DE102009002262A1 - Prebiotic hand dishwashing detergents - Google Patents

Prebiotic hand dishwashing detergents

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Publication number
DE102009002262A1
DE102009002262A1 DE102009002262A DE102009002262A DE102009002262A1 DE 102009002262 A1 DE102009002262 A1 DE 102009002262A1 DE 102009002262 A DE102009002262 A DE 102009002262A DE 102009002262 A DE102009002262 A DE 102009002262A DE 102009002262 A1 DE102009002262 A1 DE 102009002262A1
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Germany
Prior art keywords
preferably
characterized
use according
prebiotic
wt
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
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DE102009002262A
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German (de)
Inventor
Detlef Buisker
Christian Dr. Nitsch
Rainer Dr. Simmering
Heinz-Dieter Soldanski
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to DE102009002262A priority Critical patent/DE102009002262A1/en
Publication of DE102009002262A1 publication Critical patent/DE102009002262A1/en
Application status is Withdrawn legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/94Mixtures with anionic, cationic, or non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143Sulfonic acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/883Aminimide (= ammonioamidates)
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/886Ampholytes containing P
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/90Betaines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/92Sulfobetaines Sulfitobetaines

Abstract

A prebiotic surfactant combination can be used to maintain desired skin germs or to inhibit the growth of unwanted skin germs in the use of detergents and cleaners and for the preparation of a prebiotic detergent or cleaning agent.

Description

  • The The invention relates to the use of a prebiotic effective Surfactant combination for the preservation of desired skin germs or to inhibit the growth of unwanted skin germs Users of detergents and cleaning agents as well as for the production a prebiotic washing or cleaning agent.
  • The human skin surface is of a variety of different Germs colonized. While some of these germs are harmful are and for example acne or various skin diseases can cause (so-called "pathogenic germs"), emanates from others a positive effect (so-called "saprophyte Skin bacteria "). These saprophytes can through her Growth Keep harmful germs in check and practice such a protective function. It is therefore desirable to affect the skin flora so that pathogenic bacteria after Possibility reduced and promoted saprophyte germs become.
  • The use of prebiotic plant extracts in cosmetic or pharmaceutical preparations for skin treatment is already known. So, for example, deals EP 1658088 A1 with prebiotic active plant extracts used in topical cosmetic or pharmaceutical compositions.
  • Certain Practice in detergents and cleaners used surfactants or surfactant mixtures a negative influence on the skin flora. It would be therefore beneficial if this harmful influence is minimized could or even surfactants could be used protect the desirable germs or even theirs Promote growth and growth of pathogenic germs inhibit. Of course, this applies in particular to such cleaning applications, where there is direct skin contact with the detergent.
  • A Object of the present invention was therefore the provision a detergent whose surfactants in as low as possible Measure negatively affect the skin flora or even one exert positive influence.
  • Surprised It has now been found that a combination of certain surfactants the preservation of the skin flora serves.
  • One The subject of the present invention is therefore the use of a prebiotic effective surfactant combination to preserve desirable Skin germs when using washing and cleaning agents.
  • Next the maintenance of the desired saprophyte germs, the surfactant combination Also counteract the colonization of the skin by pathogenic germs.
  • One Another object of this invention is therefore the use of a prebiotic effective surfactant combination for the inhibition of Growth of unwanted skin germs in the user of washing and detergents
  • The Surfactant combination is suitable for the production of a washing and cleaning agent with prebiotic effect.
  • Yet Another object of the invention is therefore the use of a prebiotic effective surfactant combination for the production a prebiotic washing or cleaning agent.
  • at This washing or cleaning agent may preferably be a hand dishwashing detergent or a laundry detergent.
  • in the The present invention relates to fatty acids or Fatty alcohols or their derivatives - if not otherwise indicated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives preferably having 6 to 22 carbon atoms. The former are in particular because of their vegetable base than on renewable resources based on ecological reasons preferred, but without the teaching of the invention on them to restrict. In particular, for example, the oxo-alcohols obtainable by the ROELEN's oxo synthesis or their derivatives used accordingly.
  • Whenever alkaline earth metals are mentioned below as counterions for monovalent anions, so This means that the alkaline earth metal, of course, only in half - sufficient to charge balance - amount of substance as the anion is present.
  • Substances which also serve as ingredients of cosmetic products are referred to below, where appropriate, according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds carry an INCI name in English, plant ingredients are listed exclusively in Linnaeus in Latin, so-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI names are the International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997) issued by The Cosmetic, Toiletry and Fragrance Association (CTFA), 1101 17th Street, NW, Suite 300, Washington, DC, 20036, USA, and more than 9,000 INCI names, as well as references to more than 37,000 trade names and technical designations including related distributors from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook assigns to the ingredients one or more chemical classes (Chemical Classes), such as Polymeric Ethers, and one or more functions, such as Surfactants Cleansing Agents, which in turn will be further explained and to which reference may also be made hereinafter.
  • The Specification CAS means that it is the following sequence of numbers is a name of the Chemical Abstracts Service.
  • So far not explicitly stated otherwise, refer to indicated quantities in weight percent (wt.%) on the total agent. Refer to these percentage quantities are based on active contents.
  • surfactants
  • According to the invention a surfactant combination used, which is a prebiotic Has effect. This surfactant combination preferably contains at least one fatty alcohol ether sulfate and at least one betaine surfactant and / or alkyl polyglycoside and optionally secondary Alkanesulfonate.
  • alkyl ether
  • Alkyl ether sulfates (fatty alcohol ether sulfates, INCI alkyl ether sulfates) are products of sulfation reactions on alkoxylated alcohols. In this context, the person skilled in the art generally understands, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the context of the present invention preferably with longer-chain alcohols, ie with aliphatic straight-chain or one or more branched, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably straight-chain, acyclic, saturated, alcohols having 6 to 22, preferably 8 to 18, in particular 10 to 16 and particularly preferably 12 to 14 carbon atoms. In general, from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions, a complex mixture of addition products of different degrees of ethoxylation (n = 1 to 30, preferably 1 to 20, especially 1 to 10, particularly preferably 2 to 4). Another embodiment of the alkoxylation is the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Very particularly preferred for the purposes of the present invention are low-ethoxylated fatty alcohols having 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 2 EO, such as Na-C 12-14 fatty alcohol + 2EO sulfate.
  • The contains agents used in the invention in a preferred embodiment, one or more alkyl ether sulfates in an amount of 1 to 30% by weight, preferably 6 to 25% by weight, particularly preferably 8 to 20% by weight.
  • alkylsulfonates
  • Preferably contain the agents used in the invention furthermore one or more alkyl sulfonates. The alkyl sulfonates (INCI Sulfonic acids) usually have an aliphatic straight-chain or mono- or polysubstituted, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably branched, acyclic, saturated, alkyl radical with 6 to 22, preferably 9 to 20, in particular 11 to 18 and particularly preferably 14 to 17 carbon atoms.
  • Accordingly, suitable alkyl sulfonates are the saturated alkanesulfonates, the unsaturated olefin sulfonates and the ether sulfates which are derived formally from the alkoxylated alcohols on which the alkyl ether sulfates are based, in which terminal ether sulfonates (n-ether sulfonates) are attached to the Polyether chain bonded sulfonate function and internal ether sulfonates (i-ether sulfonates) with the alkyl-linked sulfonate function distinguishes.
  • Preference according to the invention is given to the alkanesulfonates, in particular alkanesulfonates having a branched, preferably secondary, alkyl radical, for example the secondary alkanesulfonate sec. Na C 13-17 alkanesulfonate (INCI Sodium C14-17 Alkyl Sec Sulfonate).
  • The contains agents used in the invention preferably one or more secondary alkanesulfonates in an amount of 0 to 8 wt .-%, preferably 1.5 to 6 wt .-%.
