
the first aspect of the invention comprises formation of a film
comprising the antioxidant in step (a), e.g. by leaving a
solution or liquid composition comprising the antioxidant and
the hydrogen peroxide to dry on the surface. Step (c) is
advantageously effected using a hard surface cleaning
composition again comprising the antioxidant and the hydrogen
peroxide so that soil is removed and new antioxidant is applied
at the same time, thus effectively combining step (c) of the
first process according to the first aspect of the invention
with step (a) of a subsequent process according to this aspect
of the invention. Step (c) is optionally followed by a rinsing
step, usually with water.
Again, whilst not being bound by any theory or explanation it
is believed that hydrogen peroxide generally assists in soil
removal by decomposition of hydrogen peroxide on the hard
surface thus generating minuscule oxygen bubbles which help
loosening and lifting the soil from the surface.
The antioxidant in the liquid composition used in the process
may be any synthetic or natural radical scavenging antioxidant
as hereinbelow further described. Preferably the antioxidant is
a natural antioxidant. The liquid compositions preferable
comprise at least 0.050 by weight of antioxidant, more
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preferably 0.1% - 10% by weight, even more preferably at least
0.20. Amounts of more than 20 or even 1o are generally not
required and less than 10 or even at most 0.5 are generally
sufficient. Mixtures of antioxidants may be used as well.
The compositions used in the process also comprise hydrogen
peroxide, preferably in an amount of 0.1-100, more preferably
at least 10. Higher amounts than 5o are generally not required
and may cause damage to sensitive surfaces.
The compositions used in the process optionally, but preferably
contain one or more surfactants as hereinbelow further
described. Additionally they may contain other optional
ingredients conventionally used in cleaning compositions.
As used herein, the term "soil" encompasses all kinds of
staining or soiling of organic or inorganic origin, whether
visible or invisible to the naked eye, including soiling of
solid debris and/or with bacteria or other pathogens. As
outlined, the invention is particularly effective for easier
removal of fatty soil, more specifically aged or baked-on fatty
soil. Usually such fatty soil, as often found e.g. on kitchen
surfaces, comprises an oil/fat component in combination with
other soil components such as food remains of starchy and/or
proteinaceous nature, dust, lime scale deposits, etc. The
invention is also effective for removing lime scale, water
marks and similar stains.
The present invention may also deliver one or more other
benefits such as improved tactile properties of the surface
(e.g. smoothness) during and/or after cleaning, reduction of
rancid smell and less darkening of the soil before cleaning,
less surface corrosion and less noise during cleaning.
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Methods, uses and compositions and other products according to
the present invention are useful for treating any household
hard surfaces in for example kitchens and bathrooms including
cooker tops, extractor fans, work surfaces, cooking utensils,
crockery, tiles, floors, baths, toilets, wash basins, showers,
dishwashers, taps, sinks, and glass and enamel surfaces in
general. These surfaces may, for example, consist of paint
(e.g. painted or lacquered wood), plastics, glass, ceramic or
metal (e. g. stainless steel or chrome).
Antioxidants
As disclosed in Ingold K.V. Adv.Chem.Ser.75, 296-305 (1968)
"Inhibition of Auto-oxidation", antioxidants fall into two
groups, namely primary or chain-breaking antioxidants which
react with lipid radicals to form more stable radicals, and
secondary (or preventative) antioxidants which reduce the rate
of chain initiation by various mechanisms. Further
antioxidants may be classified as synthetic or "natural", i.e.
derived from natural products.
The following are classes, sub-classes and specific examples of
antioxidants, which may be used in methods, uses, articles and
compositions according to the present invention. As used
herein, the term "antioxidant" in the singular embraces one
antioxidant as well as two or more antioxidant materials in
combination.
A. Svnthetic Antioxidants
In general, primary antioxidants are subdivided into chain-
breaking acceptors and chain-breaking donors.
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Chain-breaking acceptors (sometimes called "preventative
antioxidants") reduce oxidation rates by decomposing
hydroperoxides into (non-radical) stable end products.
