Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Antimicrobial aqueous multiphase cleaner
Field of the Invention
The invention relates to antimicrobial aqueous
multiphase liquid cleaners which can be emulsified
temporarily by shaking, to the use thereof for the
cleaning and/or disinfection or sanitation of hard
surfaces, to a product comprising the composition and
to a process for the preparation thereof.
Background of the Invention
Cleaners which can be used universally for all
hard, wet or damp wipable surfaces in the domestic and
commercial sectors are known as all-purpose cleaners
and are largely neutral to slightly alkaline aqueous
liquid products which comprise 1 to 30% by weight
surfactants, 0 to 5% by weight of builders (e. g.
citrates, gluconates, soda, polycarboxylates), 0 to 10%
by weight of hydrotropic agents (e. g. alcohols, urea),
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 sector as bath cleaners, by contrast, such
cleaners are often rendered acidic by the addition of
acids in order that they can more readily remove lime
and water marks. They are mostly used as ca. 1%
strength solutions in water, but also neat for local
stain removal. Ready-to-use all-purpose cleaners are
also available commercially as spray cleaners.
Such aqueous liquid cleaners are usually in the
form of homogeneous stable solutions or dispersions.
The use of certain, in particular hydrophobic,
components in such cleaners for improving the cleaning
performance can, however, result in this homogeneity
being lost and inhomogeneous compositions being
obtained, the acceptance of which by the consumer is to
be regarded as low. In such cases, there is a need for
the alternative formulation of compositions which,
despite their inhomogeneity, have a defined external
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appearance and use form which is acceptable to the
consumer.
Furthermore, in addition to the high primary
detergency, such a cleaner is nowadays increasingly
expected to also have antimicrobial action. To this
end, antimicrobial active ingredients, for example
surface-active quaternary compounds, are incorporated
into the cleaners. The use of antimicrobial active
ingredients in most cases severely restricts
flexibility during formulation of a cleaner since, for
example, the pH has to be matched to the antimicrobial
active ingredients and, depending on the antimicrobial
active ingredient, incompatibilities with certain
further ingredients arise, such as the incompatibility
of surface-active quaternary compounds with the highly
cleaning-effective anionic surfactants. For this
reason, the antimicrobial action is usually realized at
the expense of the detergency.
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 8 to 25%
by weight, based on the total composition, of at least
one surfactant, and the lower phase at least 6% by
weight, based on the total composition, of dissolved
sodium hexametaphosphate of the formula I
~Na I 4Na
Na ~ ~ ~ --ONa
L J ~p_2~
in which n is a mean 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.
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German Laid-Open Applications 195 O1 184,
195 O1 187 and 195 01 188 (Henkel KGaA) disclose hair-
treatment compositions in the form of a two-phase
system which have one oil phase and one water phase,
where the oil phase is based on silicone oil or
paraffin oil, and are temporarily miscible by
mechanical action.
Summary of the Invention
The object of the present invention was to
provide storage-stable compositions with high
detergency and antimicrobial action for the cleaning
and/or disinfection or sanitation of hard surfaces in a
form which is easy to handle and acceptable for the
consumer.
The invention provides an aqueous liquid
multiphase surfactant-containing cleaner having at
least two continuous phases, which has at least one
lower aqueous phase I and an upper aqueous phase II
which is immiscible with the first phase and which can
be temporarily converted into an emulsion by shaking,
and which comprises at least one antimicrobial active
ingredient.
The invention likewise provides for the use of
a composition according to the invention for the
cleaning and/or disinfection or sanitation of hard
surfaces .
Within the scope of the teaching according to
the invention, the terms disinfection, sanitation,
antimicrobial action and antimicrobial active
ingredient have the meanings customary in the art,
which are given, for example, by K.H. Wallhaul3er in
"Praxis der Sterilisation, Desinfektion -
Konservierung . Keimidentifizierung - Betriebshygiene
[Practice of sterilization, disinfection -
preservation: microbe identification - plant hygiene"]
(5th Ed. - Stuttgart; New York: Thieme, 1995). While
disinfection in the narrower sense of medical practice
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means the killing of, theoretically all, infection
microbes, sanitation means the elimination as far as
possible of all microbes, including saprophytic ones
which are normally harmless for man. In this
connection, the degree of disinfection or sanitation is
dependent on the antimicrobial action of the
composition used, which decreases with decreasing
content of antimicrobial active ingredient or
increasing dilution of the composition for use.
Within the scope of the present invention,
temporary means that, preferably, 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 within 2 minutes to 10 hours, and the final
2% of the cracking into the phase state prior to
shaking takes place within a further 15 minutes to
50 hours.
Furthermore, within the scope 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 solution thereof only in situ with
neutralization, even if the respective alternative is
not always explicitly formulated in the present
teaching. In this respect, for example, potassium
citrate and the combination of citric acid/sodium
hydroxide are equivalent alternatives.
Finally, within the scope of the present
invention, if a certain component can 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.
As well as an antimicrobial action, the
compositions according to the invention are notable for
high detergency, in particular on fat-containing
soilings, when applied neat or in dilute form. The
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multiphase nature, in particular the two-phase nature,
permits the realization of antimicrobial action and
also high detergency. A particular advantage is the low
foaming capacity, which has a positive effect on the
detergency, of the compositions according to the
invention without the addition of foam inhibitors such
as soaps. Furthermore, the compositions exhibit
favorable residue behavior. The individual phases in
the composition are stable over a long period without,
for example, deposits forming, 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 or emulsifiers, in
particular of the hydrophobic components and perfume
oils described below. In addition, the multiphase
nature, in particular two-phase nature, permits
improvement of the chemical stability of the
composition as a result of the separation of
ingredients into separate phases.
Detailed Description of the Invention
Antimicrobial active ingredient
The composition according to the invention comprises,
for the antimicrobial action, at least one
antimicrobial active ingredient, preferably chosen from
the group of alcohols, aldehydes, antimicrobial acids
or salts thereof, carboxylic esters, acid amides,
phenols, phenol derivatives, diphenyls,
diphenylalkanes, urea derivatives, oxygen- and
nitrogen-acetals and -formats, benzamidines,
isothiazoles and derivatives thereof, such as
isothiazolines and isothiazolinones, phthalimide
derivatives, pyridine derivatives, antimicrobial
surface-active compounds, guanidines, antimicrobial
amphoteric compounds, quinolines, 1,2-dibromo-2,4-
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dicyanobutane, iodo-2-propynylbutyl carbamate, iodine,
iodophores and peroxides, in particular chosen from
ethanol, n-propanol, isopropanol, 1,3-butanediol,
phenoxyethanol, 1,2-propylene glycol, glycerol,
undecylenic acid, citric acid, lactic acid, benzoic
acid, salicylic acid, thymol, 2-benzyl-4-chlorophenol,
2,2'-methylenebis(6-bromo-4-chlorophenyl), 2,4,4'-
trichloro-2'-hydroxydiphenyl ether, N-(4-chlorophenyl)-
N-(3,4-dichlorophenyl)urea, N,N'-(1,10-decanediyldi-1-
pyrid-4-ylidene)bis(1-octanamine) dihydrochloride,
N,N'-bis(4-chlorophenyl)-3,12-diimino-2,4,11,13-tetra-
azatetradecanediimide amide, antimicrobial quaternary
surface-active compounds, guanidines, amphoteric
agents, particularly preferably at least one
antimicrobially active surface-active quaternary
compound, most preferably containing an ammonium,
sulfonium, phosphonium, iodonium or arsonium group, as
described, for example, by K.H. Wallhauf3er in "Praxis
der Sterilisation, Desinfektion - Konservierung
Keimidentifizierung - Betriebshygiene [Practice of
sterilization, disinfection - preservation: microbe
identification - plant hygiene"] (5th Ed. - Stuttgart;
New York: Thieme, 1995).
