Note: Descriptions are shown in the official language in which they were submitted.
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"Acidic aqueous multiphase cleaner"
Field of the Invention
The invention relates to acidic aqueous
multiphase liquid surfactant-containing cleaners which
can be emulsified temporarily by shaking and can be
used for the cleaning of hard surfaces, to a process
for their preparation and to the use thereof for the
cleaning of hard surfaces.
Background of the Invention
Cleaners which can be used universally for all
hard, wet or damp wipable surfaces for domestic and
commercial use are known as so-called all-purpose
cleaners and are largely neutral to slightly alkaline
aqueous liquid products which comprise from 1 to 30o by
weight of surfactants, from 0 to 5% by weight of
builders (e. g. citrates, gluconates, soda,
polycarboxylates), from 0 to 10% by weight of
hydrotropic agents (e.g. alcohols, urea), from 0 to 10%
by weight of water-soluble solvents (e. g. alcohols,
glycol ethers), and, if desired, inter alia skin
protectants, dyes and fragrances. For use in the
sanitary field as so-called bath cleaners, by contrast,
such cleaners are often rendered acidic by the addition
of acids in order to be able to better remove lime and
water spots. They are mostly used as about to strength
solutions in water, but also neat for local stain
removal. Ready-to-use all-purpose cleaners are also
available commercially as so-called spray cleaners.
Aqueous liquid cleaners of this type are
usually in the form of homogeneous stable solutions or
dispersions. The use of certain, in particular
hydrophobic, components in such cleaners can, however,
lead to this homogeneity being lost and inhomogeneous
compositions being obtained, the acceptance of which by
the consumer is assessed as low. In such cases there is
a need for alternative formulation of compositions
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which, despite their inhomogeneity; have a defined
external appearance and use form which is acceptable to
the consumer.
European Patent Application 116 422 describes a
liquid hair or body shampoo having two aqueous phases
which can be dispersed temporarily in one another by
shaking and where both phases are miscible with water
in any ratio. Here, the upper phase comprises from 8 to
25% by weight, based on the overall composition, of at
least one surfactant, and the lower phase' at least 6%
by weight, based on the overall composition, of
dissolved sodium hexametaphosphate of the formula I,
ONa ONa OWa
NaQ--I I P-ODia <<)
O ~ o
cp-Zi
in which n is an average value of about 12. Optionally,
further builder salts may be present in the lower
phase. Surfactants which may be present are anionic,
cationic, amphoteric and/or nonionic surfactants, at
least one anionic surfactant preferably being present.
German Laid-Open specifications 195 Ol 184,
'187 and '188 (Henkel KGaA) disclose hair-treatment
compositions in the form of a two-phase system which
has one oil phase and one water phase, the oil phase
being based on silicone oil or paraffin oil, an3 are
temporarily miscible by mechanical action.
The object of the present invention was to
provide high-performance and storage-stable
compositions for the cleaning of hard surfaces, in
particular in the sanitary field, in a defined
inhomogeneous form which is easy to handle and
acceptable to the consumer.
Description of the Invention
The invention provides an aqueous liquid
mu~a_.phase surfactant-containing cleaner having at
least two continuous phases, which has at least one
lower aqueous phase I and an upper aqueous phase II
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which is immiscible with the first phase and which can
be temporarily converted into an emulsion by shaking,
and which comprises at least one acid and, in the form
of the temporary emulsion, has a pH of less than 7.
The invention likewise provides for the use of
a composition according to the invention for the
cleaning of hard surfaces.
For the purposes of the present invention,
temporary means that 90% of the cracking of the
emulsion formed by shaking into the separate phases at
temperatures of from about 20°C to about 40°C takes
place over the course of 2 minutes to 10 hours, and the
last 2% of the cracking into the phase state prior to
shaking takes place over the course of a further 15
minutes to 50 hours.
