Note: Descriptions are shown in the official language in which they were submitted.
CA 02320536 2000-09-25
1
MULTIPHASE CLEANER WITH ANTIMICROBIAL ACTION
Field of the Invention
The invention relates to multiphase liquid cleaners with
antimicrobial action which can be emulsified temporarily by
shaking, and which can be used for the cleaning of hard
surfaces, in particular glass, to a product comprising the
composition, and to a method for the cleaning and/or
disinfection or sanitation of hard surfaces.
Background of the Invention
The hard-surface cleaners customary today are usually
aqueous preparations in the form of a stable solution or
dispersion which comprise, as essential active ingredients,
surface-active substances, organic solvents and optionally
complexing agents for the hardness constituents of water,
abrasive substances and alkalis which have a cleaning
action. Cleaners intended primarily for the cleaning of
glass and ceramic surfaces are often formulated as solutions
of the active ingredient in a mixture of water and water-
miscible organic solvents, primarily lower alcohols and
glycol ethers. Examples of such compositions are given in
German laid-open application 22 20 540, US patent
specifications 3 839 234 and 3 882 038, and in European
patent applications 344 847 and 393 772.
In the case of the use of cleaners, in addition to the
requirement for high cleaning performance, as simple and
convenient as possible an application of the compositions is
also required. In most cases it is expected that the
compositions produce the desired effect even after a single
application without further measures. In this connection,
especially in the case of application to smooth surfaces, in
particular those like glass or ceramic which are able to
reflect in a sparkling manner, difficulties arise because
compositions which clean well in most cases do not dry
streak-free, while those compositions which dry essentially
CA 02320536 2000-09-25
2
without visible residues have only a limited cleaning
action.
In order, for an acceptable residue behavior, to achieve a
sufficient cleaning action, in particular against greasy
soilings, it is necessary to also add relatively large
amounts of more or less volatile alkalis in addition to
organic solvents to the cleaners. In this regard, ammonia
and alkanolamines in particular have been used. However,
relatively high concentrations of ammonia or amines bring
about, as well as a notable odor nuisance, a corresponding
increase in the pH in the cleaner solution with the
consequence that relatively sensitive surfaces, such as, for
example, paint surfaces, are significantly attacked by these
cleaners.
There therefore continues to be a need for cleaners which,
for a high cleaning performance, do not have said
disadvantages.
Moreover, in addition to the high primary detergency of such
a cleaner, an antimicrobial action is nowadays also
increasingly expected. To this end, antimicrobial active
ingredients, for example surface-active quaternary
compounds, are incorporated into the cleaners.
German laid-open application 39 10 170 describes
compositions, used as mouthwashes, for bacterial desorption
from solid surfaces and living tissue, which are in the form
of a 2-phase preparation and which, upon shaking, form a
temporary oil-in-water emulsion of limited life span, the
aqueous phase comprising about 50 to 97% by weight and the
water-immiscible oil phase about 3 to 50% by weight. A
content of about 0.003 to 2% by weight of an amphiphilic
cationic agent, for example a cationic surfactant, is
essential, in an amount which permits the formation of the
oil-in-water emulsion, this emulsion cracking and separating
CA 02320536 2000-09-25
3
about 10 seconds to 30 minutes after its formation. Anionic
surfactants impair the antibacterial action. Other
surfactants are not mentioned.
European patent application 0 195 336 describes care
compositions, which can be emulsified by shaking, for
sensitive surfaces, in particular plastic surfaces or
compact disks which, in addition to an aqueous phase, also
comprise an organic phase which consists of the
chlorofluorocarbon (CFC) 1,1,2-trichloro-1,2,2-tri-
fluoroethane. In addition, the compositions are free from
wax. However, because of their environment-damaging
properties, in particular in connection with the ozone hole,
the use of CFCs should be reduced or, better still, avoided.
German laid-open applications 195 O1 184, 195 O1 187 and
195 O1 188 (Henkel KGaA) disclose hair-treatment
compositions in the form of a 2-phase system, which have an
oil phase and a water phase, the oil phase preferably being
based on silicone oil, and which are temporarily miscible by
mechanical action.
Sua~ary of the Invention
The object of the present invention was then to provide
high-performance, storage-stable, easy-to-handle and
antimicrobially effective compositions for the cleaning of
hard surfaces.
In a first embodiment, the invention provides a liquid
multiphase cleaner having at least two continuous phases,
which has at least one aqueous phase I and a nonaqueous
liquid phase II which is immiscible with this aqueous phase,
and which can be converted temporarily into an emulsion by
shaking, and which comprises at least one antimicrobial
active ingredient.
