WO2001021753A1 - Detergent aqueux antimicrobien a plusieurs phases - Google Patents

Detergent aqueux antimicrobien a plusieurs phases Download PDF

Info

Publication number
WO2001021753A1
WO2001021753A1 PCT/EP2000/008957 EP0008957W WO0121753A1 WO 2001021753 A1 WO2001021753 A1 WO 2001021753A1 EP 0008957 W EP0008957 W EP 0008957W WO 0121753 A1 WO0121753 A1 WO 0121753A1
Authority
WO
WIPO (PCT)
Prior art keywords
phase
acid
weight
agent
composition according
Prior art date
Application number
PCT/EP2000/008957
Other languages
German (de)
English (en)
Inventor
Georg Meine
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP00967670A priority Critical patent/EP1214395A1/fr
Priority to AU77761/00A priority patent/AU7776100A/en
Publication of WO2001021753A1 publication Critical patent/WO2001021753A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions

Definitions

  • Antimicrobial aqueous multiphase detergent
  • the invention relates to antimicrobial aqueous multiphase liquid cleaning agents which can be temporarily emulsified by shaking, their use for cleaning and / or disinfection or sanitation of hard surfaces, a product containing the agent and a process for their production.
  • Universally usable cleaning agents for all hard, wet or damp wipeable surfaces in the household and business are known as so-called all-purpose cleaners and are predominantly neutral to weakly alkaline aqueous liquid products, the 1 to 30 wt .-% surfactants, 0 to 5 wt .-% builder (e.g. citrates, gluconates, soda, polycarboxylates) 0 to 10% by weight of hydrotropes (e.g. alcohols, urea), 0 to 10% by weight water-soluble solvents (e.g. alcohols, glycol ethers) and optionally u. a. Contain skin protection agents, dyes and fragrances.
  • the 1 to 30 wt .-% surfactants 0 to 5 wt .-% builder (e.g. citrates, gluconates, soda, polycarboxylates) 0 to 10% by weight of hydrotropes (e.g. alcohols, urea), 0 to 10% by weight water-
  • Such aqueous liquid cleaners are usually in the form of homogeneous, stable solutions or dispersions.
  • certain, in particular hydrophobic, components in such cleaning agents to improve cleaning performance can result in this homogeneity being lost and inhomogeneous agents being obtained, the acceptance of which can be assessed as low by the consumer.
  • alternative formulations are required which, despite their inhomogeneity, have a defined external appearance and application form which is acceptable to the consumer. 1
  • antimicrobial agents for example surface-active quaternary compounds
  • surface-active quaternary compounds are incorporated into the cleaning agents.
  • the use of antimicrobial agents usually limits the flexibility in the formulation of a cleaning agent significantly, since, for example, the pH must be adapted to the antimicrobial agents and, depending on the antimicrobial agent, there are incompatibilities with certain other ingredients, such as the incompatibility of surface-active quaternary compounds with the highly effective anionic surfactants. Therefore, the antimicrobial effect is usually realized at the expense of the cleaning effect.
  • European patent application 116 422 describes a liquid hair or body shampoo with two aqueous phases which can be temporarily dispersed into one another by shaking, and both phases being miscible with water in any ratio.
  • the upper phase contains 8 to 25% by weight, based on the total composition, of at least one surfactant and the lower phase contains at least 6% by weight, based on the total composition, of dissolved sodium hexametaphosphate of the formula I,
  • n stands for an average of approximately 12. Additional builder salts can optionally be contained in the lower phase.
  • Anionic, cationic, amphoteric and / or nonionic surfactants can be contained as surfactants, preferably at least one anionic surfactant being contained.
  • hair treatment agents in the form of a 2-phase system which have an oil phase and a water phase, the oil phase being based on silicone oil or paraffm oil and being able to be mixed briefly by mechanical action.
  • the object of the present invention was to provide storage-stable agents with high cleaning performance and antimicrobial activity for cleaning and / or disinfection or sanitation of hard surfaces in an easily manageable form which is acceptable to the consumer.
  • the invention relates to an aqueous, liquid, multi-phase surfactant-containing cleaning agent with at least two continuous phases, which has at least one lower aqueous phase I and one upper aqueous phase II which is immiscible with this phase and can be temporarily converted into an emulsion by shaking, and the at least one contains antimicrobial agent.
  • the invention also relates to the use of an agent according to the invention for cleaning and / or disinfecting or sanitizing hard surfaces.
  • disinfection, sanitation, antimicrobial action and antimicrobial active substance have the customary meaning as used, for example, by KH Wallophußer in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene” (5th edition - Stuttgart; New York : Thieme, 1995) is reproduced.
  • disinfection in the narrower sense of medical practice means the killing of - theoretically - all infectious germs
  • sanitation means the greatest possible elimination of all - including the saprophytic - germs, which are normally harmless to humans.
  • the extent of disinfection or sanitation depends on the antimicrobial effect of the agent used, which decreases with decreasing antimicrobial agent content or increasing dilution of the agent for use.
  • temporary is understood to mean that preferably 90% of the demixing of the emulsion formed by shaking into the separated phases takes place at temperatures of about 20 ° C. to about 40 ° C. within 2 minutes to 10 hours and the last 2% of the segregation into the phase state before shaking is carried out within a further 15 minutes to 50 hours.
  • citric acid which can be used both as an acid for pH adjustment and as a phase separation aid and builder.
  • the agents according to the invention are notable for high cleaning performance, in particular on greasy soiling, in the case of diluted and undiluted use.
  • the multi-phase, in particular two-phase enables the realization of an antimicrobial effect and at the same time high cleaning performance.
  • a particular advantage is the low foaming power, which has a positive effect on the cleaning performance, of the agents according to the invention without the addition of foam inhibitors such as soaps.
  • the agents show favorable residue behavior.
  • the individual phases on average are stable for a long time without z. B. form deposits, and the transfer into a temporary emulsion remains reversible even after frequent shaking.
  • the agents enable the stable incorporation of components which can only be stably incorporated into single-phase aqueous solutions or stable emulsions or microemulsions by using solvents, solubilizers or emulsifiers, in particular the hydrophobic components and perfume oils described below.
  • the multi-phase, in particular two-phase enables the chemical stability of the agent to be improved by separating ingredients into separate phases.
  • the agent according to the invention contains at least one antimicrobial active ingredient, preferably selected from the groups of alcohols, Aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, surface active agents, pyridine derivatives, pyridine derivatives Compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides, in particular selected from ethanol, n-propanol, i-propyl, i-
  • the agent according to the invention particularly preferably contains at least one quaternary ammonium compound (QAV) with an antimicobial action according to the general formula (R'XR ") ⁇ ") ⁇ ) ⁇ XT, in which R 1 to R 1V are identical or different C 1 -C 22 -alkyl radicals , C 7 -C 8 aralkyl radicals or heterocyclic radicals, with two or in the case of an aromatic integration as in pyridine even three radicals together with the nitrogen atom the heterocycle, for.