The composition according to the invention
particularly preferably comprises at least one
quaternary ammonium compound (QAC) having antimicrobial
action according to the general formula
(RI) (RII) (Rzzz) (Rw) N+X-, in which RI to RI° are identical
or different C1-C22-alkyl radicals, C~-C28-aralkyl
radicals or heterocyclic radicals, where two, or in the
case of an aromatic incorporation, such as in pyridine,
even three radicals, together with the nitrogen atom,
form the heterocycle, e.g. a pyridinium or
imidazolinium compound, and X- is halide ions, sulfate
ions, hydroxide ions or similar anions. For optimum
antimicrobial action, at least one of the radicals
preferably has a chain length of 8 to 18, in particular
12 to 16, carbon atoms.
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QACs can be prepared by reacting tertiary
amines with alkylating agents, such as, for example,
methyl chloride, benzyl chloride, dimethyl sulfate,
dodecyl bromide, and also ethylene oxide. The
alkylation of tertiary amines having one long alkyl
radical and two methyl groups proceeds particularly
readily, and the quaternization of tertiary amines
having two long radicals and one methyl group can also
be carried out using methyl chloride under mild
conditions. Amines which have three long alkyl radicals
or hydroxyl-substituted alkyl radicals are not very
reactive and are preferably quaternized using dimethyl
sulfate.
Suitable QACs are, for example, benzalkonium
chloride (N-alkyl-N,N-dimethylbenzylammonium chloride,
CAS No. 8001-54-5), Benzalkon B (m,p-dichloro-
benzyldimethyl-C12-alkylammonium chloride, CAS No.
58390-78-6), benzoxonium chloride (benzyldodecylbis(2-
hydroxyethyl)ammonium chloride), cetrimonium bromide
(N-hexadecyl-N,N-trimethylammonium bromide, CAS No.
57-09-0), benzethonium chloride (N,N-dimethyl-N-[2-2-
[p- ( 1, 1, 3 , 3 -tetramethylbutyl ) phenoxy] ethoxy] ethyl ] -
benzylammonium chloride, CAS No. 121-54-0),
dialkyldimethylammonium chlorides, such as di-n-
decyldimethylammonium chloride (CAS No. 7173-51-5-5),
didecyldimethylammonium bromide (CAS No. 2390-68-3),
dioctyldimethylammonium chloride, 1-cetylpyridinium
chloride (CAS No. 123-03-5) and thiazoline iodide (CAS
No. 15764-48-1) and mixtures thereof. Particularly
preferred QACs are the benzalkonium chlorides
containing C$-C18-alkyl radicals, in particular C12-C14-
alkylbenzyldimethylammonium chloride.
In a further particularly preferred embodiment
of the invention, the composition comprises, as
antimicrobial active ingredient(s), at least one
antimicrobial acid, preferably organic acid,
particularly preferably chosen from the group
comprising undecylenic acid, citric acid, lactic acid,
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benzoic acid, salicylic acid, formic acid and acetic
acid, and mixtures thereof, most preferably chosen from
the group comprising lactic acid, benzoic acid,
salicylic acid and formic acid and mixtures thereof, in
particular mixtures of salicylic acid with formic acid,
lactic acid and/or benzoic acid, for example mixtures
of salicylic acid with formic acid.
The content of at least one antimicrobial
active ingredient, preferably at least one surface
active quaternary compound and/or an antimicrobial
acid, in particular at least one surface-active
quaternary ammonium compound and/or an organic acid, is
usually 0.1 to 10% by weight, preferably 0.2 to 5% by
weight, in particular 0.5 to 3% by weight, particularly
preferably 1 to 2% by weight, for example 1.5% by
weight.
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
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 to phase II and
further 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 particular embodiment of the invention,
one or both of the continuous phases I and II comprise
parts, preferably 0.1 to 25% by volume, in particular
0.2 to 15% by volume, based on the volume of the
respective continuous phase, of the other phase in each
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case as dispersant . Here, the continuous phase I or I I
is then reduced by the part by volume which is
distributed as dispersant in the other phase in each
case. Preference is given here to compositions in which
phase I is emulsified in phase II in amounts of from
0.1 to 25% by volume, preferably 0.2 to 15% by volume,
based on the volume of phase II.
In a further particular 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 II in a volume ratio of from 90:10
to 10:90, preferably 75:25 to 25:75, in particular
65:35 to 35:65, particularly preferably 60:40 to 40:60,
most preferably 55:45 to 45:55, for example 50:50.
surfactants
The compositions according to the invention can
comprise, as surfactant component, one or more
nonionic, anionic, 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
customarily 0.01 to 30% by weight, preferably 0.1 to
20% by weight, in particular 1 to 15% by weight,
particularly preferably 3 to 12% by weight, most
preferably 5 to 10% by weight, where any antimicrobial
surface-active compounds which may be present are
regarded in terms of amount not as surfactants but as
antimicrobial active ingredients.
Nonionic surfactants
Suitable nonionic surfactants are, for example,
C6-C22-alkyl alcohol polyglycol ethers, alkyl
polyglycosides and nitrogen-containing surfactants and
also di-C1-C1z-alkyl sulfosuccinates or mixtures
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thereof, in particular of the first two. The
compositions comprise nonionic surfactants in amounts,
based on the composition, of customarily 0 to 30% by
weight, preferably 0.1 to 20% by weight, in particular
1 to 14% by weight, particularly preferably 3 to 12% by
weight, most preferably 5 to 10% by weight, for example
8.5% by weight. Presumably, nonionic surfactants, with
their nonionic character, advantageously contribute to
the individual phases in the composition being stable
over a long period without, for example, the formation
of deposits, and to the conversion to a temporary
emulsion remaining reversible even after frequent
shaking.
C6-C22-alkyl alcohol polypropylene glycol/poly
ethylene glycol ethers are preferred known nonionic
surfactants. They can be described by the formula II,
R10- (CHZCH (CH3) O) p (CHZCH20) e-H, in which Rl is a linear or
branched, aliphatic alkyl and/or alkenyl radical having
6 to 22, preferably 8 to 18, in particular 10 to 16,
carbon atoms, p is 0 or numbers from 1 to 3, and a is
numbers from 1 to 20.
The C6-Czz-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 oxo alcohols, the branched-chain primary
alcohols obtainable by oxo synthesis, or to fatty
alcohols, in particular to fatty alcohols. Typical
examples are polyglycol ethers of the formula II in
which R1 is an alkyl radical having 8 to 18 carbon
atoms, p is 0 to 2 and a is numbers from 2 to 7.
Preferred representatives are, for example, Clo-C14-
fatty alcohol+1P0+6E0 ethers (p - l, a - 6) , Cl2-C16-
fatty alcohol+5.5E0 (p - 0, a - 5.5) , Clz-Cl8-fatty
alcohol+7E0 ethers (p - 0, a - 7) and isodecanol+6E0
(R1 - isomeric mixture of Clo-oxo alcohol radicals, (p =
0, a = 6) and mixtures thereof. In preferred mixtures,
at least one representative of the formula II having a
linear alkyl radical R1 is combined with at least one
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representative of the formula II having one branched
alkyl radical R1, for example C12-Cis-fatty alcohol+5.5E0
and isodecanol+6E0. Here, it is further preferred that
the linear alkyl radical contains more carbon atoms
than the branched alkyl radical.
It is also possible to use terminally capped
C6-CZZ-alkyl alcohol polyglycol ethers, i.e. compounds
in which the free OH group in the formula II is
etherified. The terminally capped C6-C2z-alkyl alcohol
polyglycol ethers can be obtained by relevant methods
of preparative organic chemistry. Preference is given
to reacting C6-Cz2-alkyl alcohol polyglycol ethers in
the presence of bases with alkyl halides, in particular
butyl chloride or benzyl chloride. Typical examples are
mixed ethers of the formula II in which R1 is a
technical-grade fatty alcohol radical, preferably Cla/i4-
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 (APGs) of the formula III, Rz0 [G] X, in
which R2 is a linear or branched, saturated or
unsaturated alkyl radical having 8 to 22 carbon atoms,
[G] is a glycosidically 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
arithmetical parameter which is in most cases a
fraction. Preference is given to using alkyl glycosides
having a mean degree of oligomerization x of from 1.1
to 3Ø From an application-related viewpoint,
preference is given to those alkyl glycosides whose
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degree of oligomerization is less than 1.7 and in
particular is between 1.2 and 1.6. The glycosidic sugar
used is preferably xylose, but in particular glucose.