CA 02320536 2000-09-25
4
For the purposes of the present invention, immiscible,
nonaqueous phase means a phase not based on water as
solvent, where, in the nonaqueous phase II, a certain
amount, based on phase II, of water of customarily no more
than 20% by weight, preferably no more than 15% by weight,
in particular no more than 10% by weight, particularly
preferably no more than 5% by weight, may be present in
completely dissolved form.
In the simplest case, a composition according to the
invention consists of a continuous aqueous phase which
consists of the entire phase I, and a continuous nonaqueous
liquid phase which consists of the entire 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, part of phase I is in the form of continuous phase
I, which represents the continuous aqueous phase of the
composition, and another part is emulsified as discontinuous
phase I in the continuous nonaqueous phase II. Analogous
statements apply for phase II and further continuous phases.
In a second embodiment, the invention provides a method for
the cleaning and/or disinfection or sanitation of hard
surfaces, in which a cleaner according to the invention is
converted temporarily into an emulsion by shaking, applied
to the surface to be cleaned and/or disinfected or
sanitized, preferably by spraying, and this surface is then
cleaned and/or disinfected or sanitized, if necessary by
wiping with an absorbent soft article.
For the purposes of the teaching according to the invention,
the terms disinfection, sanitation, antimicrobial action and
antimicrobial active ingredient have the customary
specialist meanings given, for example, by K.H. WallhauBer
in "Praxis der Sterilisation, Desinfektion - Konservierung:
Keimidentifizierung - Betriebshygiene" [Practice of
CA 02320536 2000-09-25
Sterilization, Disinfection - Preservation: Germ
Identification - Plant Hygiene] (5th edition - Stuttgart;
New York: Thieme, 1995). While disinfection in the narrower
sense of medical practice means the killing of, in theory
5 all, infection germs, sanitation means the elimination as
far as possible of all germs, including saprophytic ones
which are normally harmless for humans. In this connection,
the extent 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.
The compositions according to the invention exhibit separate
phases which can be emulsified for use, remain homogeneous
during use and then again form separate phases, and have an
antimicrobial action. Furthermore, as well as their high
detergency, the compositions according to the invention are
notable for an overall high storage stability. Thus, the
individual phases in the composition are stable over a long
period without the formation of, for example, deposits, and
conversion to a temporary emulsion remains reversible even
after frequent shaking. In addition, the physical form of
the compositions according to the invention avoids per se
the problem of stabilization of a composition formulated as
an emulsion. Separation of ingredients into separate phases
can additionally promote the chemical stability of the
composition. In addition, the compositions according to the
invention exhibit excellent residue behavior. Greasy
residues are largely avoided, meaning that the surface shine
is retained without rinsing being necessary.
Detailed Description of the Invention
The content of at least one antimicrobial active ingredient
in the composition according to the invention is usually
0.001 to 20% by weight, preferably 0.01 to 10% by weight, in
particular 0.02 to 5% by weight, particularly preferably
CA 02320536 2000-09-25
6
0.05 to 1.5% by weight and most preferably 0.1 to 0.5% by
weight.
The composition according to the invention comprises, for
the antimicrobial action, at least one antimicrobial active
ingredient, preferably chosen from the group of alcohols,
amines, aldehydes, antimicrobial acids or salts thereof,
carboxylic esters, acid amides, phenols, phenol derivatives,
diphenyls, diphenylalkanes, urea derivatives, oxygen-,
nitrogen-acetals and formals, benzamidines, isothiazolines,
phthalimide derivatives, pyridine derivatives, antimicrobial
surface-active compounds, guanidines, antimicrobial
amphoteric compounds, quinolines, 1,2-dibromo-2,4-di-
cyanobutane, iodo-2-propynylbutyl carbamate, iodine,
iodophores and peroxo compounds, halogen compounds and any
mixtures of the above.