  • betaine
  • Suitable betaines are the alkylbetaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably satisfy formula I, R 1 - [CO-X- (CH 2 ) n ] x -N + (R 2 ) (R 3 ) - (CH 2 ) m - [CH (OH) -CH 2 ] y -Y - (I) in which R 1 is a saturated or unsaturated C 6-22 alkyl, preferably C 8-18 alkyl group, preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group,
    X is NH, NR 4 with the C 1-4 -alkyl radical R 4 , O or S,
    n is a number from 1 to 10, preferably 2 to 5, in particular 3,
    x is 0 or 1, preferably 1,
    R 2 , R 3 are independently a C 1-4 alkyl radical, optionally hydroxy-substituted, such as. B. a hydroxyethyl radical, but especially a methyl radical,
    m is a number from 1 to 4, in particular 1, 2 or 3,
    y is 0 or 1 and
    Y is COO, SO 3 , OPO (OR 5 ) O or P (O) (OR 5 ) O, wherein R 5 is hydrogen H or C 1-4 alkyl.
  • The alkyl and alkylamido betaines, betaines of the formula I having a carboxylate group (Y - = COO - ) are also called carbobetaines.
  • Preferred betaines are the alkylbetaines of the formula (Ia), the alkylamidobetaines of the formula (Ib), the sulfobetaines of the formula (Ic) and the amidosulfobetaines of the formula (Id), R 1 -N + (CH 3 ) 2 -CH 2 COO - (Ia) R 1 -CO-NH- (CH 2 ) 3 -N + (CH 3 ) 2 -CH 2 COO - (Ib) R 1 is -N + (CH 3 ) 2 -CH 2 CH (OH) CH 2 SO 3 - (Ic) R 1 -CO-NH- (CH 2 ) 3 -N + (CH 3 ) 2 -CH 2 CH (OH) CH 2 SO 3 - (Id) in which R 1 has the same meaning as in formula I.
  • Especially preferred betaines are the carbobetaines, in particular the carbobetaines of the formula (Ia) and (Ib), most preferably the Alkylamidobetaines of the formula (Ib).
  • Examples of suitable betaines and sulfobetaines are the following compounds designated as INCI: almondamidopropyl betaines, apricotamidopropyl betaines, avocadamidopropyl betaines, babassuamidopropyl betaines, behenamidopropyl betaines, behenyl betaines, betaines, canolamidopropyl betaines, caprylic / capramidopropyl betaines, carnitines, cetyl betaines, cocamidoethyl betaines, cocamidopropyl Betaines, cocamidopropyl hydroxysultaines, coco-betaines, coco-hydroxysultaines, coco / oleamidopropyl betaines, coco-sultaines, decyl betaines, dihydroxyethyl oleyl glycinates, dihydroxyethyl soy glycinates, dihydroxyethyl stearyl glycinates, dihydroxyethyl tallow glycinates, dimethicones, propyl PG-betaines, erucamidopropyl hydroxysultaines, Hydrogenated Tallow Betaine, Isostearamidopropyl Betaine, Lauramidopropyl Betaine, Lauryl Betaine, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaine, Minkamidopropyl Betaine, Myristamidopropyl Betaine, Myristyl Betaine, Oleamidopropyl Betaine, Oleamidopropyl Hydroxysult aine, oleyl betaines, olivamidopropyl betaines, palmamidopropyl betaines, palmitamidopropyl betaines, palmitoyl carnitines, palm kernelamidopropyl betaines, polytetrafluoroethylene acetoxypropyl betaines, ricinoleamidopropyl betaines, sesamidopropyl betaines, soyamidopropyl betaines, stearamidopropyl betaines, stearyl betaines, tallowamidopropyl betaines, Tal lowamidopropyl hydroxysultaine, tallow betaine, tallow dihydroxyethyl betaine, undecylenamidopropyl betaine and wheat germamidopropyl betaine. A preferred betaine is, for example, cocamidopropyl betaine (cocoamidopropylbetaine).
  • The contains agents used in the invention preferably one or more betaines in an amount of 0 to 15 Wt .-%, preferably 1.5 to 12 wt .-%, particularly preferably 2 to 6% by weight.
  • Alkylpolyglykoside
  • The alkylpolyglycosides (APG) are particularly preferred sugar surfactants within the scope of the teaching according to the invention and preferably satisfy the general formula R i O (AO) a [G] x in which R i is a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 , preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms, [G] for a glycosidically linked sugar residue and x for a number from 1 to 10 and AO for an alkyleneoxy group, for. Example, an ethyleneoxy or Propylenoxygruppe, and a for the average degree of alkoxylation of 0 to 20.
  • Here, the group (AO) a may also contain different alkyleneoxy, z. B. ethyleneoxy or propyleneoxy, wherein it is then a at the average Gesamtalkoxylierungsgrad, ie the sum of Ethoxylierungs- and Propoxylierungsgrad acts. Unless stated below or otherwise, the alkyl radicals R i of the APG are linear unsaturated radicals having the stated number of carbon atoms.
  • APG are nonionic surfactants and are known substances that according to the relevant procedure of preparative organic chemistry can be obtained. The index number x indicates the degree of oligomerization (DP degree), i. H. the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While x is in a given connection must always be integer and above all the values x = 1 to 6, the value x is for a given Alkyl glycoside an analytically determined arithmetic size, which usually represents a fractional number. Preferably Alkyl glycosides with a mean degree of oligomerization x of 1.1 used up to 3.0. From an application point of view, such are Alkyl glycosides are preferred whose degree of oligomerization is less than Is 1.7 and in particular between 1.2 and 1.6. As glycosidic Sugar is preferably used xylose, but especially glucose.
  • The alkyl or alkenyl radical R i can be derived from primary alcohols having 8 to 18, preferably 8 to 14 carbon atoms. Typical examples are caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, and technical mixtures thereof, such as those obtained during the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from ROELEN's oxosynthesis.
  • Preferably, however, the alkyl or alkenyl radical R i is derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol. Also to be mentioned are elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof.
  • Particularly preferred APG are not alkoxylated (a = 0) and satisfy the formula RO [G] x , in which R is as previously described for a linear or branched, saturated or unsaturated alkyl radical having 4 to 22 carbon atoms, [G] for a glycosidically linked sugar radical, preferably glucose residue, and x is a number from 1 to 10, preferably 1.1 to 3, in particular 1.2 to 1.6. Accordingly, preferred alkyl polyglycosides are, for example, C 8-10 and C 12-14 alkyl polyglucoside having a DP degree of 1.4 or 1.5, especially C 8-10 alkyl-1,5-glucoside and C 12-14 alkyl-1,4-glucoside.
  • The contains agents used in the invention preferably one or more alkylpolyglycosides in an amount from 0 to 15% by weight, preferably 1.5 to 12% by weight, more preferably 2 to 6 wt .-%.
  • solvent
  • The obtained from the surfactant combination according to the invention Washing or cleaning agent is preferably an aqueous one Medium. In addition to its water content, it may be advantageous in addition one or more water-soluble organic solvents contain, usually in an amount of 0.1 to 10 wt .-%, preferably 1 to 8 wt .-%.
  • The Solvent is within the scope of the invention Teaching as required, in particular as a hydrotrope, viscosity regulator and / or cold stabilizer used. It has a solution-promoting effect, prevents the formation of liquid crystalline phases and has a share in the formation of clear products. The viscosity the agent according to the invention decreases with increasing amount of solvent. Too much solvent However, it can cause excessive viscosity drop. Finally, it decreases with increasing amount of solvent the cold cloud and clear point of the invention Agent.