The alkyl or alkenyl radical RZ (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 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.
Further nonionic surfactants which may be
present are nitrogen-containing surfactants, e.g. fatty
acid polyhydroxyamides, 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.
In a preferred embodiment, the compositions
according to the invention comprise one or more
nonionic surfactants, preferably C6-C22-alkyl alcohol
polyglycol ethers and/or alkyl polyglycosides, in
particular C6-C22-alkyl alcohol polyglycol ethers.
Anionic surfactants
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Suitable anionic surfactants are the preferred
C6-Czz-alkyl sulfates, C6-Czz-alkyl ether sulfates, i . e.
the sulfation products of the alcohol ethers of the
formula II, and/or anion-active sulfonic acids or salts
thereof, the sulfonates, and also C6-Czz-carboxamide
ether sulfates, mono-C1-Clz-alkyl sulfosuccinates,
C6-Czz-alkyl polyglycol ether carboxylates, C6-Czz-N-acyl
taurides, C6-Czz-N-sarcosinates and C6-Czz-alkyl
isethionates and mixtures thereof.
Within the meaning of the teaching according to
the invention, anion-active sulfonic acids are sulfonic
acids of the formula R-S03H which carry a partially or
completely straight-chain and/or branched and/or
cyclic, and also partially or completely saturated
and/or unsaturated and/or aromatic C6_32-hydrocarbon
radical R, for example C6-22-alkanesulfonic acids, C6-zz-
a,-olefinsulfonic acids, sulfonated C6-Czz-fatty acids
and C1_zz-alkyl-C6_lo-arenesulfonic acids, such as C1_zz-
alkylbenzenesulfonic acids or C1_zz-alkylnaphthalene-
sulfonic acids, preferably linear C8-16-alkylbenzene-
sulfonic acids, in particular linear Clo-i4-alkyl-,
Clo-13-alkyl- and Clz-alkylbenzenesulfonic acids.
The anionic surfactants 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 tetraalkyl-
ammonium salts, and in the case of the anion-active
sulfonic acids, also in the form of the acid, e.g.
dodecylbenzenesulfonic acid, Clo-Ci3-alkylbenzene-
sulfonic acid and/or Clo-C14-alkyl benzenesulfonic acid.
If the sulfonic acid is used, it is usually partially
or completely neutralized, depending on the pH of the
composition to be established, in situ using one or
more corresponding bases, e.g. alkali metal hydroxides
and alkaline earth metal hydroxides, in particular
sodium hydroxide, potassium hydroxide and magnesium
hydroxide, and ammonia or mono-, di-, tri- or
tetraalkylamine, to give the abovementioned salts. The
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compositions comprise one or more anionic surfactants
in amounts, based on the composition, of from 0 to less
than 30% by weight, preferably 0.1 to 20% by weight, in
particular 0.5 to 10% by weight, most preferably 0.7 to
5% by weight, for example 1 or 1.2% 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 establish the pH, lead to clouding
in the region of the boundary layer between phases I
and II. This problem is counteracted by the use of
citric acid or citrate. A further improvement occurs,
however, during neutralization of the alkylbenzene-
sulfonic 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 the 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
up to 5% by weight, preferably from 0.1 to 2% by
weight.
However, if cationic antimicrobial active
ingredients, such as surface-active quaternary
compounds, in particular quaternary ammonium compounds,
are used, the compositions preferably comprise,
according to the above quantities, as low a content as
possible of anionic surfactants including soaps and, in
a particularly preferred embodiment of the invention,
are entirely free from anionic surfactants including
soaps since the latter are frequently incompatible with
the antimicrobially active quaternary compounds to a
greater or lesser extent. In this connection, it is
self-evident to the person skilled in the art that he
must verify the compatibility of the anionic
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surfactants with the antimicrobial active ingredients
with regard to the antimicrobial action.
Amphoteric surfactants
Suitable amphoteric surfactants are, for
example, betaines of the formula (R3) (R4) (RS)N+CHzC00-,
in which R3 is an alkyl radical having 8 to 25,
preferably 10 to 21, carbon atoms which is optionally
interrupted by heteroatoms or heteroatom groups, and R4
and RS are identical or different alkyl radicals having
1 to 3 carbon atoms, in particular Clo-C22-alkyldi-
methylcarboxymethylbetaine and C11-C1-,-alkylamidopropyl-
dimethylcarboxymethylbetaine. The compositions comprise
one or more amphoteric surfactants in amounts, based on
the composition, of 0 to 15% by weight, preferably 0.01
to 10% by weight, in particular 0.1 to 5% by weight.
Cationic surfactants
Suitable cationic surfactants are, for example,
the above-described surface-active quaternary
compounds, in particular the surface-active quaternary
ammonium compounds. If surface-active quaternary
compounds are not already present as antimicrobial
active ingredients, the compositions comprise one or
more cationic surfactants in amounts, based on the
composition, of from 0 to 10% by weight, preferably
0.01 to 5% by weight, in particular 0.1 to 3% by
weight.
Hydrophobic components
In a particularly advantageous embodiment of
the invention, the compositions comprise one or more
hydrophobic components. The hydrophobic components not
only improve the cleaning action on hydrophobic
contaminants such as grease soiling, but additionally
have a positive effect on the phase separation and the
reversibility thereof. Here, the form, defined as
inhomogeneous, of the multiphase compositions according
to the invention permits stable incorporation, in
particular also in relatively large amounts, of the
hydrophobic components, which can only be stably
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incorporated into single-phase aqueous solutions or
stable emulsions or microemulsions using solvents,
stabilizers or emulsifiers in, in most cases, very
limited amounts.
Suitable hydrophobic components are, for
example, dialkyl ethers having identical or different
C4- to C14-alkyl radicals, in particular linear dioctyl
ethers; monomeric or homo- or hetropolymeric, in
particular monomeric and homodi- and trimeric CZ-C4-
alkylene glycols which have been etherified, esterified
and/or etherified/esterified with aliphatic or aromatic
alcohols, e.g. methanol, ethanol, n-propanol,
n-butanol, tert-butanol or phenol, or carboxylic acids,
e.g. acetic acid or carbonic acid, for example the
products sold under the trade name Dowanol~ from Dow
Chemical, and those sold under the trade name Arcosolv~
and Arconate~ from Arco Chemical and which are referred
to below by their INCI name in accordance with the
International Dictionary of Cosmetic Ingredients from
The Cosmetic, Toiletry, and Fragrance Association
(CTFA), e.g. Butoxydiglycol (Dowanol~ DB),
Methoxydiglycol (Dowanol~ DM), PPG-2 Methyl Ether
(Dowanol~DPM), PPG-2 Methyl Ether Acetate (Dowanol~
DPMA), PPG-2 Butyl Ether (Dowanolo DpnB), PPG-2 Propyl
Ether (Dowanol~ DPnP), Butoxyethanol (Dowanol~ EB),
Phenoxyethanol (Dowanol~ EPh), Methoxyisopropanol
(Dowanol~ PM), PPG-1 Methyl Ether Acetate (Dowanol~
PMA), Butoxyisopropanol (Dowanol~ PnB), Propylene
Glycol Propyl Ether (Dowanol~ PnP), Phenoxyisopropanol
(Dowanol~ PPh), PPG-3 Methyl Ether (Dowanol~ TPM) and
PPG-3 Butyl Ether (Dowanol~ TPnB) and Ethoxyisopropanol
(Arcosolv PE), tert-Butoxyisopropanol (Arcosolv PTB),
PPG-2 tert-Butyl Ether (Arcosolv DPTB) and
Propylenecarbonate (Arconate~ PC), in particular PPG-2
Propyl Ether (Dipropyleneglycol-n-butyl ether,
(Dowanol~ DPnP); hydrocarbons having a boiling range
from 100 to 300°C, in particular 140 to 280°C, e.g.
aliphatic hydrocarbons having a boiling range from 145
CA 02320541 2000-09-25
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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 various dialkyl ethers, of dialkyl
ethers and etherified or esterified mono- or polymeric
Cz-C4-alkylene glycols, 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.