  • a pyridinium or imidazolinium compound form represent and X ⁇ halide ions, sulfate ions, hydroxide ions or similar anions.
  • at least one of the residues preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
  • QAV are by reacting tertiary amines with alkylating agents, such as. B. methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as. B. methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • the alkylation of tertiary amines with one long alkyl residue and two Methyl groups are particularly easy to achieve, and the quaternization of tertiary amines with two long residues and one methyl group can also be carried out with the aid of methyl chloride under mild conditions.
  • Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are not very reactive and are preferably quaternized with dimethyl sulfate.
  • Suitable QAC are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkon B (m, /> - dichlorobenzyldimethyl-Ci2-alkylammonium chloride, CAS No. 58390-78 -6), benzoxonium chloride (benzyl-dodecyl-bis- (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No.
  • benzetonium chloride N, N -Dimethyl-N- [2- [2 - [ ⁇ - (l, l, 3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] - benzylammonium chloride, CAS No. 121-54-0
  • dialkyldimethylammonium chlorides such as di - «- decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammonium chloride, 1-cetylpyridinium chloride (CAS No.
  • QAV thiazoline iodide
  • Particularly preferred QAV are the benzalkonium chlorides with C 8 -C 8 -alkyl radicals, in particular C 2 -C] 4 -alkyl-benzyl-dimethylammonium chloride.
  • the agent contains at least one antimicrobial acid, preferably organic acid, particularly preferably selected from the group comprising undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, formic acid and acetic acid, as the antimicrobial agent (s) and mixtures thereof, most preferably selected from the group comprising lactic acid, benzoic acid, salicylic acid and formic acid and mixtures thereof, in particular mixtures of salicylic acid with formic acid, lactic acid and / or benzoic acid, for example mixtures of salicylic acid with formic acid.
  • organic acid particularly preferably selected from the group comprising undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, formic acid and acetic acid
  • the antimicrobial agent (s) and mixtures thereof most preferably selected from the group comprising lactic acid, benzoic acid, salicylic acid and formic acid and mixtures thereof, in particular mixtures of salicylic acid with formic acid, lactic acid and
  • the content of at least one antimicrobial active ingredient is usually 0.1 to 10% by weight, preferably 0.2 to 5% by weight, in particular 0.5 to 3% by weight, particularly preferably 1 to 2% by weight, for example 1.5% by weight.
  • an agent according to the invention consists of a lower continuous phase, which consists of the entire phase I, and an upper continuous phase, which consists of the entire phase II.
  • one or more continuous phases of an agent according to the invention can also contain parts of another phase in emulsified form, so that in such an agent, for example, phase I is partly present as continuous phase I, which is the lower continuous phase of the agent, and one other part than discontinuous phase I is emulsified in the upper continuous phase II.
  • phase II and other continuous phases are examples of phase II.
  • the continuous phases I and II are delimited from one another by a sharp interface.
  • one or both of the continuous phases I and II contain parts, preferably 0.1 to 25% by volume, in particular 0.2 to 15% by volume, based on the volume of the respective continuous phase each other phase as a dispersant.
  • the continuous phase I or II is then reduced by the volume that is distributed as a dispersant in the other phase.
  • Agents in which phase I is emulsified in phase II in amounts of 0.1 to 25% by volume, preferably 0.2 to 15% by volume, based on the volume of phase II, are preferred.
  • part of the two phases is present as an emulsion of one of the two phases in the other phase, this emulsion not being present due to two sharp interfaces, an upper and a lower one parts of phases I and II involved in the emulsion are delimited.
  • the agents according to the invention contain phase I and phase II in a volume ratio of 90:10 to 10:90, preferably 75:25 to 25:75, in particular 65: 35 to 35: 65, particularly preferably 60: 40 to 40: 60, extremely preferably 55: 45 to 45: 55, for example 50:50.
  • the agents according to the invention can contain one or more nonionic, anionic, amphoteric or cationic surfactants or surfactant mixtures from one, several or all of these classes of surfactants as the surfactant component.
  • the compositions contain surfactants in amounts, based on the composition, of usually 0.01 to 30% by weight, preferably 0.1 to 20% by weight, in particular 1 to 15% by weight, particularly preferably 3 to 12% by weight .-%, very preferably 5 to 10 wt .-%, wherein any antimicrobial surface-active compounds contained are not considered in terms of quantity as surfactants but as antimicrobial agents.
  • nonionic surfactants are, for example, C 6 -C 22 alkyl alcohol polyglycol ethers, alkyl polyglycosides and nitrogenous surfactants or also sulfo-succinic acid di-C] -C 2 -alkyl esters or mixtures thereof, especially the first two.
  • the compositions contain nonionic surfactants in amounts, based on the composition, of usually 0 to 30% by weight, preferably 0.1 to 20% by weight, in particular 1 to 14% by weight, particularly preferably 3 to 12% by weight. %, most preferably 5 to 10% by weight, for example 8.5% by weight.
  • non-ionic surfactants with their nonionic character advantageously contribute to the fact that the individual phases are stable on average over a long period of time without z. B. form deposits, and the transfer to a temporary emulsion remains reversible even after frequent shaking.
  • C 6 -C 22 alkyl alcohol polypropylene glycol / polyethylene glycol ethers are preferred known nonionic surfactants. They can be described by the formula II, R I O- (CH 2 CH (CH 3 ) O) p (CH 2 CH2 ⁇ ) e -H, in which R 1 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 8 to 18, in particular 10 to 16, carbon atoms,? stands for 0 or numbers from 1 to 3 and e stands for numbers from 1 to 20.
  • the C 6 -C 22 -alkyl alcohol polyglycol ethers of the formula II can be obtained by addition of propylene oxide and / or ethylene oxide to alkyl alcohols, preferably to oxo alcohols, the branched-chain primary alcohols obtainable by oxosynthesis, or to fatty alcohols, in particular to fatty alcohols.
  • Typical examples are polyglycol ethers of the formula II in which R 1 is an alkyl radical having 8 to 18 carbon atoms, p is 0 to 2 and e is a number from 2 to 7.
  • At least one representative of formula II with a linear alkyl radical R 1 is combined with at least one representative of formula II with a branched alkyl radical R 1 , for example and isodecanol + 6-EO. It is further preferred here that the linear alkyl radical comprises more carbon atoms than the branched alkyl radical.
  • End-capped C 6 -C 22 alkyl alcohol polyglycol ethers can also be used, ie compounds in which the free OH group in the formula II is etherified.
  • the end-capped C 6 -C 22 alkyl alcohol polyglycol ethers can be obtained by the relevant methods of preparative organic chemistry.
  • C 6 -C 22 -Alkyl alcohol polyglycol ethers are preferably reacted in the presence of bases with alkyl halides, in particular butyl or benzyl chloride.
  • Typical examples are mixed ethers corresponding to formula II in which R 1 is a technical fatty alcohol radical, preferably Ci 2 / ⁇ 4 -Kokosalkylrest,> 0, and e is 5 to 10 are provided, which are closed with a Butylgmppe.
  • Preferred nonionic surfactants are furthermore alkyl polyglycosides (APG) of the formula III, R OfG] * , in which R is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms, [G] is a glycosidically linked sugar radical and x is a number from 1 to 10.
  • APG are non-ionic surfactants and are known substances that can be obtained using the relevant methods of preparative organic chemistry.