  • Suitable solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C 1-20 -hydrocarbons, preferably C 2-15 -hydrocarbons, having at least one hydroxy group and optionally one or more ether functions COC, ie the carbon atom chain interrupting oxygen atoms.
  • Preferred solvents are the - optionally unilaterally etherified with a C 1-6 alkanol - C 2-6 alkylene glycols and poly-C 2-3 alkylene glycol having an average of 1 to 9 identical or different, preferably the same, alkylene glycol groups per molecule as well C 1-6 -alcohols, preferably ethanol, n-propanol or isopropanol, especially ethanol.
  • exemplary Solvents are the following according to INCI named compounds: alcohol (ethanol), buteth-3, butoxydiglycol, Butoxyethanol, butoxyisopropanol, butoxypropanol, n-butyl alcohol, t-butyl alcohol, butylene glycol, butyloctanol, diethylene glycol, Dimethoxydiglycol, dimethyl ether, dipropylene glycol, ethoxydiglycol, Ethoxyethanol, ethyl hexanediol, glycol, hexanediol, 1,2,6-hexanetriol, Hexyl alcohol, hexylene glycol, isobutoxypropanol, isopentyl diol, Isopropyl alcohol (iso-propanol), 3-methoxybutanol, methoxy diglycol, Methoxyethanol, methoxyisopropanol, methoxymethylbutanol, methoxy PEG-10, methylal, methyl alcohol, methyl hexyl ether, methyl propanediol, Neopentyl glycol, PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-6 methyl Ethers, pentylene glycol, PPG-7, PPG-2-buteth-3, PPG-2 butyl ether, PPG-3 butyl ether, PPG-2 methyl ether, PPG-3 methyl ether, PPG-2 Propyl ether, propanediol, propyl alcohol (n-propanol), propylene glycol, Propylene glycol butyl ether, propylene glycol propyl ether, tetrahydrofurfuryl Alcohol, trimethylhexanol.
  • Particularly preferred solvents are the unilaterally etherified with a C 1-6 alkanol poly-C 2-3 alkylene glycol having an average of 1 to 9, preferably 2 to 3, ethylene or propylene glycol, for example PPG-2 methyl ether (dipropylene glycol monomethyl ether).
  • Preferably the solvent is selected from the group comprising methanol, ethanol, propanol, isopropanol, ethylene glycol, Propylene glycol and mixtures thereof.
  • Most preferred solvents are the C 2-3 alcohols ethanol, n-propanol and / or iso-propanol, especially ethanol.
  • When Solubilizers, in particular for perfume and dyes may be other than those described above Solvents, for example, alkanolamines and alkylbenzenesulfonates be used with 1 to 3 carbon atoms in the alkyl radical.
  • Other nonionic surfactants
  • The containing the surfactant combination according to the invention Agent may additionally contain one or more other nonionic Containing surfactants, usually in an amount of 0.001 to 10 wt .-%, preferably 0.01 to 6 wt .-%, in particular 0.1 to 4 wt .-%, particularly preferably 0.2 to 2 wt .-%.
  • nonionic Surfactants in the context of the invention are alkoxylates, such as polyglycol ethers, Fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped Polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also suitable are block polymers of ethylene oxide and propylene oxide and fatty acid alkanolamides and fatty acid polyglycol ethers. Important classes of nonionic according to the invention Surfactants are also the amine oxides and the sugar surfactants.
  • Fettalkoholpolyglykolether
  • Under Fettalkoholpolyglykolethern according to the invention with ethylene (EO) and / or propylene oxide (PO) alkoxylated, unbranched or branched, saturated or unsaturated C 10-22 -alcohols having a degree of alkoxylation up to 30 to understand, preferably ethoxylated C 10-18 fatty alcohols an ethoxylation degree of less than 30, preferably with a degree of ethoxylation of 1 to 20, in particular from 1 to 12, particularly preferably from 1 to 8, most preferably from 2 to 5, for example C 12-14 fatty alcohol ethoxylates with 2, 3 or 4 EO or a mixture of the C 12-14 fatty alcohol ethoxylates with 3 and 4 EO in a weight ratio of 1 to 1 or isotridecyl alcohol ethoxylate with 5, 8 or 12 EO. They may preferably be contained in an amount of 0.1 to 3 wt .-%, particularly preferably 0.5 to 2 wt .-%.
  • amine oxides
  • The amine oxides suitable in accordance with the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides. Preferred amine oxides satisfy formula II, R 6 R 7 R 8 N + -O - (II) R 6 - [CO-NH- (CH 2 ) w ] z -N + (R 7 ) (R 8 ) -O - (II) in the R 6 is a saturated or unsaturated C 6-22 alkyl radical, preferably C 8-18 alkyl, in particular a saturated C 10-16 alkyl radical, for example a saturated C 12-14 alkyl radical, in the Alkylamidoaminoxiden via a Carbonylamidoalkylengruppe -CO-NH- (CH 2 ) z - and in the alkoxyalkylamine oxides via an oxaalkylene group -O- (CH 2 ) z - is bonded to the nitrogen atom N, where z is in each case a number from 1 to 10, preferably 2 to 5, in particular 3,
    R 7 , R 8 are independently a C 1-4 alkyl radical, optionally hydroxy-substituted, such as. B. is a hydroxyethyl radical, in particular a methyl radical.
  • Examples suitable amine oxides are the following according to INCI named compounds: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxides, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide, Decyltetradecylamines oxides, diaminopyrimidines oxides, dihydroxyethyl C8-10 alkoxypropylamines oxides, dihydroxyethyl C9-11 alkoxypropylamines Oxides, dihydroxyethyl C12-15 alkoxypropylamines oxides, dihydroxyethyl Cocamine oxides, dihydroxyethyl lauramine oxides, dihydroxyethyl stearamines Oxides, Dihydroxyethyl Tallowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallowamine Oxide, Hydroxyethyl Hydroxypropyl C12-15 Alkoxypropylamines oxides, isostearamidopropylamines oxides, isostearamidopropyl Morpholine oxides, Lauramidopropylamine oxides, Lauramine oxides, methyl Morpholine Oxide, Milkamidopropyl Amine Oxide, Minkamidopropylamine Oxides, myristamidopropylamine oxides, myristamine oxides, myristyl / cetyl Amine oxides, Oleamidopropylamine oxides, Oleamine oxides, Olivamidopropylamine Oxides, palmitamidopropylamine oxides, palmitamine oxides, PEG-3 lauramines Oxides, Potassium Dihydroxyethyl Cocamine Oxides Phosphate, Potassium Trisphosphonomethylamine oxides, sesamidopropylamine oxides, soyamidopropylamines Oxides, stearamidopropylamines oxides, stearamines oxides, tallow amidopropyl amines Oxides, tallowamine oxides, undecylenamidopropylamine oxides and wheat Germamidopropylamine oxides. A preferred amine oxide is, for example Cocamidopropylamine oxides (cocoamidopropylamine oxide). Amine oxides can preferably in amounts of 1 to 8 wt .-%, particularly preferably 2 be contained to 6 wt .-%.
  • sugar surfactants
  • Sugar surfactants are known surface-active compounds, which include, for example, the sugar surfactant classes of the alkyl glucose esters, aldobionamides, gluconamides (sugar acid amides), glycerolamides, glycerol glycolipids, polyhydroxy fatty acid amide sugar surfactants (sugar amides) and alkyl polyglycosides. In addition to the alkyl polyglycosides which are preferred in the context of the teaching according to the invention, the sugar amides and their derivatives, in particular their ethers and esters, are further preferred sugar surfactants. The ethers are the products of the reaction of one or more, preferably one, sugar hydroxy group with a compound containing one or more hydroxy groups, for example C 1-22 alcohols or glycols such as ethylene and / or propylene glycol, the sugar hydroxy group also Polyethylene glycol and / or polypropylene glycol can carry. The esters are the reaction products of one or more, preferably one, sugar hydroxy group with a carboxylic acid, in particular a C 6-22 fatty acid.