Particularly preferred mixtures of hydrophobic
components are mixtures of dialkyl ethers and
etherified or esterified mono- or polymeric CZ-C4-
alkylene glycols, for example of di-n-octyl ether and
dipropylene glycol n-butyl ether (PPG-2 Propyl Ether).
The compositions comprise hydrophobic
components in amounts, based on the composition, of
from 0 to 20% by weight, preferably 0.1 to 15% by
weight, in particular 1 to 12% by weight, particularly
preferably 2 to 10 % by weight, most preferably 3 to 8%
by weight, e.g. 5% by weight.
Phase-se~arat~on auxiliaries
The compositions according to the invention can
comprise one or more phase-separation auxiliaries.
Examples of suitable phase-separation auxiliaries are
the alkali metal halides and alkaline earth metal
halides, in particular chlorides, and alkali metal and
alkaline earth metal sulfates and nitrates, in
particular sodium chloride and potassium chloride and
sodium sulfate and potassium sulfate, and also ammonium
chloride and ammonium sulfate, or mixtures thereof.
Being strong electrolytes which increase the ionic
strength, such salts aid phase separation as a result
of the salt effect. In this connection, sodium chloride
has proven particularly effective. The compositions
CA 02320541 2000-09-25
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comprise phase-separation auxiliaries in amounts, based
on the composition, of from 0 to 30% by weight,
preferably 1 to 20% by weight, in particular 3 to 15%
by weight, most preferably 5 to 12% by weight.
Surprisingly, we have found that the use of
acids, preferably organic acids such as carboxylic
acids and/or inorganic acids, particularly preferably
at least one acid chosen from the group consisting of
salicylic acid, lactic acid, benzoic acid and boric
acid, also stabilizes phase separation of the
compositions.
The addition of additional acids nP,~",;t~ a
reduction in, for example, the proportion of citric
acid, where stable phase separation of the cleaner is
maintained.
If 13~ by weight of citric acid and 9~ by
weight of monoethanolamine, based on the cleaner
composition, are used in the presence of sodium
benzoate, it is possible to obtain a phase separation
of the cleaner composition of about 1/3 lower phase to
about 2/3 upper phase.
If lactic acid is used, for the same citric
acid contents, the phase ratio of the cleaner can be
adjusted to about 40 parts of lower phase and 60 parts
of upper phase.
By reducing the water content of the cleaner
composition, the phase ratio, for a proportion of 12$
by weight of citric acid and a suitable amount of
monoethanolamine, can be shifted to 30 parts of upper
phase and 70 parts of lower phase.
If 3~ by weight of sodium benzoate, 14~ by
weight of citric acid and 10~ by weight of
monoethanolamine are used, a phase ratio of the cleaner
composition of l:l can be produced. If 3$ by weight of
lactic acid, 13~ by weight of citric acid and 12~ by
weight of monoethanolamine are used, the proportion of
the lower phases can be increased.
Builders
CA 02320541 2000-09-25
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Furthermore, the composition according to the
invention preferably comprises one or more builders, in
particular for improving the detergency. Suitable
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 hydroxides
and alkaline earth metal hydroxides, in particular
sodium hydroxide and potassium hydroxide, ammonia and
amines, in particular mono- and triethanolamine, and
mixtures thereof. These also include the salts of
glutaric acid, succinic acid, adipic acid, tartaric
acid and benzenehexacarboxylic acid, and aminotri-
methylenephosphonic acid, hydroxyethane-1,1-di-
phosphonic acid, 1-aminoethane-1,1-diphosphonic acid,
ethylenediaminetetra(methylenephosphonic acid), di-
ethylenetriaminepenta(methylenephosphonic acid), 2-
phosphonobutane-1,2,4-tricarboxylic acid, phosphonates
and phosphates, for example the sodium salts of
methanediphosphonic acid, the pentasodium triphosphate,
commonly known as sodium tripolyphosphate, or sodium
hexametaphosphate and, for example, a mixture of
condensed orthophosphates of the formula I in which n
is a mean value of about 12.
Particularly preferred builders are citric acid
or citrates, in particular sodium citrate, and
aminotrimethylenephosphonic acid, and mixtures thereof
in which the weight ratio of citric acid or citrate,
based on citric acid, to aminotrimethylenephosphonic
acid is preferably 1:10 to 100:1, in particular 1:1 to
40:1, particularly preferably 2:1 to 20:1, most
preferably 5:1 to 10:1, for example 8:1.
If the builder is also to act as pH-stabilizing
buffer, then alkali metal and alkaline earth metal
carbonates and bicarbonates, preferably sodium
carbonate (soda), are preferred, in particular together
with citric acid or citrate, optionally generated in
CA 02320541 2000-09-25
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situ from citric acid and hydroxide, e.g. sodium
citrate or potassium citrate, particularly preferably
together with the above-described mixture of citric
acid or citrate and aminotrimethylenephosphonic acid.
Within the scope of the present invention,
unless expressly stated otherwise, the citrates are the
salts of the triply deprotonated citric acid. However,
the mono- and dihydrogen citrates can also be used
according to the invention.
The compositions comprise buildings in amounts,
based on the composition, of from 0 to 30% by weight,
preferably 0.1 to 20% by weight, in particular 1 to 15%
by weight, particularly preferably 3 to 12% by weight,
most preferably 5 to 10% by weight, for example 7.3% by
weight. Here, said salts can also be used in the form
of their corresponding acids or bases, which are then
partially or completely neutralized depending on the pH
to be established. Equally, said acids can be used in
the form of their salts, preferably their alkali metal,
alkaline earth metal, ammonium and mono-, di- or
trialkanolammonium salts, in particular mono-, di- or
triethanolammonium salts, or mixtures thereof, in
particular their sodium salts, for example citric acid
in the form of its monohydrate citric acid~1H20 instead
of citrate. The builder salts additionally act here as
phase-separation auxiliaries. In particular, the
complexing builders also serve to ensure a clear use
solution when the compositions are used with hard
water.
A preferred builder is citrate, optionally
generated in situ from citric acid and hydroxide, 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 and/or potassium citrate, since citrates
combine builder and phase-separation auxiliary
properties in a particularly advantageous manner.
CA 02320541 2000-09-25
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An advantageous alkali builder is potassium
hydroxide since it has a particularly positive effect
on the phase separation, the clarity and color
brilliance of the phases, and on the sharpness and lack
of or freedom from clouding of the phase boundary
layer.
Perfume oils
Furthermore, the composition according to the
invention preferably comprises one or more perfume oils
since, in addition to the fragrance effect, they aid
phase separation and considerably improve detergency,
in particular in amounts greater than 0.9% by weight.
But the incorporation, in particular of relatively
large amounts, of perfume oils into single-phase
aqueous solutions or stable emulsions or microemulsions
frequently causes problems and renders necessary the
use of solvents, solubilizers or emulsifiers without,
however, being able to stabilize relatively large
perfume oil contents. Here, the great advantage of the
form, defined as inhomogeneous, of the multiphase
compositions according to the invention comes into
play, which permits a stable incorporation of the
perfume oils, in particular also in relatively large
amounts.