Here, the antimicrobial active ingredient can be 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, dihydracetic acid, o-phenylphenol,
N-methylmorpholinium acetonitrile (MMA), 2-benzyl-
4-chlorophenol, 2,2'-methylenebis(6-bromo-4-chlorophenol),
4,4'-dichloro-2'-hydroxydiphenyl ether (dichlosan),
2,4,4'-trichloro-2'-hydroxydiphenyl ether (trichlosan),
chlorhexidine, N-(4-chlorophenyl)-N-
(3,4-dichlorophenyl)urea, N,N'-(1,10-decanediyldi-
1-pyridinyl-4-ylidene)bis(1-octanamine) dihydrochloride,
N,N'-bis-(4-chlorophenyl)-3,12-diimino-
2,4,11,13-tetraazatetradecanediimide amide, glucoprotamines,
antimicrobial surface-active quaternary compounds,
guanidines, including the bi- and polyguanidines, such as,
for example, 1,6-bis(2-ethylhexylbiguanidohexane)
dihydrochloride, 1, 6-di (N1,N1' -phenyldiguanido-NS,NS' ) hexane
tetrahydrochloride, 1, 6-di (N1,N1' -phenyl-N1,N1' -
methyldiguanido-NS,NS' ) hexane dihydrochloride, 1, 6-di (N1,N1' -
CA 02320536 2000-09-25
7
o-chlorophenyldiguanido- NS,NS')hexane dihydrochloride,
1, 6-di (N1,N1' -2, 6-dichlorophenyldiguanido-NS,NS' ) hexane
dihydrochloride, 1, 6-di [Nl,Nl' -~3- (p-methoxyphenyl) diguanido-
NS,NS' ] hexane dihydrochloride, 1, 6-di (N1,N1' -a-methyl-(3-
phenyldiguanido-NS,NS' ) hexane dihydrochloride, 1, 6-di (N1,N1' -
p-nitrophenyldiguanido-N5,N5')hexane dihydrochloride, co:w-
di (N1,N1' -phenyldiguanido-NS,NS' ) -di-n-propyl ether
dihydrochloride, w : cu' -di (Nl, Nl' -p-chlorophenyldiguanido-
N5, NS' ) -di-n-propyl ether tetrahydrochloride, 1, 6-di (Nl, Nl' -
2,4-dichlorophenyldiguanido-NS,NS')hexane
tetrahydrochloride, 1,6-di(N1,N1'-p-methylphenyldiguanido-
N5, NS' ) hexane dihydrochloride, 1, 6-di (N1, N1' -
2,4,5-trichlorophenyldiguanido-NS,NS')hexane tetra-
hydrochloride, 1, 6-di [N1,N1' -a- (p-chlorophenyl) ethyldi-
guanido-N5, NS' ] hexane dihydrochloride, w : cu' -di (Nl, Nl' -p-
chlorophenyldiguanido-NS,NS')-m-xylene dihydrochloride,
1, 12-di (N1,N1' -p-chlorophenyldiguanido-NS,NS' ) dodecane
dihydrochloride, 1, 10-di (N1,N1' -phenyldiguanido-NS,NS' ) decane
tetrahydrochloride, 1,12-di(N1,N1'-phenyldiguanido-
NS,NS' ) dodecane tetrahydrochloride, 1, 6-di (N1,N1' -o-
chlorophenyldiguanido-NS,NS')hexane dihydrochloride, 1,6-di-
(N1,N1' -o-chlorophenyldiguanido-NS,NS' ) hexane
tetrahydrochloride, ethylenebis(1-tolylbiguanide),
ethylenebis(p-tolylbiguanide), ethylene-
bis(3,5-dimethylphenylbiguanide), ethylenebis(p-tert-
amylphenylbiguanide), ethylenebis(nonylphenylbiguanide),
ethylenebis(phenylbiguanide), ethylenebis(N-
butylphenylbiguanide), ethylenebis(2,5-dyethoxyphenyl-
biguanide), ethylenebis(2,4-dimethylphenylbiguanide),
ethylenebis(o-diphenylbiguanide), ethylenebis(mixed amyl-
naphthylbiguanide), N-butylethylenebis(phenylbiguanide),
trimethylenebis(o-tolylbiguanide), N-butyl-
trimethylenebis(phenylbiguanide) and the corresponding
salts, such as acetates, gluconates, hydrochlorides,
hydrobromides, citrates, bisulfites, fluorides,
polymaleates, N-cocoalkyl sarcosinates, phosphites,
hypophosphites, perfluorooctanoates, silicates, sorbates,
CA 02320536 2000-09-25
8
salicylates, maleates, tartrates, fumarates,
ethylenediaminetetraacetates, iminodiacetates, cinnamates,
thiocyanates, arginates, pyromellitates,
tetracarboxybutyrates, benzoates, glutarates, mono-
fluorophosphates, perfluoropropionates and any mixtures
thereof. Also suitable are halogenated xylol and cresol
derivatives, such as p-chlorometacresol or p-chlorometa-
xylol, amphoteric agents, and natural antimicrobial active
ingredients of vegetable origin (e. g. from spices or herbs)
or of animal origin, and microbial origin. Preference may be
given to using antimicrobially active surface-active
quaternary compounds, a natural antimicrobial active
ingredient of vegetable origin and/or a natural
antimicrobial active ingredient of animal origin, most
preferably at least one natural antimicrobial active
ingredient of vegetable origin from the group which includes
caffeine, theobromine and theophylline and essential oils
such as eugenol, thymol and geraniol, and/or at least one
natural antimicrobial active ingredient of animal origin
from the group which includes enzymes such as milk protein,
lysosyme and lactoperoxidase, and/or at least one
antimicrobially active surface-active quaternary compound
having an ammonium, sulfonium, phosphonium, iodonium or
arsonium group, peroxo compounds and chlorine compounds.
