Note: Descriptions are shown in the official language in which they were submitted.
CA 02292967 1999-12-17
A Water-based Multiphase Cleaning Composition
This invention relates to water-based, multiphase, liquid surfactant-
containing cleaning compositions containing citric acid or citrate which can
be temporarily emulsified by shaking and which may be used to clean hard
surfaces, to a process for their production and to their use for cleaning hard
surfaces and to the use of citric acid or citrate in this multiphase cleaning
composition as a phase separation aid or for reducing clouding in the
vicinity of the boundary layer between the phases and to corresponding
processes for the production of such multiphase cleaning compositions
using citric acid or citrate for phase separation or for reducing the clouding
mentioned above.
Universally usable cleaning compositions for all wet-wipe or damp-
wipe surfaces in the home and in the institutional sector are known as so-
called multipurpose cleaners and represent predominantly neutral to
weakly alkaline water-based liquid products which contain 1 to 30% by
weight of surfactants, 0 to 5% by weight of builders (for example citrates,
gluconates, soda, polycarboxylates), 0 to 10% by weight of hydrotropes (for
example alcohols, urea), 0 to 10% by weight of water-soluble solvents (for
example alcohols, glycol ethers) and optionally inter alia skin-care agents,
dyes and fragrances. Corresponding cleaners are generally used in the
form of an approximately 1 % solution in water, although they may even be
used in undiluted form for local stain removal. In addition, ready-to-use
multipurpose cleaners are marketed as so-called spray cleaners.
The water-based liquid cleaners in question are normally present as
homogeneous stable solutions or dispersions. However, the effect of using
certain, more particularly hydrophobic, components in such cleaning
compositions can be that this homogeneity is lost and inhomogeneous
compositions with very little consumer appeal are obtained. In cases such
as these, there is a need for the alternative formulation of compositions
which, despite their inhomogeneity, have a defined appearance acceptable
to the consumer and are user-friendly.
CA 02292967 1999-12-17
2
European patent application 116 422 describes a liquid hair or body
shampoo comprising two aqueous phases which can be temporarily
dispersed in one another by shaking and which are both miscible with
water in any ratio. The upper phase contains 8 to 25% by weight, based
on the composition as a whole, of at least one surfactant while the lower
phase contains at least 6% by weight, based on the composition as a
whole, of dissolved sodium hexametaphosphate corresponding to formula
I' ONa ONa ONa
Na0-P-O P-O P-ONa (I)
o
° ~ ,".~
in which n has an average value of about 12. The lower phase may
optionally contain other builder salts. The surfactants present may be
anionic, cationic, amphoteric and/or nonionic surfactants, at least one
anionic surfactant preferably being present.
DE-OSS 195 01 184, 195 01 187 and 195 01 188 (Henkel KGaA)
relate to hair treatment compositions in the form of a two-phase system
which comprise an oil phase and a water phase, the oil phase being based
on silicone oil or paraffin oil, and which can be mixed in a short time by
mechanical action.
In the case of a two-phase composition, such as that known from
European patent application 116 422, unwanted clouding of the individual
phases in their non-dispersed separated state can readily occur,
particularly after shaking one or more times. Streak-like clouding can
occur, above all in the vicinity of the boundary layer. Such clouding is
unattractive to the consumer and can even be misinterpreted as a sign of a
product which has become unusable. In addition, renewed phase
separation may occur only partly, if at all, after shaking one or more times,
leading to an undefined appearance of the product which does not appeal
to the consumer.
CA 02292967 1999-12-17
3
The problem addressed by the present invention was to provide
high-performance storage-stable compositions for cleaning hard surfaces
in a defined inhomogeneous, easy-to-handle form acceptable to the
consumer which would not have any of the problems described above.
In a first embodiment, the present invention relates to a water-
based, liquid, multiphase, surfactant-containing cleaning composition with
at least two continuous phases which contains at least one lower aqueous
phase I and an upper aqueous phase II immiscible therewith, which can be
temporarily converted into an emulsion by shaking and which contains citric
acid and/or at least one citrate.
