Europaisches Patentamt

(19) European Patent Office

Office europeen
peen des brevets
brevets EP 0 379 256 B1

(12) E U R O P E A N PATENT S P E C I F I C A T I O N

(45) Date of publication and mention (51) mt ci.6: C1 1 D 1/825, C1 1 D 3/20,

of the grant of the patent: C1 1 D 3 / 4 8
15.05.1996 Bulletin 1996/20

(21) Application number: 90200105.6

(22) Date of filing: 16.01.1990

(54) Acidic disinfectant all-purpose liquid cleaning composition

Saure, desinfizierende flussige Allzweckreinigungsmittel
Detergents acides, disinfectants et liquides pour tous usages

(84) Designated Contracting States: • Wisniewski, Karen Lee

AT BE CH DE DK ES FR GB IT LI LU NL SE Bound Brook, New Jersey (US)
• Rao, Nandakumar Seshagiri
(30) Priority: 17.01.1989 US 297807 Hockessin, Delaware (US)

(43) Date of publication of application: (74) Representative:

25.07.1990 Bulletin 1990/30 Smulders, Theodorus A.H.J., Ir. et al
Vereenigde Octrooibureaux
(73) Proprietor: Colgate-Palmolive Company Nieuwe Parklaan 97
New York, N.Y. 10022-7499 (US) NL-2587 BN 's-Gravenhage (NL)

(72) Inventors: (56) References cited:

• Cook, William Jimmy GB-A- 2 106 927 GB-A- 2 203 339
New York, New York (US) JP-A-53 021 205 US-A- 3 753 916
• Dixit, Nagaraj Shripad US-A- 4 532 066 US-A- 4 648 987
Plainsboro, New Jersey (US)

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CO Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give
notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in
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a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art.
a.
99(1) European Patent Convention).
LU
Printed byJouve, 75001 PARIS(FR)
 EP 0 379 256 B1

Description

FIELD OF THE INVENTION

5 The present invention relates to the formulation of a stable, acidic disinfectant all-purpose liquid cleaning compo-
sitions for use on hard surfaces. The compositions are effective in removing soap scum, fatty deposits and mineral
deposits while simultaneously disinfecting the hard surfaces being cleaned. Cleaning is provided by incorporation of
a lower alkyl mono and/or dicarboxylic organic acid and an acid-stable nonionic surfactant system consisting essentially
of an acid stable water-soluble nonionic surfactant and an acid stable water-dispersible nonionic surfactant. The pH
10 of the composition is about 2-4 and preferably 2.5-3.0. Disinfecting properties are provided by incorporation of an acid-
stable, water soluble disinfectant compound such as a germicidal quaternary ammonium compound, chlorhexidine or
glutaraldehyde. A cationic or anionic soil-releasing agent which is substantive to the cleaned surfaces is preferably
included in the compositions of the invention to facilitate removal of soils such as soap scum during subsequent clean-
ings of the surface.
15
BACKGROUND OF THE INVENTION

The prior art is replete with liquid all purpose hard surface cleaning compositions which are generally comprised
of two types. The first type is a particulate aqueous suspension having water-insoluble abrasive particles suspended
20 therein, which particles are palpable. Some of the cleaners of this type suffer a stability problem while others have
received poor acceptance by consumers because of their "gritty" feel which causes many people to be reluctant to use
them for fear of scratching the surface to be cleaned. The second type is the liquid detergent without suspended
abrasive and this latter type is often preferred by consumers. While the liquid hard surface cleaner without abrasives
is generally a mixture of a surfactant and builder salt in an aqueous medium, the product formulations in the market
25 place have varied widely in composition.
The presence of builder salts as an essential ingredient in all purpose hard surface cleaning compositions to
improve cleaning and to maintain an alkaline pH range, is disclosed in U.S. Patents 4,576,738 and 4,597,887, and in
European Patent Applications 0165885 and 0080749 and in UK Patent Application 2166153A.
However, these prior art all-purpose liquid detergents containing detergent builder salts or other equivalents tend
30 to leave films, spots or streaks on cleaned unrinsed surfaces, particularly shiny surfaces such as glass or stainless
steel. Thus, such liquids require thorough rinsing of the cleaned surfaces which is a time-consuming chore for the user.
In order to overcome the problem of rinsing associated with the prior art all-purpose liquids, U.S. Patent No.
4,017,409 teaches that paraffin sulfonate with a reduced concentration of inorganic phosphate builder salt may be
employed. However, such compositions are often unacceptable from an environmental point of view based upon the
35 phosphate content. Phosphate-free all-purpose liquids have been disclosed which contain a major proportion of a
mixture of anionic and nonionic detergents with minor amounts of glycol ether solvent and organic amine as shown in
U.S. Patent No. 3,935,130. This approach has not been completely satisfactory due to excessive foaming from the
high levels of organic detergents necessary to achieve cleaning and due to deposition of soap residue on the cleaned
surfaces, leading to residual streaks and spots.
40 In order to overcome the disadvantages associated with the builder salts, Japanese Patent Kokai 52-77111 and
European Patent Application 0,151 ,517 have used organic acids to improve detergency of builder-free detergent com-
positions. These compositions also contain an organic solvent as an essential ingredient which functions to dissolve
greasy soil and soap scum, i.e., to improve detergency. Japanese patent 52-77111 uses one or more organic acids
selected from the group consisting of glycolic acid, lactic acid, citric acid, malic acid and malonic acid. European Patent
45 Application 0,151,517 uses at least one water-soluble dicarboxylic acid having a 5-7 carbon chain length, which includes
glutaric, adipic and pimelic acids.
The inclusion of a grease-removing organic solvent in an all purpose liquid cleaner composition for the degreasing
of hard surfaces, is also disclosed in the above cited patents as well as others. Cleaning compositions containing a
high boiling water-miscible organic solvent such as propylene glycol or ethylene glycol-monobutyl ether are disclosed
so in GB Patent 2166153A; a binary solvent system of Pinane and an ethylene glycol - or propylene glycol - monoethyl
or monobutyl ether is disclosed in U.S. Patents 4,576,738 and 4,597,887; a dual solvent system of dipropylene glycol
methyl ether and mineral spirits is disclosed in U.S. Patent 4,673,524; and a propylene glycol monomethyl ether and/or
dipropylene glycol monomethyl ether as a penetrant to penetrate road film is disclosed in U.S. Patent 4,670,171 .
The prior art also discloses acidic liquid cleaning compositions containing organic solvents. A microemulsion-based
55 acid composition containing phosphoric ester surf actants, hydrocarbon solvents and phosphoric acid for use as an
all-purpose metal surface cleaner is disclosed in U.S. Patent 4,540,448. U.S. Patent 4,501,680 discloses an acidic
liquid detergent for cleaning ceramic tiles without eroding the grout between the tiles. This composition contains two
acids (i.e., glutaric acid and phosphoric acid), a nonionic surfactant, and an organic solvent.