Furthermore, for the purposes of the present
invention - unless expressly stated otherwise, the use
of a salt is just as possible as the use of the
corresponding acid/base pair of the salt which produces
the salt or its solution only in situ with
neutralization, even if the respective alternative is
not always explicitly formulated in the present
teaching. In this respect, potassium citrate and the
combination of citric acid/potassium hydroxide or
potassium alkylbenzenesulfonate and the combination
alkylbenzenesulfonic acid/potassium hydroxide are equal
alternatives.
Finally, for the purposes of the present
invention, if it is possible for a particular component
to be used for different purposes, then its use may be
described more than once below, knowingly or
unknowingly. This is true, for example, for citric
acid, which is used both as an acid to adjust the pH
and as a phase-separation auxiliary and builder, and
also for anion-active sulfonic acids, which act both as
acids and as anionic surfactants.
The compositions according to the invention are
notable for high cleaning performance when applied neat
or in dilute form - both in the bathroom and the
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kitchen. Moreover the compositions exhibit a favorable
residue behavior. The individual phases in the
composition are stable over a long period without, for
example, the formation of deposits, and conversion to a
temporary emulsion remains reversible even after
frequent shaking. Furthermore, the compositions permit
the stable incorporation of components which can be
stably incorporated into single-phase aqueous solutions
or stable emulsions or microemulsions only through the
use of solvents, solubilizers and emulsifiers. In
addition, separation of ingredients into separate
phases can promote the chemical stability of the
composition.
The pH of the compositions according to the
invention is usually 1 to 6.5, preferably 2 to 6, in
particular 2.5 to 5.5, particularly preferably 3 to 5,
most preferably 3.5 to 4.5.
To set the pH according to the invention, the
compositions comprise at least one acid. Suitable acids
are inorganic acids, for example the mineral acids,
e.g. hydrochloric acid, and organic acids, for example
saturated or unsaturated C1_6-mono-, -di- and
-tricarboxylic acids and -hydroxycarboxylic acids
having one or more hydroxyl groups, e.g. citric acid,
malefic acid, formic acid and acetic acid, amidosulfuric
acid, C6_22-fatty acids and anion-active sulfonic acids,
and mixtures thereof, e.g. the succinic acid/glutaric
acid/adipic acid mixture obtainable under the tradename
Sokalan~ DCS from BASF.
If necessary, it is additionally possible to
use one or more alkalis, for example the alkali metal,
alkaline earth metal and ammonium hydroxides and
carbonates, and ammonia, preferably sodium and
potassium hydroxide, particular preference being given
to potassium hydroxide.
Anion-active sulfonic acids for the purposes of
the teaching according to the invention are sulfonic
acids of the formula R-S03H which carry a partially or
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completely straight-chain and/or branched and/or
cyclic, and partially or completely saturated and/or
unsaturated and/or aromatic C6_32-hYdrocarbon radical R,
for example C6_22-alkanesulfonic acids, C6_22-a-
olefinsulfonic acids and Cl_22-alkyl-C6_lo-arenesulfonic
acids, such as Cl_22-alkylbenzenesulfonic acids or Cl_22-
alkylnaphthalenesulfonic acids, preferably linear Ca_ls-
alkylbenzenesulfonic acids, in particular linear Clo_14-
alkyl-, Clo-13-alkyl- and C12-alkylbenzenesulfonic acids .
Particularly preferred acids are citric acid,
preferably used in the form of its monohydrate citric
acid 1H20, and the anion-active sulfonic acids, and
combinations of citric acid with one or more anion-
active sulfonic acids, in particular with alkylarene-
sulfonic acids. The citric acid combines in an
advantageous manner acid, builder and phase-separation
auxiliary properties, while the anion-active sulfonic
acids act as an acid and anionic surfactant at the same
time.
The composition according to the invention
comprises one or more acids in an amount by weight
which suffices for setting the desired acidic pH and
which can be chosen according to the strength and molar
mass of the respective acids, and which is usually
between 0.1 and 30% by weight, in particular between 1
and 20o by weight. In some instances it may be
advantageous, particularly when the acid, as described
above and also below, also satisfies other functions at
the same time, to use more acid than is required to set
the pH. In this case, compositions according to the
invention additionally comprise one or more alkalis.
