JP2003510411A - Liquid multiphase cleaning composition - Google Patents

Abstract

  (57) [Summary] The present invention discloses a liquid multi-phase cleaning composition comprising at least two continuous phases. The composition according to the invention consists of at least one aqueous phase (I) and a non-aqueous liquid phase (II) that is immiscible with said aqueous phase (I) and can be temporarily transformed into an emulsion by shaking. , And may also contain at least one antimicrobial active ingredient. The composition of the present invention can be used with a spray dispenser and can be used in a method of cleaning and / or disinfecting or sanitizing hard surfaces, especially glass surfaces. According to the method of the present invention, the emulsion is temporarily converted to an emulsion by shaking and applied, preferably by spraying, to the surface to be cleaned and / or disinfected or sanitized, whereby such a surface is After washing and / or disinfection or sanitary treatment, such surfaces can be wiped with a hygroscopic soft article, if desired.

Description

Detailed Description of the Invention

TECHNICAL FIELD The present invention relates to a multi-phase liquid detergent composition which can be temporarily converted into an emulsion by shaking (this composition is used for cleaning a hard surface such as glass). ), A product comprising the composition and a method for cleaning and / or disinfecting or sanitizing hard surfaces.

(Prior Art) Currently, the cleaning agent used for cleaning a hard surface is generally a stable aqueous solution or dispersion composition. The essential active ingredients are surface-active substances, organic solvents,
Optional complexing agents for hard water components, abrasive materials and wash alkaline components.
Particularly in detergents intended to clean the surface of glass or ceramics, the active ingredient is often formulated as a solution in which the ingredient is dissolved, the solvent being a mixture of water and a water-miscible organic solvent, Lower primary alcohols and glycol ethers are used. Such detergents are found in the patent literature (eg DE-A-22 50 5
40, US 3 839 234, US 3 882 038, EP-A-344 847 and 393 772).

[0003] In general, a cleaning agent is required to have a high cleaning ability and be as simple and convenient as possible when used. In most cases, it is expected that the detergent will exert its cleaning action in a single wash and will not be further processed.
In this regard, there are problems when cleaning smooth surfaces, especially when cleaning glass or ceramic surfaces that can be mirror-likely sensitive. This is because a cleaning agent that exhibits sufficient cleaning performance cannot be dried without leaving streak marks, whereas a cleaning agent that can be dried without substantially leaving a visible residue is a limited cleaning agent. This is because it only works.

In order to achieve an acceptable residue behavior, in particular an acceptable grease flaw, with sufficient cleaning performance, it is necessary to add very large amounts of somewhat volatile alkali and organic solvents to the cleaning agent. . For this reason ammonia and alkanolamines are used in particular. However, since ammonia and amine are used at relatively high concentrations, they add a very unpleasant odor and increase the pH value of the detergent solution. Is significantly eroded by.

Therefore, it is necessary to develop a cleaning composition that exhibits high cleaning performance without the above-mentioned drawbacks.

Currently, in addition to high basic cleaning performance, the need for antibacterial activity is also increasing.
For this purpose, antibacterial active ingredients such as surface-active quaternary compounds are incorporated into the detergent.

DE-A-39 10 170 discloses a composition used as a mouthwash for removing bacterial deposits from solid surfaces and living tissues. This composition exists in a biphasic form and, when shaken, can form a transient O / W emulsion for a limited period of time. In such compositions, the aqueous phase makes up about 50-97% by weight and the water-immiscible oil phase makes up about 3-50% by weight. An essential feature of the present invention is that it contains an amphipathic cationic substance such as a cationic surfactant in an amount (about 0.003 to 2% by weight) capable of forming an O / W type emulsion. But this emulsion is
After its formation, it decomposes and separates after 10 seconds to 30 minutes. Anionic surfactants are detrimental to antimicrobial activity. Also other surfactants are not disclosed.

EP-A-0 195 336 The disclosed shaken emulsifiable care compositions are for use on sensitive surfaces such as plastic surfaces and compact disc surfaces, and include trifluorocarbon (CFC ) Contains an organic phase consisting of 1,1,2-trichloro-1,2,2-trifluoromethane. Moreover, the composition is free of wax. However, since chlorofluorocarbons are involved in environmental destruction, especially in the formation of ozone holes, the use amount thereof should be reduced, and preferably the use thereof should be excluded.

DE-A-195 01 184, DE-A-195 01 187 and DE-A-195 01 188 (Henkel KGaA) disclose hair treatment compositions in two-phase form. The composition has an oil phase, which is preferably based on silicone oil, and an aqueous phase, which phases can be temporarily mixed by mechanical action.

(Problems to be Solved by the Invention) Therefore, a problem to be solved by the present invention is to provide a hard surface which exhibits high cleaning performance and storage stability, is easy to handle, and has antibacterial activity. A cleaning composition for cleaning is provided.

DISCLOSURE OF THE INVENTION According to the first aspect of the present invention, the present invention comprises at least one aqueous phase (I),
A multiphase liquid comprising at least two continuous phases consisting of said aqueous phase (I) and a non-aqueous liquid phase (II) which is immiscible and which can be temporarily converted into an emulsion by shaking. In the detergent composition, the detergent composition is provided with at least one antibacterial active ingredient.

The term “immiscible, non-aqueous phase” As used herein, the term “immiscible, non-aqueous phase” means a phase that is not based on water as a solvent, eg a non-aqueous phase. (II) contains only a predetermined amount of water, for example, based on the phase (II), 20 wt% or less, preferably 15 wt% or less, more preferably 10 wt% or less, particularly preferably Contains less than 5% by weight of water, which is present in completely dissolved form.

[0013] Phase composition of the present invention, when the most simple structure, comprising a continuous aqueous phase comprising a phase (I) per se, a continuous and non-aqueous phase of phase (II) itself. However, in the compositions of the present invention, one or more continuous phases may comprise part of another phase in emulsified form, such that in such compositions, for example, phase (I) Partially present as a continuous phase (I) (referred to as a continuous aqueous phase of the composition) and in a continuous non-aqueous phase (II) as a partially emulsified state as a discontinuous phase (I). it can. Similar conditions apply to phase (II) and other continuous phases.