Accordingly, the invention further provides for
the use of perfume oils in a liquid multiphase cleaner
having at least two continuous phases, which has at
least one lower aqueous phase I and an upper aqueous or
nonaqueous phase II which is immiscible with the first
phase and can be converted temporarily into an emulsion
by shaking, for improving detergency. The composition
in accordance with the use is preferably an aqueous
liquid multiphase surfactant-containing cleaner
comprising at least two continuous phases, which has at
least one lower aqueous phase I and an upper aqueous
phase II which is immiscible with the first phase, in
particular is a composition according to the invention.
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The components of the suitable perfume oils
described below are followed by numbers in brackets,
e.g. "(5.0)", which are examples of information about
the composition of the respective perfume oil in % by
weight, based on the perfume oil. Thus, "geraniol
(105.0)" means that the perfume oil may contain
geraniol, for example, in an amount of 105.0% by
weight.
A suitable perfume oil having a freshly fruity
scent note comprises, for example, Dynascone 10 (5.0),
Cyclovertal (7.5), hexyl acetate (35.0), ally)
heptanoate (200.0), amyl butyrate (5.0), prenyl acetate
(10.0), aldehyde C 14, so-called, (70.0), Manzanate
(15.0), Melusat (30.0), ortho-tert-butylcyclohexyl
acetate (200.0), cinnamaldehyde (5.0), isobornyl
acetate (10.0), Dihydrofloriffone TD (2.5), Floramat
(100.0), phenyl ethyl alcohol (30.0), geraniol (105.0),
cyclohexyl salicylate (150.0) and citronellol (20.0).
A suitable perfume oil having a fresh floral
scent note comprises, for example, bergamot oil
(250.0), Messina lemon oil (50.0), citronella) (2.0),
sweet orange oil (50.0), lavender oil (50.0), terpine
oil (50.0), lilial (100.0), phenylethyl alcohol (80.0),
citronellol (100.0), geraniol (20.0), benzyl acetate
(60. 0) , isoraldein 70 (50. 0) , ylang (30. 0) , ambroxan
10% in IPM (1.0), heliotropin (47.0) and Habanolide
(60.0) .
A suitable perfume oil having a citrus scent
note comprises, for example, orange oil (710.0),
a-pinene (130.0), ~i-pinene (20.0), y-terpinene (95.0)
and Litsea cubeba oil (55.0).
The content of one or more perfume oils is
usually 0 . 1 to 15 % by weight, preferably 0 . 5 to 10% by
weight, in particular 1 to 5% by weight, particularly
preferably 1.5 to 4% by weight, most preferably 2 to 3%
by weight, e.g. 2.5% by weight.
Enzymes
CA 02320541 2000-09-25
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In a particular embodiment of the invention,
the composition comprises one or more enzymes.
Suitable enzymes are those customary in
detergents and cleaners, for example proteases (e. g.
BLAP 260 L~, BLAP S 260 SLD~, BLAP S 260 ALD ,
BLAP S 260 LDP and BLAP S 260 from Biozym or Durazym~,
Savinase~ and Alcalase~ from Novo Nordisk) , amylases
(e. g. Termamyl~ from Novo Nordisk), cellulases (e. g.
KAC 500 from Kao, Celluzyme~ from Novo Nordisk) ,
lipases (e. g. Lipase 100 L~ and Lipolase 100 T from
Novo Nordisk) and peroxidases and reductases.
The nonionic surfactants generally and the
alkyl polyglycosides specifically improve the storage
stability of the enzyme-containing variant as much as
citric acid or its salts and also the hydrophobic
components, in particular the optionally etherified or
esterified mono- or polymeric C2-C4-alkylene glycols,
e.g. the products sold under the trade names Dowanol~~
Arcosolo and Arconate~, and polyethylene glycols and
derivatives thereof. In this connection, the inventive
multiphase nature of the composition has an
advantageous effect on the stability of the enzymes,
which is presumably attributable to the concentration
of the enzymes in the upper phase II which is richer in
the aforementioned stabilizing components and, in terms
of ionic strength, is less ionic.
The pH of the compositions according to the
invention can be varied over a wide range from strongly
acidic via neutral to highly alkaline, but is
preferably in a range from 1 to 12, in particular 2 to
11. In this connection, the pH dependency of the
antimicrobial action of the active ingredients) used,
which is either known to the person skilled in the art
or can be deduced by routine experiments, is to be
taken into account. Thus, the pH is to be chosen to be
as optimal as possible for the antimicrobial action of
the respective antimicrobial active ingredient(s),
CA 02320541 2000-09-25
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and/or, if a certain pH is stipulated for a certain
cleaning purpose, the antimicrobial active
ingredients) is/are to be chosen accordingly. Within
the scope of the present invention, the pH of the
compositions according to the invention means the pH of
the composition in the form of the temporary emulsion.
In a neutral variant, the pH is from above 6 to
below 8, preferably 6.5 to 7.5 and in particular about
7.
In a preferred embodiment of the invention, the
compositions are rendered alkaline with a pH of from 8
to 12, preferably 8 to 11, in particular 8 to 10.5, for
example between 8 and 9, e.g. 8.3, for moderate
alkalinity, or above 9 to 10.5, 11 or even 12, e.g. 10,
for greater alkalinity. This is particularly preferable
if antimicrobial quaternary compounds are used since
their antimicrobial action generally increases with
increasing pH while it is occasionally completely
lacking in the acid range below a pH of 3.
Suitable pH regulators are first acids, such as
the mineral acids, e.g. hydrochloric acid, but in
particular citric acid, and, secondly, the
abovementioned alkaline builders, preferably sodium
hydroxide, but in particular potassium hydroxide
because of the advantages already given.
For stabilization or buffering of the pH, the
composition according to the invention comprises, in a
particular embodiment, small amounts of corresponding
buffer substances, in the alkaline variant described,
for example soda or sodium bicarbonate.
In a likewise preferred embodiment of the
invention, the compositions are rendered acidic with a
pH of from 1 to 6, preferably 2 to 6, in particular 3
to 5.5, particularly preferably 3.5 to 5, for example
4, 4.4 or 4.5. To set such a pH, the compositions
comprise at least one acid. Inorganic acids, for
example the mineral acids, e.g. hydrochloric acid, and
organic acids, for example saturated or unsaturated
CA 02320541 2000-09-25
-25-
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 from BASF under the trade name Sokalan~ DCS
are suitable. 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
alkylarenesulfonic acids. Citric acid combines
properties of acid, builder and phase-separation
auxiliary in an advantageous manner, while the anion-
active sulfonic acids simultaneously act as acid and
anionic surfactant. Where appropriate, one or more
alkalis can additionally be used, for example the
alkali metal, alkaline earth metal and ammonium
hydroxides and carbonates, and ammonia, preferably
sodium hydroxide and potassium hydroxide, particular
preference being given to potassium hydroxide.
V1SCOSItV
The viscosity of the composition according to
the invention is preferably 5 to 1000 mPa~s, in
particular 10 to 500 mPa~s, particularly preferably
200 mPa~s, at 20°C, measured using a rotational
viscometer from Brookfield of the LVT or LVDV-II+ type
with Small Sample Adapter at a rotational rate of
30 min-1, where the spindle used as measurement element
according to Brookfield is to be chosen such that the
moment of rotation is in a favorable range and the
measurement range is not exceeded. In this connection,
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
CA 02320541 2000-09-25
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To adjust the viscosity, the composition
according to the invention can comprise one or more
thickeners, preferably in an amount of from 0.01 to 5%
by weight, in particular 0.05 to 2.5% by weight,
particularly preferably 0.1 to 1% by weight.