Chain-breaking donors, also called "hydrogen-donating
antioxidants or radical scavengers, function by competing with
organic materials for peroxy radicals.
B. Natural Antioxidants
Natural antioxidant compounds are particularly preferred.
Natural components have a particular appeal to many consumers.
Particularly preferred are those antioxidants that are
considered to be safe for use on surfaces that may come into
contact with food preparations.
Diverse sources of natural materials exhibiting antioxidant
activity have been reported including herbs, spices, cereals,
coffee and beans, oils and seeds, tea leaves and protein
hydrolysates. The active compounds, isolated from the extracts,
responsible for exhibiting antioxidant activity include
compounds from the chemical classes: tocopherols, flavanoids,
phospholipids, organic acids and their derivatives, tannins,
melanoidins, terpenoids, sterols, Maillard reaction products
and amino acids. Depending on the structure the antioxidants
may be water-soluble or oil-soluble; both types are useful for
the present invention.
Carnosol, carnosic acid, rosmanol, rosmarinic acid,
rosmariquinone and rosmaridiphenol are known as active
components of rosemary leaves which exhibit antioxidant
activity. Furthermore, two major phenolic antioxidant
components, gallic acid and eugenol are derived from cloves.
Of the large number of compounds isolated from the extracts of
herbs and spices such as sage, marjoram, oregano and thyme,
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some are known to have potent antioxidant properties. Other
natural antioxidants include ~i-carotene, caffeic, quinic and
ferulic acid, and esters of caffeic acid with sterols
(sitosterol, campesterol, gramisterol and cycloartenol). The
sterol and triterpene alcohol esters of caffeic acid are not
suitable. Further such compounds known to exhibit potent
antioxidant activity include cinnamic, sinapic, vanillic,
syringic and coumaric acids.
Cardanol is a mixture of monohydroxyl phenols with a meta (3-)
15-carbon chain on the phenyl ring. It is isolated as a
distillate from cashew nut shell liquid. Anacardic acid (3-n-
pentadecylsalicylic acid) is the main component (80-85%) while
cardanol (3-n-pentadecyl-phenol) and cardol (3-n-pentadecyl-
resorcinol) and methyl cardanol (2-methyl-5-n-pentadecyl-
resorcinol) are present in smaller amounts. Cardol and
cardanol are commercially available. Oryzanol refers to a group
of esterified sterols, which have been reacted with ferulic
acid (4-hydroxy-3-methoxycinnamic acid) having high molecular
weight and low volatility. Sesamol, sesaminol and sesamolino
compounds are constituents of sesame oil and have antioxidant
properties. Sesamol readily undergoes oxidation to sesamol
dimer and further oxidation yields the sesamol quinone dimer.
Tocopherols provide strong antioxidant activity. Under certain
conditions tocopherols can form higher molecular weight
materials in oils e.g. dimers, trimers, etc. Tocotrienols are
a related class of compounds with the structural difference
being an unsaturated side chain instead of a saturated phytyl
chain. The antioxidant activity of tocotrienols is less than
that exhibited by tocopherols.
The class of flavanoids is divided into subgroups of which the
major members include flavanols, flavones, isoflavones,
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anthocyanins, catechins, proanthocyanidins and aurones.
Related compounds include cinnamic and ferulic acids and their
esters, some of which are precursors to flavanoids. Tealeaves
are a rich, inexpensive and readily available source of
5 flavanoids (mainly catechins). When oxidised the flavanoids
form polymers with complex polyphenolic structures, themselves
showing antioxidant activity. Epigallocatechin gallate can be
extracted from tea in synergism with ascorbic acid, tocopherol,
citric and tartaric acids.
10 Rutin and chlorogenic acid also exhibit antioxidant properties,
having sugar moieties attached to aromatic functionality.
Compounds of this type are particularly interesting since they
can partition between aqueous and organic (lipid) phases.
Another group of natural antioxidants is the tannins, tannic
acid and related compounds. It is a broad group of plant
derived polyphenolic compounds. The tannins are characterised
by their ability to precipitate proteins.