According to a second aspect of the present invention, the present invention provides a method for cleaning and / or disinfecting or sanitizing a hard surface (particularly a glass surface), which comprises the cleaning composition of the present invention. , Temporarily convert to emulsion by shaking,
Applied to a surface to be cleaned and / or disinfected or sanitized, preferably by spraying, whereby such surface is cleaned and / or disinfected or sanitized, and if necessary such surface is moistened Provided is a method of wiping with a flexible soft article.

The term “disinfection, sanitary treatment, antibacterial activity or antibacterial active ingredient” as used herein, has the meaning known in the literature. Have [eg, KH Wallhaeusser: Praxis
der Sterilisation, Desinfektion-Konservierung: Keimidentifizierung-B
etriebshygiene "(Practice of Sterilization, Disinfection-Preservation
) Germ Identification-Plant Hygiene) (5th edition, Stuttgart; New York: Thie
me, 1995)]. The narrow term "disinfection" in medical use theoretically means to kill all infectious bacteria, and the term "hygienic treatment" usually removes all bacteria including harmful bacteria to humans. It means removing as much as possible. The degree of disinfection or hygienic treatment depends on the antibacterial activity of the composition used, which antibacterial activity decreases with decreasing content of antibacterial active ingredient or increasing dilution of the composition.

The composition of the present invention exhibits separate phases, which can be emulsified during use, retain homogeneity during use, and then again form a separate phase, and of the present invention. The composition can exhibit antibacterial activity. Moreover, the compositions of the present invention can exhibit very high overall storage stability as well as high cleaning performance. Therefore,
Each phase can show good stability over long periods without the formation of precipitates etc., and also its conversion properties to transient emulsions are reversible, even after frequent shaking. In addition, in addition, the physical form of the compositions of the present invention can avoid the stabilization problems of conventional compositions that have themselves been formulated as emulsions. Partitioning each component into a separate phase can further facilitate the chemical stability of the composition. In addition, the compositions of the present invention can exhibit excellent residue behavior. That is, viscous residues can be largely avoided, whereby the surface gloss can be retained without the need for rinsing.

Dosage: Antibacterial active ingredient According to the invention, the content of at least one antibacterial active ingredient in the composition is generally
It is 0.001 to 20% by weight, preferably 0.01 to 10% by weight, more preferably 0.02 to 5% by weight, particularly preferably 0.05 to 1.5% by weight, most preferably 0.1 to 0.5% by weight.

Antibacterial Active Ingredient No. 1 The composition of the present invention may contain at least one antibacterial active ingredient for antibacterial activity. The antibacterial active ingredient is preferably selected from the group consisting of: Alcohols, amines, aldehydes, antibacterial acids and salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyl, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formal, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives , Antibacterial surfactant compound, guanidine, antibacterial amphoteric compound, quinoline, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynylbutylcarbamate, iodine, iodohole, peroxo compound, halogen compound And a mixture of the above substances.

Antibacterial Active Ingredient 2 The antibacterial active ingredient is selected from the group consisting of the following substance groups. Ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, dihydroacetic acid, o-phenylphenol,
N-methylmorpholine acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylene-bis- (6-bromo-4-chlorophenol), 4,4'-dichloro-2'-hydroxydiphenyl ether (Dichitosan), 2, 4, 4'-trichloro-2'-hydroxydiphenyl ether (trichitosan), chlorohexidine, N- (4-chlorophenyl) -N-3,4-dichlorophenyl) urea, N, N '-(1 , 10-Decandiyldi-1-pyridinyl-4-ylidene) -bis- (1-octaneamine) dihydrochloride, N, N'-bis- (4-chlorophenyl) -3,12-diimino-2,4,11 13-Tetraazatetradecanediimidamide, glucoprotamine, quaternary antibacterial surfactant compounds, guanidines such as bi and polyguanidines such as 1,6-bis- (2-ethylhexyl biguanide hexane) dihydrochloride, 1,6-di _{- (N 1, N 1 '} - Enirujiguanido -N _5, N ₅ ') hexane tetrahydrochloride, 1, 6-di _{- (N 1, N 1'} - phenyl -N _1, N ₁ - Mechirujiguanido -N _5, N ₅ ') hexane dihydrochloride, 1, 6-Di- (N ₁ , N ₁ '-o-chlorophenyldiguanide-N ₅ , N ₅ ') Hexanedihydrochloride, 1, 6-di- (N ₁ , N ₁ '-2,6-dichlorophenyldig Anide-N ₅ ,, N ₅ ') hexanedihydrochloride, 1,6-di- [N ₁ N ₁ ' -β- (p-methoxyphenyl) diguanide-N ₅ , N ₅ '] hexanedihydrochloride, 1, 6- di - (N ₁ N ₁ '-α- methyl -β- phenyl jig biguanide -N _5, N _5') hexane dihydrochloride, 1, 6-di _{- (N 1, N 1 '} -p- nitro Phenyldiguanide-N ₅ , N ₅ ') Hexanedihydrochloride, ω: ω-di- (N ₁ , N ₁ ' -Phenyldiguanide-N ₅ , N ₅ ') -Di-n-propyl ether dihydro Chloride, ω: ω'-di- (N ₁ , N ₁ '-p-chlorophenyldiguanide-N ₅ , N ₅ ') -di-n-propyl ether tetrahydrochloride, 1, 6-di- (N ₁ , N ₁ ' -2, 4-dichlorophenyldiguanide-N ₅ , N ₅ ') hexanetetrahydrochloride, 1, 6-di- (N ₁ , N ₁ '-p-methyl-phenyldiguanide-N ₅ , N ₅ ') hexanedihydrochloride, 1, 6-di- (N ₁ , N ₁ '-2, 4, 5-trichlorophenyl jig biguanide -N _5, N ₅ ') hexane tetrahydrochloride, 1, 6-di _{- [N 1, N 1'} -α- (p- chlorophenyl) Echirujiguanido -N _5, N ₅ '] hexane Dihydrochloride, ω: ω-di- (N ₁ , N ₁ '-p-chlorophenyldiguanide-N ₅ , N ₅ ') -m-xylene dihydrochloride, 1, 12-di- (N ₁ , N ₁ '-p-chlorophenyl jig biguanide -N _5, N _5') dodecane dihydrochloride, 1, 10-di _{- (N 1, N 1 '} - phenyl jig biguanide -N _5, N _5') decane tetrahydrochloride, 1, 12-di _{- (N 1, N 1 '} - phenyl jig biguanide -N _5, N _5') de Kang tetrahydrochloride, 1, 6-di _{- (N 1, N 1 '} -o- chlorophenyl jig biguanide -N _5, N _5') hexane dihydrochloride, 1, 6-di _{- (N 1, N 1 '} - o- chlorophenyl jig biguanide -N _5, N ₅ ') hexane tetrahydrochloride, ethylene - bis - (1-tolylbiguanide), ethylene - bis - (p-tolylbiguanide), ethylene bis - (3,5-dimethylphenyl Biguanide), ethylene-bis- (p-tert. Amylphenyl biguanide), ethylene-bis- (nonylphenyl biguanide), ethylene-bis- (phenyl biguanide), ethylene-bis- (N-butylphenyl biguanide), ethylene bis -(2,5-diethoxyphenyl biguanide), ethylene-bis- (2,4-dimethylphenyl biguanide), ethylene-bis- (o-diphenyl biguanide), ethylene-bis- (mixed amylnaphthyl biguanide) ), N-butylethylene bis (phenyl biguanide), trimethylene-bis- (o-tolyl biguanide), N-butyl trimethylene-bis- (phenyl biguanide) and corresponding salts such as acetate, gluconate, Hydrochloride, hydrobromide, citrate, bisulfate, fluoride, polymaleate, N-cocoalkyl sarcosinate, phosphite, hydrophosphite, perfluorooctoate, silicate, sorbate, salicylate, maleate , Tartrate, fumarate, ethylenediaminetetraacetate, iminodiacetate, cinnamate, thiocinnamate, alginate, pyromellitate, tetracarboxybutyrate, benzoate, glutarate, monofluorophosphate, perfluoropropionate and Mixture of these. Further, the following substances are also suitable. Halogenated xylol and cresol derivatives, such as p-chloro-m-cresol or p-chloro-m-xylene, and natural antibacterial actives from botanical sources (eg spices or herbs), natural antibacterial actives from animal sources And natural antimicrobial active ingredients derived from microbial sources can also be used. Preferred antimicrobial active ingredients are antimicrobial surfactant quaternary compounds, natural antimicrobial active ingredients from plant sources and / or natural antimicrobial active ingredients from animal sources, more preferably caffeine, theobromine and theophylline and At least one natural antibacterial active ingredient and / or an enzyme such as an essential oil selected from the group consisting of eugenol, thymol and geraniol, and / or at least one natural antibacterial activity derived from an animal source selected from the group consisting of milk protein, lysozyme and lactoperoxidase Component and / or at least one antimicrobial surfactant quaternary compound containing an ammonium, sulfonium, phosphonium, iodonium or arsonium group. Substances derived from microbial sources, so-called Bakteriozine, can also be used.