Phases
In the simplest case, a composition according
to the invention consists of a lower continuous phase,
which consists of the whole of phase I, and of an upper
continuous phase, which consists of the whole of phase
II. One or more continuous phases of a composition
according to the invention can, however, also comprise
parts of another phase in emulsified form, meaning that
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in such a composition, for example, some of phase I is
in the form of continuous phase I, which is the lower
continuous phase of the composition, and some is
emulsified as discontinuous phase I in the upper
continuous phase II. The same applies for phase II and
other continuous phases.
In a preferred embodiment of the invention, the
continuous phases I and II are delimited from one
another by a sharp interface.
In a further preferred embodiment of the
invention, one or both of the continuous phases I and
II comprise parts, preferably from 0.1 to 25% by
volume, in particular from 0.2 to 15o by volume, based
on the volume of the respective continuous phase, of
the other phase in each case as dispersant. Here, the
continuous phase I or II is then reduced by the volume
part, which is distributed as dispersant in the other
phase in each case. Particular preference is given in
this connection to compositions in which phase I is
emulsified in phase II in amounts of from 0.1 to 25o by
volume, preferably from 0.2 to 15o by volume, based on
the volume of phase II.
In a further preferred embodiment of the
invention, in addition to the continuous phases I and
II, part of the two phases is in the form of an
emulsion of one of the two phases in the other phase,
this emulsion being delimited by two sharp interfaces,
one upper and one lower, from the parts of phases I and
II not involved in the emulsion.
The compositions according to the invention
comprise phase I and phase II in a volume ratio of from
90:10 to 10:90, preferably from 75:25 to 25:75, in
particular from 65:35 to 35:65.
Hydrophobic components
In a particularly advantageous embodiment of
the invention, the compositions comprise one or more
hydrophobic components. The hydrophobic components
improve not only the cleaning action on hydrophobic
contaminants such as grease soiling, but additionally
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have a positive action on the phase separation and the
reversibility thereof. Suitable hydrophobic components
are, for example, dialkyl ethers having identical or
different C4- to C14-alkyl radicals, in particular
linear dioctyl ether; hydrocarbons having a boiling
range from 100 to 300°C, in particular from 140 to
280°C, e.g. aliphatic hydrocarbons having a boiling
range from 145 to 200°C, isoparaffins having a boiling
range from 200 to 260°C; essential oils, in particular
limonene and the pine oil extracted from pine roots and
stumps; and also mixtures of these hydrophobic
components, in particular mixtures of two or three of
said hydrophobic components. Preferred mixtures of
hydrophobic components are mixtures of different
dialkyl ethers, of dialkyl ethers and hydrocarbons, of
dialkyl ethers and essential oils, of hydrocarbons and
essential oils, of dialkyl ethers and hydrocarbons and
essential oils and of these mixtures. The compositions
comprise hydrophobic components in amounts, based on
the composition, of from 0 to 20o by weight, preferably
from 0.1 to 14o by weight, in particular from 0.5 to
10% by weight, most preferably from 0.8 to 7% by
weight.
Phase-separation auxiliaries
The compositions according to the invention can
comprise phase-separation auxiliaries. Suitable phase-
separation auxiliaries are, in addition to citric acid
and citrates, for example the alkali metal and alkaline
earth metal halides, in particular chlorides, and
sulfates and nitrates, in particular sodium and
potassium chloride and sulfate, and ammonium chloride
and sulfate, and mixtures thereof. Being strong
electrolytes, and increasing the ionic strength, said
salts aid phase separation as a result of the salt
effect. In this connection, sodium chloride has proven
particularly effective, while sodium sulfate and in
particular magnesium sulfate have a lower phase
separation action. The compositions comprise phase-
separation auxiliaries in amounts, based on the
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composition, of from 0 to 30% by weight, preferably 1
to 20o by weight, in particular 3 to 15o by weight,
most preferably from 5 to 12% by weight.