2
 EP 0 379 256 B1

However, none of the above-cited prior art, including the acidic all purpose cleaners, provides cleaning composi-
tions which simultane- ously disinfect the hard surfaces being cleaned.
However, non-acidic disinfectant compositions containing the combination of a quaternary ammonium germicidal
compound and a nonylphenolethylene oxide condensate in an aqueous solution are disclosed in U.S. Patent No.
5 3,01 7,278 for use in sterilizing medical and dental instruments and in U.S. Patent No. 3,052,604 for direct application
to human and animal tissue surfaces to promote wound healing.
Also, U.S. Patent No. 3,223,643 discloses a liquid acid detergent-sanitizer composition of pH 2.5 - 3.5 containing
phosphoric acid, a C8-C18alkyl dimethyl benzyl ammonium chloride sanitizer, and an alkylaryl polyether alcohol having
about 5 to 7.5 ethylene oxide units. The nonionic detergent and the quaternary ammonium compound are in a 1:1 ratio
10 in the disclosed compositions.
U.S. Patent No. 4,661 ,523 discloses a concentrated acidic disinfectant composition having a pH of 3.5-4 which
contains a synergistic bactericidal mixture of aldehydes and a quaternary ammonium compound, phosphonocarboxylic
acid, and an amino-polycarboxylic acid salt, in an aqueous or aqueous-organic solvent vehicle.
German Patent Appln. 3445901 discloses a disinfectant agent concentrate in an aqueous or aqueous-organic
is solvent medium containing a synergistic mixture of hydrogen peroxide, a quaternary ammonium compound, a biguanide
as the antimicrobial disinfectant agent, a complexing agent such as alkane poly-phosphonic acids and salts thereof to
stabilize the hydrogen peroxide, an acid such as boric acid or phosphoric acid in an amount to provide a pH of 3-7 and
optionally a nonionic and/or amphoteric surfactant.
U.S. Patent No. 3,223,643, U.S. Patent No. 4,661 ,523and German Patent Appln. 3445901 are all acidic disinfecting
20 cleaners. However, all of these prior art compositions incorporate phosphate acids and consequently have associated
problems concerning environmental safety.
US-A-4 648 987 describes a laundry prewash composition, which includes a cosurfactant system with a hydro-
phobic nonionic surfactant and a hydrophilic nonionic surfactant.
In US-A-4 532 066 acidic aqueous polishing cleansers are described which comprise an oxalate salt, and which
25 are weakly acidic.
GB-A-2 106 927 relates to a thickened liquid toilet bowl cleaner comprising an organic acid.
None of the above-mentioned disinfectant cleaning compositions provide a stable acidic disinfectant all-purpose
liquid cleaning composition with improved removal of soap scum in the absence of detergent builders, organic solvents
and phosphate compounds. In addition, unlike the cleaning compositions of the present invention, the prior art corn-
so positions are unable to provide a cleaned surface such that the removal of soil during subsequent cleanings is signif-
icantly enhanced.

SUMMARY OF THE INVENTION

35 It has been found that a stable homogenous, acidic disinfectant all-purpose liquid cleaning composition having
improved cleaning and disinfecting properties with minimal damage to hard surfaces can be prepared in accordance
with the present invention in the absence of a builder salt and an organic solvent. The compositions comprise (a) from
about 0.5-4% by weight of a nonionic surfactant system containing a mixture of an acid stable water soluble nonionic
surfactant and an acid stable water dispersible nonionic surfactant in approximately a 4:1 to 4:3 ratio by weight of
40 soluble to dispersible surfactant; (b) at least 0.1% by weight of an acid stable disinfectant compound; (c) about 3-7%
by weight of an organic acid selected from the group consisting of a C-,_6 aliphatic monocarboxylic acid, dicarboxylic
acid and mixtures thereof, and; (d) optionally 0-2% of an acid stable cationic or anionic soil releasing agent, in an
aqueous medium. The liquid cleaning compositions have a pH of approximately 2-4 and may be in the form of dilute
solutions or dilute microemulsions. These acidic cleaning compositions are particularly suitable for cleaning hard sur-
45 faces such as plastic, vitreous and metal surfaces, and more specifically grout, stainless steel, glass and ceramic tile.
The instant novel liquid cleaner penetrates soil efficiently, spreads quickly and disinfects with little or no damage to the
hard surfaces being cleaned. The present compositions exhibit improved efficacy in removing soap scum and mineral
deposits and, therefore, have particular utility in the cleaning of bathrooms and kitchens.
Accordingly, the primary object of the present invention is to provide an acidic disinfectant liquid cleaning compo-
50 sition which effectively disinfects and removes soils, particularly soap scum and mineral deposits, from hard surfaces
without damaging the cleaned surface. An additional object of the invention is to provide said acidic disinfectant liquid
cleaning composition also containing a surface soil releasing agent functional at acid pH to facilitate removal of soil
during subsequent cleanings of the previously cleaned surface.
In a preferred embodiment of the invention, the liquid all purpose disinfectant cleaning compositions comprise, by
55 weight, about 2-4% of a nonionic detergent system wherein the ratio of acid-stable water soluble nonionic surfactant
to acid-stable water dispersible nonionic surfactant is about 3:1 to 3:2, at least 0.1% of a water soluble, acid stable
germicidal or antimicrobial compound, about 3-5% of a C-,_6 aliphatic dicarboxylic acid mixture, about 0.25-1% of an
acid stable cationic or anionic soil release treatment agent in an aqueous medium, said liquid cleaning composition

3
 EP 0 379 256 B1

having a pH of about 2.5-3.