  • the index number x in the general formula III indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10.
  • Alkyl glycosides with an average degree of oligomerization x of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl glycosides are preferred whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.6.
  • Xylose, but especially glucose, is preferably used as the glycosidic sugar.
  • the alkyl or alkenyl radical R can be derived from primary alcohols having 8 to 22, preferably 8 to 14, carbon atoms. Typical examples are capronalcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from ROELEN's oxosynthesis.
  • the alkyl or alkenyl radical R is preferably derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol.
  • Elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures should also be mentioned.
  • Nitrogen-containing surfactants may be included as further nonionic surfactants, e.g. B. fatty acid polyhydroxyamides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxamides which have alkyl groups with 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
  • the degree of ethoxylation of these compounds is generally between 1 and 20, preferably between 3 and 10.
  • Ethanolamide derivatives of alkanoic acids with 8 to 22 C atoms, preferably 12 to 16 C atoms, are preferred.
  • the particularly suitable compounds include the lauric acid, myristic acid and palmitic acid monoethanolamides.
  • the agents according to the invention contain one or more nonionic surfactants, preferably C 6 -C 22 alkyl alcohol polyglycol ethers and / or alkyl polyglycosides, in particular C 6 -C 22 alkyl alcohol polyglycol ethers.
  • nonionic surfactants preferably C 6 -C 22 alkyl alcohol polyglycol ethers and / or alkyl polyglycosides, in particular C 6 -C 22 alkyl alcohol polyglycol ethers.
  • Suitable anionic surfactants are the preferred C 6 -C 22 alkyl sulfates, C 6 -C 22 alkyl ether sulfates, ie the sulfation products of the alcohol ethers of the formula II, and / or anionic sulfonic acids or their salts, the sulfonates, but also C 6 - C 22 -carboxylic acid amidethersulfate, sulfosuccinic acid-C ⁇ -C 1 - alkyl, C 6 -C 22 - ether carboxylates Alkylpolyglykol-, C 6 -C 22 N-acyl taurides, C 6 -C 22 N-sarcosinates and C 6 -C 22 alkyl isethionates or mixtures thereof.
  • Anionally active sulfonic acids in the sense of the teaching according to the invention are sulfonic acids of the formula R-SO 3 H which have a partially or completely straight-chain and / or branched and / or cyclic and partially or completely saturated and / or unsaturated and / or aromatic C 6 .
  • 32 -C hydrocarbon radical R carry, for example C 6-22 alkane sulfonic acids, C 6 - 22 ⁇ -olefin sulfonic acids, sulfonated C 6 -C 22 fatty acids and C 6- ⁇ 0 -arenesulfonic acids such as C ⁇ -22- alkylbenzenesulfonic acids or C ⁇ - 22 -alkylnaphthalenesulfonic acids, preferably linear C 8- ⁇ 6 -alkylbenzenesulfonic acids, especially linear C 10- ⁇ 4 -alkyl, C 10- i 3 -alkyl - And C ⁇ -alkylbenzenesulfonic acids.
  • the anionic surfactants are in the form of their alkali metal and alkaline earth metal salts, in particular sodium, potassium and magnesium salts, as well as ammonium and mono-, di-, tri- or tetraalkylammonium salts and in the case of anionic sulfonic acids also in the form of the acid, for.
  • alkali metal and alkaline earth metal hydroxides especially sodium, potassium and magnesium hydroxide, and ammonia or mono-, di-, tri- or tetraalkylamine, - depending on the pH of the agent to be adjusted partially or completely - neutralized to the aforementioned salts
  • Agents contain one or more anionic surfactants in amounts, based on the composition, of 0 to less than 30% by weight, preferably 0.1 to 20% by weight, in particular 0.5 to 10% by weight, most preferably 0.7 to 5% by weight, for example 1 or 1.2% by weight.
  • the agents according to the invention can also use soaps, i.e. Alkali or ammonium salts of saturated or unsaturated C6-C22 fatty acids.
  • the soaps can be used in an amount of up to 5% by weight, preferably from 0.1 to 2% by weight.
  • the agents When using cationic antimicrobial agents such as surface-active quaternary compounds, especially quaternary ammonium compounds, however, the agents preferably contain as little anionic surfactants as possible, including soaps, and in a particularly preferred embodiment of the invention are completely free of anionic surfactants, including soaps, since these often have more or are less compatible with the antimicrobial quaternary compounds. It is self-evident for the person skilled in the art that he must verify the compatibility of the anionic surfactants with the antimicrobial active substances with regard to the germ-reducing effect.
  • Suitable amphoteric surfactants are, for example, betaines of the formula R) (R 4 ) (R) N + CH 2 COO " , in which R 3 is an alkyl radical with 8 to 25, preferably 10 to 21, carbon atoms and R 4 and R, optionally interrupted by heteroatoms or heteroatom groups 5 identical or different alkyl radicals with 1 to 3 carbon atoms, in particular C 0 -C 22 -alkyl-dimethylcarboxymethylbetaine and Cn-C ⁇ -alkyl-amidopropyl-dimethylcarboxymethylbetaine.
  • the compositions contain one or more amphoteric surfactants in amounts, based on the composition, of 0 to 15% by weight, preferably 0.01 to 10% by weight, in particular 0.1 to 5% by weight.
  • Cationic surfactants are, for example, betaines of the formula R) (R 4 ) (R) N + CH 2 COO " , in which R 3 is an alkyl radical with 8 to 25,
  • Suitable cationic surfactants are, for example, the surface-active quaternary compounds described above, in particular the surface-active quaternary ammonium compounds. If surface-active quaternary compounds are not already present as antimicrobial active ingredients, the compositions contain one or more cationic surfactants in amounts, based on the composition, of 0 to 10% by weight, preferably 0.01 to 5% by weight, in particular 0 , 1 to 3% by weight.
  • the compositions contain one or more hydrophobic components.
  • the hydrophobic components not only improve the cleaning effect against hydrophobic impurities such as greasy dirt, but also have a positive effect on the phase separation and its reversibility.
  • the defined inhomogeneous form of the multiphase agents according to the invention enables stable incorporation - in particular also in larger amounts - of the hydrophobic components which are used in single-phase aqueous solutions or stable emulsions or microemulsions only through the use of solvents, solubilizers or emulsifiers in mostly very limited amounts can be incorporated stably.
  • Suitable hydrophobic components are, for example, dialkyl ethers with the same or different C 4 -C 4 -alkyl radicals, in particular linear dioctyl ether; with aliphatic or aromatic alcohols, e.g. As methanol, ethanol, propanol, n-butanol, tert-butanol or phenol, or carboxylic acids, e.g. B.
  • acetic or carbonic acid etherified-esterified and / or etherified monomeric or homo- or heteropolymeric, especially monomeric and homodi- and trimeric, C 2 - - alkylene glycols, for example those under the trade name Dowanor from Dow Chemical and the under the trade names Arcosolv and Arconate from Arco Chemical and hereinafter referred to with their / NCT name in accordance with the International Dictionary of Cosmetic Ingredients by The Cosmetic, Toiletry, and Fragrance Association (CTFA), e.g. B.
  • CTFA Cosmetic, Toiletry, and Fragrance Association
  • Butoxydiglycol Dowanol ® DB
  • Methoxydiglycol Dowanof DM
  • PPG-2 Methyl Ether Dowanof DPM
  • PPG-2 Methyl Ether Acetate Dowanof DPM ⁇
  • PPG-2 Butyl Ether Dowanof DPnB
  • PPG-2 Propyl Ether Dowanof DPnP
  • Butoxyethanol Dowanof EB
  • Phenoxyethanol Dowanof EPh
  • Methoxyisopropanol Dowanof PM
  • PPG-1 Methyl Ether Acetate Dowanof PMA
  • Butoxyisopropanol Dowanof PnB
  • Propylene Glycol Propyl Ether Dowanof PnP
  • Phenoxyisopropanol Dowanof PPh
  • PPG-3 Methyl ether Dowanof TPM
  • PPG-3 butyl ether Dowanof TPnB
