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WO2008145446A1 - Agent de lavage ou de nettoyage à effet antibactérien - Google Patents

Agent de lavage ou de nettoyage à effet antibactérien Download PDF

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Publication number
WO2008145446A1
WO2008145446A1 PCT/EP2008/054210 EP2008054210W WO2008145446A1 WO 2008145446 A1 WO2008145446 A1 WO 2008145446A1 EP 2008054210 W EP2008054210 W EP 2008054210W WO 2008145446 A1 WO2008145446 A1 WO 2008145446A1
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WO
WIPO (PCT)
Prior art keywords
washing
cleaning agent
acid
cleaning
sodium
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.)
Ceased
Application number
PCT/EP2008/054210
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German (de)
English (en)
Inventor
Georg Meine
Andrea Eutebach
Mirko Weide
Piotr Malecki
Carine Wattebled
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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
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Publication of WO2008145446A1 publication Critical patent/WO2008145446A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/18—Liquid substances or solutions comprising solids or dissolved gases
    • A61L2/186—Peroxide solutions
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • A61L2103/50—
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2202/00—Aspects relating to methods or apparatus for disinfecting or sterilising materials or objects
    • A61L2202/10—Apparatus features
    • A61L2202/17—Combination with washing or cleaning means

Definitions

  • the invention relates to a washing or cleaning agent containing surfactant (s), other conventional ingredients of detergents or cleaners and an antimicrobial composition.
  • the invention also relates to an antimicrobially active composition, the use of the washing or cleaning agent or the antimicrobially active composition and processes for their preparation.
  • Antimicrobially active compositions and their use in detergents or cleaners are known in the art. Frequently, the disinfectants used are halogen-containing substances or phenol derivatives or other aromatic hydrocarbons, which can be regarded as problematic for reasons of environmental compatibility. Other, more compatible microbicides have only a limited spectrum of activity or are effective only under certain physical conditions. However, for household applications, there is a high demand for antimicrobial compositions that are effective against a broad spectrum of microorganisms while being environmentally friendly; Natural ingredients are also desirable.
  • mold spores can also come in the household to contamination with various microorganisms.
  • mold spores as well as bacteria such as Salmonella, settle on hard surfaces in the kitchen, which come into contact with appropriately contaminated food.
  • both the surfaces of the sanitary facilities as well as toothbrushes and other items for body cleansing with various microorganisms come into contact.
  • mold spores can occur, for example, on damp walls, in humidifiers and air conditioning systems or, for example, in garbage containers.
  • a washing or cleaning agent containing surfactant (s) and other conventional ingredients of detergents or cleaners, wherein the agent contains an antimicrobial active composition which has been formed from a water-soluble silver salt and a complexing agent.
  • the antimicrobially active composition has been formed from a water-soluble silver salt, a mixture of complexing agents, in particular a first complexing agent and a second complexing agent.
  • a washing or cleaning composition containing such an antimicrobial composition exhibits an even greater germicidal effect and is effective on a broader spectrum of germs.
  • the complexing agent (s) is selected from the group consisting of methylglycinediacetic acid (MGDA), ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), tripolyphosphate (TPP), citrates, phosphonates, arsenates, selenates, crown ethers, polyamines , especially diamines and triamines, sodium thiosulfate, ammonium thiosulfate, sodium sulfite, ammonia and mixtures thereof.
  • MGDA methylglycinediacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • TPP tripolyphosphate
  • the negative decadic logarithm of the complex formation constants K B , the pK B value, of the complexing agent (s) with Ag + ions is greater than or equal to 1 and preferably greater than or equal to 5.
  • the cause for the improved effect when using a plurality of complexing agents is presumably the presence of different silver complexes in the antimicrobially active composition and thus in the washing or cleaning agent which is mixed with one another and with the dissolved silver salt, the silver salt. Aqua complex, stand in balance.