DETAILED DESCRIPTION OF THE INVENTION

5 The acidic disinfectant liquid detergent compositions of the present invention are in the form of stable aqueous
solutions or microemulsions. The compositions comprise water, an organic acid or a mixture of organic acids, a mixture
of acid-stable water-soluble and water-dispersible nonionic surfactants and a water soluble, acid-stable germicidal or
disinfectant compound. Optionally, a cationic or anionic soil releasing compound which is substantive to the surface
being cleaned may be included in the composition in order to reduce subsequent adhesion of soil and provide easier
10 recleaning of the treated surface. Additional minor ingredients commonly used in the preparation of cosmetically and
commercially acceptable liquid detergent compositions may also be present in the composition of the present invention
and will be obvious to those skilled in the art upon practicing the invention. These minor ingredients include, but are
not limited to, acid stable perfumes and fragrances, compatible coloring agents, viscosifiers and the like.
The active detergent ingredient of the present all-purpose liquid detergent composition consists essentially of a
is mixture of acid-stable water soluble and water dispersible nonionic surfactants. The mixture of surfactants acts syn-
ergistically to provide rapid and efficient spreading of the detergent composition over the surface to be cleaned. The
synergistic mixture of nonionic surfactants provides improved detergency against soils such as soap scum and mineral
deposits when compared to commercially available acidic liquid hard surface cleaning products but with less damage
to surfaces as compared with with the most acidic of such commercial products.
20 The nonionic surfactants useful in the present inventive compositions must be stable at the acid pH of the liquid
detergent composition. They are generally the condensation product of an organic aliphatic or alkyl aromatic hydro-
phobic compound and hydrophilic ethylene oxide or propylene oxide groups. Hydrophobic compounds having a car-
boxy, hydroxy, or an amido group or an amino group with a free hydrogen can be condensed with ethylene oxide,
polyethylene glycol or propylene oxide to form a nonionic detergent. The length of the polyetheneoxy or polypropeneoxy
25 chain can be adjusted during the condensation reaction to achieve a desired ratio of hydrophobic and hydrophilic
elements. The length of the hydrophilic (polar) chain relative to the length of the hydrophobic (nonpolar) component
also determines the degree of solubility of the nonionic detergent in water, i.e the degree of polarity.
The degree of solubility in water of nonionic surfactants is characterized and predicted in the art by the hydrophile/li-
pophile balance (HLB) of the surfactant molecule. Nonionic detergents which are more lipophilic, that is oil soluble,
30 have low HLB numbers. These form dispersions when agitated in water. High HLB numbers correspond to increased
water solubility of the nonionic detergent. For nonionic detergents, the HLB number is directly related to the relative
molar ratio of ethylene oxide and/or propylene oxide to the alkyl chain of the molecule.
The most useful mixtures of nonionic surfactants for purposes of the invention are the acid stable condensation
products of higher alcohols containing 8 to 20 carbon atoms in straight or branched chain configuration, preferably
35 containing 8 to 14 carbon atoms.
The water soluble nonionic surfactant component of the surfactant mixture has a minimum HLB number of ap-
proximately 11 and forms a translucent to clear dispersion or a clear solution when mixed with water. Examples of
water soluble nonionic surfactants useful in the present invention include, but are not limited to, Cg--,-, alcohols con-
densed with 8 ethoxyethylene radicals (for example Neodol 91-8 available from Shell Oil Co) which have an HLB
40 number of approximately 13.9 and Cg.-,-, alcohols condensed with 6 ethoxyethylene radicals (for example Neodol 91 -6
available from Shell Oil Co.) with an HLB number of approximately 12.5. Other water soluble nonionic surfactants
having HLB numbers of 11 or greater which are useful in the present invention are well known in the art, such as those
nonionic surfactants which are the condensation products of an alkyl phenol with ethylene oxide (the nonyl phenols)
or higher alcohols condensed with a combination of ethylene oxide and propylene oxide (the Pluronics) having a ter-
45 minal ethoxylate group.
The water-dispersible nonionic surfactant component of the surfactant mixture of the present invention is charac-
terized by an HLB number of about 7-10. These surfactants, being more lipophilic, form a milky dispersion when agitated
in water. Examples of water-dispersible nonionic surfactants useful in the present invention include Cg-C-,-, alkanol
ethoxylates having 2.5 moles of ethylene oxide per mole of alcohol (for example Neodol 91-2.5 available from Shell
so Oil Co. having HLB = 8.5). Additional examples of suitable water-dispersible nonionic surfactants and may be selected
from such surfactant groups as the nonylphenols and the Pluronics as described above.
Nonionic surfactant mixtures are assayed for their synergistic properties in two assay systems. Spreading prop-
erties of the surfactant mixture are assessed on clean glass surfaces. Approximately 20 microliters of a surfactant
mixture containing a total concentration of surfactant of less than 5% is placed as a droplet on a clean glass surface
55 and allowed to sit undisturbed for approximately two minutes. At that time, the diameter of the surfactant drop is meas-
ured. A diameter of at least about 20 mm indicates a synergistic effect on surface spreading for the surfactant mixture.
Under similar test conditions, a deionized water drop spreads to approximately 8 mm in diameter and surfactant solu-
tions which do not exhibit enhanced spreading reach a maximum diameter of about 15 mm.

4
 EP 0 379 256 B1

The soil cleaning or detergency properties of the nonionic surfactant mixtures are determined using the Roll-up
test, in which 9 ml of the surfactant mixture to be tested is added to a vial containing approximately 10 microliters of
oleic acid placed in the vial as a droplet. The amount of time required for the oleic acid droplet to rise to the surface of
the liquid is measured. A colored dye may be added to the oleic acid for improved visibility. Decreasing roll-up time is
5 indicative of increasing detergent efficacy, and effective detergents generally exhibit a roll-up time of 60 seconds or
less. Effective acid-stable nonionic surfactant mixtures in accordance with the invention provide roll-up times of about
60 seconds or less when tested in this system. Within nonionic surfactant ratios of 3:1 to 3:2 by weight, roll-up times
of about 30 seconds or less were obtained using Neodol 91 -8 (water soluble) in combination with Neodol 91 -2.5 (water
dispersible) in an acidic aqueous medium. Samples consisting of Neodol 91 -8 in combination with Neodol 91 -2.5 also
10 showed roll-up times of less than 60 seconds within the range of weight ratios of 4:1 to 4:3. These synergistic surfactant
mixtures eliminate the need for grease-removing organic solvents such as are conventionally used in liquid hard surface
cleaning compositions. The mixtures remain stable over a wide range of temperatures.
The liquid cleaner of the present invention cleans soap scum soil and removes mineral deposits through the action
of both the nonionic surfactant system and, additionally, at least one organic acid selected from the group consisting
is of lower aliphatic monocarboxylic acids and dicarboxylic acids in an amount of about 3-7% by weight of the composition.
Representative members of the aliphatic acids include C-, -C6 alkyl and alkenyl monobasic acids and dibasic acids such
as glutaric acid, succinic acid, propionic acid, adipic acid, hydroxyacetic acid and mixtures thereof. Glutaric acid is
preferred, however, a mixture of the dibasic acids, adipic, glutaric and succinic acids is easily available commercially
and is useful in the inventive compositions. The ratio of the acids in the foregoing mixture is adjusted to maximize water
20 solubility of the mixture by employing glutaric acid, the most water-soluble of these three saturated aliphatic dibasic
acids, as the major component. Generally, the weight ratio of adipic acid:glutaric acid: succinic acid is selected to be
within the range of 1-3:1-8: 1-5, and preferably within the range of 1-2:1-6:1-3. The organic acids provide moderate
acidity to the cleaning compositions of present invention and thereby enhance cleaning performance, particularly re-
moval of soap scum from tiles and other hard surfaces, with very little damage to the grout between the tiles and with
25 reduced irritation to the skin of the user.
A third essential ingredient present in the liquid cleaning composition of the present invention is an acid-stable
antimicrobial, germicidal or disinfectant compound comprising at least about 0.1% by weight of the composition. Suit-
able antimicrobial germicidal and disinfectant compounds are well known in the art and include chlorhexidine, acid
stable germicidal quaternary ammonium compounds (e.g. Variquat 50 Mc marketed by Sherex or BTC 21 25 Mmarketed
30 by Onyx) glutaraldehyde, formaldehyde, and betaines. Minor amounts, up to about 2%, of isopropyl alcohol may also
be included in the composition to enhance the antimicrobial effect, particularly against Pseudomonas. It will be obvious
to those skilled in the art that useful antimicrobials may be cationic, nonionic or anionic as long as the compound
selected is acid stable and does not interact with other components of the composition, maintaining germicidal activity
without adversely affecting the cleaning properties of the composition.
35 The pH of the acidic liquid detergent composition is adjusted to maximize the antimicrobial effect of the disinfecting
agent while maintaining effective cleaning of soap scum and oily soils. Generally, the pH is from about 2-4, preferably
about 2.5-3. In addition to providing efficient cleaning, this pH range is less damaging to the cleaned surface and less
irritating to the skin than the commercially available acidic cleaners.
Optionally, an acid-stable cationic or anionic soil releasing agent may be included in the composition in an amount
40 of about 0.25% to 2% by weight, preferably 0.25-1 % weight. The soil releasing agent must be substantive to the surface
being cleaned at the pH of the liquid cleaning composition and acts to inhibit subsequent redeposition and/or adhesion
of soils, particularly soap scum and mineral deposits, on the cleaned surface. Although the applicants do not wish to
be bound by any theory of operation, it is believed that the cleaned surface is modified by the deposition of the soil
releasing agent, which provides for easier removal of soils during subsequent cleanings. Compounds which promote
45 surface hydration are believed to be the most efficient soil releasing agents for the present cleaning compositions.
The soil releasing agent may be cationic or anionic, selected to be acid-stable and compatible with the other
components of the composition, especially the disinfectant. Compounds useful for their soil releasing properties include
antistatic polymers consisting of recurring monomers of beta [trialkyl ammonium] ethyl methacrylate (wherein the alkyl
group attached to the ammonium moiety may be ethyl or methyl) and styrene maleic anhydride polymers with antifog-
50 ging properties.
The antistatic polymers useful as soil releasing agents in the present invention have the following basic structure:
o