  • hydrophobic components B. aliphatic hydrocarbons with a boiling range of 145 to 200 ° C, isoparaffins with a boiling range of 200 to 260 ° C; essential oils, in particular limonene and pine oil extracted from pine roots and stumps; and also mixtures of these hydrophobic components, in particular mixtures of two or three of the hydrophobic components mentioned.
  • Preferred mixtures of hydrophobic components are mixtures of various dialkyl ethers, of dialkyl ethers and etherified or esterified mono- or polymeric C 2 -C 4 -alkylene glycols, of dialkyl ethers and hydrocarbons, of dialkyl ethers and ethereal oils, of hydrocarbons and ethereal oils, of dialkyl ethers and hydrocarbons and essential oils and of these mixtures.
  • Particularly preferred mixtures of hydrophobic components are mixtures of dialkyl ethers and etherified or esterified mono- or polymeric C 2 -C 4 -alkylene glycols, for example di- ⁇ -octyl ether and dipropylene glycol - «- butyl ether (PPG-2 propyl ether).
  • compositions contain hydrophobic components in amounts, based on the composition, of 0 to 20% by weight, preferably 0.1 to 15% by weight, in particular 1 to 12% by weight, particularly preferably 2 to 10% by weight , most preferably 3 to 8% by weight, e.g. B. 5% by weight. ⁇
  • the agents according to the invention can contain one or more phase separation aids.
  • Suitable phase separation aids are, for example, the alkali metal and alkaline earth metal halides, in particular chlorides and sulfates and nitrates, in particular sodium and potassium chloride and sulfate, and also ammonium chloride and sulfate or mixtures thereof.
  • Such salts as strong electrolytes which increase the ionic strength, support the phase separation through the salt effect.
  • Sodium chloride has proven to be particularly effective here.
  • the compositions contain phase separation aids in amounts, based on the composition, of 0 to 30% by weight, preferably 1 to 20% by weight, in particular 3 to 15% by weight, extremely preferably 5 to 12% by weight.
  • acids preferably organic acids such as carboxylic acids and / or inorganic acids, particularly preferably at least one acid selected from the group consisting of salicylic acid, lactic acid, benzene acid and boric acid, also stabilizes the phase separation of the agents.
  • the proportion of citric acid can be reduced, for example, while maintaining a stable phase separation of the cleaning agent.
  • phase separation of the detergent composition from about 1/3 lower to about 2/3 upper phase can be obtained.
  • phase ratio of the cleaning agent can be adjusted to about 40 parts lower and 60 parts upper phase with the same citric acid contents.
  • the phase ratio can be shifted to 30 parts of the upper and 70 parts of the lower phase with a proportion of 12% by weight of citric acid and a suitable amount of monoethanolamine.
  • the agent according to the invention preferably contains one or more builders, in particular to improve the cleaning performance.
  • Suitable builders are, for example, alkali metal citrates, gluconates, nitrilotriacetates, carbonates and bicarbonates, in particular sodium citrate, gluconate and nitrilotriacetate, and sodium and potassium carbonate and bicarbonate, and also alkali metal and alkaline earth metal hydroxides, in particular sodium and potassium Ammonia and amines, especially mono- and triethanolamine, or their mixtures.
  • These also include the salts of glutaric acid, succinic acid, adipic acid, tartaric acid and benzene hexacarboxylic acid, as well as aminotrimethylenephosphonic acid, hydroxyethane-1,1-diphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, ethylenediamine-tetra (methylenephonic acid), diethylenetriamine-penta (methylenephosphonic acid) 2-phosphonobutane-l, 2,4-tricarboxylic acid, phosphonates and phosphates, for example the sodium salts of methane diphosphonic acid, the pentasodium triphosphate known as sodium tripolyphosphate or Sodium hexametaphosphate such as a mixture of condensed orthophosphates of the formula I, in which n stands for an average of about 12.
  • Particularly preferred builders are citric acid or citrates, in particular sodium citrate, and aminotrimethylenephosphonic acid and mixtures thereof, in which the weight ratio of citric acid or citrate, based on citric acid, to aminotrimethylenephosphonic acid is preferably 1 to 10 to 100 to 1, in particular 1 to 1 up to 40 to 1, particularly preferably 2 to 1 to 20 to 1, most preferably 5 to 1 to 10 to 1, for example 8 to 1.
  • alkali metal and alkaline earth metal carbonates and bicarbonates preferably sodium carbonate (soda) are preferred, in particular together with citric acid or - optionally generated in situ from citric acid and hydroxide - citrate, e.g. As sodium or potassium citrate, particularly preferably together with the mixture of citric acid or citrate and aminotrimethylenephosphonic acid described above.
  • citrates - unless expressly stated otherwise - are the salts of triple deprotonated citric acid.
  • the mono- and dihydrogen citrates can also be used according to the invention.
  • compositions contain builders in amounts, based on the composition, of 0 to 30% by weight, preferably 0.1 to 20% by weight, in particular 1 to 15% by weight, particularly preferably 3 to 12% by weight , most preferably 5 to 10% by weight, for example 7.3% by weight.
  • the salts mentioned can also be used in the form of their corresponding acids or bases, which are then partially or completely neutralized depending on the pH to be set.
  • the acids mentioned can also be used in the form of their salts, preferably their alkali metal, alkaline earth metal, ammonium and mono-, di- or trialkanolarnmonium salts, in particular mono-, di- or triethanolammonium salts, or mixtures thereof, in particular their sodium salts , for example citric acid in the form of its monohydrate citric acid IH 2 O instead of citrate.
  • the builder salts also act as phase separation aids.
  • the complexing builders also serve in particular for ensure a clear application solution when using the agents with hard water.
  • a preferred builder is - optionally generated in situ from citric acid and hydroxide - citrate from the group of alkali metal, alkaline earth metal, ammonium and mono-, di- or trialkanolammonium citrates, preferably mono-, di- or triethanolammonium citrates, or their Mixtures, especially sodium citrate and / or potassium citrate, since citrates combine builder and phase separation aid properties in a particularly advantageous manner.
  • An advantageous alkaline builder is potassium hydroxide, since it has a particularly positive effect on the phase separation, the clarity and color brilliance of the phases as well as the sharpness and low or non-opacity of the phase boundary layer.
  • the agent according to the invention preferably also contains one or more perfume oils since, in addition to the scent effect, they support the phase separation and significantly improve the cleaning performance - in particular in amounts above 0.9% by weight.
  • perfume oils in particular regularly cause problems when they are incorporated, especially in larger quantities, into single-phase aqueous solutions or stable emulsions or microemulsions and make it necessary to use solvents, solubilizers or emulsifiers, but without being able to stabilize larger perfume oil contents. This is where the great advantage of the defined inhomogeneous form of the multi-phase agents according to the invention comes into play, which enables the perfume oils to be incorporated in a stable manner, especially in larger quantities.
  • the invention furthermore relates to the use of perfume oils in a liquid multiphase cleaning agent with at least two continuous phases, which has at least one lower aqueous phase I and one upper aqueous or non-aqueous phase II which is immiscible with this phase and temporarily shakes into one by shaking Emulsion can be transferred to improve cleaning performance.
  • the agent according to the use is preferably an aqueous liquid multiphase surfactant-containing cleaning agent with at least two continuous phases, the at least one lower aqueous phase I and one with this phase has immiscible upper aqueous phase II, in particular an agent according to the invention.