Quaternary Ammonium Compounds According to one preferred embodiment of the present invention, the composition of the present invention comprises at least one formula:
A quaternary ammonium compound (QAC) represented by (R ¹ ) (R ² ) (R ³ ) (R ⁴ ) N ⁺ X ⁻ may be contained. In the above formula, R ^{1 to} R ⁴ are the same or different and each is a C _1-22 alkyl group, a C _7-28 aralkyl group or a heterocyclic group, or two or three (of aromatic compound formation such as pyridine). And the nitrogen atom together form a heterocyclic compound, for example a pyridinium or imidazolinium compound,
X ⁻ means a halogen ion, a sulfate ion, a hydroxide ion or a similar anion. From the standpoint of optimal antibacterial activity, the at least one substituent may suitably have a carbon chain length of 8-18, more preferably 12-16.

Preparation of Quaternary Ammonium Compounds Quaternary ammonium compounds can be obtained by reacting a tertiary amine with an alkylating agent such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide and ethylene oxide. . Suitably, a tertiary amine having one long alkyl chain and two methyl groups is alkylated. Quaternization of tertiary amines containing two long chains and one methyl group can also be carried out with methyl chloride under mild conditions. Amines containing three long alkyl chains or hydroxy-substituted alkyl chains lack reactivity and are preferably quaternized with dimethyl sulfate.

Examples of Quaternary Ammonium Compounds Suitable quaternary ammonium compounds (QAC) are, for example, the following substances. Benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalcon B (m, p-dichlorobenzyldimethyl-C ₁₂ -alkylammonium chloride, CAS No. 58390-78-6), Benzoxanium chloride (benzyldodecyl-bis- (2-hydroxyethyl))
Ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethylammonium bromide, CAS No. 57-09-0), benzethonium chloride (N, N-dimethyl-N- [2- [2- [2- [P- (1,1,3,3-Tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0), dialkyldimethylammonium chloride, eg di-n-decyldimethylammonium Chloride (CAS No. 7173-51-5-5), Didecyldimethylammonium bromide (CAS No. 2390-68-3), Dioctyldimethylammonium chloride, 1-cetylpyridinium chloride (CAS No. 123-03-5) And thiazoline iodide (CAS No. 15764-48-1) and mixtures thereof. A preferred QAC is a _C8-18 alkyl group-containing benzammonium chloride, more preferably a _C12-14 alkylbenzyldimethylammonium chloride. The benzalkonium halides and / or the substituted benzalkonium halides are
It is commercially available and, for example, the followings are exemplified. Barquat® (Lonza), Marquat® (Mason), Variquat® (Witco / Sherex), Hyamine® (Lonza), Bardac® (Lonza). Other commercially available antibacterial active ingredients are N- (3-chloroallyl) hexaminium chlorides such as Dowicide® and Dowicil® (Dow).
, Benzethonium chloride, such as Hyamine® 1622 (Rohm & Haas
), Methylbenzethonium chloride, such as Hyamine® 10X (Rohm
& Haas), cetylpyridinium chloride, such as cepacol chloride (Merre
ll Labs).