In a second embodiment, the present invention relates to the use of
a water-based, liquid, multiphase, surfactant-containing cleaning
composition with at least two continuous phases, which contains at least
one lower aqueous phase I and an upper aqueous phase II immiscible
therewith, which can be temporarily converted into an emulsion by shaking
and which contains citric acid and/or at least one citrate, for cleaning hard
surfaces.
In a third embodiment, the present invention relates to a process for
the production of a composition according to the invention by mixing
directly from its raw materials, subsequent intermixing and, in a final step,
leaving the composition to stand for separation of the temporary emulsion.
In a fourth embodiment, the invention relates to the use of citric acid
and/or at least one citrate in a water-based, liquid, multiphase, surfactant-
containing cleaning composition comprising at least two continuous
phases, which contains at least one lower aqueous phase I and an upper
aqueous phase II immiscible therewith and which can be temporarily
converted into an emulsion by shaking, as a phase separation auxiliary
and/or for reducing clouding in the vicinity of the boundary layer between
phases I and II.
In a fifth embodiment, the present invention relates to a process for
the production of a water-based, liquid, multiphase, surfactant-containing
CA 02292967 1999-12-17
4
cleaning composition with at least two continuous phases, which contains
at least one lower aqueous phase I and an upper aqueous phase II
immiscible therewith and which can be temporarily converted into an
emulsion by shaking, characterized in that citric acid and/or at least one
citrate is used as a phase separation auxiliary and/or for reducing clouding
in the vicinity of the boundary layer between phases I and II.
In the context of the present invention, "temporarily" is understood to
mean that 90% of the separation of the emulsion formed by shaking into
the separate phases takes place in 2 minutes to 10 hours at temperatures
of about 20°C to about 40°C, the final 2% of the separation into
the phase
state before shaking taking place over another 15 minutes to 50 hours.
According to the present invention, it is possible - unless otherwise
expressly stated - to use a salt and, with equal effect, the corresponding
acid/base pair of the salt which is only formed in situ through neutralization
of the salt or its solution, even if the particular alternative is not always
explicitly mentioned in the present teaching. Accordingly, potassium citrate
for example and the citric acid/potassium hydroxide combination or
potassium alkyl benzenesulfonate and the alkyl benzenesulfonic
acid/potassium hydroxide combination represent equivalent alternatives.
Insofar as the following observations relate to one of the subjects of
the invention, they apply equally to the other subjects of the invention,
unless otherwise specifically stated.
According to the invention, citric acid or citrate advantageously
combine building and phase-separation promoting properties. Accordingly,
the compositions according to the invention are distinguished by high
cleaning performance in diluted and undiluted form, particularly against
obstinate fatty soil in undiluted form. In addition, the compositions
according to the invention show favorable residue behavior. The individual
phases in the composition are stable in storage for long periods, i.e. for
example do not form any deposits, and the conversion into a temporary
emulsion remains reversible, even after frequent shaking. In addition, the
CA 02292967 1999-12-17
separation of ingredients into separate phases can promote the chemical
stability of the composition.
A particular advantage of the invention lies in the high transparency
of the continuous phases I and II and in the substantially or even
5 completely clouding-free boundary layer between them.
The compositions according to the invention contain citric acid
and/or at least one citrate in a quantity of normally 0.1 to 30% by weight,
preferably 1 to 20% by weight, more preferably 2 to 15% by weight and
most preferably 4 to 12% by weight. The quantity to be selected for a
certain concentration of citrate ions depends upon the nature of the cations
in the form used which may be, on the one hand, the light protons of the
acidic carboxyl groups and/or, on the other hand, heavier metallic cations
or optionally alkylated ammonium ions.
Citric acid may be used, for example, in the form of its monohydrate
citric acid ~ 1 H20.
In the context of the present invention, the citrates are the salts of
3x-deprotonated citric acid, unless otherwise specifically stated. However,
the mono- and dihydrogen citrates may also be used in accordance with
the invention.
One group of suitable citrates are, for example, the alkali metal,
alkaline earth metal, ammonium and mono-, di- and trialkanolammonium
citrates, preferably mono-, di- and triethanolammonium citrates, and
mixtures thereof. Sodium citrate and potassium citrate are particularly
suitable.