55

These antistatic compounds are poly beta-trialkyl ammonium ethyl methacrylates (herein abbreviated as AAEM)

5
 EP 0 379 256 B1

wherein the alkyl groups (R) may be methyl or ethyl or a mixture thereof, and X is an anion which may be a halide such
as chloride, an alkyl sulfate such as methyl sulfate or lauryl sulfate or an ethoxylated alkyl sulfate or mixtures thereof.
A preferred antistatic polymer for use as a soil releasing agent in the present invention is poly beta [methyl diethyl
ammonium] ethyl methacrylate methyl sulfate (herein abbreviated as MDAEM). MDAEM has the following basic struc-
5 ture:

\ / \ / \ ir — Et x-
/ V W

wherein Me is methyl, Et is ethyl and X is methyl sulfate. The molecular weight of the polymer is about 2,000-500,000.
MDAEM is available commercially as an opaque, moderately viscous emulsion having a pH of 6-8 and a specific
is gravity of 1. It is completely miscible in water. The active antistatic ingredients constitute approximately 15-20% by
weight and the volatile ingredients constitute approximately 80-85% by weight of the commercial product, which is
stable, will not decompose or polymerize, and is incompatible with oxidizing or reducing agents. Because sodium lauryl
sulfate is present in the commercial preparation, the polymer is present as a 3:1 mixture of the methyl sulfate and lauryl
sulfate forms. The inclusion of the soil-release agent MDAEM in the present novel acid disinfectant all-purpose liquid
20 cleaning composition provides significantly enhanced soil removal on subsequent cleaning of pretreated surfaces.
Thus, during recleaning of a previously cleaned surface, soil removal of soap scum from a hard surface such as bath-
room tile or the like can be effected with significantly less effort as compared to the use of commercially available
products.
The balance of the novel acidic disinfectant liquid cleaning composition is water, preferably distilled water, reduced
25 by any optional ingredients which may be present. Generally, the proportion of water in the compositions is about 88%
to 94% by weight of the composition. Those skilled in the art will readily appreciate that minor amounts of additional
ingredients may be optionally present to provide cosmetically appealing products and increase consumer acceptability.
Examples of such adjuvants include acid-stable coloring agents, fragrances, perfumes, viscosifiers, and pH adjusting
agents such as 50% sodium hydroxide.
so In final form, the all-purpose liquid detergents are homogeneous aqueous compositions which exhibit stability at
both reduced and increased temperatures. More specifically, such compositions remain stable in the range of 5°C to
40°C. The liquids are readily pourable and free flowing from any suitable container or may be sprayed from a pump-
type sprayer.
The compositions are directly ready for use. Only minimal rinsing is needed and substantially no residue or streaks
35 are left behind on the cleaned surface. Because the compositions are free of detergent builders such as alkali metal
polyphosphates they are environmentally acceptable and provide a better "shine" on cleaned hard surfaces.
Typically, the inventive compositions are prepared simply by combining all of the ingredients in a suitable mixing
vessel or container. Generally, the various ingredients can be added sequentially, or all at once, to form an aqueous
solution of each or all of the essential ingredients. Preferably, when a fragrance is present, the fragrance is first dissolved
40 in the water dispersible nonionic surfactant which is then added to the other ingredients in aqueous acid solution. When
the surfactant/fragrance mixture is added to the aqueous acid solution containing the remaining ingredients, the solution
may become slightly hazy. If a cationic disinfectant compound is added to the aqueous mixture, the fragrance becomes
completely solubilized and the final mixture is clear as well as stable. The compositions may be prepared at room
temperature.
45 In use, the compositions of this invention are applied to the surfaces to be cleaned with a cloth or sponge or by
spraying onto ceramic or other surfaces which have been soiled by accumulations of insoluble soaps, mineral deposits,
and oily soils. The cleaning compositions, without added thickeners, are of about the viscosity of water but may be
thinner than water. The material will usually be allowed to remain on the surface to be cleaned for a period from 10
seconds to 5 or 10 minutes, but preferably such contact time will be from about 30 seconds to five minutes or from 1
so to 3 minutes. The liquid cleaner composition may then be removed either by wiping or rinsing with water. These com-
positions leave substantially no spots or streaks whether or not they are rinsed from the cleaned surface.
The compositions of the invention provide enhanced cleaning with less acidity as compared to commercially avail-
able cleaners and, therefore, are less damaging to the cleaned surface. Microscopic examinations of the grout between
tiles shows no erosion or other deterioration after cleaning as compared to commonly available cleaning compositions.
55 The following examples illustrate the acidic liquid disinfectant cleaning compositions of the described invention.
Unless otherwise specified, all percentages are by weight. The exemplified compositions are illustrative only and do
not limit the scope of the invention.

6
 EP 0 379 256 B1

EXAMPLE 1

INGREDIENT WEIGHT %
DAGS1 5.0
Neodol 91 -82 1.5
Neodol 91 -2.53 0.7
BTC 21 25M4 (50% solution) 0.4
Water QS
pH 2.5
1. Dicarboxylic acids mixture of 11.6% adipic, 57.5% glutaric and 27% succinic acids in the form of water soluble white flakes having the formula
HOOC-(CH2)2_4-COOH marketed by Dupont.
2. Cg-C-i-i alcohol E08:1 marketed by Shell Oil Co.
75 3. Cg-C-i-i alcohol E02.5:1 marketed by Shell Oil Co.
4. Benzalkonium chloride [CgH5CH2N(CH3)2Cg_ig alkylmixture]+Cr marketed by Onyx.