According to one preferred embodiment of the invention, the composition of the invention comprises at least two antibacterial active ingredients, in particular the composition comprises in phase (I) at least one water-soluble antibacterial active ingredient. An active ingredient (eg, a quaternary surfactant compound (eg, benzalkonium chloride) and / or an antibacterial active acid (eg, benzoic acid or salicylic acid), and at least one other antibacterial active ingredient (eg, eugenol) in phase (II). , Thymol or geraniol).

According to another preferred embodiment of the present invention, the composition of the present invention is substantially free of trifluorocarbon (CFC). That is, the non-aqueous liquid phase (II) is not based on trifluorocarbon. More specifically, since trifluorocarbons have an adverse effect on the environment, the composition of the present invention preferably contains no trifluorocarbon at all, and only a very small amount up to about 5% by weight, based on the total amount of the composition. The above trifluorocarbon can be included.

According to a preferred embodiment of the invention, the continuous phases (I) and (II) can be contoured with respect to each other by well-defined boundaries.

According to a particularly preferred embodiment of the present invention, one or both of the continuous phases (I) and (II) comprises in each phase a part of the other phase as dispersant and of each continuous phase. 0.1-40% by volume, preferably 0.2-35% by volume, more preferably 0.2-35% by volume, particularly preferably 0.5-30% by volume, most preferably 1-20% by volume, based on volume. It can be included in an amount.
Therefore, the continuous phases (I) and (II) are reduced in each phase by the part of the volume distributed as dispersant in the other phase. According to a particularly preferred embodiment of the invention, phase (I) is present in phase (II) in an amount of 0.1 to 40% by volume, based on the volume of phase (II).
Preferably emulsified in an amount of 0.2 to 35% by volume (eg about 33% by volume).

According to another preferred embodiment of the present invention, in addition to the continuous phases (I) and (II), some of these two phases are also provided as emulsions of one of the two phases. Of the phase (I) and the portion of phase (II) that does not contain the emulsion from the (1) upper phase boundary and (1) lower phase boundary.
It is separated by one boundary (preferably two distinct boundaries).

The composition of the present invention is preferably 5 to 95% by volume of phase (I) and 95 to 5% by volume of phase (I).
I) can be included.

According to a preferred embodiment of the invention, the composition comprises 35-95% by volume of phase (I) and 5-65% by volume of phase (II), more preferably 55-95% by volume. % Phase (I) and 5 to 45
% Of phase (II), particularly 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 (II). (I) and 25
, 20 or 15% by volume of phase (II). In addition, the continuous phase (I) is
Suitably, it corresponds to the lower phase and the continuous phase (II) corresponds to the upper phase.

According to a preferred embodiment of the invention, the water-immiscible phase (II) is based on aliphatic petroleum hydrocarbons and / or terpene hydrocarbons. Petroleum hydrocarbons preferably have a boiling range of 130-260 ° C, more preferably 140-240 ° C, particularly preferably 150-220 ° C, for example C _9-13 -isoparaffin ( Boiling range 184-217 ℃
), Which is a commercially available product (eg, Shellsol® T, Deutsche Shell
Chemie AG (Eschborn)). Suitable terpene hydrocarbons are citrus oils, for example orange oil taken from the peel of oranges, orange terpenes present in orange oil, especially limonene or pine oil, tall oil extracted from roots and mixtures thereof. Also, phase (II) can consist entirely of aliphatic petroleum hydrocarbons and / or terpene hydrocarbons. In this regard, according to a preferred embodiment of the present invention, petroleum hydrocarbons, preferably 60 to 10 based on the phase (II) are used.
It may be included in an amount of 0% by weight, more preferably 90-99.99% by weight, particularly preferably 95-99.9% by weight, most preferably 97-99% by weight.

Dose: Surfactant According to one preferred embodiment of the invention, suitable surfactant substances are, in particular, those belonging to the group of anionic and / or nonionic surfactants. is there. The composition comprises one or more anionic and / or nonionic surfactants, the anionic surfactant being present especially in phase (I). The amount of anionic surfactant is generally not more than 10% by weight, preferably 0, based on phase (I).
0.01 to 5% by weight, more preferably 0.01 to 0.5% by weight, and particularly preferably 0.1 to 0.3% by weight. When the composition of the present invention contains a nonionic surfactant, the concentration of the surfactant in phase (I) is generally 3% by weight or less, preferably 0.001% or less based on phase (I). -0.3 wt%, more preferably 0.001-0.1 wt%, the concentration of the surfactant in phase (II) is generally 5 wt% or less, preferably 0.001-0.5 wt%, more preferably 0. 001 to 0.2% by weight, particularly preferably 0.005 to 0.1% by weight, most preferably 0.
0.01 to 0.05% by weight.

According to one preferred embodiment of the present invention, the one or more anionic surfactants are C _{8 to} C ₁₈ (particularly about C ₁₂ ) alkylbenzene sulfonates, C _{8 to} C ₂₀ alkane sulphones. salts, C ₈ -C ₁₈ monoalkyl sulfates, C ₈ -C ₁₈ alkyl polyglycol ether sulfate (including ethylene oxide 2 to 6 mol in ether group)
, A substance selected from the group consisting of sulfosuccinates having 8 to 18 carbon atoms in the alcohol residue and mixtures thereof.

Salt Form of Anionic Surfactant The anionic surfactant is preferably used as the sodium salt, but other alkali metal salts or alkaline earth metal salts such as magnesium salts, ammonium salts or amines. It can be used in the form of a salt.

Examples of such surfactants are sodium cocoalkylsulfate, sodium sec-alkanesulfonate having about 15 carbon atoms, and sodium dioctylsulfosuccinate. C ₁₂ -C ₁₄ fatty alkyl sulfates and 2EO containing sodium lauryl ether sulfate are particularly preferred.

However, according to the above quantitative data, when using cationic antibacterial active ingredients, for example surface-active quaternary compounds, especially quaternary ammonium compounds, the compositions according to the invention are preferably, to the extent possible. It has a low content of anionic surfactants (including soaps) and, according to one preferred embodiment of the invention, no anionic surfactants (including soaps). This is because the anionic surfactant is more or less immiscible with the antibacterial active quaternary compound. In this regard, it is clear to the person skilled in the art that it is necessary to investigate the miscibility of anionic surfactants with antimicrobial active ingredients which exhibit a microbial-reducing action.