Surfactants
The compositions according to the invention can
comprise, as surfactant component, anionic, nonionic,
amphoteric or cationic surfactants or surfactant
mixtures of one, more than one or all of these classes
of surfactant . The compositions comprise surfactants in
amounts, based on the composition, of from 0.01 to 30%
by weight, preferably from 0.1 to 20o by weight, in
particular from 1 to 14% by weight, most preferably
from 3 to 10% by weight.
Anionic surfactants
Suitable anionic surfactants are the preferred
C6_22-alkyl sulfates, C6-C22-alkyl ether sulfates, i . a .
the sulfation products of the alcohol ethers of the
formula II, and/or C6-C22-alkylbenzenesulfonates, in
particular dodecylbenzenesulfonate, but also C6-C22-
alkanesulfonates, C6-Cz2-a-olefinsulfonates, sulfonated
C6-C22-fatty acids, C6-C22-carboxamide ether sulfates,
mono-C1-C12-alkyl sulfosuccinate, C6-C22-alkylpolyglycol
ether carboxylate, C6-C22-N-aryl taurides, C6-C22-N-
sarcosinates and C6-C2z-alkyl isethionates and mixtures
thereof. They are used in the form of their alkali
metal and alkaline earth metal salts, in particular
sodium, potassium and magnesium salts, and also
ammonium and mono-, di-, tri- and tetraalkylammonium
salts, and in the case of the sulfonates, also in the
form of their corresponding acid, e.g.
dodecylbenzenesulfonic acid. If sulfonic acid is used,
this is usually neutralized in situ with one or more
corresponding bases, e.g. alkali metal and alkaline
earth metal hydroxides, in particular sodium, potassium
and magnesium hydroxide, and ammonia or mono-, di-,
tri- or tetraalkylamine, to give the abovementioned
salts. The compositions comprise anionic surfactants in
amounts, based on the composition, of from 0 to 30o by
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weight, preferably 0.1 to 20o by weight, in particular
1 to 14% by weight, most preferably 2 to 10% by weight.
The use of the particularly preferred
alkylbenzenesulfonic acids may, particularly if the
content of sodium chloride is high and/or sodium
hydroxide is used to adjust the pH, lead to clouding in
the region of the boundary layer between phases I and
II. Citric acid or citrate already counteracts this
problem according to the invention. A further
improvement occurs, however, during neutralization of
the alkylbenzenesulfonic acid with potassium hydroxide
which, in this regard, has a particularly positive
effect on the phase separation, the clarity of the
phases and the sharpness, and also lack of or freedom
from clouding of the phase boundary layer.
Because of their foam-suppressing and
thickening properties, the compositions according to
the invention can also comprise soaps, i.e. alkali
metal or ammonium salts of saturated or unsaturated C6-
C2z-fatty acids. The soaps can be used in an amount of
up to 5o by weight, preferably from 0.1 to 2o by
weight.
Nonionic surfactants
Suitable nonionic surfactants are, for example,
C6-C22-alkyl alcohol polyglycol ethers, alkyl
polyglycosides, and nitrogen-containing surfactants or
else di-C1-C12-alkyl sulfosuccinates or mixtures
thereof, in particular of the first two. The
compositions comprise nonionic surfactants in amounts,
based on the composition, of from 0 to 30o by weight,
preferably 0.1 to 20% by weight, in particular 0.5 to
14o by weight, most preferably 1 to 10% by weight.
C6-C22-alkyl alcohol polypropylene
glycol/polyethylene glycol ethers are preferred known
nonionic surfactants. They can be described by the
formula II, R10-(CH2CH(CH3)O)p(CH2CH20)e-H, in which R1 is
a linear or branched, aliphatic alkyl and/or alkenyl
radical having 8 to 22 carbon atoms, p is 0 or a number
from 1 to 3, and a is a number from 1 to 20.