Substances of microbial origin, so called bacteriocines, can
also be used.
In a preferred embodiment, the composition according to the
invention comprises at least one quaternary ammonium
compound (QAC) with antimicrobial action according to the
general formula (R1) (Rz) (R3) (R4) N+ X-, in which R1 to R4 are
identical or different Cl-C22-alkyl radicals, C~-Cz8-aralkyl
radicals or heterocyclic radicals, where two, or in the case
of an aromatic incorporation as in pyridine, even three
radicals, together with the nitrogen atom, form the
heterocycle, e.g. a pyridinium or imidazolinium compound,
and X- are halide ions, sulfate ions, hydroxide ions or
CA 02320536 2000-09-25
9
similar anions. For optimal antimicrobial action, preferably
at least one of the radicals has a chain length of from 8 to
18, in particular 12 to 16, carbon atoms.
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
hydroxysubstituted alkyl radicals are less reactive and are
preferably quaternized using dimethyl sulfate.
Examples of suitable QACs are benzalkonium chloride
(N-alkyl-N,N-dimethylbenzylammonium chloride, CAS No. 8001-
54-5), benzalkone B (m,p-dichlorobenzyldimethyl-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), benzetonium
chloride (N,N-dimethyl-N- [2 [2- [p-
(1,1,3,3-tetramethylbutyl)phenoxy]ethoxy]ethyl]benzyl-
ammonium chloride, CAS No. 121-54-0), dialkyl-
dimethylammonium chlorides such as di-n-decyl-
dimethylammonium 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 having C8-C18-alkyl radicals, in
particular C12-C14-alkylbenzyldimethylammonium chloride.
Benzalkonium halides and/or substituted benzalkonium halides
are, for example, commercially available as Barquat~ ex
Lonza, Marquat~ ex Mason, Variquat~ ex Witco/Sherex and
CA 02320536 2000-09-25
Hyamine~ ex Lonza, and Bardac~ ex Lonza. Further
commercially available antimicrobial active ingredients are
N-(3-chloroallyl)hexaminium chloride such as Dowicide~ and
Dowicil~ ex Dow, benzethonium chloride such as Hyamine~ 1622
5 ex Rohm & Haas, methylbenzethonium chloride such as Hyamine~
lOX ex Rohn & Haas, cetylpyridinium chloride such as cepacol
chloride ex Merrell Labs.
In a particular embodiment of the invention, the composition
10 comprises two or more antimicrobial active ingredients, in
particular at least one water-soluble antimicrobial active
ingredient in phase I, for example a surface-active
quaternary compound such as benzalkonium chloride and/or an
antimicrobial acid such as benzoic acid or salicylic acid,
and at least one further antimicrobial active ingredient in
phase II, for example an essential oil such as eugenol,
thymol or geraniol.
In a further preferred embodiment of the invention, the
composition is essentially CFC-free, i.e. the nonaqueous
liquid phase II is not based on CFCs. In this connection,
because of the negative environmental effects of these
compounds, the compositions according to the invention
preferably comprise no CFCs at all, where small amounts,
based on the overall composition, of up to about 5% by
weight can still be tolerated.
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 40% by volume, in particular 0.2 to 35% by volume,
particularly preferably 0.5 to 30% by volume, most
preferably 1 to 20% by volume, based on the volume of the
respective continuous phase, of the other phase in each case
CA 02320536 2000-09-25
11
as dispersant. Here, the continuous phase I or II is then
reduced by the part by volume which is distributed as
dispersant in the other phase in each case. Particular
preference is given here to compositions in which phase I is
emulsified in phase II in amounts of from 0.1 to 40% by
volume, in particular 0.2 to 35% by volume, for example
about 33% 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, preferably sharp, interfaces, one upper and one lower,
from the parts of the phases I and II not involved in the
emulsion.
The compositions according to the invention preferably
comprise 5 to 95% by volume of phase I and 95 to 5% by
volume of phase II.
In a further preferred embodiment of the invention, the
composition comprises 35 to 95% by volume of phase I and 5
to 65% by volume of phase II, in particular 55 to 95% by
volume of phase I and 5 to 45% by volume of phase II, most
preferably 70 to 90% by volume of phase I and 10 to 30% by
volume of phase II, for example 75, 80 or 85% by volume of
phase I and 25, 20 or 15% by volume of phase II. In
addition, the continuous phase I preferably represents the
lower phase, and the continuous phase II the upper phase.