Potassium citrate or the use of citric acid in combination with
potassium hydroxide has a particularly positive effect on phase separation,
on the clearness of the phases and on the sharpness of and the substantial
or complete absence of clouding from the phase boundary layer.
Accordingly, a preferred composition according to the invention in its
first embodiment contains potassium citrate and/or citric acid in combina-
tion with potassium hydroxide.
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6
Accordingly, in a preferred use according to the invention in its
fourth embodiment, potassium citrate and/or citric acid in combination with
potassium hydroxide is used.
Accordingly, in a preferred process according to the invention in its
fifth embodiment, potassium citrate and/or citric acid in combination with
potassium hydroxide is used.
In the most simple case, a composition according to the invention
comprises a lower continuous phase consisting of the entire phase I and an
upper continuous phase consisting of the entire phase II. However, one or
more continuous phases of a composition according to the invention may
also contain parts of another phase in emulsified form, so that in a
composition such as this part of phase I for example is present as
continuous phase I, which represents the lower continuous phase of the
composition, while another part is emulsified as discontinuous phase I in
the upper continuous phase II. The same applies to phase II and other
continuous phases.
In one preferred embodiment of the invention, the continuous
phases I and II are demarcated from one another by a sharp interface.
In another preferred embodiment of the invention, one or both of the
continuous phases I and II contain parts, preferably 0.1 to 25% by volume
and more preferably 0.2 to 15% by volume, based on the volume of the
particular continuous phase, of the other phase as dispersant. Accordingly,
the continuous phase I or II is reduced by that part by volume which is
distributed as dispersant in the other phase. Particularly preferred
compositions are characterized in that phase I is emulsified in phase II in
quantities of 0.1 to 25% by volume and preferably in quantities of 0.2 to
15% by volume, based on the volume of phase II.
Another preferred embodiment of the invention is characterized in
that, besides the continuous phases I and I I, part of the two phases is
present as an emulsion of one of the two phases in the other phase, this
emulsion being demarcated by two sharp interfaces, namely an upper
CA 02292967 1999-12-17
7
interface and a lower interface, from the other parts of phases I and II
which are not involved in the emulsion.
The compositions according to the invention contain phase I and
phase II in a ratio volume of 90:10 to 10:90, preferably 75:25 to 25:75 and
more preferably 65:35 to 35:65.
In one particularly advantageous embodiment of the invention, the
compositions contain one or more hydrophobic components. Suitable
hydrophobic components are, for example, dialkyl ethers with the same or
different C4_~4 alkyl chains, more particularly dioctyl ethers; hydrocarbons
with a boiling range of 100 to 300°C, more particularly 140 to
280°C, for
example aliphatic hydrocarbons with a boiling range of 145 to 200°C,
isoparaffins with a boiling range of 200 to 260°C; essential oils, more
particularly limonene and pine oil extracted from pine roots and stubs; and
also mixtures of these hydrophobic components, more particularly mixtures
of two or three of the hydrophobic components mentioned. Preferred
mixtures of hydrophobic components are mixtures of different dialkyl
ethers, mixtures of dialkyl ethers and hydrocarbons, mixtures of dialkyl
ethers and essential oils, mixtures of hydrocarbons and essential oils,
mixtures of dialkyl ethers and hydrocarbons and essential oils and mixtures
of these mixtures. The compositions contain hydrophobic components in
quantities, based on the composition, of 0 to 20% by weight, preferably 0.1
to 14% by weight, more preferably 0.5 to 10% by weight and most
preferably 0.8 to 7% by weight.
Besides citric acid and/or citrate, the compositions according to the
invention may contain one or more other phase separation auxiliaries.