Nonionic Surfactant No. 1 The above-mentioned nonionic surfactant is particularly a C _{8 to} C ₁₈ alcohol polyglycol ether, that is, an etherified alcohol having a C _{8 to} C ₁₈ alkyl group +2 to 15 EO (
Ethylene oxide unit), C _{8 to} C ₁₈ carboxy polyglycol ether + 2 to 15 EO
, C ₁₂ -C ₁₈ ethoxylated fatty amine + 2～8EO having a fatty acid group, C ₁₄ -C _{2 0} long chain amine oxides, long-chain alkyl poly having a C ₈ -C ₁₄ alkyl group and 1 to 3 glycoside units It is a glycoside. According to one preferred embodiment of the invention, the composition according to the invention comprises, as one or more nonionic surfactants, the group consisting of ethoxylates of long-chain alcohols, alkyl polyglycosides and mixtures thereof. It may include a substance of choice. Examples of such surfactants are oleyl cetyl alcohol + 5EO, nonylphenol alcohol + 10EO, lauric acid diethanolamide, cocoalkyldimethylamine and polyglycosides (average glucose unit 1.4).

Nonionic Surfactants No. 2 In the aqueous phase, suitable nonionic surfactants are likewise ethylene oxide adducts of long-chain alcohols, especially from _{4 to} 8 mol of C _{4 to} C ₈ fatty alcohols. ethylene oxide adducts, alkyl polyglycosides, for example, alkyl polyglycosides having glucose units to C ₈ -C ₁₀ alkyl groups and 2. In the non-aqueous phase (II), particularly suitable nonionic surfactants are fatty alcohol polyglycol ethers, in particular fatty alcohol polyglycol ether + 2 to 8 EO, for example oleylcetyl alcohol + 5 EO ether, and / or fatty acid polyglycol ether ( FAE
), Especially FAE + 2-10 EO, for example tallow fatty acid + 6 EO ether. Furthermore, in the case of nonionic surfactants, especially for alcohol polyglycol ethers and carboxylic polyglycol ethers, for phase (II), the degree of ethoxylation is a relatively short chain carbon chain length of low ethoxylation degree or The carbon chain lengths are matched to combine the relatively long chain carbon chain lengths of the relatively high degree of ethoxylation.

According to one particularly preferred embodiment of the present invention, the composition of the present invention comprises one or more anionic and nonionic surfactants. In this connection, the combinations of the anionic surfactants of phase (I) with the nonionic surfactants of phase (II) are, for example, particularly advantageous: A combination of a fatty alcohol sulfate and / or a fatty alcohol polyglycol ether sulfate (phase (I)) with a fatty alcohol polyglycol ether and / or a fatty acid polyglycol ether (FAE) (phase (II)), in particular C ₁₂ To C ₁₄ fatty alcohol sulphate and / or C _{12 to} C ₁₄ fatty alcohol polyglycol ether sulphate (preferably + 2EO) (phase (I)) and a nonionic surfactant, in particular C _{16 to} C _18. Fatty alcohol polyglycol ether (preferably +
2 to 8 EO) and / or C _{14 to} C ₁₈ fatty acid polyglycol ether (preferably,
+2 to 10 EO) (Phase (II)) combination.

Organic Solvent No. 1 Further, the cleaning agent of the present invention may contain one or more water-soluble organic solvents. According to one preferred embodiment of the invention, phase (I) comprises one or more organic solvents, preferably 0.1 to 15% by weight, preferably 1% based on said phase (I). -10% by weight, more preferably 1-10% by weight, most preferably 4-7% by weight, for example about 5 or 6% by weight.

Organic Solvents 2 Illustrative of suitable organic solvents are water-soluble hydrocarbons having one or more hydroxyl groups, preferably C _{2 to} C ₆ , especially C ₂ or C ₃ alcohols and glycols and These ethers (glycol ethers or ethers in the form of ether alcohols) and mixtures thereof.

Alcohols and ether alcohols The alcohols used are especially ethanol, isopropanol and n-propanol. Suitable ether alcohols are compounds which exhibit sufficient water solubility, preferably compounds having not more than 10 carbon atoms in the molecule. Examples of ether alcohols are ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol mono t-butyl ether and propylene glycol monoethyl ether, among which ethylene glycol monobutyl ether and propylene glycol monobutyl ether are It is suitable. When alcohol and ether alcohol are used together, the weight ratio is preferably 1: 2 to 4: 1. Ethanol is particularly suitable for the purposes of the invention.

According to a preferred embodiment of the present invention, the composition of the present invention comprises one or more water-soluble organic solvent, which organic solvent is preferably a lower alcohol having 2 or 3 carbon atoms. A substance selected from the group consisting of lower glycols having 2 or 3 carbon atoms, glycol ethers having up to 10 carbon atoms and mixtures thereof, especially ethanol.

The composition of the invention is a temporary emulsion by shaking (preferably up to 3 shakes, more preferably up to 2 shakes, particularly preferably 1 shake). Can be converted to. The temporary emulsion formed by shaking is stable for 0.5-10 minutes, preferably 1
It can exhibit rest for ~ 5 minutes, more preferably 1.5-4 minutes, the emulsion on the one hand immediately after shaking and without re-destruction before the end of application, and on the other hand a relatively long-lasting state. It will not be retained for a period of time. The term "stability" as used herein means that the transient emulsion produced by shaking can retain its morphology after a certain time at a rate of at least 90% by volume of the composition. . The principle for adjusting the selection and concentration of the base and active ingredients, as well as the final properties of the composition of the invention, lies in the viscosity adjustment of each phase.