Antioxidant structure
Preferred antioxidants for the purpose of this invention~are
natural antioxidants which contain a 1,2-dihydroxybenzene or
1,4-dihydroxybenzene substructure, or a derivative thereof in
which the H of one OH has been replaced by an organic group.
The organic group may be -R or -COR wherein R is preferably a
(substituted) alkyl, alkenyl, carbocyclic or heterocyclic group
Suitable examples of compounds having the 1,2-dihydroxy-
benzene(derivative) substructure are caffeic, ferulic,
rosmarinic, and vanillic acid and their amides, esters, salts
and similar derivatives, as well as sesamol and its
derivatives. Suitable examples of compounds having the 1,4-
dihydroxybenzene derivative substructure are the tocopherols
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and tocotrienols wherein part of the benzene ring and one of
the phenolic oxygens together form part of a condensed
heterocyclic ring.
A specific and very useful subclass of compounds having the
1,2-dihydroxybenzene substructure is formed by those having the
3,4,5-trihydroxybenzoyl structure or substituted derivatives
thereof. Thus, gallic acid and its natural derivatives are
suitable. Particularly suitable are tannic acid and tannins.
Tannic acid and tannins contain a plurality of 3,4,5-
trihydroxybenzoyl units whereby the benzoyl group of one unit
forms an ester bond with a phenolic oxygen of the next unit.
Tannic acid is the most preferred antioxidant for the purposes
of this invention. It is sometimes denoted as gallotannic acid
or penta- (m-digalloyl) -glucose (C76H52046) ~ However,
commercially available tannic acid is usually obtained from
plant or nut galls, tree barks and other plant parts. The term
"tannic acid" as used herein is to be taken to embrace all such
materials. As already mentioned, tannin-containing extracts of
tea (e. g. as utilised in the compositions of JP-A-07/228,892)
are very low in tannic acid content.
Another preferred group of antioxidants are the tocopherols,
particularly ~-tocopherol.
The liquid compositions
The compositions may be applied to the surface neat or in
diluted form. Suitable liquid compositions include solutions,
dispersions or emulsions of the antioxidant material in a
solvent. The solvent is preferably water, or a mixture of
organic solvent and water.
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Preferred compositions have a neutral or slightly acidic pH
i.e. at most 7, preferably at most 6, especially at most 5.5 or
even 4.5 or less. However, it is preferred that the
compositions should not be too acidic, in order to avoid damage
to acid sensitive surfaces; preferably the pH is at least 1.5
or even 2, more preferably at least 2.5. Most preferably, the
pH is in the region from 3 to 4.5.
The liquid composition may be in the form of a thin or viscous
liquid or gel or in the form of foam, mousse of paste. It is
especially preferred if the liquid is viscous or gel-like
having a viscosity of at least 100 mPas, preferably at least
150 or even 200 mPas, as measured at a shear rate of 21s-1
(Brookefield viscometer, 20°C), but preferably no more than
5,000 mPas, more preferably at most 2000 mPas. Shear thinning
viscous liquids or gels enhance the pleasing sensory effect of
the antioxidant during cleaning of a hard surface and are
particularly appealing to the consumer and therefore a
preferred embodiment of the invention. The viscosity may be
brought about by an "internal structuring system" employing one
or more surfactants, water, and (usually) electrolyte, to
create an ordered or liquid crystalline phase within the
composition. Alternatively or additionally a thickening polymer
may be added, many of which are known in the art, for example
polycarboxylate type polymers such as poly(meth)acrylates,
polymaleic acids and copolymers of (meth)acrylic acid andlor
malefic anhydride with various other vinylic monomers, or
polysaccharides such as cellulose derivatives or vegetable or
microbial gums e.g. xanthan gum, guar gum and the like. Of
course the thickening polymers should be stable in the presence
of hydrogen peroxide.
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Foams and mousses are normally supplied from a dispenser who
gassifies or aerates the product dispensed therefrom.