Suitable other phase separation auxiliaries are, for example, the alkali
metal and alkaline earth metal halides, more particularly chlorides, and
sulfates and also nitrates, more particularly sodium and potassium chloride
and sulfate, and ammonium chloride and sulfate or mixtures thereof,
sodium chloride being particularly preferred. Salts such as these as strong
electrolytes support phase separation through the salt effect. The
CA 02292967 1999-12-17
8
compositions contain phase separation auxiliaries in quantities, based on
the composition, of 0 to 30% by weight, preferably 1 to 20% by weight,
more preferably 3 to 15% by weight and most preferably 5 to 12% by
weight. These phase separation auxiliaries are used in particular when the
ionic strength produced by the other ionic compounds present does not
produce the required phase separation.
The compositions according to the invention may contain anionic,
nonionic, amphoteric or cationic surfactants or surfactant mixtures of one,
several or all of these classes of surfactants as their surfactant component.
The compositions contain surfactants in quantities, based on the
composition, of 0.01 to 30% by weight, preferably 0.1 to 20% by weight,
more preferably 1 to 14% by weight and most preferably 3 to 10% by
weight.
Suitable nonionic surfactants are, for example, C8_~8 alkyl alcohol
polyglycol ethers, alkyl polyglycosides and nitrogen-containing surfactants
or even sulfosuccinic acid di-C~_~2-alkyl esters or mixtures thereof,
particularly mixtures of the first two. The compositions contain nonionic
surfactants in quantities, based on the composition, of 0 to 30% by weight,
preferably 0.1 to 20% by weight, more preferably 0.5 to 14% by weight and
most preferably 1 to 10% by weight.
C8_~$ alkyl alcohol polypropylene glycol/polyethylene glycol ethers
represent preferred known nonionic surfactants. They may be described
by formula II:
R'O-(CH2CH(CH3)O)p(CH2CH20)e-H (II)
in which R' is a linear or branched aliphatic alkyl and/or alkenyl group
containing 8 to 18 carbon atoms, p is 0 or a number of 1 to 3 and a is a
number of 1 to 20.
The Ca_~$ alkyl alcohol polyglycol ethers corresponding to formula II
may be obtained by addition of propylene oxide and/or ethylene oxide onto
CA 02292967 1999-12-17
9
alkyl alcohols, preferably fatty alcohols. Typical examples are polyglycol
ethers corresponding to formula II, in which R' is an alkyl group containing
8 to 18 carbon atoms, p is 0 to 2 and a is a number of 2 to 7. Preferred
representatives are, for example, C~0.~4 fatty alcohol+1 PO+6E0 ether (p =
1, a = 6) and C~2_~$-fatty alcohol+7E0 ether (p = 0, a = 7) and mixtures
thereof.
End-capped C$_~8 alkyl alcohol polyglycol ethers, i.e. compounds in
which the free OH group in formula II is etherified, may also be used. The
end-capped C8_~8 alkyl alcohol polyglycol ethers may be obtained by
relevant methods of preparative organic chemistry. C8_~$ alkyl alcohol
polyglycol ethers are preferably reacted with alkyl halides, more particularly
butyl or benzyl chloride, in the presence of bases. Typical examples are
mixed ethers corresponding to formula II, in which R' is a technical fatty
alcohol moiety, preferably a C~2,~4 cocoalkyl moiety, p is 0 and a is a
number of 5 to 10, which are end-capped with a butyl group.
Other preferred nonionic surfactants are alkyl polyglycosides (APGs)
corresponding to formula III:
R20[G]x (II I)
in which RZ is a linear or branched, saturated or unsaturated alkyl group
containing 8 to 22 carbon atoms, [GJ is a glycosidic sugar unit and x is a
number of 1 to 10. APGs are nonionic surfactants and represent known
substances which may be obtained by the relevant methods or preparative
organic chemistry. The index x in general formula III indicates the degree
of oligomerization (DP degree), i.e. the distribution of mono- and
oligoglycosides, and is a number of 1 to 10. Whereas x in a given
compound must always be an integer and, above all, may assume a value
of 1 to 6, the value x for a certain alkyl glycoside is an analytically
determined calculated quantity which is generally a broken number. Alkyl
glycosides with an average degree of oligomerization x of 1.1 to 3.0 are
CA 02292967 1999-12-17
preferably used. Alkyl glycosides with a degree of oligomerization of less
than 1.7 and, more particularly, between 1.2 and 1.6 are preferred from the
applicational point of view. Xylose, but especially glucose is preferably
used as the glycidic sugar.