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The C6-C2z-alkyl alcohol polyglycol ethers of
the formula II can be obtained by addition of propylene
oxide and/or ethylene oxide to alkyl alcohols,
preferably to fatty alcohols. Typical examples are
polyglycol ethers of the formula II in which R1 is an
alkyl radical having 8 to 22 carbon atoms, p is 0 to 2,
and a is a number from 2 to 7. Preferred
representatives of, for example, Clo-C14-fatty
alcohol+1P0+6E0 ethers (p - 1, a - 6) and ClZ-C18-fatty
alcohol+7E0 ethers (p - 0, a - 7), and mixtures
thereof .
It is also possible to use terminally capped C6-
Cz2-alkyl alcohol polyglycol ethers, i.e. compounds in
which the free OH group in the formula II is
etherified. The terminally capped C6-C22-alkyl alcohol
polyglycol ethers can be obtained by appropriate
methods of preparative organic chemistry. Preference is
given to reacting C6-C22-alkyl alcohol polyglycol ethers
in the presence of bases with alkyl halides, in
particular butyl or benzyl chloride. Typical examples
are mixed ethers of the formula II in which R1 is a
technical-grade fatty alcohol radical, preferably
C1zi14-cocoalkyl radical, p is 0, and a is from 5 to 10,
which have been capped with a butyl group.
Preferred nonionic surfactants are also alkyl
polyglycosides (APG) of the formula III, R20 [G] X, in
which RZ is a linear or branched, saturated or
unsaturated alkyl radical having 8 to 22 carbon atoms,
[G] is a glycosidally linked sugar radical, and x is a
number from 1 to 10. APGs are nonionic surfactants and
are known substances which can be obtained by the
relevant methods of preparative organic chemistry. The
index number x in the general formula III gives the
degree of oligomerization (degree of DP), i.e. the
distribution of mono- and oligoglycosides, and is a
number between 1 and 10. While x in a given compound
must always be an integer and here can assume in
particular the values x = 1 to 6, the value x for a
certain alkyl glycoside is an analytically determined
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arithmetical parameter, which in most cases is a
fraction. Preference is given to using alkyl glycosides
having an average degree of oligomerization x from 1.1
to 3Ø From a technical viewpoint, preference is given
to those alkyl glycosides whose degree of oligomer-
ization is less than 1.7 and is in particular between
1.2 and 1.6. The glycosidic sugar used is preferably
xylose, but in particular glucose.
The alkyl or alkenyl radical R2 (formula III)
can be derived from primary alcohols having 8 to 22,
preferably 8 to 14 carbon atoms. Typical examples are
caproic alcohol, caprylic alcohol, capric alcohol and
undecyl alcohol, and technical-grade mixtures thereof,
as are produced, for example, in the course of the
hydrogenation of technical-grade fatty acid methyl
esters or in the course of the hydrogenation of
aldehydes from the ROELEN oxo synthesis.
However, the alkyl or alkenyl radical Rz is
preferably derived from lauryl alcohol, myristyl
alcohol, cetyl alcohol, palmoleyl alcohol, stearyl
alcohol, isostearyl alcohol or oleyl alcohol. Further
examples are elaidyl alcohol, petroselinyl alcohol,
arachidyl alcohol, gadoleyl alcohol, behenyl alcohol,
erucyl alcohol, and technical-grade mixtures thereof.
Other nonionic surfactants which may be present
are nitrogen-containing surfactants, e.g. fatty acid
polyhydroxyamide, for example glucamides, and
ethoxylates of alkylamines, vicinal diols and/or
carboxamides which have alkyl groups containing 10 to
22 carbon atoms, preferably 12 to 18 carbon atoms. The
degree of ethoxylation of these compounds is generally
between 1 and 20, preferably between 3 and 10.
Preference is given to ethanolamide derivatives of
alkanoic acids having 8 to 22 carbon atoms, preferably
12 to 16 carbon atoms. Particularly suitable compounds
include lauric acid monoethanolamide, myristic acid
monoethanolamide and palmitic acid monoethanolamide.