Preferred compositions are either low foaming, or if foaming or
applied as a foam, the foam easily collapses, thus obviating
the need to subsequently rinse or wipe the surface again to
remove foam. Thereby the amount of antioxidant remaining on the
surface is maximised.
Surfactants:
A composition according to (or for use in) the invention can
comprise detergent surfactants which are generally chosen from
anionic, nonionic, amphoteric, zwitterionic or cationic
surfactants. The compositions generally comprise at least 0.050,
preferably at least 0.1, 0.2, 0.5 or even 1o by weight, but not
more than 45o usually at most 25, 15 or even 10o by weight of
total surfactant. Preferably the compositions comprise at least
an anionic and/or nonionic surfactant, more preferably at least a
nonionic surfactant.
Suitable synthetic (non-soap) anionic surfactants are water-
soluble salts of organic sulphuric acid esters and sulphonic
acids that have in the molecular structure an alkyl group
containing from 8 to 22 carbon atoms.
Examples of such anionic surfactants are water soluble salts of:
- (primary) long chain (e. g. 8-22 C-atom) alcohol sulphates
(hereinafter referred to as PAS), especially those obtained by
sulphating the fatty alcohols produced by reducing the glycerides
of tallow or coconut oil;
- alkyl benzene sulphonates, such as those in which the alkyl
group contains from 6 to 20 carbon atoms;
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- secondary alkanesulphonates;
Also suitable are salts of:
- alkyl glyceryl ether sulphates, especially those ethers of
the fatty alcohols derived from tallow and coconut oil;
- fatty acid monoglyceride sulphates;
- sulphates of the reaction product of one mole of a fatty
alcohol and from 1 to 6 moles of ethylene oxide;
- salts of alkylphenol ethyleneoxy-ether sulphates with from 1
to 8 ethyleneo~y units per molecule and in which the alkyl groups
contain from 4 to 14 carbon atoms;
- the reaction product of fatty acids esterified with
isethionic acid and neutralised with alkali;
and mixtures of the above.
The preferred water-soluble synthetic anionic surfactants are the
alkali metal (such as sodium and potassium) and alkaline earth
metal (such as calcium and magnesium) salts of alkyl-
benzenesulphonates and mixtures with olefinsulphonates and alkyl
sulphates, and the fatty acid mono-glyceride sulphates. The most
preferred anionic surfactants are alkyl-aromatic sulphonates such
as alkylbenzenesulphonates 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 alkylbenzenesulphonates or
of alkyl-toluene-, -xylene- or -phenolsulphonates,
alkylnaphthalene-sulphonates, ammonium diamylnaphthalene-
sulphonate, and sodium dinonyl-naphthalene- sulphonate.
If synthetic anionic surfactant is to be employed the amount
present in the compositions of the invention, it will generally
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be at least 0.20, preferably at least 0.50, more preferably at
least l.Oo, but not more than 20o, preferably at most 100, more
preferably at most 80.
Suitable nonionic surfactants can be broadly described as
5 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
attached to any particular hydrophobic group can be readily
10 adjusted to yield a water-soluble compound having the desired
balance between hydrophilic and hydrophobic elements. This
enables the choice of nonionic surfactants with the right HLB.
Particular examples include the condensation product of aliphatic
alcohols having from 8 to 22 carbon atoms in either straight or
15 branched chain configuration with ethylene oxide, such as a
coconut oil ethylene oxide condensates 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 800 of ethyleneoxy groups by weight and having a
molecular weight of from 5,000 to 11,000.
Other examples are: alkylglycosides which are condensation
products of long chain aliphatic alcohols and saccharides;
tertiary amine oxides of structure RRRNO, where one R is an alkyl
group of 8 to 18 carbon atoms and the other Rs are each alkyl or
hydroxyalkyl groups of 1 to 3 carbon atoms, for instance
dimethyldodecylamine oxide; tertiary phosphine oxides of
structure RRRPO, where one R is an alkyl group of 8 to 18 carbon
atoms and the other Rs are each alkyl or hydroxyalkyl groups of 1
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to 3 carbon atoms, for instance dimethyl-dodecylphosphine oxide;
and dialkyl sulphoxides of structure RRSO where one 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. Ethoxylated aliphatic
alcohols are particularly preferred.