5 The alkyl or alkenyl group R2 in formula III may be derived from
primary alcohols containing 8 to 18 and preferably 8 to 14 carbon atoms.
Typical examples are caproic alcohol, caprylic acid, capric alcohol and
undecyl alcohol and the technical mixtures thereof obtained, for example,
in the hydrogenation of technical fatty acid methyl esters or in the
10 hydrogenation of aldehydes from ROELEN's oxosynthesis.
However, the alkyl or alkenyl group R2 is preferably derived from
lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl
alcohol, isostearyl alcohol or oleyl alcohol. Elaidyl alcohol, petroselinyl
alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol
and technical mixtures thereof may also be mentioned.
Other suitable nonionic surfactants are nitrogen-containing
surfactants, for example fatty acid polyhydroxyamides, for example
glucamides, and ethoxylates of alkyl amines, vicinal diols and/or carboxylic
acid amides which contain C~o_22 and preferably C~2_~s alkyl groups. The
degree of ethoxylation of these compounds is generally between 1 and 20
and preferably between 3 and 10. Ethanolamide derivatives of C8_22 and
preferably C~2_~6 alkanoic acids are preferred. Particularly suitable
compounds include lauric acid, myristic acid and palmitic acid
monoethanolamides.
Suitable anionic surfactants are the preferred C8_~s alkyl sulfates,
C$_~$ alkyl ether sulfates, i.e. the sulfation products of alcohol ethers
corre-
sponding to formula II, and/or C8_~s alkyl benzenesulfonates, more particu-
larly dodecyl benzenesulfonate, but also Ca_~8 alkane sulfonates, C8_~8 a-
olefin sulfonates, sulfonated C8_~8 fatty acids, C$_22 carboxylic acid amide
ether sulfates, sulfosuccinic acid mono-C~_~2-alkyl esters, Ca_~8 alkyl poly-
glycol ether carboxylates, C$_~8 N-acyl taurides, C8_~$ N-sarcosinates and
CA 02292967 1999-12-17
11
C8_~s alkyl isethionates and mixtures thereof. They are used in the form of
their alkali metal and alkaline earth metal salts, more particularly sodium,
potassium and magnesium salts, and ammonium salts and mono-, di-, tri-
and tetraalkyl ammonium salts and - in the case of the sulfonates also in
the form of their corresponding acid, for example dodecyl benzenesulfonic
acid. Where sulfonic acid is used, it is normally neutralized to the above-
mentioned salts in situ with one or more corresponding bases, for example
alkali metal and alkaline earth metal hydroxides, more particularly sodium,
potassium and magnesium hydroxide, and ammonia or mono-, di-, tri- or
tetraalkyl amine. The compositions contain anionic surfactants in quanti-
ties, based on the composition, of 0 to 30% by weight, preferably 0.1 to
20% by weight, more preferably 1 to 14% by weight and most preferably 2
to 10% by weight.
Where the particularly preferred alkyl benzenesulfonic acids are
used, clouding can occur in the vicinity of the boundary layer between
phases I and II, particularly if the sodium chloride content is high and/or
sodium hydroxide is used for neutralization. According to the invention,
this problem is countered by citric acid or citrate alone. However, a further
improvement is obtained where the alkyl benzenesulfonic acid is
neutralized with potassium hydroxide which has a particularly positive
effect on phase separation, on the clearness of the phases and on the
sharpness of and substantial or complete absence of clouding from the
phase boundary layer.
By virtue of their foam-suppressing properties, soaps, i.e. alkali
metal or ammonium salts of saturated or unsaturated Cs_22 fatty acids, may
also be present in the compositions according to the invention. The soaps
may be used in a quantity of up to 5% by weight and are preferably used in
a quantity of 0.1 to 2% by weight.