In a likewise preferred embodiment, the water-immiscible
phase II is based on aliphatic petroleum hydrocarbons and/or
terpene hydrocarbons. The petroleum hydrocarbons preferably
have a boiling point range from 130 to 260°C, in particular
from 140 to 240°C, particularly preferably from 150 to
220°C, such as, for example, the Cg_lg-isoparaffins having a
boiling point range from 184 to 217°C, available, for
CA 02320536 2000-09-25
12
example, as She11so1~ T from Deutsche Shell Chemie AG
(Eschborn). Preferred terpene hydrocarbons are citrus oils
such as the orange oil obtained from the skin of oranges,
the orange terpenes present therein, in particular limonene,
or pine oil, the tall oil extracted from roots and stumps,
and mixtures thereof. Phase II can also consist entirely of
aliphatic petroleum hydrocarbons and/or terpene
hydrocarbons. In this connection, phase II comprises
petroleum hydrocarbons preferably in amounts of from 60 to
100% by weight, particularly preferably 90 to 99.99% by
weight, in particular 95 to 99.9% by weight, most preferably
97 to 99% by weight.
Suitable surface-active substances for the compositions
according to the invention are surfactants, in particular
from the classes of anionic and nonionic surfactants. The
compositions preferably comprise one or more anionic and/or
nonionic surfactants, where the anionic surfactants are in
particular present in phase I. The amount of anionic
surfactant, based on the phase I, is usually no more than
10% by weight, preferably between 0.01 and 5% by weight, in
particular between 0.01 and 0.5% by weight, particularly
preferably between 0.1 and 0.3% by weight. If the
compositions comprise nonionic surfactants, the
concentration thereof preferably in phase I, based on phase
I, is usually no greater than 3% by weight, preferably
between 0.001 and 0.3% by weight and in particular between
0.001 and 0.1% by weight, and in phase II, based on phase
II, is usually no greater than 5% by weight, preferably
between 0.001 and 0.5% by weight and in particular between
0.001 and 0.2% by weight, particularly preferably between
0.005 and 0.1% by weight, most preferably between 0.01 and
0.05% by weight.
Suitable as one or more anionic surfactants are preferably
C8-C1$-alkylbenzenesulfonates, in particular having about 12
carbon atoms in the alkyl moiety, C8-C2o-alkanesulfonates,
CA 02320536 2000-09-25
13
Ce-C18-monoalkyl sulfates, C$-C18-alkyl polyglycol ether
sulfates having 2 to 6 ethylene oxide units (EO) in the
ether moiety and sulfosuccinates having 8 to 18 carbon atoms
in the alcohol radicals, and mixtures thereof.
The anionic surfactants are preferably used as sodium salts,
but can also be present as other alkali metal or alkaline
earth metal salts, for example magnesium salts, and in the
form of ammonium or amine salts.
Examples of such surfactants are sodium cocoalkyl sulfate,
sodium sec-alkanesulfonate having about 15 carbon atoms and
sodium dioctyl sulfosuccinate. Fatty alkyl sulfates having
12 to 14 carbon atoms, and also sodium lauryl ether sulfate
having 2 EO have proven particularly suitable.
However, in accordance with the above quantitative data, if
cationic antimicrobial active ingredients, such as surface-
active quaternary compounds, in particular quaternary
ammonium compounds, are used, the compositions preferably
comprise as low as possible a content of anionic surfactant
including soaps and, in a particularly preferred embodiment
of the invention, are entirely free from anionic surfactants
including soaps, since the latter are frequently more or
less incompatible with the antimicrobially active quaternary
compounds. In this connection, it is self-evident for the
person skilled in the art that he or she must verify the
compatibility of the anionic surfactants with the
antimicrobial active ingredients with regard to the germ-
reducing action.
Nonionic surfactants which may be mentioned are especially
C8-C18-alcohol polyglycol ethers, i.e. ethoxylated alcohols
having 8 to 18 carbon atoms in the alkyl moiety and 2 to 15
ethylene oxide units (EO), Ce-C18-carboxylic polyglycol
esters having 2 to 15 EO, ethoxylated fatty acid amides
having 12 to 18 carbon atoms in the fatty acid moiety and 2
CA 02320536 2000-09-25
14
to 8 EO, long-chain amine oxides having 14 to 20 carbon
atoms and long-chain alkyl polyglycosides having 8 to 14
carbon atoms in the alkyl moiety and 1 to 3 glycoside units.