  • sugar amides
  • Particularly preferred sugar amides satisfy the formula R'C (O) N (R '') [Z], in which R 'is a linear or branched, saturated or unsaturated acyl radical, preferably a linear unsaturated acyl radical, with 5 to 21, preferably 5 to 17, in particular 7 to 15, particularly preferably 7 to 13 carbon atoms, R "represents a linear or branched, saturated or unsaturated alkyl radical, preferably one linear unsaturated alkyl radical having from 6 to 22, preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms, a C 1-5 -alkyl radical, in particular a methyl, ethyl, propyl, isopropyl, n- Butyl, isobutyl, tert-butyl or n-pentyl, or hydrogen and Z is a sugar residue, ie a Monosaccharidrest stand. Particularly preferred sugar amides are the amides of glucose, the glucamides, for example lauroyl-methyl-glucamide.
  • Further anionic surfactants
  • The containing the surfactant combination according to the invention Agent may additionally contain one or more other anionic Containing surfactants, usually in an amount of 0.001 to 5 wt .-%, preferably 0.01 to 4 wt .-%, in particular 0.1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, extremely preferably 0.5 to 1.5 wt .-%, for example 1 wt .-%.
  • suitable Further anionic surfactants are in particular aliphatic sulfates such as fatty alcohol sulfates, monoglyceride sulfates and ester sulfonates (Sulfofatty acid esters), lignosulfonates, alkylbenzenesulfonates, Fatty acid cyanamides, anionic sulfosuccinic acid surfactants, Fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), Fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates.
  • Suitable further anionic surfactants are also anionic gemini surfactants having a diphenyl oxide basic structure, 2 sulfonate groups and an alkyl radical on one or both benzene rings according to the formula - O 3 S (C 6 H 3 R) O (C 6 H 3 R ') SO 3 - in which R is an alkyl radical with, for example, 6, 10, 12 or 16 carbon atoms and R 'is R or H (Dowfax ® Dry hydrotropes Powder with C 16 alkyl radical (s); INCI Sodium Hexyldiphenyl ether sulfonates, Disodium decyl phenyl ether disulfonates, Disodium lauryl phenyl ether disulfonates, Disodium Cetyl phenyl ether disulfonates) and fluorinated anionic surfactants, in particular perfluorinated alkylsulfonates such as ammonium C 9/10 -Perfluoroalkylsulfonat (Fluorad ® FC 120) and perfluorooctane sulfonic acid potassium salt (Fluorad ® FC 95 ).
  • Anionic sulfosuccinic acid surfactants
  • Particularly preferred further anionic surfactants are the anionic sulfosuccinic acid surfactants sulfosuccinates, sulfosuccinamates and sulfosuccinamides, especially sulfosuccinates and sulfosuccinamates, most preferably sulfosuccinates. The sulfosuccinates are the salts of the monoesters and diesters of sulfosuccinic acid HOOCCH (SO 3 H) CH 2 COOH, while the sulfosuccinamates are the salts of the monoamides of sulfosuccinic acid and the sulfosuccinamides are the salts of the diamides of sulfosuccinic acid.
  • at the salts are preferably alkali metal salts, ammonium salts and mono-, di- or Trialkanolammoniumsalze, for example, mono-, Di- or triethanolammonium salts, in particular to lithium, sodium, Potassium or ammonium salts, particularly preferably sodium or ammonium salts, extremely preferably sodium salts.
  • In the sulfosuccinates, one or both carboxyl groups of the sulfosuccinic acid is preferably with one or two identical or different unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alcohols having 4 to 22, preferably 6 to 20, in particular 8 to 18 , more preferably 10 to 16, most preferably 12 to 14 carbon atoms esterified. Particularly preferred are the esters of unbranched and / or saturated and / or acyclic and / or alkoxylated alcohols, in particular unbranched, saturated fatty alcohols and / or unbranched, saturated, with ethylene and / or propylene oxide, preferably ethylene oxide, alkoxylated fatty alcohols having a degree of alkoxylation of 1 to 20, preferably 1 to 15, in particular 1 to 10, more preferably 1 to 6, most preferably 1 to 4. The monoesters are preferred in the context of the present invention over the diesters. A particularly preferred sulfosuccinate is Sulfobernsteinsäurelaurylpolyglykolester-di-sodium salt (lauryl EO sulfosuccinate, di-sodium salt; INCI Disodium Laureth Sulfosuccinate), for example, as Tego ® sulfosuccinate F 30 (Goldschmidt) with a sulfosuccinate of 30 parts by weight % is commercially available.
  • In the sulfosuccinamates or sulfosuccinamides, one or both form carboxyl groups of the sulfosuccinic acid preferably with a primary or secondary amine having one or two identical or different, unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alkyl radicals having 4 to 22 , preferably 6 to 20, in particular 8 to 18, more preferably 10 to 16, most preferably 12 to 14 carbon atoms carries, a carboxylic acid amide. Especially preferred are unbranched and / or saturated and / or acyclic alkyl radicals, in particular unbranched, saturated fatty alkyl radicals.
  • Also suitable are, for example, the following according to INCI sulfosuccinates and sulfosuccinamates, which in International Cosmetic Ingredient Dictionary and Handbook Ammonium Dinonyl Sulfosuccinate, Ammonium Lauryl Sulfosuccinate, Diammonium Dimethicone Copolyol Sulfosuccinate, Diammonium Lauramido-MEA Sulfosuccinate, Diammonium Lauryl Sulfo Succinate, Diammonium Oleamido PEG-2 Sulfosuccinate, Diamyl Sodium Sulfosuccinate, Dicapryl Sodium Sulfosuccinate, Dicyclohexyl Sodium Sulfosuccinate, Diheptyl Sodium Sulfosuccinate , Dihexyl Sodium Sulfosuccinate, Diisobutyl Sodium Sulfosuccinate, Dioctyl Sodium Sulfosuccinate, Disodium Cetearyl Sulfosuccinate, Disodium Cocamido MEA Sulfosuccinate, Disodium Cocamido MIPA Sulfosuccinate, Disodium Cocamido PEG-3 Sulfosuccinate, Disodium Coco Glucoside Sulfosuccinate, Disodium Cocoyl Butyl Gluceth-10 Sulfosuccinate, Disodium C12-15 Pareth Sulfosuccinate, Disodium Deceth-5 Sulfosuccinate, Disodium Deceth-6 Sulfosuccinate, Disodium Dihydroxyethyl Sulfosuccinyl undecylenate, Disodium Dimethicone Copolyol Sulfosuccinate, Disodium Hydrogenated Cottonseed Glyceride Sulfosuccinate, Disodium Isodec yl Sulphosuccinates, Disodium Isostearamido MEA Sulfosuccinates, Disodium Isostearamido MIPA Sulfosuccinates, Disodium Isostearyl Sulfosuccinates, Disodium Laneth-5 Sulfosuccinates, Disodium Lauramido MEA Sulfosuccinates, Disodium Lauramido PEG-2 Sulfosuccinates, Disodium Lauramido PEG-5 Sulfosuccinates, Disodium Laureth-6 Sulfosuccinates , Disodium Laureth-9 Sulfosuccinate, Disodium Laureth-12 Sulfosuccinate, Disodium Lauryl Sulfosuccinate, Disodium Myristamido MEA Sulfosuccinate, Disodium Nonoxynol-10 Sulfosuccinate, Disodium Oleamido MEA Sulfosuccinate, Disodium Oleamido MIPA Sulfosuccinate, Disodium Oleamido PEG-2 Sulfosuccinate, Disodium Oleth -3 sulfosuccinates, disodium oleyl sulfosuccinates, disodium palmitamido PEG-2 sulfosuccinates, disodium palmitoleeamido PEG-2 sulfosuccinates, disodium PEG-4 cocamido MIPA sulfosuccinates, disodium PEG-5 lauryl citrate sulfosuccinates, disodium PEG-8 palm glycerides sulfosuccinates, disodium ricinoleamido MEA- Sulfosuccinate, Disodium Sitostereth-14 Sulfosuccina Disodium stearamido MEA sulfosuccinates, disodium stearyl sulfosuccinamates, disodium stearyl sulfosuccinates, disodium tallamido MEA sulfosuccinates, disodium tallowamido MEA sulfosuccinates, disodium tallow sulfosuccinamates, disodium tridecyl sulfosuccinates, disodium undecylenamido MEA sulfosuccinates, disodium undecylenamido PEG-2 sulfosuccinates, disodium wheat Germamido MEA Sulfosuccinate, Disodium Wheat Germamido PEG-2 Sulfosuccinate, Di-TEA Oleamido PEG-2 Sulfosuccinate, Ditridecyl Sodium Sulfosuccinate, Sodium Bisglycol Ricinosulfosuccinate, Sodium / MEA Laureth-2 Sulfosuccinate and Tetrasodium Dicarboxyethyl Stearyl Sulfosuccinamate. Yet another suitable sulfosuccinamate is disodium C 16-18 alkoxypropylene sulfosuccinamate.