Suitable thickeners are organic natural
thickeners (agar agar, carragheenan, 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 entirely synthetic thickeners (polyacrylic and
polymethacrylic compounds, vinyl polymers, poly-
carboxylic 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 the International Dictionary of Cosmetic
Ingredients from The Cosmetic, Toiletry, and Fragrance
Association (CTFA): Carbomer), which are also referred
to as carboxyvinyl polymers. Such polyacrylic acids are
available inter alia from BFGoodrich under the trade
name 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 formed preferably with C1_4-alkanols (INCI
Acrylates Copolymer), which include, 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
CA 02320541 2000-09-25
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methyl methacrylate (CAS 25852-37-3) and which are
available, for example, from Rohm & Haas under the
trade names 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, which include, for example, the copolymers
of Clo-so-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 and its monoesters preferably formed
with C1_4-alkanols (INCI Acrylates/C10-30 Alkyl Acrylate
Crosspolymer), and which are available, for example,
from BFGoodrich under the trade name Carbopol~, e.g.
the hydrophobicized Carbopol~ ETD 2623 and Carbopol~
1382 (INCI Acrylates/C10-30 Alkyl Acrylate
Crosspolymer), and Carbopol~ AQUA 30 (formerly Carbopol~
EX 473) .
Preferred thickeners are the polysaccharides
and heteropolysaccharides, in particular the
polysaccharide gums, for example gum arabic, agar,
alginates, carragheenans 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, but are preferably used in 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-,
hydroxypropylmethyl- or hydroxyethylmethylcellulose 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
CA 02320541 2000-09-25
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molecular weight of from 2 to 15x106, and is available,
f or exampl a , from Kel co unde r the t rade name Kel trol ~,
e.g. as a cream-colored powder Keltrol~ T (transparent)
or as white granules Keltrol~ RD (readily dispersible).
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, in
particular, polymers, soil release active ingredients,
solvents (e. g. ethanol, isopropanol, glycol ethers),
solubilizers, hydrotropic agents (e. g. sodium
cumenesulfonate, octyl sulfate, butyl glucoside, butyl
glycol), cleaning promoters, disinfectants, antistats,
preservatives (e. g. glutaraldehyde), bleaching systems
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 12% by
weight. The lower use limit depends on the type of
auxiliary and additive and can, for example in the case
of dyes, be up to 0.001% by weight and below. The
amount of auxiliaries and additives is preferably
between 0.01 and 7% by weight, in particular 0.1 and 4%
by weight.
A preferred auxiliary and additive comprises
dyes, since the addition thereof can result in the
phases being 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. Accordingly, the invention further
provides a process for the preparation of a composition
according to the invention by blending directly from
its raw materials, subsequently mixing thoroughly and
CA 02320541 2000-09-25
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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 lead to phase separation
according to the invention on its own. 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.
The composition according to the invention is
sprayable and can therefore be used in a spray
dispenser. Accordingly, the invention further provides
a product comprising a composition according to the
invention and a spray dispenser. The spray dispenser is
preferably a manually activated spray dispenser, in
particular chosen from the group comprising aerosol
spray dispensers, self-pressurizing spray dispensers,
pump spray dispensers and trigger spray dispensers, in
particular pump spray dispensers and trigger spray
dispensers with a container made from transparent
polyethylene or polyethylene terephthalate. Spray
dispensers are described in more detail in WO 96/04940
(Procter & Gamble) and the US patents cited therein
relating to spray dispensers, to all of which reference
is made in this respect and whose contents are herewith
incorporated into this application.
Particularly suitable cleaning compositions as
listed in Tables 2-9 can comprise Texapon SPN 70 as
Ci2-C14-fatty alcohol 1,3-EO ether sulfate sodium salt,
Hostapur SAS 60 as alkanesulfonate sodium salt, APG
600 UP-w as alkyl polyglycoside, Dehyton PK 45 OKA as
betaine derivative and Dehydol PO 5 as fatty alcohol
ethoxylate.
CA 02320541 2000-09-25
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Examples
The compositions E1 to E51 according to the
invention were prepared as described above. Tables 1-9
give composition in % by weight, pH and the quantified
volume ratio of the upper phase II to the lower phase
I. Unless stated otherwise, the compositions E1 to E51
comprise water ad 100. If necessary, in the case of E1
to E51, the pH can be adjusted by adding hydroxides
such as NaOH and/or KOH.
Compositions E1, E2 and E3 comprised a perfume
oil with a citrus scent note, consisting of 700.0% by
weight of orange oil, 130.0% by weight of a-pinene,
20.0% by weight of (3-pinene, 95.0% by weight of
y-terpinene and 55.0% by weight of Litsea Cubeba oil.
Analogous compositions E1', E2' and E3'
comprise, by contrast with the compositions E1, E2 and
E3, a perfume oil with a freshly fruity note,
consisting of 5.0% by weight of Dynascone 10, 7.5% by
weight of Cyclovertal, 35.0% by weight of hexyl
acetate, 200.0% by weight of allyl heptanoate, 5.0% by
weight of amyl butyrate, 10.0% by weight of prenyl
acetate, 70.0% by weight of aldehyde C 14, so-called,
15.0% by weight of Manzanate, 30.0% by weight of
Melusat, 200.0% by weight of ortho-tert-butylcyclohexyl
acetate, 5.0% by weight of cinnamaldehyde, 10.0% by
weight of isobornyl acetate, 2.5% by weight of
dihydrofloriffone TD, 100.0% by weight of Floramat,
30.0% by weight of phenylethyl alcohol, 105.0% by
weight of geraniol, 150.0% by weight of cyclohexyl
salicylate and 20.0% by weight of citronellol.
Further analogous compositions E1', E2' and E3'
comprise, in contrast to the compositions El, E2 and
E3, a perfume oil with a fresh floral scent note,
consisting of 250.0% by weight of bergamot oil, 50.0%
by weight of Messina lemon oil, 2.0% by weight of
citronellal, 50.0% by weight of sweet orange oil, 50.0%
by weight of lavender oil, 50.0% by weight of
terpineol, 100.0% by weight of lilial, 80.0% by weight
CA 02320541 2000-09-25
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of phenylethyl alcohol, 100.0% by weight of
citronellol, 20.0% by weight of geraniol, 60.0% by
weight of benzyl acetate, 50.0% by weight of isoraldein
70, 30.0% by weight of ylang, 1.0% by weight of
Ambroxan 10% in IPM, 47.0% by weight of heliotropin and
60.0% by weight of Habanolide.
Table 1
Composition E1 E2 E3
Clz-Cls-fatty alcohol+5.5E02 - -
Clz-Cle-fatty alcohol+7E0 - 1 1
Dodecylbenzenesulfonic - 3 3
acid
Isodecanol+6E0 6.5 - -
PPG-2 butyl ether 5.0 - -
Cll-C13-isoparaffins (INCI- 2 2
C9-13 Isoparaffin)~a~
Clz-C14-alkylbenzyl- 1.5 - -
dimethylammonium chloride
Salicylic acid - 0.6 0.6
Formic acid - 1.6 -
Aminotrimethylenephosphonic0.5 - -
acid
Citric acid~H20 4.0 3.4 8
NaOH 2.6 - -
KOH - 1.1 2.5
Sodium carbonate 0.2 - -
Isopropanol - 2 2
Perfume (see below) 2.5 1 1
Dye <O.OOl~b~ <0.001~~ <0.001~~
Water, demineralized ad 100 ad 100 ad 100
pH 9.9 3.6 3.8
Appearance Phase II/Phase clear/ clear/ clear/
I
clear clear clear
II:I volume ratio 50:50 50:50 50:50
Color Phase II/Phase I green/ blue/ blue/
colorless colorless colorless
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ShellsolA T (Shell Chemicals in Europe, DE) having a
boiling range from 200 to 260°C
~b~ Colour Index designation: C.I. 42080 or Acid Blue 7
~°~ Colour Index designation: C.I. 61568 or Solvent Blue 104
All of the compositions had two continuous
phases which temporarily formed a creamy emulsion upon
shaking. Even after repeated shaking, phases separated
out 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, the composition displayed
no visible change, and in particular the composition
could be reversibly converted into the temporary
emulsion by shaking as before.
The compositions were judged by test subjects
to be visually pleasing and easy to handle and
achieved, in neat form and in dilute form, good
cleaning results, in particular in the case of the
removal of fat-containing soilings in the form of the
grime caused in the kitchen as a result of the
preparation of fat- or oil-containing food.