The amount of nonionic surfactant to be employed in the cleaning
composition of the invention will preferably be at least 0.10,
more preferably at least 0.20, most preferably at least 0.5 or
even 1o by weight. The maximum amount is suitably 150, preferably
10o and most preferably 7%.
The compositions may contain amounts of both anionic and nonionic
surfactants which are chosen, bearing in mind the level of
electrolyte present, so as to provide a structured liquid
detergent composition, i.e. one which is 'self-thickened'. Thus,
in spite of the presence of organic solvent, thickened liquid
cleaning compositions can be made without the need to employ any
additional thickening agent and which nevertheless have a long
shelf life over a wide temperature range.
The weight ratio of anionic surfactant to nonionic surfactant may
vary, taking the above considerations in mind, and will depend on
their nature, but is preferably in the range of from 1:9 to 9:1,
more preferably from 1:4 to 4:1, According to an embodiment
illustrating any aspect of the invention, the compositions may
comprise from 0.1.o to 2o by weight of antioxidant(s), from 1 to
4o by weight of hydrogen peroxide, from 0 to 200, preferably from
0.2o to 10% by weight of a water-soluble, synthetic anionic
sulphate or sulphonate surfactant salt containing an alkyl
radical having from 8 to 22 carbon atoms in the molecule, and
from 0.2 to 7o by weight of an ethoxylated nonionic surfactant
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derived from the condensation of an aliphatic alcohol having from
8 to 22 carbon atoms in the molecule with ethylene oxide, such
that the condensate has from 2 to 15 moles of ethylene oxide per
mole of aliphatic alcohol, the balance being other optional
ingredients and water.
Suitable amphoteric surfactants 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 group substituted by an anionic water-solubilising
group, for instance sodium 3-dodecylamino-propionate, sodium 3-
dodecylaminopropane sulphonate and sodium N-2-hydroxydodecyl-N-
methyl taurate.
Suitable cationic surfactants that optionally can be employed are
quaternary ammonium salts having one or two aliphatic groups of
from 8 to 18 carbon atoms and two or three small aliphatic (e. g.
methyl) groups, for instance cetyltrimethyl ammonium bromide.
Suitable zwitterionic surfactants that optionally can be employed
are derivatives of aliphatic quaternary ammonium, sulphonium and
phosphonium compounds having an aliphatic group of from 8 to 18
carbon atoms and an aliphatic group substituted by an anionic
water-solubilising group, for instance 3-(N,N-dimethyl-N-
hexadecylammonium) propane-1-sulphonate betaine, 3-(dodecyl
methyl sulphonium) propane-1-sulphonate betaine and 3-
(cetylmethyl phosphonium) ethane sulphonate betaine.
Further examples of suitable surfactants are compounds commonly
used as surface-active agents given in the well-known textbooks
"Surface Active Agents" Vol.l, by
Schwartz & Perry, Interscience 194, Vol.2 by Schwartz, Perry &
Berch, Interscience 1958, in the current edition of
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"McCutcheon's Emulsifiers and Detergents" published by
Manufacturing Confectioners Company or in "Tenside-
Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.
The compositions according to the invention can contain other
ingredients which aid in their cleaning performance. For example,
the composition can contain detergent builders such as
nitrilotriacetates, polycarboxylates, citrates, dicarboxylic
acids, water-soluble phosphates (especially ortho-, pyro- or
poly-phosphates or mixtures thereof), zeolites and mixtures
thereof in an amount of up to 25%. If present, the builder
preferably will form at least 0.1% of the composition.
Metal ion sequestrants such as ethylenediaminetetraacetates,
polyphosphonates (DEQUEST~TM~-range) and the (ortho, gyro, poly)
phosphoric acids/phosphates (hereinafter collectively referred to
as "phosphate"), and a wide variety of poly-functional organic
acids (particularly citric acid) and salts, can also optionally
be employed provided they are compatible with the antioxidant.