This composition is prepared by adding DAGS to the formula amount of water to form an acidic aqueous solution,
to which is added either simultaneously or sequentially the Neodols and the BTC. If necessary, 50% sodium hydroxide
is added to adjust the pH to 2.5. A clear stable aqueous composition is formed having improved clean ing and disinfecting
properties.
The acidic disinfectant cleaning composition of Example 1 was tested comparatively against commercially available
cleaning compositions for cleaning performance in a soap scum removal test. Four comparative tests were conducted,
each consisting of the composition of Example 1 against a single commercial cleaner. Etched white ceramic tiles (4.25
in. x 4.25 in.) were sprayed with a 250 g/l solution of CaCI2 • 2H20 followed by a red dyed 5% sodium oleate solution.
After permitting the tiles to dry for one hour at 30°C, the soiling procedure was repeated. The soil so produced was
uniform and reproducible within acceptable limits. After the second soil layer was dried, the tiles were mounted in a
Gardner Abrasion Tester (Pacific Scientific Gardner-Neotec Instrument Div.) equipped with two cellulose sponges
measuring 5cm x 5cm x 5cm. Three grams of the liquid cleaning composition being tested were pipetted onto the
sponge holding 5gms water, and the soiled tiles were subjected to 20 back and forth strokes of the sponge (abrader
cycles). A reflectometer was used to measure the reflectance before and after the 20 abrader cycles and the % soil
removal was determined. The results obtained are set forth in Table 1 below:

TABLE 1
PERCENT SOAP SCUM REMOVAL OF COMPOSITION OF THE INVENTION VERSUS COMMERCIAL
CLEANING COMPOSITIONS
Test No. Example 1 pH Dow Disinfectant Lysol Disinfectant Lime Away3 pH Scrub Free 4 pH
2.5 Bathroom Basin, Tub &Tile2 0.5 1.0
Cleaner1 pH 12 Cleaner pH 12
1 52% 15%
2 49% — 11%
3 47% — — 65%
4 69% — — — 80%
Dow Consumer Products, Inc.
Lehn &Fink Products, Division of Sterling Drug, Inc.
'Benckiser Consumer Products, Inc.
Benckiser Consumer Products, Inc.

The Standard Deviation of the above results is plus or minus 5 soil removal percent units.
The above results demonstrate that the acidic cleaning composition of the present invention is markedly superior
to commercially available alkaline compositions in cleaning efficacy. As compared to commercial acidic cleaners, the
present composition provides slightly inferior cleaning of soap scum but is considerably less acidic than these com-
mercial formulas and therefore less irritating to the skin of the user. Moreover, the composition of the invention has
disinfectant properties.

7
 EP 0 379 256 B1

EXAMPLE 2

Formulas A and B were prepared as shown below:

5 FORMULA A:
INGREDIENT WEIGHT%
DAGS 5.0
Neodol 91-8 1.5
10 Neodol 91-2.5 0.7
BTC 21 25M (50% solution) 0.4
Perfume 0.2
Water QS
15 FORMULA B:
DAGS 5.0
Neodol 91-8 1.5
Neodol 91-2.5 0.7
20 BTC 21 25M (50% solution) 0.4
Perfume 0.2
MDAEM1 (15-20% solution) 1.4
Water QS
Commercially available preparation consisting of 15-20% polymer, 5-10% isopropanol, 3-5% N-octanol, 3-5% sodium acetate, 1-3% terpene hy-
25 drocarbons and 3-5% sodium lauryl sulfate.

Formula A was prepared by separately dissolving the fragrance in Neodol 91 -2.5 and adding Neodol 91 -8 to form
a Neodol-fragrance mixture. An acid water solution was made by dissolving DAGS in the formula amount of water to
which was added the perfume-Neodol mixture. A slightly hazy solution was formed. The benzalkonium chloride was
30 added to the acid water solution which clarified the haziness, and the pH was adjusted to a pH of 2.5, as needed, by
the addition of a 50% sodium hydroxide solution.
Formula B was prepared in the same way as Formula A except that MDAEM was added to the acidic aqueous
solution containing perfume, BTC and the Neodols. Optionally, 2.0% isopropanol may be included in Formula B for
cosmetic purposes, to clarify the slightly hazy composition which results when MDAEM is added to the formulation.
35 Isopropanol does not interfere with the cleaning performance of the composition and other low molecular weight alco-
hols may be substituted for isopropanol for purposes of producing a clear composition containing MDAEM. Inclusion
of about 2.0% of a low molecular weight alcohol, particularly isopropanol, provides the additional advantage to the
composition of enhancing the antimicrobial properties of the disinfectant cleaner.
Formula A and Formula B above were compared for cleaning performance in the soap scum removal test set forth
40 in Example 1, using 20 abrader cycles. The results are presented in Table 2:

TABLE 2
PERCENT SOAP SCUM REMOVAL
FORMULA
A B
67% 65%

These results demonstrate that inclusion of the soil-releasing agent MDAEM does not interfere with the first-time
cleaning performance of the acidic liquid disinfectant detergent composition of the present invention.

EXAMPLE 3

Formulas C and D were prepared as shown below:

8
 EP 0 379 256 B1

FORMULA C:
INGREDIENT WEIGHT %
DAGS 5.0
Neodol 91-8 1.5
Neodol 91-2.5 0.7
Chlorhexidine 0.2
Water QS
FORMULA D:
DAGS 5.0
Neodol 91-8 1.5
Neodol 91-2.5 0.7
15
Chlorhexidine 0.2
MDAEM (15-20% solution) 2.3
Water QS

20 Formulas C and D were prepared as described in Example 2 for the corresponding compositions. The results of
the soap scum removal tests for Formulas C and D are given in Table 3 below:

TABLE 3
PERCENT SOAP SCUM REMOVAL
FORMULA
C D
Test #1 49% 60%
30 Test #2 52% 65%

EXAMPLE 4

Formulas E and F were prepared as shown below:

35
Ingredient Weight %

FORMULA E:

40 DAGS 5.0
Neodol 91-8 1.5

Neodol 91-2.5 0.7

45 V a r i q u a t 50 MC (50% s o l u t i o n ) 0.4
Water QS

FORMULA F:

so DAGS 5.0
Neodol 91-8 1.5
Neodol 91-2.5 0.7
V a r i q u a t 50 MC (50% s o l u t i o n ) 0.4
MDAEM (15-20% s o l u t i o n ) 2.3
55 Water QS
To test for ease of recleaning, ceramic tiles were cleaned with Formulas E and F under normal ambient conditions
of temperature and humidity, rinsed with distilled water and patted dry. The tiles were then soiled as described in the

9
 EP 0 379 256 B1

soap scum removal test of Example 1 and recleaned, also under normal ambient conditions of temperature and hu-
midity, using a non-acidic conventional cleaning composition comprised of an aqueous solution of 1:1 by weight Neodol
91 -6 and Neodol 91 -2.5. Ten abrader cycles were used for the recleaning step, which represents one-half the number
of abrader cycles used in the first-cleaning tests described in Examples 1-3. The results of this recleaning test are
5 given in Table 4 below:

TABLE 4
PERCENT SOAP SCUM REMOVAL ON RECLEANING

10 PRETREATMENT FORMULA
E F
24% 95%

As shown in Table 4, pretreatment of the test tiles with the inventive composition F containing a soil releasing agent
provided 95% soil removal with 10 abrader cycles. Pretreatment with formula E without the soil releasing agent provided
only 24% soil removal with an equivalent amount of scrubbing in the recleaning test. These results demonstrate that
ease of recleaning is significantly enhanced by inclusion of the soil releasing agent in the inventive composition.
Ease of recleaning was found to improve as humidity levels were increased above about 35% humidity.

Claims

1. A stable acidic disinfectant all-purpose liquid cleaning composition comprising by weight:

25
(a) about 0.5-4% of a mixture of acid stable nonionic surfactants, said mixture consisting essentially of a water
soluble nonionic surfactant and a water dispersible nonionic surfactant in a weight ratio of water-soluble to
water-dispersible surfactant of from about 4:1 to 4:3;
(c) at least 0.1% of an acid stable antimicrobial compound; and
3o (d) from about 0-2% of an acid-stable cationic or anionic soil releasing agent; and
(e) the balance water,

characterized in that said liquid cleaning composition further comprises:

(b) about 3-7% of an organic acid selected from the group consisting of C-,_6 aliphatic monocarboxylic acids,
C-|_6 aliphatic dicarboxylic acids and mixtures thereof; so that said liquid cleaning composition having a pH of
about 2-4.