  • Preferred anionic sulfosuccinic are imidosuccinate, mono-Na-sulfosuccinic acid diisobutyl ester (Monawet MB ® 45), mono-Na-sulfosuccinic acid di-octyl ester (Monawet MO-84 ® R2W, Rewopol SB ® DO 75), mono-Na sulfosuccinic acid di-tridecyl (Monawet ® MT 70) Fettalkoholpolyglykolsulfosuccinat-Na-NH 4 salt (sulfosuccinate S-2), di-Na-sulfosuccinic acid mono-C 12/14 3EO ester (Texapon ® SB-3) , Natruimsulfobernsteinsäurediisooctylester (Texin DOS 75 ®) and di-sodium sulfosuccinic acid mono-C 12/18 ester (Texin 128-P ®), in particular with the inventive ternary surfactant with respect to the drain and / or drying behavior synergistically acting mono- Na-sulfosuccinic acid di-octyl ester.
  • In a particular embodiment contains the inventive As anionic sulfosuccinic acid surfactants one or several sulfosuccinates, sulfosuccinamates and / or sulfosuccinamides, preferably sulfosuccinates and / or sulfosuccinamates, in particular Sulfosuccinates, in an amount of usually 0.001 to 5 wt .-%, preferably 0.01 to 4 wt .-%, in particular 0.1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, extremely preferably 0.5 to 1.5 wt .-%, for example 1 wt .-%.
  • Other amphoteric surfactants
  • To the amphoteric surfactants (amphoteric surfactants, zwitterionic surfactants), in the from the inventive surfactant combination obtained means can be used Alkylamidoalkylamines, alkyl substituted amino acids, acylated Amino acids or biosurfactants, of which the Alkylamidoalkylamine preferred within the scope of the teaching according to the invention become.
  • alkylamidoalkylamines
  • The alkylamidoalkylamines (INCI alkylamido alkylamines) are amphoteric surfactants of the formula (III) R 9 -CO-NR 10 - (CH 2 ) i -N (R 11 ) - (CH 2 CH 2 O) j - (CH 2 ) k - [CH (OH)] l -CH 2 -Z-OM ( III) in which R 9 is a saturated or unsaturated C 6-22 alkyl, preferably C 8-18 alkyl group, preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group,
    R 10 is a hydrogen atom H or a C 1-4 -alkyl radical, preferably H,
    i is a number from 1 to 10, preferably 2 to 5, in particular 2 or 3,
    R 11 is a hydrogen atom H or CH 2 COOM (to M su),
    j is a number from 1 to 4, preferably 1 or 2, in particular 1,
    k is a number from 0 to 4, preferably 0 or 1,
    l is 0 or 1, where k = 1 when l = 1,
    Z is CO, SO 2 , OPO (OR 12 ) or P (O) (OR 12 ), wherein R 12 is a C 1-4 alkyl radical or M (su), and
    M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, eg. B. protonated mono-, di- or triethanolamine, is.
  • Preferred representatives satisfy the formulas IIIa to IIId, R 9 -CO-NH- (CH 2 ) 2 -N (R 11 ) -CH 2 CH 2 O-CH 2 -COOM (IIIa) R 9 -CO-NH- (CH 2 ) 2 -N (R 11 ) -CH 2 CH 2 O-CH 2 CH 2 -COOM (IIIb) R 9 -CO-NH- (CH 2 ) 2 -N (R 11 ) -CH 2 CH 2 O-CH 2 CH (OH) CH 2 -SO 3 M (IIIc) R 9 -CO-NH- (CH 2 ) 2 -N (R 11 ) -CH 2 CH 2 O-CH 2 CH (OH) CH 2 -OPO 3 HM (IIId) in which R 11 and M have the same meaning as in formula (III).
  • exemplary Alkylamidoalkylamines are the following according to INCI named compounds: cocoamphidipropionic acid, cocobetainamido Amphopropionates, DEA-cocoamphodipropionates, disodium caproamphodiacetates, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium capryloamphodipropionate, disodium cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium Laureth-5 carboxyamphodiacetate, disodium lauroamphodiacetate, disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-isodeceth-7 carboxyamphodiacetate, disodium stearoamphodiacetate, Disodium Tallowamphodiacetate, Disodium Wheatgermamphodiacetate, Lauroamphodipropionic Acid, Quaternium-85, Sodium Caproamphoacetate, Sodium Caproamphohydroxypropylsulfonate, Sodium Caproamphopropionate, Sodium Capryloamphoacetate, Sodium Capryloamphohydroxypropyl sulfonates, sodium capryloamphopropionate, Sodium Cocoamphoacetate, Sodium Cocoamphohydroxypropylsulfonate, Sodium Cocoamphopropionate, Sodium Cornamphopropionate, Sodium Isostearoamphoacetate, Sodium isostearoamphopropionate, sodium lauroamphoacetate, sodium Lauroamphohydroxypropylsulfonates, Sodium Lauroampho PG-Acetate Phosphates, Sodium Lauroamphopropionate, Sodium Myristoamphacetate, Sodium Oleoamphoacetate, Sodium Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate, Sodium Ricinoleoamphoacetate, Sodium Stearoamphoacetate, Sodium Stearoamphohydroxypropyl sulfonates, sodium stearoamphopropionate, Sodium Tallamphopropionate, Sodium Tallowamphoacetate, Sodium Undecylenoamphoacetate, Sodium Undecylenoamphopropionate, Sodium Wheat Germamphoacetate and Trisodium Lauroampho PG-Acetate Chloride Phosphate.