The compositions preferably comprise one or more nonionic
surfactants from the group of ethoxylates of longer-chain
alcohols, alkyl polyglycosides and mixtures thereof.
Examples of such surfactants are oleyl cetyl alcohol having
5 EO, nonylphenol having 10 EO, lauric acid dyethanolamide,
cocoalkyldimethylamine oxide and cocoalkyl polyglucoside
having, on average, 1.4 glucose units.
Preferred nonionic surfactants in the aqueous phase are, as
well as the addition products of ethylene oxide and longer-
chain alcohols, in particular fatty alcohols, having in
particular 4 to 8 ethylene oxide units, the alkyl
polyglycosides, and of these in turn the representatives
having 8 to 10 carbon atoms in the alkyl moiety and up to 2
glucose units. In the nonaqueous phase II particularly
preferred nonionic surfactants are fatty alcohol polyglycol
ethers having in particular 2 to 8 EO, for example oleyl
cetyl alcohol + 5 EO ether, and/or fatty acid polyglycol
esters (FAE) having in particular 2 to 10 EO, for example
tallow fatty acid + 6 EO ester. Furthermore, in the case of
the nonionic surfactants, in particular the alcohol
polyglycol ethers and carboxylic polyglycol esters, for
phase II, the degree of ethoxylation is matched to the
carbon chain length such that relatively short carbon chains
having lower degrees of ethoxylation, or relatively long
carbon chains having relatively high degrees of ethoxylation
are combined.
In a particular embodiment of the invention, the
compositions comprise one or more anionic and nonionic
surfactants. In this connection, combinations of anionic
surfactant in phase I and nonionic surfactant in phase II
are particularly advantageous, for example combinations of
fatty alcohol sulfates and/or fatty alcohol polyglycol ether
CA 02320536 2000-09-25
sulfates in phase I with fatty alcohol polyglycol ethers
and/or FAEs in phase II, in particular C12_C14-fatty alcohol
sulfates and/or Cl2_C14-fatty alcohol polyglycol ether
sulfates having, preferably, 2 ethylene oxide units (EO) in
5 phase I and nonionic surfactant, in particular C16_Cla-fatty
alcohol polyglycol ethers having, preferably, 2 to 8 EO
and/or C14_Cla-fatty acid polyglycol esters having,
preferably, 2 to 10 EO, in phase II.
10 Furthermore, the cleaners according to the invention can
comprise one or more water-soluble organic solvents. The
amount of one or more organic solvents in phase I is
preferably 0.1 to 15% by weight, in particular 1 to 10% by
weight, particularly preferably 2 to 8.5% by weight, most
15 preferably 4 to 7% by weight, for example about 5 or 6% by
weight, based on the aqueous phase I.
Examples of suitable solvents are water-soluble hydrocarbons
having one or more hydroxyl groups, preferably the alcohols
and glycols having 2 to 6 carbon atoms, in particular 2 or 3
carbon atoms, and ethers thereof in the form of the glycol
ethers or ether alcohols, and mixtures thereof.
The alcohols used are in particular ethanol, isopropanol and
n-propanol. Suitable ether alcohols are sufficiently water-
soluble compounds having, preferably, no more than 10 carbon
atoms in the molecule. Examples of such ether alcohols are
ethylene glycol monobutyl ether, propylene glycol monobutyl
ether, dyethylene glycol monobutyl ether, propylene glycol
monotertiary-butyl ether and propylene glycol monoethyl
ether, of which, in turn, ethylene glycol monobutyl ether
and propylene glycol monobutyl ether are preferred. If
alcohol and ether alcohol are used alongside one another,
the weight ratio of the two is preferably between 1:2 and
4:1. Ethanol is particularly preferred for the purposes of
the invention.
CA 02320536 2000-09-25
16
In a preferred embodiment, the composition according to the
invention comprises one or more water-soluble organic
solvents from the group of lower alcohols having 2 or 3
carbon atoms, of glycols having 2 or 3 carbon atoms and of
glycol ethers having up to 10 carbon atoms, and mixtures
thereof, in particular ethanol.
The compositions can be converted into the emulsion
temporary in accordance with the invention by shaking
preferably up to three times, in particular up to twice,
particularly preferably once, the temporary emulsion
generated by shaking being stable over a period sufficient
for convenient application of the composition of from about
0.5 to 10 min, preferably 1 to 5 min, in particular 1.5 to
4 min, i.e. on the one hand does not crack again directly
after shaking has finished, and on the other hand does not
persist over a relatively long period. In this connection,
stable means that after the respective time, at least 90% by
volume of the composition is still in the form of the
temporary emulsion generated by shaking. As well as the
selection and concentration of the base components and
active components, a rule for adjusting the ultimate
properties of the compositions according to the invention
consists in controlling the viscosity of the individual
phases.