  • a suitable perfume oil with a fresh fruity fragrance contains, for example, Dynascone 10 (5.0), Cyclovertal (7.5), Hexylacetat (35.0), Allylheptanoat (200.0), Amylbutyrat (5.0), Prenylacetate (10, 0), aldehyde C 14 SOG (70.0), manzanate (15.0), melusate (30.0), ortho tert-butylcyclohexyl acetate (200.0), cinnamaldehyde (5.0), isobomylacetate (10.0), Dihydrofloriffone TD (2.5), floramate (100.0), phenylethyl alcohol (30.0), geraniol (105.0), cyclohexyl salicylate (150.0) and citronellol (20.0).
  • a suitable perfume oil with a fresh, floral fragrance contains, for example, bergamot oil (250.0), lemon oil Messina (50.0), citronellal (2.0), orange oil sweet (50.0), lavender oil (50.0), terpineol ( 50.0), Lilial (100.0), Phenylethyl alcohol (80.0), Citronellol (100.0), Geraniol (20.0), Benzyl acetate (60.0), Isoraldein 70 (50.0), Ylang ( 30.0), Ambroxan 10% in IPM (1.0), Heliotropin (47.0) and Habanolide (60.0).
  • a suitable perfume oil with an aromatic fragrance contains, for example, orange oil (710.0), ⁇ -pinene (130.0), ⁇ -pinene (20.0), ⁇ -terpinene (95.0) and Litsea Cubeba oil (55.0) ,
  • the content of one or more perfume oils is usually 0.1 to 15% by weight, preferably 0.5 to 10% by weight, in particular 1 to 5% by weight, particularly preferably 1.5 to 4% by weight , most preferably 2 to 3% by weight, e.g. B. 2.5% by weight.
  • the agent contains one or more enzymes.
  • Customary in detergents and cleaning agents enzymes for example proteases (z are suitable.
  • proteases z are suitable.
  • nonionic surfactants in general, and the alkyl polyglycosides improve in particular the storage stability of the enzyme-containing embodiment as well as the citric acid or its salts and the hydrophobic components, in particular the - optionally etherified or esterified - mono- or polymeric C2-C4 alkylene glycols, e.g. , B. the products sold under the trade names Dowanof, Arcosolv ® and Arconate ® as well as polyethylene glycols and their derivatives.
  • the multiphase nature of the agent according to the invention has an advantageous effect on the stability of the enzymes, which is presumably due to the enrichment of the enzymes in the above-mentioned stabilizing components and - in terms of ionic strength - less ionic upper phase II.
  • the pH of the agents according to the invention can be varied over a wide range, from strongly acidic to neutral to highly alkaline, but a range from 1 to 12, in particular 2 to 11, is preferred accessible through routine tests - pH dependence of the antimicrobial effect of the antimicrobial agent (s) used must be taken into account.
  • the pH should be as optimal as possible for the antimicrobial effect of the respective antimicrobial active ingredient (s) and / or if a specific pH value is specified for a specific cleaning purpose, the antimicrobial active ingredient (s) should be selected accordingly.
  • the pH of the agents according to the invention is to be understood as the pH of the agent in the form of the temporary emulsion.
  • the pH is above 6 to below 8, preferably 6.5 to 7.5 and in particular about 7.
  • the agents are alkaline with a pH of 8 to 12, preferably 8 to 11, in particular 8 to 10.5, for example between 8 and 9, e.g. B. 8.3, for moderate alkalinity or over 9 to 10.5, 11 or even 12, e.g. B. 10, for greater alkalinity.
  • This is particularly preferred when using antimicrobial quaternary compounds, since their antimicrobial activity generally increases with increasing pH, while occasionally they are completely absent in the acidic range below pH 3.
  • Suitable pH regulators are, on the one hand, acids such as the mineral acids, e.g. B. hydrochloric acid, but especially citric acid, and on the other hand the aforementioned alkaline builders, preferably sodium hydroxide, but especially because of the advantages already mentioned potassium hydroxide.
  • the agent according to the invention contains, in a special embodiment, small amounts of corresponding buffer substances, in the alkaline embodiment described, for example, soda or sodium bicarbonate.
  • the agents are acidified with a pH of 1 to 6, preferably 2 to 6, in particular 3 to 5.5, particularly preferably 3.5 to 5, for example 4, 4.4 or 4 ; 5.
  • the agents contain at least one acid.
  • Inorganic acids for example the mineral acids, for. Hydrochloric acid, and organic acids, for example saturated or unsaturated C ⁇ -6 mono-, di- and tricarboxylic acids and hydroxycarboxylic acids with one or more Hydroxygrappen, z.
  • Sokalan ® DCS succinic glutaric acid-adipic acid mixture.
  • Particularly preferred acids are citric acid, preferably used in the form of its monohydrate citric acid-IH 2 O, and the anionic sulfonic acids and combinations of citric acid with one or more anionic sulfonic acids, in particular with alkylarene sulfonic acids.
  • Citric acid advantageously combines acid, builder and phase separation aid properties, while the anionic sulfonic acids act simultaneously as an acid and an anionic surfactant.
  • one or more alkalis can also be used, for example the alkali metal, alkaline earth metal and Ammonium hydroxides and carbonates and ammonia, preferably sodium and potassium hydroxide, with potassium hydroxide being particularly preferred.
  • the viscosity of the agent according to the invention at 20 ° C. is preferably 5 to 1,000 mPa-s, in particular 10 to 500 mPa-s, particularly preferably 10 to 200 mPa-s, measured using a Brookfield rotary viscometer of the LVT or LVDV-II + type with small sample adapter at a speed of 30 min "1 , whereby the Brookfield spindle used as the measuring body should be selected so that the torque is in a favorable range and the measuring range is not exceeded.
  • spindle 31 is preferred and - if required for viscosities above about 240 mPa-s - preferably use spindle 25.
  • the agent according to the invention can contain one or more thickeners, preferably in an amount of 0.01 to 5% by weight, in particular 0.05 to 2.5% by weight, particularly preferably 0.1 to 1% by weight. -%, contain.
  • Suitable thickeners are organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein), organic modified natural substances (carboxymethyl cellulose and other cellulose ethers, hydroxyethyl- and propyl cellulose and the like, core meal ether), organic fully synthetic thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides) and inorganic thickeners (polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas).
  • organic natural thickeners agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin,
  • the polyacrylic and polymethacrylic compounds include, for example, the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (/ NC7 name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry, and Fragrance Association ( CTFA): Carbomer), also called Carboxyvinylpolymers are called.
  • a polyalkenyl polyether in particular an allyl ether of sucrose, pentaerythritol or propylene
  • CTFA Cosmetic, Toiletry, and Fragrance Association
  • Such polyacrylic acids are available, inter alia, from BFGoodrich under the trade name Carbopof, e.g. B.
  • Carbopof 940 (molecular weight approx.4,000,000), Carbopof 941 (molecular weight approx.1,250,000) or Carbopof 934 (molecular weight approx.3,000,000).
  • the following also include the following acrylic acid copolymers: (i) copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters (INCI acrylates copolymer), preferably formed with C 4 -4 -alkanols, to which, for example, the copolymers of Methacrylic acid, butyl acrylate and methyl methacrylate (G4S designation according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) belong and which, for example, from Rohm & Haas under the trade names Aculyn and Acusof are available, e.g.