  • Alkyl substituted amino acids
  • Preferred alkyl-substituted amino acids (INCI alkyl-substituted amino acids) according to the invention are monoalkyl-substituted amino acids according to formula (IV), R 13 -NH-CH (R 14 ) - (CH 2 ) u -COOM '(IV) in which R 13 is a saturated or unsaturated C 6-22 alkyl, preferably C 8-18 alkyl group, preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group,
    R 14 is a hydrogen atom H or a C 1-4 -alkyl radical, preferably H,
    u is a number from 0 to 4, preferably 0 or 1, in particular 1, and
    M 'is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. Protonated mono-, di- or triethanolamine, is
    alkyl-substituted imino acids according to formula (V), R 15 -N - [(CH 2 ) v -COOM ''] 2 (V) in which R 15 represents a saturated or unsaturated C 6-22 alkyl, preferably C 8-18 alkyl group, preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group,
    v is a number from 1 to 5, preferably 2 or 3, in particular 2, and
    M '' is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. B. protonated mono-, di- or triethanolamine, where M '' in the two carboxy groups may have the same or two different meanings, for. B. hydrogen and sodium or may be twice sodium, is
    and mono- or dialkyl-substituted natural amino acids according to formula (VI), R 16 -N (R 17 ) -CH (R 18 ) -COOM '''(VI) in which R 16 is a saturated or unsaturated C 6-22 alkyl, preferably C 8-18 alkyl group, preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group,
    R 17 is hydrogen or C 1-4 alkyl, optionally hydroxy or amine substituted, e.g. A methyl, ethyl, hydroxyethyl or aminopropyl radical,
    R 18 is the residue of one of the 20 natural α-amino acids H 2 NCH (R 18 ) COOH, and
    M '''is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. B. protonated mono-, di- or triethanolamine, is.
  • Particularly preferred alkyl-substituted amino acids are the aminopropionates according to formula (IVa), R 13 -NH-CH 2 CH 2 COOM '(IVa) in which R 13 and M 'have the same meaning as in formula (IV).
  • exemplary Alkyl-substituted amino acids are the following according to INCI named compounds: aminopropyl laurylglutamine, cocaminobutyric Acid, cocaminopropionic acid, DEA-lauraminopropionate, disodium Cocaminopropyl iminodiacetate, disodium dicarboxyethyl cocopropylenediamine, Disodium Lauriminodipropionate, Disodium Steariminodipropionate, Disodium Tallowiminodipropionate, Lauraminopropionic Acid, Lauryl Aminopropylglycines, lauryl diethylenediaminoglycines, myristaminopropionic Acid, Sodium C12-15 Alkoxypropyl Iminodipropionate, Sodium Cocaminopropionate, Sodium Sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl methylaminopropionate, TEA-lauraminopropionate and TEA-myristaminopropionate.
  • Acylated amino acids
  • Acylated amino acids are amino acids, in particular the 20 natural α-amino acids which carry on the amino nitrogen the acyl radical R 19 CO of a saturated or unsaturated fatty acid R 19 COOH, where R 19 is a saturated or unsaturated C 6-22 alkyl radical, preferably C 8-18 Alkyl, in particular a saturated C 10-16 alkyl radical, for example a saturated C 12-14 alkyl radical. The acylated amino acids may also be used as the alkali metal salt, alkaline earth metal salt or alkanolammonium salt, e.g. As mono-, di- or triethanolammonium, are used. Exemplary acylated amino acids are the acyl derivatives summarized under INCI under Acids, eg. Sodium Cocoyl Glutamate, Lauroyl Glutamic Acid, Capryloyl Glycine or Myristoyl Methylalanine.
  • Amphotensidkombinationen
  • In a particular embodiment of the invention is a Combination of two or more different amphoteric surfactants, in particular a binary Amphotensidkombination used.
  • The Amphotensidkombination preferably contains at least a betaine, especially at least one alkylamidobetaine, especially preferably cocoamidopropylbetaine.
  • Further, the amphoteric surfactants preferably contains at least one amphoteric surfactant is selected from the group comprising Natriumcarboxyethylkokosphosphoethylimidazolin (Phosphoteric ® TC-6), C 8/10 -Amidopropylbetain (INCI caprylic / Capramidopropyl Betaine, Betaine Tego ® 810), N-2-hydroxyethyl-N-carboxymethyl -fettsäureamido-ethylamine-Na (Rewoteric ® AMV) and N-caprylic / capric amidoethyl-N-ethyletherpropionat-Na (Rewoteric AMVSF ®) and the betaine 3- (3-cocoamido-propyl) dimethylammonium-2-hydroxypropane (INCI sultaines; Rewoteric AM CAS ®) and the Alkylamidoalkylamin N- [N '(N''-2-hydroxyethyl-N''- carboxyethylaminoethyl) -essigsäureamido] -N, N-dimethyl-N-coco-ammonium betaine (Rewoteric QAM ® 50 ), in particular together with cocoamidopropylbetaine.
  • In a further particular embodiment the agent according to the invention one or more amphoteric surfactants in an amount of more than 8% by weight. In yet another special Embodiment contains the inventive Means one or more amphoteric surfactants in an amount of less as 2% by weight.
  • Cationic surfactants
  • The containing the surfactant combination according to the invention Agent may additionally contain one or more cationic surfactants (Cationic surfactants), usually in an amount from 0.001 to 5 wt .-%, preferably 0.01 to 4 wt .-%, in particular 0.1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, extremely preferably 0.5 to 1.5 wt .-%, for example 1 wt .-%.
  • preferred cationic surfactants are the quaternary surfactants Compounds, in particular with an ammonium, sulfonium, phosphonium, Iodonium or arsonium group, also called antimicrobial agents are known. Through the use of quaternary surface active Compounds with antimicrobial activity may be the agent with a antimicrobial effect be designed or its optionally due to other ingredients already existing antimicrobial Effect can be improved.
  • Particularly preferred cationic surfactants are the quaternary ammonium compounds (QAV, INCI quaternary ammonium compounds) according to the general formula (R I ) (R II ) (R III ) (R IV ) N + X - , in which R I to R IV are the same or various C 1-22 -alkyl radicals, C 7-28 -Aralkylreste or heterocyclic radicals, wherein two or in the case of an aromatic inclusion as in the pyridine even three radicals together with the nitrogen atom, the heterocycle, z. A pyridinium or imidazolinium compound, and X - are halide ions, sulfate ions, hydroxide ions or like anions. For optimum antimicrobial activity, preferably at least one of the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
  • QAC are by reaction of tertiary amines with alkylating agents, such as Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced. The alkylation of tertiary Amines with a long alkyl radical and two methyl groups succeed especially easy, even the quaternization of tertiary Amines with two long residues and one methyl group can help with of methyl chloride under mild conditions become. Amines containing three long alkyl radicals or hydroxy-substituted alkyl radicals are poorly reactive and are preferred with dimethyl sulfate quaternized.
  • Suitable QACs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (m, p-dichlorobenzyl-dimethyl-C 12 -alkylammonium chloride, CAS No. 58390-78 -6), benzoxonium chloride (benzyldodecyl-bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No. 57-09-0), benzetonium chloride (N, N Dimethyl N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzyl ammonium chloride, CAS No. 121-54-0), dialkyldimethylammonium chlorides such as di-n- decyl-dimethyl-ammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyl-dimethyl-ammonium chloride, 1-cetylpyridinium chloride (CAS No. 123-03-5) and Thiazoline iodide (CAS No. 15764-48-1) and mixtures thereof. Preferred QACs are the benzalkonium chlorides having C 8 -C 18 -alkyl radicals, in particular C 12 -C 14 -alkyl-benzyl-dimethylammonium chloride. A particularly preferred QAC is the Kokospentaethoxymethylammoniummethosulfat (INCI PEG-5 Cocomonium Methosulfate; Rewoquat CPEM ®).
  • to Avoidance of possible incompatibilities of the cationic Surfactants with the anionic according to the invention Surfactants will be anionic surfactant as possible and / or as little as possible cationic surfactant used or in a particular embodiment of the invention dispensed entirely with cationic surfactants.
  • Water-soluble salts
  • The containing the surfactant combination according to the invention Detergent may further contain one or more water-soluble Salts included. It may be inorganic and / or organic Salts act, in a preferred embodiment it is at least one inorganic salt.