Viscosity and viscosity modifier The viscosity of the aqueous phase (I) is preferably 0.1 to 200 mPa · s, more preferably 0.5 to 100 m.
Pa · s, particularly preferably 1 to 60 mPa · s, most preferably 5 to 20 mPa · s (Brookfield viscometer DV-II +, spindle 31, rotation speed 20 min ⁻¹ , 20 ° C.). To this end, the composition or existing phase comprises one or more regulators.
The dose of viscosity modifier is usually up to 0.5% by weight, preferably 0.00, based on phase (I).
An amount of 1 to 0.3% by weight, more preferably 0.01 to 0.2% by weight, particularly preferably 0.02 to 0.1.
% By weight. Suitable viscosity modifiers are especially synthetic polymers, such as homopolymers and / or copolymers of acrylic acid or derivatives thereof and salts thereof, for example:
A commercially available product [Carbopol (registered trademark) Goodrich], more preferably a crosslinked acrylic acid copolymer [Carbopol (registered trademark) EDT 2623] is used. Other acrylic polymers disclosed in WO 97/38076 are likewise suitable viscosity modifiers, the disclosure of which is hereby incorporated by reference.

Volatile Alkali Furthermore, the composition of the present invention may comprise a volatile alkali in phase (I). The volatile alkali is preferably ammonia and / or one or more alkanolamines (containing up to 9 carbon atoms in the molecule). Suitable alkanolamines are ethanolamines, of which monoethanolamine is preferred. The content of ammonia and / or alkanolamine is 0.01 to 3% by weight, more preferably 0.02 to 1% by weight, particularly preferably 0.05 to 0.5% by weight, based on phase (I).

Carboxylic Acid In addition to the volatile alkali, the composition of the present invention may further comprise a carboxylic acid in phase (I). The equivalent ratio of (amine and / or ammonia) / (carboxylic acid) is preferably 1: 0.9 to 1: 0.1. Suitable carboxylic acids are mono-, di- or polycarboxylic acids having up to 6 carbon atoms. Depending on the equivalent weight ratio of (amine) / (carboxylic acid), the content of carboxylic acid is based on phase (I),
It is preferably 0.01 to 2.7% by weight, more preferably 0.01 to 0.9% by weight. Examples of suitable carboxylic acids are acetic acid, gluconic acid, lactic acid, citric acid, succinic acid and adipic acid, of which acetic acid, citric acid and lactic acid are preferred. A particularly suitable carboxylic acid is acetic acid.

Auxiliaries and Additives In addition to the above-mentioned ingredients, the compositions according to the invention can contain other auxiliaries and additives of the type generally present in such compositions. The compositions of the present invention include, inter alia, dyes, perfume oils, pH adjusting agents (eg citric acid, alkanolamines or NaOH), preservatives, alkaline earth metal complexing agents, enzymes, bleaching systems and antistatic agents. Can be included. The dosage of such additives is usually less than 2% by weight in the detergent composition. The lower limit of the additive depends on its nature, for example in the case of dyes it is 0.001% by weight or less. The auxiliaries can be present, preferably in an amount of 0.01 to 1% by weight.

PH Value No. 1 The pH value of the composition of the present invention can be widely changed from strongly acidic to neutral to strongly alkaline. Preferably, the pH value is 1-12, more preferably 2-11.
In this regard, the pH dependence known to the person skilled in the art or obtainable by routine experimentation due to the antibacterial action of the antibacterial active ingredient should be taken into account. That is,
The pH should be chosen so as to obtain the best possible antimicrobial activity with the antimicrobial active ingredient and / or to predict a given pH value for a given cleaning purpose of the antimicrobial active ingredient. According to a neutral embodiment, the pH value is above 8 and
A value of less than, preferably 6.5 to 7.5, more preferably about 7.

PH Value No. 2 According to a preferred embodiment of the present invention, the composition of the present invention has been made alkaline and has a pH value of 8-12, preferably 8-11. , More preferably 8 to 10.5, particularly preferably 8 to 10.5, for example 8 to 9 (mildly alkaline) or more than 10.5.
Up to 11 or 12, for example 10 (strongly alkaline). This is particularly suitable when using antibacterial quaternary compounds. This is because the antibacterial activity usually increases as the pH value increases, while it completely disappears in the acidic range below pH 3.

PH Value No. 3 According to another preferred embodiment of the present invention, the composition of the present invention is acidified and has a pH value of 1 to 6, preferably 1.5 to. 5.5, more preferably 2-5, particularly preferably 2.2-4.5, such as 2.3, 3 or 4. This is suitable, for example, when salicylic acid is used as the antibacterial active ingredient. This is because the antibacterial activity usually increases with decreasing pH value.

According to a preferred embodiment of the invention, the composition comprises 70 to 95% by volume (preferably
70-95% by volume) aqueous phase (I) and 5-30% by volume (preferably 10-30% by volume) non-aqueous phase (II), wherein phase (I) is Based on I) 0-10% by weight anionic surfactant 0-3% by weight nonionic surfactant 0-2% by weight at least one antibacterial active ingredient 0-10% by weight water-soluble organic Solvent 0-0.5% by weight viscosity modifier 0-3% by weight volatile alkali 0-0.2% by weight perfume and up to 100% by weight water, phase (II) based on the phase (II) 0 to 100% by weight of aliphatic petroleum hydrocarbons 0 to 100% by weight of terpene hydrocarbons 0 to 10% by weight of at least one antibacterial active ingredient 0 to 5% by weight of nonionic surfactants, and 0 The total amount of aliphatic petroleum hydrocarbons and terpene hydrocarbons, comprising ~ 1% by weight of perfume, constitutes phase (II) in an amount up to 100% by weight, and consists of phases (I) and (II). Two phases At least one, at least one antimicrobial active ingredient, it can be in an amount exceeding 0% by weight on the basis of the phase, also the phase may further particularly containing a small amount of dye. According to a particularly preferred embodiment of the invention, the composition comprises 0.01% anionic surfactant.
-5% by weight, preferably 0.01-0.5% by weight, more preferably 0.1-0.3% by weight and / or a nonionic surfactant in an amount of 0.001-0.5% by weight, preferably 0.005%.
Can be included in an amount of 0.1 to 0.1% by weight, more preferably 0.01 to 0.05% by weight.

The composition of the present invention is sprayable and thus can be used with a spray dispenser.

According to a third aspect of the invention, the invention provides a product comprising the composition of the invention and a spray dispenser.