  • B the anionic non-associative polymers Aculyn ® 33 (crosslinked), Acusof 810 and Acusof 830 (CAS 25852-37-3); (ii) Crosslinked high molecular acrylic copolymers, for example the copolymers of C 10 crosslinked with an allyl ether of sucrose or pentaerythritol. 30 -alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple esters (/ NC / acrylates / C 10-30 alkyl acrylate crosspolymer), preferably formed with C -alkanols, and which belong, for example, from BFGoodrich are available under the trade name Carbopof, e.g. B.
  • Carbopof ETD 2623 and Carbopof 1382 (INCI Acrylates / C 10-30 Alkyl Acrylate Crosspolymer) and Carbopof AQUA 30 (formerly Carbopof EX 473).
  • Preferred thickeners are the polysaccharides and heteropolysaccharides, in particular the polysaccharide gums, for example gum arabic, agar, alginates, carrageenan and their salts, guar, guaran, tragacant, gellan, ramsan, dextran or xanthan and their derivatives, e.g. B. propoxylated guar, and their mixtures.
  • Other polysaccharide thickeners such as starches or cellulose derivatives, can be used alternatively, but preferably in addition to a polysaccharide rubber, for example starches of various origins and starch derivatives, e.g. B.
  • a particularly preferred polymer is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2 to 15 x 10 6 and is available, for example, from Kelco under the trade name Keltrof, e.g. , B. as cream-colored powder Keltrof T (transparent) or as white granulate Keltrof RD ( ⁇ eadily E> ispersable).
  • the agents according to the invention can contain further auxiliaries and additives as are customary in such agents.
  • auxiliaries and additives include in particular polymers, soil release agents, solvents (e.g. ethanol, isopropanol, glycol ether), solubilizers, hydrotropes (e.g. sodium cumene sulfonate, octyl sulfate, butyl glucoside, butyl glycol), cleaning enhancers, disinfectants, antistatic agents, preservatives (e.g. B. glutaraldehyde), bleaching systems and dyes as well as opacifiers or skin protection agents, as described in ⁇ P-A-522 556.
  • solvents e.g. ethanol, isopropanol, glycol ether
  • solubilizers e.g. sodium cumene sulfonate, octyl sulfate, butyl glucoside, butyl glycol
  • the amount of such additives is usually not more than 12% by weight in the cleaning agent.
  • the lower limit of use depends on the type of auxiliary and additive and can be, for example, up to 0.001% by weight and less for dyes.
  • the amount of auxiliaries and additives is preferably between 0.01 and 7% by weight, in particular 0.1 and 4% by weight.
  • a preferred auxiliary and additive are dyes, since the phases can be colored differently by their addition, which facilitates the visual perception of the separated phases and also the tracking of the emulsion formation or separation, and thus makes the handling of the agent even easier.
  • the agents according to the invention can be prepared by mixing them directly from their raw materials, then mixing them and then standing the agent to separate the temporary emulsion.
  • the invention accordingly furthermore relates to a process for producing an agent according to the invention by mixing it directly from its raw materials, then mixing it and finally standing the agent to separate the temporary emulsion.
  • the reversible phase separation is caused by the complex interplay of a number of components and their characteristics are determined.
  • the surfactant present can already lead to phase separation according to the invention. If necessary, only the additional use of hydrophobic component, builder and / or perfume causes the phase separation. Otherwise the use of phase separation aids is required.
  • the agent according to the invention is sprayable and can therefore be used in a spray dispenser.
  • Another object of the invention is accordingly a product containing an agent according to the invention and a spray dispenser.
  • the spray dispenser is preferably a manually activated spray dispenser, in particular selected from the group comprising aerosol spray dispensers, self-building spray dispensers, pump spray dispensers and trigger spray dispensers, in particular pump spray dispensers and trigger spray dispensers with a container made of transparent polyethylene or polyethylene terephthalate.
  • Spray dispensers are described in greater detail in WO 96/04940 (Procter & Gamble) and the US patents cited therein for spray dispensers, all of which are referenced in this regard and the contents of which are hereby incorporated into this application.
  • Particularly suitable detergent compositions as shown in Tables 2-9 can be used as C 2 -Ci 4 fatty alcohol-1, 3 EO ether sulfate sodium salt Texapon SPN 70, as alkane sulfonate sodium salt Hostapur SAS 60, as alkyl polyglycoside APG 600 UP-W, as betaine derivative Dehyton PK 45 OKA and as fatty alcohol ethoxylate dehydol PO 5.
  • the agents E1 to E51 according to the invention were produced as described above. Tables 1-9 show the composition in% by weight, pH value and the quantified volume ratio of the upper phase II to the lower phase I. Unless stated otherwise, the compositions contain E1 to E51 ad 100.
  • the pH adjustment in E1 to E51 can be carried out, for example, if necessary by adding hydroxides such as NaOH and / or KOH.
  • the agents E1, E2 and E3 contained a perfume oil with an aromatic fragrance, consisting of 700.0% by weight of orange oil, 130.0% by weight of o-pinene, 20.0% by weight of o-pinene , 95.0% by weight of ⁇ -terpinene and 55.0% by weight of o Litsea Cubeba oil.
  • Phase II / Phase I clear / clear clear / clear clear / clear Volume ratio II I 50:50 50:50 50:50 Color Phase II / Phase I green / colorless blue / colorless blue / colorless
  • All agents showed two continuous phases, which temporarily formed a creamy-looking emulsion when shaken. Even after repeated shaking, separate phases formed again when left standing.
  • the storage stability was checked by assessing the medium after four weeks of storage at room temperature of 20 ° C, at elevated temperature of 40 ° C or in the cold at a temperature of 5 ° C.
  • the agent showed - regardless of the storage temperature - no visually perceptible change, in particular the agent could still be reversibly transferred into the temporary emulsion by shaking.
  • the agents were assessed by the test subjects as visually appealing and easy to use and achieved good cleaning results - in undiluted as well as in diluted form - especially when removing greasy dirt in the form of the dirt caused in the kitchen by the preparation of greasy or oily dishes.
  • the antimicrobial effectiveness of the agents El to E51 was examined with a view to the reduction in the number of live germs in the quantitative suspension test based on the test method DIN EN 1276.
  • test standard DIN EN 1276 describes a test method for
  • the means E2 and E3 were able to reduce the live germ counts of all four test organisms to below the limit of quantification provided by the test method under the selected test conditions, which corresponds to reduction factors of> 10 5 .
  • agents E4 to E51 correspond essentially to agents E2 and E3 in their antimicrobial action.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un détergent liquide aqueux à plusieurs phases contenant des tensio-actifs et présentant au moins deux phases continues. Le détergent selon l'invention présente au moins une phase inférieure aqueuse I ainsi qu'une phase supérieure aqueuse II non miscible avec la phase I ; il se transforme temporairement en une émulsion lorsqu'on l'agite et contient au moins un agent antimicrobien. Combiné à un atomiseur, le détergent selon l'invention forme un produit que l'on peut utiliser pour le nettoyage, la désinfection ou l'assainissement de surfaces dures. On le prépare par premier mélange directement à partir de ses constituants, puis par mélange intime desdits constituants et enfin par repos du détergent afin de séparer l'émulsion temporaire.
PCT/EP2000/008957 1999-09-23 2000-09-14 Detergent aqueux antimicrobien a plusieurs phases WO2001021753A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP00967670A EP1214395A1 (fr) 1999-09-23 2000-09-14 Detergent aqueux antimicrobien a plusieurs phases
AU77761/00A AU7776100A (en) 1999-09-23 2000-09-14 Anti-microbial, aqueous, multi-phase cleaning agent