2. The cleaning composition according to Claim 1 wherein the water soluble nonionic surfactant is selected from the
group consisting of acid-stable nonionic surfactants having a hydrophilic/lipophilic balance (HLB) of at least about
11 and the water dispersible nonionic surfactant is selected from the group consisting of acid stable nonionic
surfactants having a hydrophilic/lipophilic balance of about 7-10.

3. The cleaning composition according to Claim 1 wherein the acid stable nonionic surfactants are selected from the
group consisting of linear fatty alcohol ethoxylates.

4. The cleaning composition according to Claim 1 wherein the mixture of acid stable nonionic surfactants comprises
about 2-4% by weight of the composition.

5. The cleaning composition according to Claim 1 wherein the ratio of water soluble to water dispersible nonionic
surfactant is 3:1 to 3:2.

6. The cleaning composition according to Claim 1 wherein the pH of the composition is 2.5-3.

7. The cleaning composition according to Claim 1 wherein the antimicrobial agent is selected from the group con-
sisting of acid stable antimicrobial quaternary ammonium compounds.

8. The cleaning composition according to Claim 1 wherein the antimicrobial agent is chlorhexidine.

10
 EP 0 379 256 B1

9. The cleaning composition according to Claim 1 wherein the organic acid is selected from the group consisting of
C2_6 alkyl and alkenyl monobasic acids, C2_6 alkyl and alkenyl dibasic acids and mixtures thereof.

10. The cleaning composition according to Claim 9 wherein the organic acid is a mixture of C2_6 aliphatic dicarboxylic
5 acids comprising about 3-5% by weight of the composition.

11. The cleaning composition according to Claim 9 wherein the organic acid mixture contains adipic, glutaric and
succinic acids in a weight ratio of 1-3:1-8:1-5, respectively.

10 12. The cleaning composition according to Claim 9 wherein the acid mixture comprises hydroxy acetic acid.

13. The cleaning composition according to Claim 1 wherein the antimicrobial agent is benzalkonium chloride.

14. The cleaning composition according to Claim 2 wherein the acid stable nonionic surfactants are selected from the
is group consisting of alkanol ethoxylates, alcohol propoxylates, alkyl phenol ethoxylates and higher alcohols con-
densed with a mixture of ethylene oxide and propylene oxide having a terminal ethoxylate group.

15. The cleaning composition according to Claim 3 wherein the mixture of nonionic surfactants consists essentially of
Cg.-,-, alcohol E0 8:1 and C9_-,-, alcohol EO 2.5:1.
20
16. The cleaning composition according to Claim 15 wherein the Cg.-,-, alcohol EO 8:1 and Cg.-,-, alcohol EO 2.5:1
comprise about 1.5% and about 0.7% of the composition by weight, respectively.

17. The cleaning composition according to Claim 1 comprising 0.25-1 % of an acid stable cationic or anionic soil releas-
es ing agent selected from the group consisting of poly beta trialkyl ammonium ethyl methacrylates having ethyl or
methyl groups attached to the ammonium moiety and styrene-maleic anhydride polymers.

18. The cleaning composition according to Claim 9 which comprises by weight 5% of a mixture of dicarboxylic acids,
said mixture consisting essentially of adipic, glutaric and succinic acids, 0.2% of an acid stable antimicrobial benzyl
30 C12-C18 alkyl dimethyl quaternary ammonium compound, about 0.4% of poly beta [methyl diethyl ammonium] ethyl
methacrylate methyl sulfate having a molecular weight of 2,000-500,000, and about 2.5% of an acid stable mixture
of nonionic surfactants consisting essentially of Cg.-,-, alcohol E0 8:1 and Cg.-,-, alcohol EO 2.5:1 in a weight ratio
of about 2:1 of the first aforementioned nonionic surfactant having a molar ratio of ethylene oxide to alcohol of 8:
1 relative to the second aforementioned nonionic surfactant having a molar ratio of ethylene oxide to alcohol of
35 2.5:1.

19. A method of simultaneously disinfecting and cleaning a hard surface comprising contacting said surface with the
composition of Claim 1 and wiping said surface to remove soil provided that therapeutical methods are excluded.

40 20. The method according to Claim 19 wherein the composition of Claim 1 contains a soil releasing agent which treats
the surface to be cleaned such that removal of soil from said surface during a second recleaning step is enhanced.

21. The method according to Claim 19 wherein the composition of Claim 1 comprises:

45 a) about 2-4% of a mixture of acid stable nonionic surfactants, said mixture consisting essentially of a water
soluble nonionic surfactant and a water dispersible nonionic surfactant in a weight ratio of water soluble to
water dispersible surfactant of from about 3:1 to 3:2;
b) about 3-5% of an organic acid selected from the group consisting of C-,_6 aliphatic monocarboxylic acids,
C-|_6 aliphatic dicarboxylic acids and mixtures thereof;
so c) at least 0.1% of an acid stable antimicrobial compound;
d) from about 0.25-1% of an acid stable cationic or anionic soil releasing agent; and,
e) the balance water, said liquid cleaning composition having a pH of about 2.5-3.

55 Patentanspriiche

1. Stabiles, saures, desinfizierendes, flussiges Allzweckreinigungsmittel, das folgendes enthalt:

11
 EP 0 379 256 B1

(a) etwa 0,5-4 Gew.-% einer Mischung aus saurestabilen, nichtionischen Tensiden, welche Mischung im
wesentlichen aus einem in Wasser loslichen, nichtionischen Tensid und einem in Wasser dispergierbaren,
nichtionischen Tensid besteht, in einem Gewichtsverhaltnis von in Wasser loslichem zu in Wasser dispergier-
barem Tensid von etwa 4:1 bis 4:3;
5 (c) etwa 0,1 Gew.-% einer saurestabilen antimikrobiellen Verbindung; und
(d) etwa 0-2 Gew.-% eines saurestabilen, kationischen oder anionischen Schmutzlosungsmittels; und
(e) Rest Wasser,

dadurch gekennzeichnet, dal3 das flussige Reinigungsmittel weiter enthalt:

10
(b) etwa 3-7 Gew.-% einer organischen Saure, ausgewahlt aus der Gruppe, bestehend aus C-|_6aliphatischen
Monocarbonsauren, C-,_6 aliphatischen Dicarbonsauren und deren Mischungen, so dal3 das flussige Reini-
gungsmittel einen pH-Wert von etwa 2-4 hat.

75 2. Reinigungsmittel nach Anspruch 1, in dem das in Wasser losliche, nichtionische Tensid aus der Gruppe ausgewahlt
ist, bestehend aus saurestabilen, nichtionischen Tensiden mit einem hydrophilen/lipophilen Rest von mindestens
etwa 11 , und das in Wasser dispergierbare, nichtionische Tensid aus der Gruppe ausgewahlt ist, bestehend aus
saurestabilen, nichtionischen Tensiden mit einem hydrophilen/lipophilen Rest von etwa 7-10.

20 3. Reinigungsmittel nach Anspruch 1, in dem die saurestabilen, nichtionischen Tenside aus der Gruppe ausgewahlt
sind, bestehend aus linearen Fettalkoholethoxylaten.