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Amphoteric surfactants
Suitable amphoteric surfactants are, for
example, betaines of the formula (R3) (R4) (RS) N'CH2C00-, in
which R3 is an alkyl radical, optionally interrupted by
heteroatoms or groups of heteroatoms, having from 8 to
25, preferably from 10 to 21, carbon atoms, and R4 and
RS are identical or different alkyl radicals having from
1 to 3 carbon atoms, in particular Clo-C22-alkyl-
dimethylcarboxymethylbetaine and Cll-C1.,-alkylamido-
propyldimethylcarboxymethylbetaine. The compositions
comprise amphoteric surfactants in amounts, based on
the composition, of from 0 to 15% by weight, preferably
from 0.01 to 10% by weight, in particular from 0.1 to
5o by weight.
Cationic surfactants
Suitable cationic surfactants are inter alia
the quaternary ammonium compounds of the formula
(R6) (R') (R8) (R9) N+X-, in which R6 to R9 are four identical
or different, in particular two long-chain and two
short-chain, alkyl radicals, and X- is an anion, in
particular a halide ion, for example didecyl-
dimethylammonium chloride, alkylbenzyldidecylammonium
chloride, and mixtures thereof. The compositions
comprise cationic surfactants in amounts, based on the
composition, of from 0 to loo by weight, preferably
from 0.01 to 5o by weight, in particular from 0.1 to 3%
by weight.
In a preferred embodiment, the compositions
according to the invention comprise anionic and
nonionic surfactants alongside one another, preferably
C6-C22-alkylbenzenesulfonates, C6-C22-alkyl sulfates
and/or C6-Cz2-alkyl ether sulfates in addition to C6-C2z-
alkyl alcohol polyglycol ethers and/or alkyl
polyglycosides, in particular C6-C2Z-
alkylbenzenesulfonates in addition to C6-C2z-alkyl
alcohol polyglycol ethers.
Builders
The compositions according to the invention can
further comprise one or more builders. Suitable
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builders are, for example, alkali metal citrates,
gluconates, nitrilotriacetates, carbonates and
bicarbonates, in particular sodium citrate, gluconate
and nitrilotriacetate, and sodium and potassium
carbonate and bicarbonate, and alkali metal and
alkaline earth metal hydroxides, in particular sodium
and potassium hydroxide, ammonia and amines, in
particular mono- and triethanolamine, or mixtures
thereof. These also include the salts of glutaric acid,
succinic acid, adipic acid, tartaric acid and
benzenehexacarboxylic acid, and phosphonates and
phosphates, for example sodium hexametaphosphate, such
as, for example, a mixture of condensed orthophosphates
of the formula I in which n is an average value of
about 12. The compositions comprise builders in
amounts, based on the composition, of from 0 to 30o by
weight, preferably 0.1 to 20% by weight, in particular
1 to 15% by weight, most preferably 2 to loo by weight.
The builder salts additionally act here as phase
separation auxiliaries.
A preferred builder is citrate from the group
of alkali metal, alkaline earth metal, ammonium and
mono-, di- or trialkanolammonium citrates, preferably
mono-, di- or triethanolammonium citrates, or mixtures
thereof, in particular sodium citrate, most preferably
potassium citrate.
A particularly preferred alkaline builder is
potassium hydroxide since it has a particularly
positive effect on the phase separation, the clarity
and color brilliance of the phases, and the sharpness
and lack of or freedom from clouding of the phase
boundary layer.
If the builder should additionally act as pH
stabilizing buffer, then alkali metal and alkaline
earth metal carbonates and bicarbonates, e.g. soda, are
preferred.
yiscositv
The viscosity of the composition according to
the invention is preferably 5 to 1000 mPa~s, in
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particular 10 to 500 mPa~s, particularly preferably 10
to 200 mPa~s, at 20°C, measured using a rotational
viscometer from Brookfield of the LVT type or LVDV-II+
with a small sample adapter at a rate of rotation of
30 min-1, where the spindle used as measurement member
is, according to Brookfield, to be chosen such that the
moment of rotation is in a favorable range and the
measurement range is not exceeded. In this context,
spindle 31 is preferred and, if necessary in cases
where the viscosities are above about 240 mPa~s,
recourse is preferably made to spindle 25.