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Table 2: 2-phase antibacterial cleaner compositions
Composition E4 E5 E6 E7 E8 E9
of C12-C14-fatty 16.0 16.0 16.0 16.0 16.0 16.0
alcohol 1,3 EO ether
sulfate sodium salt
of alkanesulfonate 8.0 8.0 8.0 8.0 8.0 8.0
sodium salt
% Of C12-14-16-alkyl - - - - - -
polyglycoside
% of cocoamidopropyl- 8.0 8.0 8.0 8.0 8.0 8.0
betain
of CB-fatty alcohol 5.0 5.0 5.0 5.0 5.0 5.0
+ 5 EO
of sodium benzoate 3.0 3.0 3.0 3.0 3.0 3.0
of ethanol 5.0 5.0 5.0 5.0 5.0 5.0
of n-propanol 5.0 5.0 5.0 5.0 5.0 5.0
of dye 0.000 0.0008 0.0008 0.0008 0.0008 0.0008
8
of perfume 0.8 0.8 26.000 0.8 0.8 0.8
80.8
of citric acid 8.0 9.0 10.0 11.0 12.0 13.0
1-hydrate
% of monoethanolamine 5.0 5.9 6.5 7.7 8.0 9.1
Appearance l.: 1.: 19 l.: 23 1.: 25 1.: 25 1.: 25
15 pts. pts. pts. pts. pts.
pts. colorl colorl colorl colorl colorl
color ., ., ., ., .,
1., clear clear clear clear clear
clear u.: 81 u.: 77 u.: 75 u.: 75 u.: 75
u.: pts. pts. pts. pts. pts.
85 blue, blue, blue, blue, blue,
pts. clear clear clear clear clear
blue,
clear
pH 5.3 5.3 5.3 5.3 5.3 5.3
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Table 3
Composition E10 E11 E12 E13 E14 E15
of C12-C14-fatty 16.0 16.0 16.0 16.0 16.0 16.0
alcohol 1,3 EO
ether sulfate
sodium salt
of 8.0 8.0 8.0 8.0 8.0 8.0
alkanesulfonate
sodium salt
% Of C12_14-16-alkyl- - - - - -
polyglycoside
% of 8.0 8.0 8.0 8.0 8.0 8.0
cocoamidopropyl-
betain
of C8-fatty 5.0 5.0 5.0 5.0 5.0 5.0
alcohol + 5 EO
of lactic acid 3.0 3.0 3.0 3.0 3.0 3.0
of ethanol 5.0 5.0 5.0 5.0 5.0 5.0
of n-propanol 5.0 5.0 5.0 5.0 5.0 5.0
% of dye 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008
of perfume 0.8 0.8 0.8 0.8 0.8 0.8
of citric acid 10.0 11.0 12.0 13.0 14.0 15.0
1-hydrate
of 9.9 10.1 11.2 11.9 12.7 13.5
monoethanolamine
Appearance 1.: 15 1.: 21 1.: 24 l.: 1.: 25 1.: 25
25
pts. pts. pts. pts. pts. pts.
colorl colorl colorl colorl colorl colorl
., ., ., ., ., .,
clear clear clear clear clear clear
u.: 85 u.: 79 u.: u.: 75 u.: 75 u.: 75
76
pts. pts. pts. pts. pts. pts.
blue, blue, blue, blue, blue, blue,
clear clear clear clear clear clear
pH 5.3 5.3 5.3 5.3 5.3 5.3
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Table 4
Composition E16 E17 E18 E19 E20 E21
of C12- 9.0 9.0 9.0 9.0 9.0 9.0
C14-fatty
alcohol 1,3
EO ether
sulfate
sodium salt
of 4.5 4.5 4.5 4.5 4.5 4.5
alkanesulfo
nate sodium
salt
of C12_14- - - - - - -
is-alkyl
polyglycosi
de
% of 4.5 4.5 4.5 4.5 4.5 4.5
cocoamidopr
opylbetain
% of Ce- 5.0 5.0 5.0 5.0 5.0 5.0
fatty
alcohol +
5
EO
of sodium 3.0 3.0 3.0 3.0 3.0 3.0
benzoate
of - _ _ _ _ -
ethanol
% of n- 7.0 7.0 7.0 7.0 7.0 7.0
propanol
% of dye 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008
% of 0.8 0.8 0.8 0.8 0.8 0.8
perfume
of citric 10.0 11.0 12.0 13.0 14.0 15.0
acid
1-hydrate
% of 7.0 7.8 8.7 9.5 10.2 11.7
monoethanol
amine
Appearance 1.: 1.: 33 1.: 40 1.: 1.: 48 1.: 50
28 45
pts. pts. pts. pts. pts. pts.
colorl colorl colorl colorl colorl colorl
., ., ., ., ., .,
clear clear clear clear clear clear
u.: 72 u.: u.: 60 u.: u.: 52 u.:
67 55 50
pts. pts. pts. pts. pts. pts.
blue, blue, blue, blue, blue, blue,
clear clear clear clear clear clear
pH 5.3 5.3 5.3 5.3 5.3 5.3
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Table 5
Composition E22 E23 E24 E25 E26 E27
of Clz- 9.0 9.0 9.0 9.0 9.0 9.0
C14-fatty
alcohol 1,3
EO ether
sulfate
sodium salt
of 4.5 4.5 4.5 4.5 4.5 4.5
alkanesulfo
nate sodium
salt
of Clz-ia- - - - - - -
is-alkyl
polyglycosi
de
% of 4.5 4.5 4.5 4.5 4.5 4.5
cocoamidopr
opylbetain
% of Cg- 5.0 5.0 5.0 5.0 5.0 5.0
fatty
alcohol +
5
EO
of lactic 3.0 3.0 3.0 3.0 3.0 3.0
acid
of - - - - - -
ethanol
% of n- 7.0 7.0 7.0 7.0 7.0 7.0
propanol
of dye 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008
% of 0.8 0.8 0.8 0.8 0.8 0.8
perfume
of citric 10.0 11.0 12.0 13.0 14.0 15.0
acid
1-hydrate
% of 9.9 10.1 11.2 11.9 12.7 13.5
monoethanol
amine
Appearance 1.: 1.: 43 1.: 1.: 55 1.: 55 1.: 55
36 50
pts. pts. pts. pts. pts. pts.
colorl colorl colorl colorl colorl colorl
., ., ., ., ., .,
clear clear clear clear clear clear
u.: 64 u.: u.: 50 u.: u.: 45 u.:
57 45 45
pts. pts. pts. pts. pts. pts.
blue, blue, blue, blue, blue, blue,
clear clear clear clear clear clear
pH 5.3 5.3 5.3 5.3 5.3 5.3
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Table 6
Composition E28 E29 E30 E31 E32 E33
of Clz- 16.0 16.0 16.0 16.0 16.0 16.0
C14-fatty
alcohol 1,3
EO ether
sulfate
sodium salt
of - - - - - -
alkanesulfo
nate sodium
salt
% of Clz-i4-2.0 2.0 2.0 2.0 2.0 2.0
is-alkyl
polyglycosi
de
% of 1.5 1.5 1.5 1.5 1.5 1.5
cocoamidopr
opylbetain
% of C8- 5.0 5.0 5.0 5.0 5.0 5.0
fatty
alcohol +
5
EO
of sodium 3.0 3.0 3.0 3.0 3.0 3.0
benzoate
of - _ _ _ _
ethanol
of n- 7.0 7.0 7.0 7.0 7.0 7.0
propanol
of dye 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008
% of 0.8 0.8 0.8 0.8 0.8 0.8
perfume
of citric 10.0 11.0 12.0 13.0 14.0 15.0
acid
1-hydrate
of 6.8 8.0 8.5 9.1 10.5 11.0
monoethanol
amine
Appearance 1.: 1.: 23 l.: 29 1.: l.: 37 1.: 38
14 33
pts. pts. pts. pts. pts. pts.