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19945506.6 1999-09-23
DE1999145506 DE19945506A1 (de) 1999-09-23 1999-09-23 Antimikrobielles wäßriges mehrphasiges Reinigungsmittel

Publications (1)

Publication Number Publication Date
WO2001021753A1 true WO2001021753A1 (fr) 2001-03-29

Family

ID=7922961

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/008957 WO2001021753A1 (fr) 1999-09-23 2000-09-14 Detergent aqueux antimicrobien a plusieurs phases

Country Status (7)

Country Link
EP (1) EP1214395A1 (fr)
AR (1) AR025743A1 (fr)
AU (1) AU7776100A (fr)
CA (1) CA2320541A1 (fr)
CO (1) CO5231223A1 (fr)
DE (1) DE19945506A1 (fr)
WO (1) WO2001021753A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004018601A1 (fr) * 2002-08-14 2004-03-04 Unilever Plc Composition biphasique obtenue par utilisation de polydextrose
US7199092B2 (en) 2002-08-22 2007-04-03 Reckitt Benckiser Inc. Multi-phase liquid hard surface cleaning and/or disinfecting compositions
US9408870B2 (en) 2010-12-07 2016-08-09 Conopco, Inc. Oral care composition
US9693941B2 (en) 2011-11-03 2017-07-04 Conopco, Inc. Liquid personal wash composition
US11026422B2 (en) 2017-09-26 2021-06-08 Ecolab Usa Inc. Acid/anionic antimicrobial and virucidal compositions and uses thereof
US11116220B2 (en) 2017-12-22 2021-09-14 Ecolab Usa Inc. Antimicrobial compositions with enhanced efficacy
EP4050088A1 (fr) 2021-02-26 2022-08-31 The Procter & Gamble Company Composition de détergent liquide pour lavage de la vaisselle à la main
WO2022182690A1 (fr) 2021-02-26 2022-09-01 The Procter & Gamble Company Composition de détergent liquide pour laver la vaisselle à la main