Thickeners
To adjust the viscosity, the composition
according to the invention can comprise one or more
thickeners, preferably in an amount of from 0 . O1 to 5 0
by weight, in particular 0.05 to 2.5% by weight,
particularly preferably 0.1 to to by weight.
Suitable thickeners are organic natural
thickeners (agar-agar, carrageen, tragacanth, gum
arabic, alginates, pectins, polyoses, guar flour, carob
seed grain, starch, dextrins, gelatin, casein), organic
modified natural substances (carboxymethylcellulose and
other cellulose ethers, hydroxyethylcellulose and
hydroxypropylcellulose and the like, bean flour ether),
organic completely synthetic thickeners ~(polyacrylic
and polymethacrylic compounds, vinyl polymers,
polycarboxylic acids, polyethers, polyimines,
polyamides) and inorganic thickeners (polysilicic
acids, clay minerals, such as montmorillonites,
zeolites, silicas).
The polyacrylic and polymethacrylic compounds
include, for example, the high molecular weight
homopolymers of acrylic acid crosslinked with a
polyalkenyl polyether, in particular an allyl ether of
sucrose, pentaerythritol or propylene (INCI name
according to International Dictionary of Cosmetic
Ingredients of The Cosmetic, Toiletry and Fragrance
Association (CTFA): Carbomer), which are also referred
to as carboxyvinyl polymers. Such polyacrylic acids are
CA 02308920 2000-OS-19
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available inter alia from BF Goodrich under the
tradename Carbopol~, e.g. Carbopol~ 940 (molecular
weight about 4,000,000), Carbopol~ 941 (molecular
weight about 1,250,000) or Carbopol~ 934 (molecular
weight about 3,000,000). They also include the
following acrylic acid copolymers: (i) copolymers of
two or more monomers from the group of acrylic acid,
methacrylic acid and its monoesters preferably formed
with C1_4-alkanols (INCI Acrylates Copolymer), to which,
for example, the copolymers of methacrylic acid, butyl
acrylate and methyl methacrylate (CAS name according to
Chemical Abstracts Service: 25035-69-2) or of butyl
acrylate and methyl methacrylate (CAS 25852-37-3)
belong, and which are available, for example, from Rohm
& Haas under the tradenames Aculyn~ and Acusol~, e.g.
the anionic nonassociative polymers Aculyn~ 33
(crosslinked), Acusol~ 810 and Acusol~ 830 (CAS 25852-
37-3); (ii) crosslinked high molecular weight acrylic
acid copolymers, to which, for example, the copolymers
of Clo_3o-alkyl acrylates, crosslinked with an allyl
ether of sucrose or of pentaerythritol, with one or
more monomers from the group of acrylic acid,
methacrylic acid or its monoesters preferably formed
with C1_4-alkanols (INCI Acrylates/C10-30 Alkyl Acrylate
Crosspolymer) belong and which are available, for
example, from BF Goodrich under the tradename
Carbopol~, e.g. the hydrophobicized Carbopol~ ETD 2623
and Carbopol~ 1382 (INCI Acrylates/C10-30 Alkyl
Acrylate Crosspolymer), and Carbopol~ AQUA 30
(previously Carbopol~ EX 473).
Preferred thickeners are the polysaccharides
and heteropolysaccharides, in particular the
polysaccharide gums, for example gum arabic, agar,
alginates, carrageens and their salts, guar, guaran,
tragacanth, gellan, ramsan, dextran or xanthan, and
their derivatives, e.g. propoxylated guar, and their
mixtures. Other polysaccharide thickeners, such as
starches or cellulose derivatives, can be used as
alternatives, although it is preferable to use them in
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addition to a polysaccharide gum, for example starches
from a wide variety of origins and starch derivatives,
e.g. hydroxyethylstarch, starch phosphate esters or
starch acetates, or carboxymethylcellulose or its
sodium salt, methyl-, ethyl-, hydroxyethyl-,
hydroxypropyl-, hydroxypropyl-methyl- or hydroxyethyl-
methyl-cellulose or cellulose acetate.