The aqueous phase I preferably has a viscosity according to
Brookfield (model DV-II+, spindle 31, rate of rotation
20 min-1, 20°C) of 0.1 to 200 mPa~s, in particular 0.5 to
100 mPa~s, particularly preferably 1 to 60 mPa~s and most
preferably 5 to 20 mPa~s. For this purpose, the composition
or the phases present may comprise one or more viscosity
regulators. The amount of viscosity regulator in phase I,
based on phase I, is usually up to 0.5% by weight,
preferably 0.001 to 0.3% by weight, in particular 0.01 to
0.2% by weight, most preferably 0.02 to 0.1% by weight.
Suitable viscosity regulators are inter alia synthetic
CA 02320536 2000-09-25
17
polymers such as the homo- and/or copolymers of acrylic acid
or derivatives thereof, and salts thereof, for example the
products available under the trade name Carbopol~ from
Goodrich, in particular the crosslinked acrylic acid
copolymer Carbopol~ EDT 2623. International application
WO 97/38076, to which reference is made in this respect and
the contents of which are hereby incorporated into this
application, lists a number of other polymers derived from
acrylic acid which are likewise suitable viscosity
regulators.
Furthermore, the compositions according to the invention can
comprise volatile alkali in phase I. As such alkali, ammonia
and/or one or more alkanolamines which can contain up to 9
carbon atoms in the molecule are preferred. Preferred
alkanolamines are the ethanolamines, and of these in turn
monoethanolamine. The content of ammonia and/or alkanolamine
is, based on phase I, preferably 0.01 to 3% by weight, in
particular 0.02 to 1% by weight, particularly preferably
0.05 to 0.5% by weight.
In addition to the volatile alkali, the compositions
according to the invention can additionally comprise
carboxylic acid in phase I, the equivalent ratio of amine
and/or ammonia to carboxylic acid preferably being between
1:0.9 and 1:0.1. Suitable carboxylic acids have up to 6
carbon atoms and are mono-, di- or polycarboxylic acids.
Depending on the equivalent weight of amine and carboxylic
acid, the content of carboxylic acid, based on phase I, is
preferably between 0.01 and 2.7% by weight, in particular
between 0.01 and 0.9% by weight. Examples of suitable
carboxylic acids are acetic acid, glycolic acid, lactic
acid, citric acid, succinic acid and adipic acid, of which
preference is given to using acetic acid, citric acid and
lactic acid. Particular preference is given to using acetic
acid.
CA 02320536 2000-09-25
18
In addition to said components, the compositions according
to the invention can comprise further auxiliaries and
additives as are customary in such compositions. These
include, in particular, dyes, perfume oils, pH regulators
(e. g. citric acid, alkanolamines or NaOH), preservatives,
complexing agents for alkaline earth metal ions, enzymes,
bleach systems and antistats. The amount of such additives
is usually no more that 2~ by weight in the cleaner. The
lower use limit depends on the nature of the additive and,
for example in the case of dyes, can be up to 0.001 by
weight and below. The amount of auxiliaries is preferably
between 0.01 and 1% by weight.
The pH of the aqueous phase I 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 - either known
to the person skilled in the art or accessible by routine
experiments - of the antimicrobial action of the
antimicrobial active ingredients) used is to be taken into
consideration. Thus, the pH is to be chosen accordingly to
be as optimal as possible for the antimicrobial action of
the respective antimicrobial active ingredients) and/or if
a certain pH is prescribed for a certain cleaning purpose of
the antimicrobial active ingredient(s).
In a neutral variant, the pH is greater than 6 to less than
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 for moderate alkalinity or greater than 9 to 10.5, 11 or
even 12, e.g. 10, for stronger alkalinity. This is preferred
particularly if antimicrobial quaternary compounds are used,
since the antimicrobial action thereof usually increases
CA 02320536 2000-09-25
19
with increasing pH, while it is sometimes completely absent
in the acid range below a pH of 3.
In a likewise preferred embodiment of the invention, the
compositions are rendered acidic with a pH of from 1 to 6,
preferably 1.5 to 5.5, in particular 2 to 5, particularly
preferably 2.2 to 4.5, for example 2.3, 3 or 4. This is
preferable, for example, if salicylic acid is used as the
antimicrobial active ingredient since the antimicrobial
action thereof usually increases with decreasing pH.