Suitable amphoteric surfactants are, for example, betaines
corresponding to the formula (R3)(R4)(R5)N+CH2C00), in which R3 is a C8_
25 and preferably C~o_2~ alkyl group optionally interrupted by hetero atoms
CA 02292967 1999-12-17
12
or groups of hetero atoms and R4 and R5 may be the same or different and
represent C~_3 alkyl groups, more particularly C~o_~8 alkyl dimethyl
carboxymethyl betaine and C»_~~ alkylamidopropyl dimethyl carboxymethyl
betaine. The compositions contain amphoteric surfactants in quantities,
based on the composition, of 0 to 15% by weight, preferably 0.01 to 10%
by weight and more preferably 0.1 to 5% by weight.
Suitable cationic surfactants are inter alia quaternary ammonium
compounds corresponding to the formula (R6)(R~)(R$)(R9)N+X), in which R6
to R9 represent four identical or different alkyl groups, more particularly
two
long-chain and two short-chain alkyl groups, and X) is an anion, more
particularly a halide ion, for example didecyl dimethyl ammonium chloride,
alkyl benzyl didecyl ammonium chloride and mixtures thereof. The compo-
sitions contain cationic surfactants in quantities, based on the composition,
of 0 to 10% by weight, preferably 0.01 to 5% by weight and more preferably
0.1 to 3% by weight.
In one preferred embodiment, the compositions according to the
invention contain anionic and nonionic surfactants alongside one another,
preferably C8_~$ alkyl benzenesulfonates, C$_~8 alkyl sulfates and/or C8_~a
alkyl ether sulfates alongside C8_~$ alkyl alcohol polyglycol ethers and/or
alkyl polyglycosides, more particularly C8_~e alkyl benzenesulfonates
alongside C8_~$ alkyl alcohol polyglycol ethers.
Besides the citric acid and/or citrate, the compositions according to
the invention may additionally contain one or more other builders. Suitable
builders are, for example, alkali metal gluconates, nitrilotriacetates,
carbonates and bicarbonates, more particularly sodium gluconate and
nitrilotriacetate and sodium and potassium carbonate and bicarbonate, and
also alkali metal and alkaline earth metal hydroxides, more particularly
sodium and potassium hydroxide, ammonia and amines, more particularly
mono- and triethanolamine, and mixtures thereof. These builders also
include the salts of glutaric acid, succinic acid, adipic acid, tartaric acid
and
benzenehexacarboxylic acid and also phosphonates and phosphates, for
CA 02292967 1999-12-17
13
example the pentasodium triphosphate better known as sodium tripoly-
phosphate or sodium hexametaphosphate, such as for example a mixture
of condensed orthophosphates corresponding to formula I, in which n has
an average value of about 12. The compositions contain builders in
quantities, based on the composition, of 0 to 20% by weight, preferably
0.01 to 12% by weight, more preferably 0.1 to 8% by weight and most
preferably 0.3 to 5% by weight. The builders additionally act as phase
separation aids.
A particularly preferred builder is potassium hydroxide because it
has a particularly positive effect on phase separation, on the clearness and
color brightness of the phases and on the sharpness of and substantial or
complete absence of clouding from the phase boundary layer.
Besides the components mentioned, the compositions according to
the invention may contain other auxiliaries and additives typically present in
such compositions. These include, in particular, polymers, soil release
agents, solvents (for example ethanol, isopropanol, glycol ether),
solubilizers, hydrotropes (for example cumene sulfonate, octyl sulfate, butyl
glucoside, butyl glycol), cleaning boosters, viscosity regulators (for example
synthetic polymers, such as polysaccharides, polyacrylates, naturally
occurring polymers and derivatives thereof, such as xanthan gum, other
polysaccharides and/or gelatin), disinfectants, antistatic agents,
preservatives, bleaching systems, enzymes, perfume, dyes and fragrances
and also opacifiers and even the skin-care agents described in EP-A-533
556. Additives such as these are normally present in the cleaning
composition in quantities of not more than 12% by weight. The lower limit
to the quantity used is determined by the nature of the additive and, in the
case of dyes for example, may be 0.001 % by weight or lower. The quantity
of auxiliaries used is preferably between 0.01 and 7% by weight and more
preferably between 0.1 and 4% by weight.