A particularly preferred polymer is the
microbial anionic heteropolysaccharide xanthan gum,
which is produced by Xanthomonas campestris and a few
other species under aerobic conditions and has a
molecular weight of from 2 to 15 x 106, and is
available, for example, from Kelco under the tradename
Keltrol~, e.g. as a cream-colored powder Keltro3~ T
(Transparent) or as white granules Keltrol~ RD (Readily
Dispersable).
Auxiliaries and additives
In addition to said components, the
compositions according to the invention can comprise
further auxiliaries and additives, as are customary in
compositions of this type. These include, for example,
perfume and fragrances, polymers, soil-release active
ingredients, solvents (e. g. ethanol, isopropanol,
glycol ether), solubilizers, hydrotropic agents (e. g.
cumenesulfonate, octyl sulfate, butyl glucoside, butyl
glycol), cleaning promoters, disinfectants, antistats,
preservatives, bleaching systems, enzymes and dyes, and
opacifiers and also skin protectants, as are described
in EP-A-522 556. The amount of such additives in the
cleaner is usually no more than 12o by weight. The
lower use limit depends on the type of additive and
can, for example in the case of dyes, be up to O.OOlo
by weight and below. The amount of auxiliaries is
preferably between 0.01 and 7% by weight, in particular
0.1 and 4o by weight.
Preferred auxiliaries and additives are perfume
and fragrances, and dyes, since the perfume and the
fragrances, as well as the scent effect, usually also
aid phase separation, while by adding dyes the phases
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can be colored differently, which makes it easier to
see the separate phases and also to monitor emulsion
formation and separation, thus making the composition
even easier to handle.
The compositions according to the invention can
be prepared by blending directly from their raw
materials, subsequently mixing thoroughly and finally
allowing the composition to stand for separation of the
temporary emulsion.
The reversible phase separation is brought
about, and its characteristics are determined, by the
complex interplay of a number of components. The
surfactant present can, together with the acid, on its
own lead to the phase separation according to the
invention. In some cases, only the additional use of
hydrophobic component, builder and/or perfume effects
phase separation. In other cases, the use of phase-
separation auxiliaries is required.
Embodiments of the invention are described by
reference to the following specific Examples which are
not to be construed as limiting.
Examples
The composition E1 according to the invention
was prepared as described above. Table 1 gives its
composition in % by weight, its pH and also the
quantified volume ratio of the lower phase I to the
upper phase II.
Table 1
Composition [~ by wt.] El
Clo-13-alkylbenzenesulfonic acid 4
Cl2-22-fatty alcohol+7E0 ether 2
Citric acid~1H20 12.7
Potassium hydroxide 6.6
Dioctyl ether 5
Xanthan, transparent (Keltrol~ T) 0.3
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Perfume 0 . 7
Water ad 100
pH 4
Phase I: phase II volume ratio 60:40
The composition thus exhibited two continuous
phases which temporarily formed a creamy-looking
emulsion upon shaking. Even after repeated shaking,
separate phases formed again upon standing.
The storage stability was tested by assessing
the composition after storage for four weeks at room
temperature of 20°C, at elevated temperature of 40°C
and in the cold at a temperature of 5°C. Irrespective
of the storage temperature, there was no visible change
in the composition and, in particular, as before, it
was possible to reversibly convert the composition into
the temporary emulsion by shaking.
The composition was judged by test subjects to
be visually pleasing and easy to handle and achieved
good cleaning results both in the bathroom and in the
kitchen - in neat and in dilute form - in particular in
the removal of lime and water spots, and grease-
containing soilings in the form of the rings of dirt
which are left in the bathtub following a bath after
the bathing water has drained away, and the soiling
which arises in the kitchen as a result of the
preparation of fat- or oil-containing foods.