Such sequestrants are particularly useful when combined with
antioxidants which may form coloured complexes with metals, such
as is the case for tannic acid, tannins and gallic acid and
derivatives. The amount of such sequestrants, if present, is
usefully between 0.05 and 5o by weight of the composition,
preferably 0.1-l0.
A further optional ingredient for compositions according to the
invention is a suds regulating material, which can be employed in
compositions 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 and ammonium salts of fatty acids containing
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from about 8 to about 24 carbon atoms, and preferably from about
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
5 oil. When employed, the amount of soap can form at least 0.005%,
preferably at least 0.1o by weight of the composition. Fatty acid
soaps such as Prifac 7901« have been found to be suitable for
this purpose.
A further example of a suds regulating material is a silicone
10 oil. Where a hydrocarbon co-solvent is present at a sufficiently
high level this may itself provide some or all of the desired
antifoaming activity.
Compositions according to the invention can also contain, in
addition to the ingredients already mentioned, various other
optional ingredients such as colorants, whiteners, optical
brighteners, soil suspending agents, detersive enzymes, gel-
control agents, freeze-thaw stabilisers, preservatives (for
example 1,2-benzisothiazolin-3-one), and hydrotropes. However,
compositions according to the invention do not contain
bactericides (other than hydrogen peroxide) in amounts suitable
to provide an antibacterial action on the skin. Generally,
bactericides, if present, are only used in amounts necessary to
prevent microbial spoilage of the composition.
As the compositions according to the invention and their use for
cleaning hard surfaces depend on the presence of hydrogen
peroxide, they do not contain alkoxylated aliphatic or
araliphatic carboxylic acids as precursors for the corresponding
peracids.
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Dispensing
Liquid compositions may be stored and dispensed by any suitable
means, such as by spray applicators. Pump dispensers (whether
spray or non-spray pumps) and pouring applicators (bottles etc)
5 are also possible. The compositions may also applied to the
surface with a wipe impregnated with the liquid composition.
EXAMPLES
In the following examples, all percentages are by weight unless
10 specifically stated otherwise.
Example 1: General purpose cleaning composition
Biodac L6S50 (nonionic) 1.20
LAS (anionic) 3.50
Tannic acid 0.500
15 Hydrogen peroxide 3.Oo
Phosphoric acid 0.420
Sodium hydroxide 0.0460
Urea l, 0 0
Perfume 0.350
20 bequest 2046 0.100
Coconut fatty acid (Prifac 7907TM) 0.300
Water to 1000
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~''nr~-I-rnl 1
As Example 1 but without tannic acid.
Evaluation
Substrate Details
A stainless steel substrate was used for cleaning tests. This
was brushed stainless steel size 380mm by 300mm (grade 304
sheet BS 1449 Pt2 1983, supplied by Merseyside Metal Services
Ltd). This size tile accommodates two areas for cleaning, one
on the left and one on the right of the tile. Each area for
cleaning is 215mm by 150mm.
Pre-cleaning of Stainless Tiles
The tiles were pre-cleaned prior to a cleaning experiment as
follows:
~ commercial liquid abrasive cleaner (Jif Cream cleaner),
cleaning with a damp J-cloth and rinsed with hot water;
~ liquid dish-washing detergent (Persil Dishwashing Liquid),
cleaning with a damp J-cloth and rinsed with hot water;
~ calcite, cleaning with a damp J-cloth and rinsed hot water,
and finally rinsed with demineralised water;
~ after allowing the tiles to drain-dry, they are wiped with a
paper towel, ensuring all calcite deposits are removed.
Application of Pre-treatment to Stainless Steel Tiles
A cardboard mount revealing the two areas of the tile to be
pre-treated was placed onto the stainless steel tile. To one
of the 215mm x 150mm areas, approximately half of a l.Oml
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22
pipetted aliquot of an example composition was applied in a
line across the top 150mm section of the pre-treatment area.