In one preferred embodiment of the invention, the compositions
contain one or more perfumes in a quantity of 0.1 to 5% by weight,
CA 02292967 1999-12-17
14
preferably in a quantity of 0.2 to 3% by weight, more preferably in a
quantity of 0.5 to 2% by weight and most preferably in a quantity of 1 to
1.5% by weight. If a hydrophobic component is simultaneously present,
the perfumes and the hydrophobic component are predominantly present in
the same phase - generally the upper phase II. This has the advantageous
effect of intensifying the fragrance released from the top of a container
holding such a composition according to the invention after it has been
opened. Through their essential oils, perfumes also influence the phase
separation properties of the compositions according to the invention, the
ratio of phase I to phase II generally shifting in favor of phase I with
increasing perfume content.
The pH value of the compositions according to the invention can be
varied over a wide range, although a range of 2.5 to 12 is preferred and a
range of 5 to 10.5 particularly preferred. In the context of the invention,
the
pH value of the compositions according to the invention is understood to be
the pH value of the composition in the form of the temporary emulsion.
In one preferred embodiment of the invention, the compositions are
adjusted to an alkaline pH value of 8 to 12, preferably 8.5 to 11.5, more
preferably 9 to 11 and most preferably 9.3 to 10.5.
Suitable pH regulators are, on the one hand, mineral acids, for
example hydrochloric acid, but especially citric acid, and on the other hand
the alkaline builders mentioned above, preferably sodium hydroxide but
especially potassium hydroxide by virtue of the advantages mentioned
above.
To stabilize or buffer the pH value, the composition according to the
invention - in one particular embodiment - contains small quantities of
corresponding buffers, for example soda in the described alkaline
embodiment.
The compositions according to the invention may be produced by
mixing directly from their raw materials, subsequent intermixing and, in a
final step, allowing the composition to stand for separation of the temporary
CA 02292967 1999-12-17
emulsion.
The composition according to the invention is sprayable and,
accordingly, may be used in a spray dispenser.
Accordingly, the present invention also relates to a product
5 containing a composition according to the invention and a spray dispenser.
The spray dispenser is preferably a hand-operated spray dispenser,
more particularly selected from the group consisting of aerosol spray
dispensers, self-pressure-generating spray dispensers, pump spray
dispensers and trigger spray dispensers, more especially pump spray
10 dispensers and trigger spray dispensers comprising a container of
transparent polyethylene or polyethylene terephthalate. Spray dispensers
are described in more detail in WO 96104940 (Procter & Gamble) and the
US patents cited therein on the subject of spray dispensers, to which
reference is made in this regard and of which the disclosures are hereby
15 incorporated in the present application.
The compositions according to the invention are used, for example,
by applying the composition temporarily converted into an emulsion by
shaking to the surface to be cleaned in quantities of about 1.5 to 10 g per
m2 and more particularly in quantities of 3 to 7 g per mz and wiping the
surface immediately afterwards with a soft absorbent material and thus
cleaning it. The compositions are applied, for example, by suitable spray
applicators, more particularly a spray dispenser or a product according to
the invention, in order to achieve uniform distribution. Sponges or cloths in
particular may be used for wiping and may be periodically rinsed out with
water in the cleaning of relatively large surfaces.
Examples
Example 1
Compositions E1 to E6 according to the invention and comparison
composition C1 were produced as described above. Table 1 below shows
their compositions in % by weight, their pH value and for E1 to E6 the
CA 02292967 1999-12-17
16
quantified ratio by volume of the lower phase I to the upper phase II. In C1,
too, the lower phase I made up slightly more than half the total volume.
Compositions E1 to E6 and C1 additionally contain 0.05% by weight of
glutaraldehyde as preservative and, except for C5, small quantities of dye
which, in the other compositions, colored the lower phase turquoise and
the upper phase blue.