Spray Dispenser The spray dispenser is preferably a manually operable spray dispenser and in particular is selected from the group consisting of: Aerosol spray dispensers, automatic compression spray dispensers, pump spray dispensers and trigger spray dispensers, especially pump spray dispensers and trigger spray dispensers with transparent polyethylene or polyethylene terephthalate containers. Spray dispensers are described in detail in WO 96/04940 (Procter & Gamble) and in the U.S. Patents cited therein for spray dispensers, the disclosures of which are hereby incorporated by reference.

The composition according to the invention preferably comprises washing the composition, which has been temporarily converted into an emulsion by shaking, in an amount of about 1.5 to 10 g / m ² , in particular 3 to 7 g / m ^2. And / or by applying to a surface to be disinfected or sanitized, immediately followed by wiping this surface with an absorbent soft product, thereby cleaning and / or disinfecting or sanitizing the surface. Can be used. The composition according to the invention is preferably applied by means of a suitable spray device, in particular a spray dispenser or the product according to the invention, whereby a distribution as homogeneous as possible can be achieved. A sponge or cloth is particularly suitable for the wiping treatment, which can often be washed with water when treating a relatively large surface.

The composition of the present invention is prepared by separately mixing each phase from the raw materials, then combining these phases and thoroughly mixing each phase to finally obtain the composition obtained. It can be prepared by standing and separating into a temporary emulsion. The composition of the invention can also be prepared by mixing directly from the raw materials, then thoroughly mixing and finally allowing the resulting composition to separate into a temporary emulsion. . If, in a phase other than the phase to which each component is assigned or in a phase other than the phase in which each component is mixed, if some component is not completely insoluble, then this other phase may result in dispersion. , As long as a solubility equilibrium can be achieved, the components can be included in corresponding proportions.

Example The composition for compositions E1 and E2 of the invention in this example is given in the table below.
Shown in 1. Aliphatic petroleum hydrocarbon used is a C ₉ -C ₁₃ isoparaffins.
The composition of the invention consists of a clear aqueous phase (I) at the bottom and a creamy emulsion phase (I) in the non-aqueous phase at the top (II). In this case, the volume of emulsified phase (I) is about 1/3 of the volume of phase (II) and the volume ratio of (phase (I)) / (emulsion phase (I) in phase (II)) is , About 80:20, and these phases are separated by well-defined boundaries. The temporary emulsion formed by shaking exhibits stability for a period of about 3 minutes sufficient for easy application of the composition, then
The phases separated again.

[0058]

[Table 1] ^[a] Carbopol (registered trademark) ETD2623 ^[b] Shellsol (registered trademark) T

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) C11D 1/22 C11D 1/22 1/28 1/28 1/29 1/29 1/60 1/60 1 / 62 1/62 1/68 1/68 1/72 1/72 3/04 3/04 3/18 3/18 3/20 3/20 3/30 3/30 3/37 3/37 3/48 3/48 (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), AU, BR, CN, CZ, DZ, HU, ID, IL, IN, JP, KR, MX, PL, RO, RU, SG, SI, SK, TR, UA, ZA (72) Inventor Heinz-Dieter Zolder Nski Germany 64-72 (72) Inventor Jürgen Nogrich Germany The Federal Republic Day -40474 Düsseldorf, Henry - Dunanto - Schuettler cell No. 7 F-term (reference) 3B201 AA01 AB52 BB21 BB95 4C058 AA30 BB07 CC01 CC02 JJ08 4H003 AB14 AB19 AB22 AB31 AC05 AC08 AE04 AE05 BA12 DA05 EA23 EB04 EB06 EB08 EB14 EB21 EB23 EB30 EB43 EC01 ED02 ED03 FA34 FA37

Claims (26)