The remaining portion of the l.Oml example composition was
similarly applied to the lower 150mm section of the area. The
cardboard mount was carefully removed from the steel tile in
readiness to wipe the applied prototype over the entire pre-
treatment area. A dampened hand-wrung J-clothTM (demineralised
water) was folded around a 150mm plastic ruler. This was used
to spread the l.Oml aliquot of the composition being tested,
over the steel surface. The prototype was spread using four
linear wipes over the designated area, two downward and two
upward wipes, and in each case 4 replicates for cleaning were
prepared. After pre-treatment application, the tiles were
allowed to dry for 2 hours before spraying with dehydrated
castor oil soil.
Soiling and Ageing the Pre-treated Stainless Steel Tiles
The spraying of the castor oil soil was carried out in a fume
cupboard under standard conditions to ensure good
reproducibility between different experiments. The soil was
r
dehydrated castor oil with 0.2o fat red 7B dye. This was
stored in the refrigerator when not in use. It was
equilibrated to ambient temperature before spraying.
The fume cupboard walls/floor and the lab-jack were covered
with paper towel. A lab-jack was used to elevate the tile to a
practical height for spraying. The lab-jack height was 200mm
and was positioned centrally at the back of the fume cupboard.
A line 40mm from the back wall of the fume cupboard was marked
on to the top of the lab-jack, this was used as the positioning
line for each steel tile before spraying. From the 40mm line
on the lab-jack, a line 270mm, in parallel, was marked on the
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base of the fume cupboard floor. This was where the Perspex
spray guide was aligned when spraying.
A commercially available gravity fill spray gun was used to
spray the oily soil onto the steel tile. The rear dial on the
gravity fill gun was rotated 360° anti-clockwise from the
closed position and the side dial was rotated 270° anti-
clockwise, again from the closed position. The gravity fill
spray gun was attached to a floor standing air compressor unit
and a pressure of 25p.s.i. was used for spraying this soil on
to the steel tiles. A clamp stand was positioned in the fume
cupboard to hold the spray gun when not in use. The dehydrated
castor oil soil was poured into the open bowl of the spray gun.
The cardboard spray mount was clipped to a stainless steel tile
and this was centrally placed, in landscape position, on the
lab-jack along the 40mm line from the rear of the fume
cupboard. The cardboard spray mount was a rectangular piece of
card, the same size as a stainless steel tile, with two cut-out
~0 areas sized 215mm by 150mm, one window area on the left side
and the other to the right, with a card separator border
between the two windows. The Perspex spray guide was
positioned in front of the first window of the tile to be
sprayed directly on the 270mm line. This area of the tile was
?5 sprayed for a total of 35 seconds starting from the top,
following the line of thelspray guide. The time taken to spray
from top to bottom was approximately 9 seconds, therefore the
track of the spray guide is traced 4 times, for each 215mm by
150mm area being sprayed. After spraying the first area of the
i0 tile, the adjacent area was sprayed in exactly the same way,
after re-aligning the Perspex spray guide in front of the
second area. Once the entire tile had been sprayed twice, it
was removed from the fume cupboard and the cardboard spray
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mount carefully removed. The sprayed tiles were stacked
directly on to an oven shelf, each stainless steel tile being
separated using an aluminium ring spacer placed in each corner.
These spacers enabled each tile to be separated by lOmm. When
all the tiles were sprayed, they were collectively placed in
the oven for ageing.
The tiles were aged at a temperature of 85°C for 1.5 hours.
The prepared tiles were not cleaned until the next day.
The effort used to remove the soil from the test surface using
a cellulosic spongecloth was measured on equipment specifically
build for the purpose which measures the effort in Ns. The
cleaning composition used to remove the soil was the
composition of Control 2. Thus, the reduction in cleaning
effort can only be attributed to the antioxidant in the pre-
treatment composition
The results for the compositions of Example 1 and the control 1
(corresponding to Example 1 minus the tannic acid) are given in
Table I. Results given are geometric means of the 4 replicate
experiments.
Table I
Treatment Average Total Effort
(Ns)
No treatment (not 8000
clean in 2
minutes)
Control 1 4500
Example 1 30