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10119923A1 (de) * 2001-04-23 2002-10-24 Henkel Kgaa Mehrphasiges Konditioniermittel
US7448556B2 (en) 2002-08-16 2008-11-11 Henkel Kgaa Dispenser bottle for at least two active fluids
DE102005019658A1 (de) * 2005-04-26 2006-11-02 Henkel Kgaa Verbesserte bakterielle Suspensionsleistung
AU2016209008B2 (en) 2015-01-23 2021-04-22 Biocidium Ip Holdco, Co. Anti-bacterial compositions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1247189A (en) * 1967-12-28 1971-09-22 Unilever Nv Liquid compositions for the treatment of natural or synthetic fibres
EP0175485A2 (fr) * 1984-08-21 1986-03-26 Reckitt And Colman Products Limited Compositions de shampooing
WO1999047635A2 (fr) * 1998-03-16 1999-09-23 Henkel Kommanditgesellschaft Auf Aktien Detergent liquide polyphase
WO2000024852A2 (fr) * 1998-10-26 2000-05-04 Reckitt Benckiser N.V. Composition de lessive ou de detergent liquide
WO2000071665A1 (fr) * 1999-05-19 2000-11-30 Henkel Kommanditgesellschaft Auf Aktien Nettoyant aqueux acide a plusieurs phases

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4388302A (en) * 1981-04-28 1983-06-14 Neomed Corporation Coacervated iodine
GB8303014D0 (en) * 1983-02-03 1983-03-09 Reckitt & Colmann Prod Ltd Liquid cleansing composition
US5378731A (en) * 1991-06-07 1995-01-03 Minnesota Mining And Manufacturing Company Medicated shampoo

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1247189A (en) * 1967-12-28 1971-09-22 Unilever Nv Liquid compositions for the treatment of natural or synthetic fibres
EP0175485A2 (fr) * 1984-08-21 1986-03-26 Reckitt And Colman Products Limited Compositions de shampooing
WO1999047635A2 (fr) * 1998-03-16 1999-09-23 Henkel Kommanditgesellschaft Auf Aktien Detergent liquide polyphase
WO2000024852A2 (fr) * 1998-10-26 2000-05-04 Reckitt Benckiser N.V. Composition de lessive ou de detergent liquide
WO2000071665A1 (fr) * 1999-05-19 2000-11-30 Henkel Kommanditgesellschaft Auf Aktien Nettoyant aqueux acide a plusieurs phases

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004018601A1 (fr) * 2002-08-14 2004-03-04 Unilever Plc Composition biphasique obtenue par utilisation de polydextrose
US6787511B2 (en) 2002-08-14 2004-09-07 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Biphasic composition induced by polydextrose
CN1294244C (zh) * 2002-08-14 2007-01-10 荷兰联合利华有限公司 聚葡萄糖诱导的二相组合物
US7199092B2 (en) 2002-08-22 2007-04-03 Reckitt Benckiser Inc. Multi-phase liquid hard surface cleaning and/or disinfecting compositions
US9408870B2 (en) 2010-12-07 2016-08-09 Conopco, Inc. Oral care composition
US9693941B2 (en) 2011-11-03 2017-07-04 Conopco, Inc. Liquid personal wash composition
US11026422B2 (en) 2017-09-26 2021-06-08 Ecolab Usa Inc. Acid/anionic antimicrobial and virucidal compositions and uses thereof
US11937602B2 (en) 2017-09-26 2024-03-26 Ecolab Usa Inc. Solid acid/anionic antimicrobial and virucidal compositions and uses thereof
US11950595B2 (en) 2017-09-26 2024-04-09 Ecolab Usa Inc. Acid/anionic antimicrobial and virucidal compositions and uses thereof
US11116220B2 (en) 2017-12-22 2021-09-14 Ecolab Usa Inc. Antimicrobial compositions with enhanced efficacy
US11930819B2 (en) 2017-12-22 2024-03-19 Ecolab Usa Inc. Antimicrobial compositions with enhanced efficacy
EP4050088A1 (fr) 2021-02-26 2022-08-31 The Procter & Gamble Company Composition de détergent liquide pour lavage de la vaisselle à la main
WO2022182690A1 (fr) 2021-02-26 2022-09-01 The Procter & Gamble Company Composition de détergent liquide pour laver la vaisselle à la main

Also Published As

Publication number Publication date
CA2320541A1 (fr) 2001-03-23
CO5231223A1 (es) 2002-12-27
AR025743A1 (es) 2002-12-11
DE19945506A1 (de) 2001-04-05
AU7776100A (en) 2001-04-24
EP1214395A1 (fr) 2002-06-19

Similar Documents

Publication Publication Date Title
WO2001010996A1 (fr) Nettoyant aqueux a phases multiples a base de tensioactifs non ioniques
DE69936516T2 (de) Reinigungsmittelzusammensetzung, die in einer mikroemulsion löslich ist
EP1126019B1 (fr) Utilisation d' une composition aqueuse multiphasique pour nettoyage des surfaces dures
DE60108549T2 (de) Reinigungsmittel für harte Oberflächen
DE69816603T2 (de) Reinigungszusammensetzungen für harte oberflächen
WO2011051175A1 (fr) Produit de nettoyage antimicrobien pour surfaces dures
DD295865A5 (de) Fluessiges reinigungsmittel
WO2000065007A2 (fr) Detergents pour surfaces dures
WO2001021753A1 (fr) Detergent aqueux antimicrobien a plusieurs phases
WO2001021752A1 (fr) Produit nettoyant aqueux a plusieurs phases
DE69722408T3 (de) Antimikrobielle reinigungszusammensetzungen mit aromatischen alkoholen oder phenolen
DE19945503A1 (de) Mehrphasiges Reinigungsmittel mit antimikrobieller Wirkung
DE19906481A1 (de) Gelförmige Reinigungsmittel für Spültoiletten
WO2000071665A1 (fr) Nettoyant aqueux acide a plusieurs phases
WO2000039270A1 (fr) Produit de nettoyage aqueux multiphase
WO2000065010A1 (fr) Produits de nettoyage pour surfaces rigides
DE10131721C1 (de) Schnell lösliches Reinigungsgel
WO2002044314A1 (fr) Detergent de lavage et de nettoyage multiphasique contenant des agents de blanchiment
DE102005019658A1 (de) Verbesserte bakterielle Suspensionsleistung
DE60314371T2 (de) Flüssiges reinigungsmittel enthaltend einen biologischen abbaubaren chelatbildner
WO2001007547A1 (fr) Agent de nettoyage pour surfaces dures
DE10063427A1 (de) Antibakterielles Reinigungsmittel
WO2013074118A1 (fr) Composition nettoyante
WO2000065012A1 (fr) Detergents pour surfaces dures
DE102006045775A1 (de) Oberflächenbehandlungsmittel

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CN CZ DZ HU ID IL IN JP KR MX PL RO RU SG SI SK TR UA ZA

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2000967670

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2000967670

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: JP