  • the amount of complexing agent used is preferably from 0.001 to 5 wt .-%, particularly preferably from 0.1 to 1, 0 wt .-%, each based on the detergent or cleaning agent.
  • a particularly antimicrobially active washing or cleaning agent is obtained when the antimicrobial active composition has been formed from a water-soluble silver salt, a first complexing agent, a second complexing agent and a biocide.
  • the biocide is a natural biocide, preferably a sesquiterpene, in particular farnesol and farnesol acetate, a terpene alcohol, in particular geraniol, eugenol, patchouli oil or a mixture thereof.
  • the biocide is preferably used in amounts of preferably 0.0001 to 1, 0 wt .-%, particularly preferably 0.001 to 0.1 wt .-%, each based on the detergent or cleaning agent.
  • these biocides also form complexes with the silver ions and thereby alone improve the antimicrobial effect of the washing or cleaning agent.
  • the compounds per se have a biocidal effect and thus also increase the spectrum of activity of the washing or cleaning agent.
  • the content of Ag + ions in the finished washing or cleaning agent is advantageously 1 to 10,000 ppm, preferably 10 to 1,000 ppm and most preferably 50 to 100 ppm. These amounts are sufficient to achieve an effective antimicrobial effect of the washing or cleaning agent.
  • the invention relates to an antimicrobial active composition obtainable by mixing a water-soluble silver salt and a complexing agent.
  • the invention also relates to the use of a washing or cleaning agent according to the invention or an antimicrobial composition according to the invention for inhibiting the growth of microorganisms on textiles and on hard household surfaces. Furthermore, the invention relates to a method for the treatment and cleaning of germinated surfaces in the home, wherein these surfaces are treated with a detergent or cleaner according to the invention or with an antimicrobially active composition according to the invention.
  • the invention relates to a process for the preparation of an antimicrobially active washing or cleaning agent, in which an aqueous silver salt solution is mixed with a complexing agent and the antimicrobial composition obtained is mixed with further constituents of the washing or cleaning agent.
  • alkaline earth metals, ammonium or aluminum cations are mentioned below as counterions for (monovalent) anions, this means, of course, that this is only present in the stoichiometric amount of substance, such as the anion, which is sufficient to balance the charge and thus to produce the neutral complex.
  • the indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service.
  • the washing or cleaning agent contains an antimicrobial active composition, which is first formed by mixing a water-soluble silver salt and a complexing agent and later mixed with the other ingredients of the washing or cleaning agent.
  • Silver or silver ions have a blocking effect on enzymes in microorganisms and thus have a high bactericidal and fungicidal action. In addition, silver has a germicidal effect. This property has been used in the past, for example, in medicine. Because of its solubility, silver nitrate is a suitable silver compound for use in washing or cleaning agents according to the invention and in the antimicrobially active compositions according to the invention. Many other silver salts, however, form insoluble precipitates, such as halides, sulfides or hydroxide. In addition, the silver ions can be easily reduced to metallic silver, which is deposited in the form of finely divided black particles. Therefore, in the incorporation into a composition and in particular in a detergent or cleaning agent, the addition of a stabilizing system makes sense, which strongly suppresses the reduction and also prevents the formation of insoluble salts.
  • Particularly suitable chelating agents include methylglycinediacetic acid (MGDA), ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), tripolyphosphate (TPP), citrates, phosphonates, arsenates, selenates, crown ethers, polyamines, especially diamines and triamines, sodium thiosulfate, ammonium thiosulfate, sodium sulfite or ammonia.
  • Particularly preferred complexing agents are MGDA, sodium thiosulfate and sodium sulfite.
  • MGDA and sodium thiosulfate MGDA and sodium sulfite
  • MGDA and ammonia MGDA, ammonia and sodium thiosulfate and MGDA, ammonia and sodium sulfite.