Table 1
Composition [% by weight E1 E2 E3 E4 E5 E6 C1
Dodecyl benzenesulfonic 4 4 4 4 3 4 4
acid
C,o_,4 fatty alcohol+1
PO+1 EO
ether - - - - 2 - -
C,2_,sfatty alcohol+7E02 2 2 2 - 2 2
ether
C,Z_,4 fatty alcohol+9E0
butyl
ether - - - - 2 - -
C8_,o alkyl-1,5-glucoside - - - - 4 - -
Citric acid 1 H20 6 6.2 6 6.5 8 6.2 -
Sodium chloride - - - - - - 6.9
Potassium hydroxide 5.5 5.6 5.5 5.78 - - -
Sodium hydroxide - - - - 4.7 5.6 0.5
Dioctyl ether 5 5 5 5 5 5 5
Perfume 0.9 0.9 0.9 0.9 0.9 0.9 0.5
Water to to to to to to
100 100 100 100 100 100to
100
pH value 9.5 9.5 9.5 9.5 9 9.5 10.15
Ratio by volume of phase
I to
phase II 60:4060:4070:3060:40 70:3060:40-
Accordingly, all compositions showed two continuous phases which
temporarily formed a creamy looking emulsion on shaking. However,
whereas the upper phase II in C1 was slightly milky and showed signs of
CA 02292967 1999-12-17
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clouding in the vicinity of the phase boundary, particularly after repeated
shaking, the compositions according to the invention contained transparent
phases with a clouding-free, sharp phase boundary and brighter colors,
even after repeated shaking.
Example 2 - Cleaning performance
The cleaning performance of compositions E1 and C2 to C6, which
were produced as described above from the ingredients listed in Table 2,
were tested both in diluted and in undiluted form.
Unless otherwise stated in the following, cleaning performance was
tested in accordance with the Qualifatsnormen fur Fuf3bodenpflege- and -
reinigungsmittel des Industrieverbandes Putz- and Pflegemiftel e. V. (IPP),
Frankfurt/M (Seifen - Ule - Fette - Wachse 1986, 112, 371-372). The test
was carried out with quantities of 10 ml of dilute test substance with a
concentration of 1.5 and 6 ml/I and soil 2 and with quantities of 6 ml of
undiluted test substance and a soil of oil, fat, white spirit and a
soot/pigment mixture.
The test is carried out by wiping a white soil carrier treated with test
soil with a sponge impregnated with the product to be tested under defined
conditions and measuring the cleaning effect photoelectrically against the
untreated white soil carrier.
A machine similar to an Erichsen 494 washability and scouring
tester (Erichsen GmbH, D-58675 Hemer-Sundwig) with a guide rail of
brass and an 820 g weight was used for wiping.
Whiteness was measured with a Dr. Lange Micro-Color color
difference measuring instrument (Dr. Lange, D-40549 DusseldorfJ and is
expressed as the average of 21 measurements per test strip.
Cleaning performance was measured in a triple determination and is
shown in Table 2 as the relative cleaning performance CPre~ in % for the
two diluted products and the undiluted product.
CA 02292967 1999-12-17
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Table 2
Composition [% by weight] E7 C2 C3 C4 C5 C6
Dodecyl benzenesulfonic 6 6 6 6 6 6
acid .
C~2_~$ fatty alcohol+7E0 4 4 4 4 4 4
ether
Sodium hydroxide 0.78 0.78 0.78 0.78 0.78 0.78
C~2_~4 fatty alcohol +2E0
ether
sulfate sodium salt 3 3 3 3 3 3
C~2_~$ cocofatty acid 1 1 1 1 1 1
Trisodium citrate 3 - - - - -
Sodium gluconate - - 3 - - -
Sodium tripolyphosphate - - - 3 - 3
Urea - - - - 5 5
Water to to to to
100 100 100 100
to
100
to
100
Cleaning performance
CP~e, diluted (1.5 ml/I) [%] 90 74 86 88 76 90
CPre, diluted (6 ml/I) [%] 102 100 98 102 09 102
CP~e, undiluted [%] 172 100 131 147 103 138
Composition E7 according to the invention not only had a
consistently better cleaning performance than the builder-free comparison
composition C1, it was also at least equivalent and generally even superior
in its cleaning performance to the other builder-containing comparison
compositions C1 to C6, this superiority being reflected in particular in the
results achieved with the undiluted compositions against obstinate soils.