In a preferred embodiment, the compositions according to the
invention 95% by volume, in particular 70
comprise to
70 to
90% by phase I comprising
volume,
of aqueous
0 to 10% by weight anionic surfactant,
of
0 to 3% by weight nonionic surfactant,
of
0 to 2% by weight at least one antimicrobial active
of
ingredient,
0 to 10% by weight water-soluble organic solvent,
of
0 to 0.5% by weight viscosity regulator,
of
0 to 3% by weight volatile alkali,
of
0 to 0.2% by weight perfume and
of
ad 100% by weight water, and
of
5 to 30% by volume,
in particular
10 to
30% by
volume,
of nonaqueous
phase
II comprising
0 to 100% by weight aliphatic petroleum hydrocarbons,
of
0 to 100% by weight terpene hydrocarbons,
of
0 to 10% by weight at least one antimicrobial active
of
ingredient,
0 to 5% by weight nonionic surfactant and
of
0 to 1% by weight perfume,
of
where the
% by
weight
figures
are
based
on
the
respective
phase, the
sum
of
the
petroleum
and
terpene
hydrocarbons
makes up phase by weight, at least one of the two
II
ad
100%
phases I and II comprises at least one antimicrobial active
ingred ient an
in amount,
based
on
the
respective
phase,
of
more han by weight,
t 0% and the
phases
may additionally
CA 02320536 2000-09-25
comprise in particular small amounts of dye. Particularly
preferably, the anionic surfactants are present in amounts
of from 0.01 to 5% by weight, preferably 0.01 to 0.5% by
weight, in particular 0.1 to 0.3% by weight, and/or the
nonionic surfactants are present in amounts of from 0.001 to
0.5% by weight, preferably 0.005 to 0.1% by weight, in
particular 0.01 to 0.05% by weight.
The composition according to the invention is sprayable and
can therefore be used in a spray dispenser.
Thirdly, the invention accordingly 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 having a container made of 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 regard
and the contents of which are hereby incorporated into this
application.
The compositions according to the invention are preferably
used by applying the composition converted temporarily into
an emulsion by shaking in amounts of about 1.5 to 10 g per
m2, in particular 3 to 7 g per m2, to the surface to be
cleaned and/or disinfected or sanitized, and directly
thereafter wiping this surface with an absorbent soft
article and cleaning and/or disinfecting or sanitizing it in
the process. The compositions are preferably applied using
suitable spray devices, in particular a spray dispenser or a
CA 02320536 2000-09-25
21
product according to the invention in order to achieve as
uniform a distribution as possible. Sponges or cloths in
particular are suitable for the wiping, which, in the case
of treatment of relatively large surfaces, can be rinsed out
with water from time to time.
The compositions according to the invention can be prepared
by separately mixing the individual phases directly from
their raw materials, subsequently combining and thoroughly
mixing the phases and finally allowing the composition to
stand for separation of the temporary emulsion. They can
also be prepared by mixing directly from their raw
materials, subsequently thoroughly mixing and finally
allowing the composition to stand for separation of the
temporary emulsion. If one component is not entirely
insoluble in a phase other than that to which the respective
component has been assigned or with which it has been
incorporated into the composition, this other phase may also
comprise corresponding proportions of the component in
question within the framework of the establishment of
solubility equilibria as a result of diffusion.
CA 02320536 2000-09-25
22
The makeup of the compositions E1 and E2 according to the
invention, given by way of example, is given in Table 1. The
aliphatic petroleum hydrocarbon used was Cg-13-isoparaffins.
The compositions comprised a transparent aqueous phase I at
the bottom and a creamy emulsion of phase I in nonaqueous
phase II at the top, the volume of emulsified phase I in
each case constituting about one third of the volume of
phase II, in a volume ratio of phase I to the emulsion of
phase I in phase II of about 80 to 20 and separated by a
sharp interface. The temporary emulsion generated by shaking
remained stable over a period of about 3 min, sufficient for
the easy application of the composition, after which the
phases separated again.
Composition [$ by weight] E1 E2
C12-14-alkylbenzyldimethylammonium
chloride 0.02 -
Salicylic acid - 0.9
Ca-lo-alkyl 1.5 glucoside 0.2 -
Sodium C12-14 fatty alcohol sulfate - 0.2
Ethanol 4.8 4.8
Crosslinked acrylic acid copolymer~a~ 0.025 0.025
Aliphatic petroleum hydrocarbon~b~ 15 15
Aqueous ammonia solution, 25%
strength by weight 0.046 0.046
Perfume 0.06 0.06
Dye < 0.001 < 0.001
Water ad 100 ad 100
pH of phase I 10 2.3
~a~ Carbopol~ ETD 2623
~b~ She11so1~ T