  • the pK value of the ß complexing with Ag + ions is preferably 1 or more, and more preferably greater than or equal. 5
  • the amount of complexing agent used to prepare the antimicrobial composition is from 55 to 90% by weight, preferably 75 to 85% by weight.
  • biocides preferably natural biocides
  • Suitable biocides preferably include natural sesquiterpenes, in particular farnesol and farnesol acetate, terpene alcohols, in particular geraniol, eugenol, patchouli oil or mixtures of these compounds.
  • Biocides for the purposes of this invention include agents used in a variety of products to kill, as the case may be, a wide range of organisms from viruses, bacteria, fungi and insects.
  • the biocides include microbicides, bactericides, fungicides, insecticides, virucides and algicides.
  • biocides for the purposes of this invention include antibiotics and compounds which prevent the morphogenesis and / or the attachment of viruses and / or bacteria to surfaces.
  • Farnesol, farnesol acetate, geraniol, eugenol and patchouli oil for example, belong to the latter class of biocides.
  • the sesquiterpene farnesol occurs in musk, linden, acacia and essential oils, such as jasmine or rose oil.
  • farnesol is well biodegradable.
  • Farnesol is used in the antimicrobially active compositions according to the invention preferably in amounts of 2 to 20 wt .-%, preferably 3 to 15 wt .-%.
  • the antimicrobial composition can be incorporated into detergents or cleaners. These contain other ingredients that further improve the performance and / or aesthetic properties of the detergent or cleaning agent.
  • preferred washing or cleaning agents additionally comprise one or more substances from the group of surfactants, builders, bleaching agents, bleach activators, bleach catalysts, thickeners, surface hydrophilicizers, enzymes, electrolytes, solvents, hydrotropes, dyes, fragrances (Perfumes and perfume carriers), pH adjusters, defoamers, soil release polymers, optical brighteners, fluorescers, grayness inhibitors, dye transfer inhibitors, antiredeposition agents, anti-wrinkling agents, anti-shrinkage agents, ironing aids, repellents and impregnating agents, corrosion inhibitors, preservatives, anti-caking agents. oxidants, antistatic agents, silicone derivatives, complexing agents, neutral filling salts, plant extracts and UV absorbers.
  • the antimicrobial composition is used in detergents or cleaners preferably in amounts of 0.01 to 5 wt .-%, particularly preferably 0.05 to 3 wt .-%.
  • the washing or cleaning agent according to the invention preferably has a content of Ag + ions of 1 to 10,000 ppm, preferably 10 to 1,000 ppm and most preferably 50 to 100 ppm.
  • the washing or cleaning agent preferably contains one or more surfactants, which may be selected from anionic, nonionic, zwitterionic and cationic surfactants and mixtures thereof.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • surfactants of the sulfonate type preferably come here C 9 .i 3 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example, from C 12 -i 8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12 -i 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of .alpha.-sulfo fatty acids esters of .alpha.-sulfo fatty acids (ester sulfonates), for example the .alpha.-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol Glycerol can be obtained.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) yl sulfates are the alkali and especially the sodium salts of the Schwefelhoffreraumester C 2 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or d 0 -C 2 o Oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • Ci 2 -Ci 6 alkyl sulfates and Ci 2 -Ci 5 alkyl sulfates and Ci 4 -Ci 5 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which can be obtained as commercial products of the Shell OiI Company under the name DAN®, are suitable anionic surfactants.
  • 2 i-alcohols such as 2-methyl-branched Cg-n-alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 -i 8 -fatty alcohols having 1 to 4 EO, are suitable. They are used in foam-damped detergents due to their high foaming behavior only in relatively small amounts, for example in amounts of 1 to 5 wt .-%. In high-foaming agents, such as hand wash, they are used in amounts of up to 25 wt .-%.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 -i 8 -fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Particularly preferred anionic surfactants are soaps.
  • Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts. But they can also be used in the form of their silver salts.