4. Reinigungsmittel nach Anspruch 1, in dem die Mischung aus saurestabilen, nichtionischen Tensiden etwa 2-4
Gew.-% des Mittels enthalt.
25
5. Reinigungsmittel nach Anspruch 1, in dem das Verhaltnis von in Wasser loslichem zu in Wasser dispergierbarem,
nichtionischem Tensid 3:1 bis 3:2 ist.

6. Reinigungsmittel nach Anspruch 1, in dem der pH-Wert des Mittels 2,5-3 ist.
30
7. Reinigungsmittel nach Anspruch 1, in dem der antimikrobielle Stoff aus der Gruppe ausgewahlt ist, bestehend aus
saurestabilen, antimikrobiellen quartaren Ammoniumverbindungen.

8. Reinigungsmittel nach Anspruch 1, in dem der antimikrobielle Stoff Chlorhexidin ist.

35
9. Reinigungsmittel nach Anspruch 1, in dem die organische Saure aus der Gruppe ausgewahlt ist, bestehend aus
C2_6 Alkyl- und Alkenyl-monobasischen Sauren, C2_6 Alkyl- und Alkenyldibasischen Sauren und deren Mischun-
gen.

40 10. Reinigungsmittel nach Anspruch 9, in dem die organische Saure eine Mischung aus C2_6 aliphatischen Dicarbon-
sauren mit etwa 3-5 Gew.-% des Mittels ist.

11. Reinigungsmittel nach Anspruch 9, in dem die organische Sauremischung Adipin-, Glutar- und Succinsaure in
einem Gewichtsverhaltnis von bzw. 1-3:1-8:1-5 enthalt.
45
12. Reinigungsmittel nach Anspruch 9, in dem die Sauremischung Hydroxyessigsaure enthalt.

13. Reinigungsmittel nach Anspruch 1, in dem der antimikrobielle Stoff Benzalkoniumchlorid ist.

so 14. Reinigungsmittel nach Anspruch 2, in dem die saurestabilen, nichtionischen Tenside aus der Gruppe ausgewahlt
sind, bestehend aus Alkanolethoxylaten, Alkoholpropoxylaten, Alkylphenolethoxylaten und hoheren Alkoholen,
kondensiert mit einer Mischung aus Ethylenoxid und Propylenoxid mit einer endstandigen Ethoxylatgruppe.

15. Reinigungsmittel nach Anspruch 3, in dem die Mischung aus nichtionischen Tensiden im wesentlichen aus Cg.-,-,
55 Alkohol EO 8:1 und C Alkohol EO 2,5:1 besteht.

16. Reinigungsmittel nach Anspruch 15, in dem der Cg.-,-, Alkohol EO 8:1 und C Alkohol EO 2,5:1 etwa 1,5 Gew.-%
bzw. etwa 0,7 Gew.-% des Mittels enthalt.

12
 EP 0 379 256 B1

17. Reinigungsmittel nach Anspruch 1, das 0,25-1% eines saurestabilen, kationischen oder anionischen Schmutzlo-
sungsmittels enthalt, ausgewahlt aus der Gruppe, bestehend aus Poly-p-trialkylammoniumethylmethacrylaten mit
Ethyl- oder Methylgruppen, gebunden an den Ammoniumanteil und Styrolmaleinsaureanhydridpolymeren.

5 18. Reinigungsmittel nach Anspruch 9, das 5 Gew.-% einer Mischung aus Dicarbonsauren enthalt, welche Mischung
im wesentlichen aus Adipin-, Glutar- und Succinsauren besteht, 0,2 Gew.-% einer saurestabilen, antimikrobiellen
Benzyl-C12-C18-alkyldimethyl-quartaren-Ammoniumverbindung, etwa 0,4 Gew.-% Poly-p-[methyl-diethylammo-
niumjethyl-methacrylat-methylsulfat mit einem Molgewicht von 2.000-500.000 und etwa 2,5 Gew.-% einer saure-
stabilen Mischung aus nichtionischen Tensiden, im wesentlichen bestehend aus Cg.-,-, Alkohol E0 8:1 und C Alko-
10 hoi EO 2,5:1 in einem Gewichtsverhaltnis von etwa 2:1 des ersten obengenannten nichtionischen Tensids mit
einem Molverhaltnis von Ethylenoxid zu Alkohol von 8:1 relativ zu dem zweiten obengenannten nichtionischen
Tensid mit einem Molverhaltnis von Ethylenoxid zu Alkohol von 2,5:1.

19. Verfahren zur gleichzeitigen Desinfizierung und Reinigung harter Oberflachen, wobei diese mit dem Mittel nach
is Anspruch 1 in Kontakt gebracht und abgewischt werden, urn Schmutz zu entfernen, vorausgesetzt, dal3 therapeu-
tische Verfahren ausgeschlossen sind.

20. Verfahren nach Anspruch 19, wobei das Mittel nach Anspruch 1 ein Schmutzlosungsmittel enthalt, das die zu
reinigende Oberflache derart behandelt, dal3 die Entfernung des Schmutzes von dieserOberflache wahrend eines
20 zweiten Nachreinigungsschrittes gefordert wird.

21. Verfahren nach Anspruch 19, wobei das Mittel nach Anspruch 1 folgendes enthalt:

(a) etwa 2-4% einer Mischung aus saurestabilen, nichtionischen Tensiden, welche Mischung im wesentlichen
25 aus einem in Wasser loslichen, nichtionischen Tensid und einem in Wasser dispergierbaren, nichtionischen
Tensidbesteht, in einem Gewichtsverhaltnis von in Wasser loslichem zu in Wasser dispergierbarem Tensid
von etwa 3:1 bis 3:2;
(b) etwa 3-5% einer organischen Saure, ausgewahlt aus der Gruppe, bestehend aus C-,_6 aliphatischen Mono-
carbonsauren, C-,_6 aliphatischen Dicarbonsauren und deren Mischungen;
30 (c) mindestens 0,1% einer saurestabilen antimikrobiellen Verbindung;
(d) etwa 0,25-1% eines saurestabilen, kationischen oder anionischen Schmutzlosungsmittels; und
(e) Rest Wasser, wobei das flussige Reinigungsmittel einen pH-Wert von etwa 2,5-3 hat.

35 Revendications

1. Une composition de liquide de nettoyage disinfectant acide tous usages stable comprenant en poids :

(a) environ 0,5-4% d'un melange d'agents tensio-actifs non-ioniques stables en presence d'acide, ledit
40 melange etant essentiellement constitue d'un agent tensio-actif non-ionique soluble dans I'eau et d'un agent
tensio-actif non-ionique dispersible dans I'eau, le rapport en poids de I'agent tensio-actif non-ionique soluble
dans I'eau sur I'agent tensio-actif non-ionique dispersible dans I'eau etant d'environ 4 : 1 a 4 : 3 ;
(c) au moins 0,1% d'un compose antimicrobien stable en presence d'acide ; et
(d) environ 0-2% d'un appret antisalissant cationique ou anionique stable en presence d'acide, et
45 (e) de I'eau pour completer,

caracterise en ce que ladite composition de liquide de nettoyage comprend en outre :

(b) environ 3-7% d'un acide organique selectionne dans le groupe constitue des acides monocarboxyliques
so aliphatiques en C-,_6, des acides dicarboxyliques aliphatiques en C-,_6 et de leurs melanges ; de sorte que
ladite composition de liquide de nettoyage ait un pH d'environ 2-4.