  • Inorganic salts which can be used according to the invention are preferably selected from the group comprising colorless water-soluble halides, sulfates, sulfites, carbonates, bicarbonates, nitrates, nitrites, phosphates and / or oxides of the alkali metals, alkaline earth metals, aluminum and / or transition metals; Furthermore, ammonium salts can be used. Particularly preferred are halides and sulfates of the alkali metals; Preferably, therefore, the inorganic salt is selected from the group comprising sodium chloride, potassium chloride, sodium sulfate, potassium sulfate and mixtures thereof. In a preferred embodiment, sodium chloride is used.
  • at the organic salts which can be used according to the invention they are in particular colorless water-soluble Alkali metal, alkaline earth metal, ammonium, aluminum and / or transition metal salts the carboxylic acids. Preferably, the salts are selected from the group comprising formate, acetate, propionate, citrate, malate, Tartrate, succinate, malonate, oxalate, lactate and mixtures thereof.
  • In a particularly preferred embodiment are doing used exclusively inorganic salts, especially preferably sodium chloride.
  • Further prebiotic effective ingredients
  • In addition to the prebiotic surfactant combination, the washing and cleaning agents obtained from it may also contain other prebiotic active substances. This may be, for example, from plant extracts, such as those from the EP 1658088 are known.
  • One Accordingly, suitable plant extract is, for example, one Conifer extract, in particular from the group of Pinaceae, or an extract from the group of Sapindaceae, Araliaceae, Lamiaceae or Saxifragaceae or mixtures thereof. Particularly preferred is the plant extract is an extract of Picea spp., in particular around an extract from Picea excelsa (synonymom Picea abies, spruce) or from Picea glauca (sugar spruce, Norway Spruce), from Pinus sp., in particular from Pinus sylvestris, from Paullinia sp. (Guarana), in particular Paullinia cubana, from Panax sp., in particular Panax ginseng (ginseng), from Lamium sp., in particular Lamium album (White Nettle), or from Ribes sp., In particular Ribes nigrum (Blackcurrant, Blackcurrant), or it is mixtures thereof. Particularly preferred prebiotic plant extracts are selected from the group comprising White Tea, Hibiscus, Mallow, Grape, Grape seed, Myrrh, Carrot / Jojoba, Calendula, Epica (Blackcurrant / Pine), White Nettle, Blackcurrant, Black Tea, Ginseng, Fruitogreen papaya and turmeric and mixtures thereof. Both Extracts may be aqueous or ethanolic Excerpts act as further extractants come under other propylene glycol, other organic solvents as well as solvent mixtures, mixtures of water and organic Solvent and carbon dioxide in question.
  • Other ingredients
  • Next the components mentioned so far, the inventive Middle contain other ingredients. These include, for example Additives to improve the drainage and drying behavior, for Adjustment of viscosity, stabilization and others customary auxiliaries and additives in manual dishwashing detergents, such as UV stabilizers, perfume, pearlescing agents, dyes, Corrosion inhibitors, preservatives, organic salts, disinfectants, Enzymes, pH adjusters and skin feel-improving or nourishing additives.
  • additives
  • to further improvement of the drainage and / or drying behavior this can be done from the surfactant combination according to the invention obtained agent one or more additives from the group of surfactants, of the polymers and the builders, usually in an amount of 0.001 to 5 wt .-%, preferably 0.01 to 4 wt .-%, in particular 0.1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, extremely preferably 0.5 to 1.5 wt .-%, for example 1 wt .-%.
  • When Additive suitable surfactants are certain of those already above described amphoteric surfactants, other anionic surfactants, nonionic surfactants and cationic surfactants, which are repeated at this point become. The content of surfactant additives is preferably so to choose the total surfactant content in the above executed quantity ranges lies.
  • To Some of the additives listed below are one or more Trade names are given in brackets, among which the respective commercial is available.
  • Polymers suitable as additives in particular maleic acid-acrylic acid copolymer, Na salt (Sokalan ® CP 5), modified polyacrylic acid Na salt are (Sokalan CP 10 ®), modified polycarboxylate Na salt (Sokalan ® HP 25) polyalkylene oxide-modified heptamethyltrisiloxane (Silwet ® L-77), polyalkylene oxide-modified heptamethyltrisiloxane (Silwet ® L-7608) and polyether (copolymers of polydimethylsiloxanes having ethylene oxide / propylene oxide segments (polyether)), preferably water-soluble linear polyether terminated polyether as Tegopren ® 5840, Tegopren ® 5843, Tegopren ® 5847, Tegopren ® 5851, Tegopren ® 5863 or Tegopren ® 5878th
  • As additives suitable builders are, in particular polyaspartic acid-Na-salt, Ethylendiamintriacetatkokosalkylacetamid (Rewopol ® CHT 12), methylglycine-Tri-Na-salt (Trilon ES ® 9964) and acetophosphonic (Turpinal SL ®).
  • Blends with surfactant or polymeric additives show in the case of Monawet MO-84 ® R2W, Tegopren ® 5843 and Tegopren 5863 ® synergism. However, the use of Tegopren grades 5843 and 5863 is less preferred when applied to hard surfaces of glass, especially glassware, since these can apply silicone surfactants to glass.
  • In a particular embodiment of the invention is based on omitted the additives mentioned.
  • thickener
  • to Thickening can do that with the invention Surfactant combination prepared in addition to one or contain several polymeric thickeners.
  • polymers Thickening agents in the context of the present invention are as Polyelectrolytes thickening polycarboxylates, preferably Homo- and copolymers of acrylic acid, especially acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, especially heteropolysaccharides, as well as other common ones thickening polymers.
  • suitable Polysaccharides or heteropolysaccharides are the polysaccharide gums, For example, gum arabic, agar, alginates, carrageenans 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, may alternatively, but preferably in addition to a polysaccharide gum, for example starches of various origin and starch derivatives, eg. B. hydroxyethyl starch, Starch phosphate esters or starch acetates, or carboxymethyl cellulose or their sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, Hydroxypropylmethyl or hydroxyethyl methyl cellulose or cellulose acetate.
  • A preferred polymeric thickener 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 2-15 × 10 6, and for example, by Fa. Kelco under the trade name Keltrol ®, z. As a cream-colored powder Keltrol ® T (transparent) or as white granules Keltrol ® RD (Readily Dispersable).
  • Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI Carbomer), which are also referred to as carboxyvinyl polymers. Such polyacrylic acids are available, inter alia, from the company. BFGoodrich under the trade name Carbopol ® , z. Carbopol ® 940 (molecular weight approximately 4,000,000), Carbopol ® 941 (molecular weight approximately 1,250,000) or Carbopol ® 934 (molecular weight approximately 3,000,000).
  • However, particularly suitable polymeric thickeners are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C 1-4 alkanols formed esters (INCI acrylates copolymer), to which example, the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and available, for example from Messrs. Rohm & Haas under the trade names Aculyn ® and Acusol ® are, for. As the anionic non-associative polymers Aculyn ® 33 (crosslinked), Acusol ® 810 and Acusol ® 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of C 10-30 alkyl acrylates with one or more mono mers from the group of acrylic acid, methacrylic acid and their simple, preferably with C 1 4- alkanols formed esters (INCI Acrylates / C10-30 alkyl acrylate crosspolymer) and which are, for example, the company. BFGoodrich under the trade name Carbopol ® are available, for. B. hydrophobized Carbopol ® and ETD2623 Carbopol ® 1382 (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymer) and Carbopol AQUA ® 30 (formerly Carbopol ® EX 473).
  • Of the Content of polymeric thickener is usually not more than 8% by weight, preferably between 0.1 and 7% by weight, more preferably between 0.5 and 6 wt .-%, in particular between 1 and 5% by weight, and most preferably between 1.5 and 4% by weight, for example between 2 and 2.5% by weight.
  • In a preferred embodiment of the invention is that Medium, however, free of polymeric thickeners.