  • the content of preferred detergents or cleaning agents on anionic surfactants is 0.1 to 30 wt .-%, preferably 1 to 25 wt .-% and in particular 3 to 22 wt .-%, each based on the total detergent or cleaning agent.
  • nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 mol Ethylene oxide (EO) per mole of alcohol used in which the alcohol radical may be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO Ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • Preferred ethoxylated alcohols include, for example C12 - 14 - alcohols containing 3 EO, 4 EO, 5.5 EO or 7 EO, C 9 n-alcohol with 7 EO, C-ms alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 12 -i 8 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C-
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols containing more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO, 40 EO or 100 EO.
  • Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention.
  • block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • nonionic surfactants in which EO and PO units are not distributed in blocks, but randomly.
  • Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.
  • nonionic surfactants are for example available under the trade name Dehydol ® (ex Cognis), preferably in this case the Dehydol ® 980.
  • x can be used as further nonionic surfactants, alkyl glycosides of the formula RO (G), in which R is a primary linear or methyl branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C-atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4.
  • Alkyl glycosides are known, mild and skin-friendly surfactants. They can be used well as sole or main surfactants.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, preferably from fatty acids of chain lengths C 12 . 18 , C 12 . 14 or C 16 -i 8 -
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be used be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • surfactants are polyhydroxy fatty acid amides of the formula (I)
  • RCO is an aliphatic acyl group having 6 to 22 carbon atoms
  • R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R-CO-N- [Z] (II) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl group or an aryl group or an oxyalkyl group having 1 to 8 carbon atoms, wherein CI_ 4 alkyl or phenyl groups being preferred
  • [Z] is a linear polyhydroxyalkyl residue, whose alkyl chain having at least two hydroxyl groups substituted, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the content of nonionic surfactants in a liquid washing or cleaning agent is preferably 1 to 40 wt .-%, preferably 3 to 30 wt .-% and in particular 5 to 20 wt .-%, each based on the total detergent or cleaning agent.
  • the composition according to the invention may also contain cationic surfactants such as esterquats and / or amphoteric surfactants.
  • amphoteric surfactants (amphoteric surfactants, zwitterionic surfactants) which can be used according to the invention include betaines, alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants, of which the betaines are preferred in the context of the teaching according to the invention.
  • Suitable betaines are the alkylbetaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably satisfy formula III, R 1 - [CO-X- (CH 2 ) n ] x -N + (R 2 ) ( R 3) - ([CH (OH) -CH 2] y -Y- IM) in which R 1 is a saturated or unsaturated C 6 - - (CH 2) m 22 alkyl, preferably C 8 -i 8 alkyl radical, in particular a saturated do-i ⁇ alkyl group, for example a saturated C 2 - 14 alkyl group,
  • X is NH, NR 4 with the d_ 4 alkyl 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
  • m is a number from 1 to 4, in particular 1, 2 or 3, y 0 or 1 and
  • Preferred betaines are the alkylbetaines of the formula (IIIa), the alkylamidobetaines of the formula (IIIb), the sulfobetaines of the formula (IIIc) and the amidosulfobetaines of the formula (IIId), R 1 -N + (CH 3 ) 2 -CH 2 COO " (IIIa)
  • betaines are the carbo-betaines, in particular the carbo-betaines of the formula (IIIa) and (IIIb), most preferably the alkylamido-betaines of the formula (IIIb).
  • 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, cocamido ethyl betaines, cocamidopropyl betaines, cocamidopropyl hydroxysultaines, coco-betaines, coco-hydroxysultaines, coco / oleamidopropyl betaines, coco-sultaines, decyl betaines, dihydroxyethyl oleyl glycinates, dihydroxyethyl soy glycinates, dihydroxyeth
  • alkylamidoalkylamines are amphoteric surfactants of the formula (IV), R 9 -CO-NR 10 - (CH 2 ), - N (R 11 HCH 2 CH 2 O) - (CH 2 ) ⁇ [CH (OH) I 1 -CH 2 -Z-OM (IV) in which R 9 is a saturated or unsaturated C 6-22 -alkyl radical, preferably C 8 -i 8 -alkyl radical, preferably a saturated C 10 -i 6 alkyl radical, for example a saturated Ci 2 - 14 -alkyl radical,
  • R 10 is a hydrogen atom H or a C
  • 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,
  • Z is CO, SO 2 , OPO (OR 12 ) or P (O) (OR 12 ), where R 12 is a d_ 4 -alkyl radical or M (su), and
  • M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. protonated mono-, di- or triethanolamine.