colorl colorl colorl colorl colorl colorl
., ., ., ., ., .,
clear clear clear clear clear clear
u.: 86 u.: u.: 71 u.: u.: 63 u.:
77 67 62
pts. pts. pts. pts. pts. pts.
blue, blue, blue, blue, blue, blue,
clear clear clear clear clear clear
pH 5.3 5.3 5.3 5.3 5.3 5.3
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Table 7
Composition E34 E35 E36 E37 E38 E39
of Clz- 16.0 16.0 16.0 16.0 16.0 16.0
C14-fatty
alcohol 1,3
EO ether
sul f ate
sodium salt
% of - _ _ _ _ _
alkanesulfo
nate sodium
salt
of Clz-i4- 2.0 2.0 2.0 2.0 2.0 2.0
is-alkyl
polyglycosi
de
of 1.5 1.5 1.5 1.5 1.5 1.5
cocoamidopr
opylbetain
of Cg- 5.0 5.0 5.0 5.0 5.0 5.0
fatty
alcohol + 5
EO
of AS 3.0 3.0 3.0 3.0 3.0 3.0
lactic acid
of - - - - - -
ethanol
of n- 7.0 7.0 7.0 7.0 7.0 7.0
propanol
% of dye 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008
of 0.8 0.8 0.8 0.8 0.8 0.8
perfume
% of citric 10.0 11.0 12.0 13.0 14.0 15.0
acid
1-hydrate
% of 9.4 9.9 11.1 11.7 12.5 13.4
monoethanol
amine
Appearance 1.: 28 1.: 31 1.: 37 1.: 40 1.: 43 l.: 45
pts. pts. pts. pts. pts. pts.
colorl colorl colorl colorl colorl colorl
., .. ., ., ., .,
clear clear clear clear clear clear
u.: 72 u.: 69 u.: 63 u.: 60 u.: 57 u.: 55
pts. pts. pts. pts. pts. pts.
blue, blue, blue, blue, blue, blue,
clear clear clear clear clear clear
pH 5.3 5.3 5.3 5.3 5.3 5.3
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Table 8
Composition E40 E41 E42 E43 E44 E45
of C12- 10.0 10.0 10.0 10.0 10.0 10.0
C14-fatty
alcohol 1,3
EO ether
sulfate
sodium salt
of 10.0 10.0 10.0 10.0 10.0 10.0
alkanesulfo
nate sodium
salt
of Clz-ia- 4 4 4 4 4 4
is-alkyl
polyglycosi
de
of 4 4 4 4 4 4
cocoamidopr
opylbetain
of CB- 5.0 5.0 5.0 5.0 5.0 5.0
fatty
alcohol + 5
EO
of sodium 3.0 3.0 3.0 3.0 3.0 3.0
benzoate
of 5.0 5.0 5.0 5.0 5.0 5.0
ethanol
of n- 5.0 5.0 5.0 5.0 5.0 5.0
propanol
% of dye 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008
% of 0.8 0.8 0.8 0.8 0.8 0.8
perfume
of citric 8.0 9.0 10.0 11.0 12.0 13.0
acid
1-hydrate
of 5.1 5.9 6.6 7.5 8.4 8.9
monoethanol
amine
Appearance 1.: 13 1.: 17 1.: 23 1.: 25 1.: 27 1.: 30
pts. pts. pts. pts. pts. pts.
colorl colorl colorl colorl colorl colorl
., ., ., ., ., .,
clear clear clear clear clear clear
u.: 87 u.: 83 u.: 77 u.: 75 u.: 73 u.: 70
pts. pts. pts. pts. pts. pts.
blue, blue, blue, blue, blue, blue,
clear clear clear clear clear clear
pH 5.3 5.3 5.3 5.3 5.3 5.3
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Table
9
Composition E46 E47 E48 E49 E50 E51
% of C12- 10.0 10.0 10.0 10.0 10.0 10.0
C14-fatty
alcohol 1,3
EO ether
sulfate
sodium salt
of 10.0 10.0 10.0 10.0 10.0 10.0
alkanesulfo
nate sodium
salt
% Of C12-14-4 4 4 4 4 4
is-alkyl
polyglycosi
de
of 4 4 4 4 4 4
cocoamidopr
opylbetain
% of CB- 5.0 5.0 5.0 5.0 5.0 5.0
fatty
alcohol +
5
EO
% of AS 3.0 3.0 3.0 3.0 3.0 3.0
lactic acid
% of 5.0 5.0 5.0 5.0 5.0 5.0
ethanol
of n- 5.0 5.0 5.0 5.0 5.0 5.0
propanol
of dye 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008
% of 0.8 0.8 0.8 0.8 0.8 0.8
perfume
of citric 8.0 9.0 10.0 11.0 12.0 13.0
acid
1-hydrate
of 7.5 8.3 8.9 9.4 10.5 11.3
monoethanol
amine
Appearance 1.: 1.: 22 1.: 24 l.: 1.: 30 1.: 30
14 27
pts. pts. pts. pts. pts. pts.
colorl colorl colorl colorl colorl colorl
., ., ., ., ., .,
clear clear clear clear clear clear
u.: 86 u.: 78 u.: u.: 73 u.: 70 u.: 70
76
pts. pts. pts. pts. pts. pts.
blue, blue, blue, blue, blue, blue,
clear clear clear clear clear clear
pH 5.3 5.3 5.3 5.3 5.3 5.3
CA 02320541 2000-09-25
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Investigation of the antimicrobial activity
The antimicrobial activity of the compositions
E1 to E51 was investigated with regard to the reduction
in live microbial count in quantitative suspension test
in accordance with the DIN EN 1276 test method.
The test standard DIN EN 1276 describes a test
method and minimum requirement for the bactericidal
action of chemical disinfectants and antiseptic
products for the food sector, industry, home and public
establishments. According to this, such products, under
simulated contamination and under the required test
conditions (test concentration 5% strength; contact
time 5 minutes at 20°C), must reduce the live microbial
count of the four reference strains Staphylococcus
aureus (ATCC 6538), Escherichia coli (ATCC 10536),
Pseudomonas aeruginosa (ATCC 15442) and Enterococcus
hirae (ATCC 10541) by at least 5 powers of ten. As
proof of antimicrobial action, reduction factors for
the live microbial count of at least 105 are not
required in every case and for the entire test
microbial spectrum. For antimicrobial action based on
the killing of test organisms, the level of
significance in the case of reduction factors of at
least 102 is to be applied, and it should not be
possible to discern gaps in activity against individual
relevant test microbes.
The formulation tested in each case was
investigated under the contamination simulated for
clean conditions (0.03% of bovine albumin). As a
departure from the stipulations of DIN EN 1276, a
higher microbial count of the test microbe suspension
was chosen to ensure that even in the case of the use
of a relatively large dilution step into the
neutralization medium (1:100 instead of 1:10), a
microbial count reduction around at least 5 powers of
ten could certainly be established. Over and above the
stipulations of the test procedure DIN EN 1276, the
test mixtures, if relevant, were evaluated over
CA 02320541 2000-09-25
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dilution series in order to also be able to include
numerically reduction factors for the live microbial
count of < 105.
For example, composition E1 under the chosen
test conditions was able to reduce the live microbial
counts of the test organisms in Staphylococcus aureus,
Escherichia coli and Enterococcus hirae to below the
determination limit intended by the test method, which
corresponds to reduction factors of > 105. Against the
Gram-negative test microbe Pseudomonas aeruginosa the
composition achieved a reduction factor in the live
microbial count of 4.6 103.
Under the chosen test conditions, the
compositions E2 and E3 were able to reduce the live
microbial count of all four test organisms to below the
determination limit provided by the test method, which
corresponds to reduction factors of > 105.
Compositions E4 to E51 essentially correspond
to compositions E2 and E3 in terms of their
antimicrobial action.
All three compositions thus exhibited
significant antimicrobial action against all test
microbes.