2. La composition de liquide de nettoyage suivant la revendication 1, dans laquelle on selectionne I'agent tensio-actif
non-ionique soluble dans I'eau dans le groupe constitue des agents tensio-actifs non-ioniques stables en presence
55 d'acide presentant un rapport hydrophile/lipophile (RHL) d'au moins environ 11 et dans laquelle on selectionne
I'agent tensio-actif non-ionique dispersible dans I'eau dans le groupe constitue des agents tensio-actifs non-ioni-
ques stables en presence d'acide presentant un rapport hydrophile/lipophile (RHL) d'environ 7-10.

13
 EP 0 379 256 B1

3. La composition de liquide de nettoyage suivant la revendication 1, dans laquelle on selectionne les agents tensio-
actifs non-ioniques stables en presence d'acide dans le groupe constitue des ethoxylates d'alcools gras lineaires.

4. La composition de liquide de nettoyage suivant la revendication 1, dans laquelle le melange d'agents tensio-actifs
5 non-ioniques stables en presence d'acide represente environ 2-4% en poids de la composition.

5. La composition de liquide de nettoyage suivant la revendication 1, dans laquelle le rapport des agents tensio-actifs
non-ioniques solubles dans I'eau sur les agents tensio-actifs non-ioniques dispersibles dans I'eau est 3 : 1 a 3 : 2.

10 6. La composition de liquide de nettoyage suivant la revendication 1, dans laquelle le pH de la composition est 2,5-3.

7. La composition de liquide de nettoyage suivant la revendication 1, dans laquelle on selectionne I'agent antimicro-
bien dans le groupe constitue des composes antimicrobiens stables en presence d'acide a base d'ammonium
quaternaire.
15
8. La composition de liquide de nettoyage suivant la revendication 1, dans laquelle I'agent antimicrobien est la chlo-
rhexidine.

9. La composition de liquide de nettoyage suivant la revendication 1, dans laquelle on selectionne I'acide organique
20 dans le groupe constitue des acides monobasiques alkyles et alkeniques en C2.6j acides dibasiques alkyles et
alkeniques en C2_6 et des melanges de ceux-ci.

10. La composition de liquide de nettoyage suivant la revendication 9, dans laquelle I'acide organique est un melange
d'acides dicarboxyliques aliphatiques en C2_6 representant environ 3-5% en poids de la composition.
25
11. La composition de liquide de nettoyage suivant la revendication 9, dans laquelle le melange d'acides organiques
contient les acides adipique, glutarique et succinique dans une proportion en poids respectivement de 1-3 : 1-8 :
1-5.

30 12. La composition de liquide de nettoyage suivant la revendication 9, dans laquelle le melange acide comprend de
I'acide hydroxyacetique.

13. La composition de liquide de nettoyage suivant la revendication 1, dans laquelle I'agent antimicrobien est le chlo-
rure de benzalkonium.
35
14. La composition de liquide de nettoyage suivant la revendication 2, dans laquelle on selectionne les agents tensio-
actifs non-ioniques stables en presence d'acide dans le groupe constitue des ethoxylates d'alkanol, de propoxy-
lates d'alcool, des ethoxylates de phenol d'alkyle et d'alcools a nombre eleve d'atomes de carbone condenses
avec un melange d'oxyde d'ethylene et d'oxyde de propylene ayant un groupe ethoxylate d'extremite.
40
15. La composition de liquide de nettoyage suivant la revendication 3, dans laquelle le melange d'agents tensio-actifs
non-ioniques est essentiellement constitue d'alcool EO en Cg.-,-, 8 : 1 et d'alcool EO en Cg.-,-, 2,5 : 1.

16. La composition de liquide de nettoyage suivant la revendication 15, dans laquelle I'alcool EO en Cg.-,-, 8 : 1 et
45 I'alcool EO en Cg.-,-, 2,5 : 1 represented respectivement environ 1,5% et environ 0,7% de la composition en poids.

17. La composition de liquide de nettoyage suivant la revendication 1 comprenant environ 0,25-1% d'un appret anti-
salissant cationique ou anionique stable en presence d'acide selectionne dans le groupe constitue par les poly-
beta-trialkyl-methacrylates d'ammonium ayant des groupes ethyles ou methyles attaches a la moitie ammonium
so et des polymeres d'anhydride styrene-maleique.

18. La composition de liquide de nettoyage suivant la revendication 9, qui comprend 5% en poids d'un melange d'aci-
des dicarboxyliques, ledit melange etant essentiellement constitue des acides adipique, glutarique et succinique,
0,2% d'un compose antimicrobien stable en presence d'acide d'ammonium quaternaire de dimethyle d'alkyle en
55 C12_18 de benzyle, environ 0,4% de poly-beta-(methyldiethylammonium)-ethylmethacrylate methylsulfate ayant
un poids moleculaire de 2.000-500.000, et environ 2,5% d'un melange stable en presence d'acide d'agents tensio-
actifs non-ioniques essentiellement constitues d'alcool EO en Cg.-,-, 8 : 1 et d'alcool EO en Cg.-,-, 2,5 : 1 dans la
proportion en poids d'environ 2 : 1 du premier agent tensio-actif non-ionique mentionne ci-dessus ayant un rapport

14
 EP 0 379 256 B1

molaire d'oxyde d'ethylene sur I'alcool de 8 : 1 par rapport au deuxieme agent tensio-actif non-ionique mentionne
ci-dessus ayant un rapport molaire d'oxyde d'ethylene sur I'alcool de 2,5 : 1.

19. Une methode de disinfection et nettoyage simultanes d'une surface dure comprenant la mise en contact de ladite
surface avec la composition de la revendication 1 et I'essuyage de ladite surface afin d'enlever la salete, pourvu
que des methodes therapeutiques soient indues.

20. La methode suivant la revendication 19, dans laquelle la composition de la revendication 1 contient un appret
antisalissant qui traite la surface a nettoyer de telle maniere que cela ameliore I'enlevement de la salete de ladite
surface au cours d'une seconde etape de nettoyage.

21. La methode suivant la revendication 19, dans laquelle la composition de la revendication 1 comprend :

a) environ 2-4% d'un melange d'agents tensio-actifs non-ioniques stables en presence d'acide, ledit melange
etant essentiellement constitue d'un agent tensio-actif non-ionique soluble dans I'eau et d'un agent tensio-
actif non-ionique dispersible dans I'eau, le rapport en poids de I'agent tensio-actif non-ionique soluble dans
I'eau sur I'agent tensio-actif non-ionique dispersible dans I'eau etant d'environ 3 : 1 a 3 : 2 ;
b) environ 3-5% d'un acide organique selectionne dans le groupe constitue des acides monocarboxyliques
aliphatiques en C-,_6, des acides dicarboxyliques aliphatiques en C-,_6 et de leurs melanges ;
c) au moins 0,1% d'un compose antimicrobien stable en presence d'acide ;
d) a partir d'environ 0,25-1% d'un appret antisalissant cationique ou anionique stable en presence d'acide, et
(e) de I'eau pour completer, ladite composition de liquide de nettoyage ayant un pH d'environ 2,5-3.

15