[Claims] 1. At least two continuous phases comprising at least one aqueous phase (I) and a non-aqueous liquid phase (II) immiscible with said aqueous phase (I), and comprising A liquid multi-phase detergent composition capable of being temporarily converted into an emulsion by the method, wherein the detergent composition contains at least one antibacterial active ingredient. 2. The composition comprises at least one antibacterial active ingredient, 0.001 to 2
0% by weight, preferably 0.01-10% by weight, more preferably 0.02-5% by weight, particularly preferably
A composition according to claim 1 containing in an amount of 0.05 to 1.5% by weight, most preferably 0.1 to 0.5% by weight. 3. The composition comprises at least one natural antibacterial active ingredient from a botanical source and / or at least one natural antibacterial active ingredient from an animal source, the former constituents being especially caffeine, theobromine and 3. A composition according to claim 1 or 2 which is selected from the group consisting of theophylline and essential oils such as eugenol, thymol and geraniol, the latter component being selected in particular from the group consisting of enzymes such as milk protein, lysozyme and lactoperoxidase. 4. The composition according to claim 1, comprising at least one surface-active quaternary compound having an ammonium group, a sulfonium group, a phosphonium group, an iodonium group or an arsonium group, in particular at least one quaternary ammonium compound.
The composition according to any one of 1. 5. The composition comprises two or more antibacterial active ingredients, in particular the composition comprises at least one water-soluble antibacterial active ingredient in phase (I) and phase (II). 5. A composition according to any of claims 1 to 4 which comprises at least one further antimicrobial active ingredient. 6. The composition according to claim 1, wherein the continuous phases (I) and (II) form a contour with each other with well-defined boundaries. 7. One or both of continuous phases (I) and (II) comprises in each phase a portion of the other phase as a dispersant, 0.1-40% by volume, based on the volume of each continuous phase,
Preferably 0.2 to 35% by volume, more preferably 0.2 to 35% by volume, particularly preferably 0.5 to 30% by volume, most preferably 1 to 20% by volume. The composition according to. 8. The phase (I) is emulsified in the phase (II) in an amount of 0.1 to 40% by volume, preferably 0.2 to 35% by volume, based on the volume of the phase (II). The composition according to any one of 1 to 7. 9. In addition to the continuous phases (I) and (II), some of these two phases are present in the other phase as an emulsion of one of the two phases, the emulsion being the emulsion. Is separated from the relevant part of phase (I) and phase (II) in which no is present by two boundaries (preferably two distinct boundaries), an upper phase boundary and a lower phase boundary. The composition according to any of the above. 10. The composition comprises 35 to 95% by volume of phase (I) and 5 to 65% by volume.
Phase (II), more preferably 55-95% by volume phase (I) and 5-45% by volume phase (II)
Composition according to any of claims 1 to 9, which particularly preferably comprises 70 to 90% by volume of phase (I) and 10 to 30% by volume of phase (II). 11. Phase (II) is an aliphatic petroleum hydrocarbon, preferably in the boiling range 13
0 to 260 ° C, more preferably 140 to 240 ° C, particularly preferably 150 to 220 ° C.
11. A composition according to any of claims 1 to 10 which comprises or is based on these hydrocarbons and / or terpene hydrocarbons, preferably orange oil and / or pine oil. 12. The phase (II) contains, based on the phase (II), an aliphatic petroleum hydrocarbon in an amount of 60 to 100% by weight, preferably 90 to 99.99% by weight, and more preferably 95 to 99.9% by weight. weight%
A composition according to any of claims 1 to 11, which particularly preferably comprises an amount of 97 to 99% by weight. 13. A composition according to any of claims 1 to 12, wherein the composition comprises one or more anionic and / or nonionic surfactants. 14. The composition comprises, as one or more anionic surfactants, a C _{8 to} C ₁₈ alkylbenzene sulfonate, a C _{8 to} C ₂₀ alkane sulfonate, a C _{8 to} C ₁₈ monoalkyl sulfate. salts, (including ethylene oxide units 2~6 mol) C ₈ ~C ₁₈ alkyl polyglycol ether sulfates, wherein comprises a material selected from the group consisting of C ₈ -C ₁₈ alkyl alcohol sulphosuccinates and mixtures thereof Item 14. The composition according to any one of items 1 to 13. 15. The composition according to claim 1, which comprises, as one or more nonionic surfactants, a substance selected from the group consisting of ethoxylates of long-chain alcohols, alkyl polyglycosides and mixtures thereof. 15. The composition according to any of 14. 16. A composition according to any of claims 1-15, wherein the composition comprises one or more anionic and nonionic surfactants. 17. Phase (I) comprises an anionic surfactant, in particular a C ₁₂ -C ₁₄ fatty alcohol sulphate and / or a C ₁₂ -C ₁₄ fatty alcohol polyglycol ether sulphate (preferably 2 mol. Phase (II) comprises a nonionic surfactant, in particular a C _{16 to} C ₁₈ fatty alcohol polyglycol ether (preferably 2 to 8 mol of ethylene oxide units). And / or C _{14 to} C ₁₈ fatty acid polyglycol ester (preferably 2 to 10 mol)
The composition according to any one of claims 1 to 16, which comprises the ethylene oxide unit of 18. The composition comprises one or more water-soluble organic solvent, which is preferably a lower alcohol having 2 or 3 carbon atoms, a lower alcohol having 2 or 3 carbon atoms.
18. The composition according to any one of claims 1 to 17, which is a substance selected from the group consisting of lower glycols, glycol ethers having up to 10 carbon atoms and mixtures thereof, especially ethanol. 19. The method according to claim 1, wherein the phase (I) contains a solvent in an amount of 0.1 to 15% by weight, preferably 1 to 10% by weight, based on the phase (I). The composition as described. 20. The composition comprises one or more viscosity modifiers, in particular homopolymers and / or copolymers of acrylic acid or derivatives thereof or salts thereof, up to 0.5% by weight, based on phase (I). An amount of, preferably 0.001 to 0.3% by weight,
A composition according to any one of claims 1 to 19 which is more preferably contained in an amount of 0.01 to 0.2% by weight, particularly preferably in an amount of 0.02 to 0.1% by weight. 21. The viscosity of phase (I) is 0.1 to 200 mPas, more preferably 0.5 to 100 mPas.
21. The composition according to any of claims 1 to 20, which is mPas, particularly preferably 1 to 60 mPas. 22. Phase (I) is a volatile alkali, in particular ammonia and / or
Or one or more alkanolamines (containing up to 9 carbon atoms in the molecule), based on phase (I), 0.01-3% by weight, more preferably 0.02-1% by weight, particularly preferably The composition according to any one of claims 1 to 21, comprising an amount of 0.05 to 0.5% by weight. 23. The composition comprises 70 to 95% by volume of an aqueous phase (I) and 5 to 30% by volume of a non-aqueous phase (II), the phase (I) being the phase (I). 0-10% by weight anionic surfactant 0-3% by weight nonionic surfactant 0-2% by weight at least one antibacterial active ingredient 0-10% by weight water-soluble organic solvent 0% by weight ~ 0.5 wt% viscosity modifier 0 ~ 3 wt% volatile alkali 0 ~ 0.2 wt% perfume, and up to 100 wt% water, phase (II), based on the phase (II), 0-100% by weight aliphatic petroleum hydrocarbons 0-100% by weight terpene hydrocarbons 0-10% by weight at least one antibacterial active ingredient 0-5% by weight nonionic surfactants, and 0-1 The total amount of aliphatic petroleum hydrocarbons and terpene hydrocarbons, containing up to 100% by weight of perfume, constitutes phase (II) in amounts up to 100% by weight, the two of which are phase (I) and phase (II). At least one of the at least one antimicrobial active ingredient composition according to any one of claims 1 to 22 in an amount exceeding 0% by weight, based on the phase. 24. The composition comprises 0.01 to 5% by weight of an anionic surfactant.
Preferably 0.01 to 0.5% by weight, more preferably 0.1 to 0.3% by weight and / or a nonionic surfactant in an amount of 0.001 to 0.5% by weight, preferably 0.005 to 0.1% by weight, The composition according to any one of claims 1 to 23, which more preferably comprises an amount of 0.01 to 0.05% by weight. 25. A product comprising the composition of any of claims 1-24 and a spray dispenser. 26. A method for cleaning and / or disinfecting or sanitizing hard surfaces, in particular glass surfaces, wherein the composition according to any of claims 1 to 24 is temporarily emulsioned by shaking. For surfaces to be cleaned and / or disinfected or sanitized,
A method, characterized in that it is preferably applied by spraying, whereby the surface is washed and / or disinfected or sanitized, and optionally wiped with a hygroscopic soft article.