  • Dicarboxylic acids (salts)
  • To stabilize the agent obtained with the surfactant combination according to the invention, in particular at high surfactant content, one or more dicarboxylic acids and / or salts thereof may be added; in particular a composition of Na salts of adipic, succinic and glutaric acid, as described, for. B. under the trade name Sokalan ® DSC is available. The use is advantageously carried out in amounts of 0.1 to 8 wt .-%, preferably 0.5 to 7 wt .-%, in particular 1.3 to 6 wt .-% and particularly preferably 2 to 4 wt .-%.
  • A Change in the dicarboxylic acid (salt) content can - in particular in amounts above 2% by weight - to a clear solution contribute to the ingredients. Also within certain limits an influence on the viscosity of the mixture by this Medium possible. Furthermore, this component influences the solubility of the mixture. This component becomes special preferably used at high surfactant contents, in particular at Tensidgehalten above 30 wt .-%.
  • can however, their use is omitted, so is the invention Agent preferably free from dicarboxylic acid (salts) n.
  • Auxiliaries and additives
  • . B. Cutina ® AGS from Cognis, for example glycol distearate, z; - in particular in hand dishwashing detergents and cleaning agents for hard surfaces - conventional auxiliaries and additives, in particular UV stabilizers, perfumes, pearlescent agents (INCI opacifying agents next to one or more further can. , or mixtures comprising such. as the Euperlane ® from. Cognis), dyes, corrosion inhibitors, preservatives (e.g., as the technical also known as Bronopol 2-bromo-2-nitropropane-1,3-diol ( CAS 52-51-7) which is commercially available is), organic salts, disinfectants, enzymes, pH-adjusting agents and skin feel-improving or skin-care additives (z. B. for example, as Myacide ® BT or as Boots Bronopol BT from Boots dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, sericerin, collagen partial hydrolyzate, various vegetable protein partial hydrolyzates, P Roteinhydrolysat-fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such. As lecithin, soybean oil, etc., plant extracts such. , Aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, AHA complexes, glycerol, urea, quaternized hydroxyethyl cellulose) in amounts of usually not more than 5% by weight.
  • PH value
  • Of the pH of the agent used according to the invention can by means of conventional pH regulators, for example acids such as mineral acids or citric acid and / or Alkalis such as sodium or potassium hydroxide, wherein - in particular with desired hand compatibility - one Range of 4 to 9, preferably 5 to 8, especially 5.5 to 7.5, is preferred.
  • For adjusting and / or stabilizing the pH, the agent according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%, preferably 0.005 to 3 wt .-%, in particular 0 , 01 to 2 wt .-%, particularly preferably 0.05 to 1 wt .-%, most preferably 0.1 to 0.5 wt .-%, for example, 0.2 wt .-%. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (INCI chelating agents). Particularly preferred buffer substances are the citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate.2H 2 O and tripotassium citrate H 2 O.
  • embodiments
  • Three hard surface cleaners E1 to E3 which can be used according to the invention have been formulated, which have a prebiotic effect due to the surfactant combination they contain. Their compositions are shown in the table below, all amounts are in wt .-% of the active ingredient. E1 E2 E3 Sodium lauryl ether sulfate 6.64 12,00 13,30 cocoamidopropyl 1.67 3.10 3.70 Sodium sec-C 14-17 alkanesulfonate 1.67 2.90 3.00 sodium chloride 1.30 - - ethanol - 1.00 2.00 Perfume 0.20 0.30 0.30 dye 0.20 0.20 0.20 water 88.32 80.50 77,50
  • Besides A comparative formulation was prepared that contains a surfactant combination from 19% by weight of a secondary alkanesulfonate, 6% by weight of a fatty alcohol ether sulfate and 2% by weight of an amine oxide. One Hand dishwashing detergent containing this surfactant combination showed no prebiotic effects.
  • QUOTES INCLUDE IN THE DESCRIPTION
  • This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.
  • Cited patent literature
    • EP 1658088 A1 [0003]
    • EP 1658088 [0086]
  • Cited non-patent literature
    • - International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997) [0015]
    • - International Cosmetic Ingredient Dictionary and Handbook [0015]
    • - International Cosmetic Ingredient Dictionary and Handbook [0061]

Claims (20)

  1. Use of a prebiotic effective Surfactant combination for the preservation of desired skin germs Users of detergents and cleaners.
  2. Use of a prebiotic surfactant combination to inhibit the growth of unwanted skin germs Users of detergents and cleaners.
  3. Use of a prebiotic surfactant combination for the preparation of a prebiotically active washing or Detergent.
  4. Use of a prebiotic surfactant combination to promote the growth of desirable skin germs with the user of detergents and cleaners.
  5. Use according to one of the claims 1 to 4, characterized in that the prebiotic effective Tenside combination at least one fatty alcohol ether sulfate and at least contains a betaine surfactant.
  6. Use according to one of the claims 1 to 4, characterized in that the prebiotic effective Tenside combination at least one fatty alcohol ether sulfate and at least contains an alkylpolyglycoside.
  7. Use according to one of the claims 1 to 5, characterized in that the prebiotic effective Surfactant combination at least one fatty alcohol ether sulfate, at least a secondary alkanesulfonate and at least one betaine surfactant includes.
  8. Use according to one of the claims 1 to 6, characterized in that the prebiotic effective Surfactant combination at least one fatty alcohol ether sulfate, at least a betaine surfactant and at least one alkylpolyglycoside.
  9. Use according to one of the claims 1 to 8, characterized in that the prebiotic effective Surfactant combination in a detergent or cleaning agent preferably in an amount of 5 to 40% by weight, based on the total composition, is included.
  10. Use according to claim 9, characterized in that the washing or cleaning agent is fatty alcohol ether sulfates in an amount of 1 to 30% by weight, preferably 6 to 25% by weight, particularly preferably contains 8 to 20 wt .-%.
  11. Use according to one of the claims 9 and 10, characterized in that the washing or cleaning agent secondary alkanesulfonates in an amount of 0 to 8% by weight, preferably contains 1.5 to 6 wt .-%.
  12. Use according to one of the claims 9 to 11, characterized in that the washing or cleaning agent Betaine surfactants in an amount of 0 to 15 wt .-%, preferably 1.5 to 12 wt .-%, particularly preferably 2 to 6 wt .-%.
  13. Use according to one of the claims 9 to 12, characterized in that the washing or cleaning agent Alkyl polyglycosides in an amount of 0 to 15 wt .-%, preferably Contains 1.5 to 12 wt .-%, particularly preferably 2 to 6 wt .-%
  14. Use according to one of the claims 9 to 13, characterized in that the washing or cleaning agent one or more water-soluble organic solvents contains.
  15. Use according to one of the claims 9 to 14, characterized in that the washing or cleaning agent contains one or more other surfactants.
  16. Use according to one of the claims 9 to 15, characterized in that the washing or cleaning agent contains one or more inorganic salts.
  17. Use according to one of the claims 9 to 16, characterized in that the washing or cleaning agent contains one or more other prebiotic active substances.
  18. Use according to one of the claims 9 to 17, characterized in that the washing or cleaning agent more, usually in detergents for Contains hard surfaces used ingredients, preferably selected from the group comprising bases, Acids, viscosity modifiers, fatty acids, Polymers, antibacterial agents, preservatives, solubilizers, Complexing agents, enzymes, dyes, fragrances, pearlescing agents, Stabilizers, pH adjusters, skin feel improving or skin care additives and mixtures thereof.
  19. Use according to one of the preceding Claims, characterized in that the prebiotic Used surfactant combination in a hand dishwashing detergent becomes.
  20. Use according to one of the claims 1 to 18, characterized in that the prebiotic surfactant combination is used in a laundry detergent.
DE102009002262A 2009-04-07 2009-04-07 Prebiotic hand dishwashing detergents Withdrawn DE102009002262A1 (en)

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