  • alkylamidoalkylamines are the following compounds designated according to INCI: cocoamphodipropionic acid, cocobetainamido amphopropionate, DEA-cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodi- acetate, sulfonate Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropyl-, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearo- amphodiacetates, Disodium Isostearoamphodipropionate, Disodium Laureth-5 Carboxyamphodi- acetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium oil- amphodipropionate, Disodium PPG-2-ls
  • Preferred alkyl-substituted amino acids are monoalkyl-substituted amino acids according to formula (V),
  • R 14 is a hydrogen atom H or a CI_ 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 (VI),
  • M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine, where M" in the two Carboxy groups may have the same or two different meanings, for example hydrogen and sodium or may be twice sodium, and mono- or dialkyl-substituted natural amino acids according to formula (VII),
  • R 18 is the radical of one of the 20 natural ⁇ -amino acids H 2 NCH (R 18 ) COOH
  • M '" is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine ,
  • alkyl-substituted amino acids are the Aminopropionate according to formula
  • R 13 is -NH-CH 2 CH 2 COOM '(Va) in which R 13 and M' have the same meaning as in formula (V).
  • Illustrative alkyl substituted amino acids are the following INCI compounds: Aminopropyl Laurylglutamine, Cocaminobutyric Acid, Cocaminopropionic Acid, DEA Lauraminopropionate, Disodium Cocaminopropyl Iminodiacetate, Disodium Dicarboxyethyl Cocopropylenediamine, Disodium Lauriminodipropionate, Disodium Steariminodipropionate, Disodium Tallowiminodipropionate, Lauraminopropionic Acid, Lauryl Aminopropylglycine, Lauryl Diethylenediaminoglycine, Myristaminopropionic Acid, Sodium C12-15 Alkoxypropyl Imidipropionate, Sodium Cocaminopropionate, Sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA Lauraminopropionate and TEA Myristaminoprop
  • Acylated amino acids are amino acids, in particular the 20 natural ⁇ -amino acids which the acyl radical R 19 CO of a saturated or unsaturated fatty acid R 19 COOH wear at the amino nitrogen, wherein R 19 is a saturated or unsaturated C 6-22 -alkyl radical, preferably C 8 -i 8- alkyl, in particular a saturated C- ⁇ O -i 6 alkyl, for example, a saturated C
  • the acylated amino acids can also be used as the alkali metal salt, alkaline earth metal salt or alkanolammonium salt, for example mono-, di- or triethanolammonium salt.
  • acylated amino acids are the acyl derivatives summarized in accordance with INCI under Amino Acids, for example sodium cocoyl glutamate, lauroyl glutamic acid, capryloyl glycine or myristoyl methylalanine.
  • Amino Acids for example sodium cocoyl glutamate, lauroyl glutamic acid, capryloyl glycine or myristoyl methylalanine.
  • Another suitable amphoteric surfactant is lecithin.
  • the compositions contain amphoteric surfactants in amounts, based on the detergent or cleaner, from 0 to 10 wt .-%.
  • the agent according to the invention may additionally contain one or more cationic surfactants.
  • Preferred cationic surfactants are the quaternary surface-active compounds, in particular having an ammonium, sulfonium, phosphonium, iodonium or arsonium group, as described, for example, by KH Wallrobußer in "Praxis der Sterilisation, Disinfection - Conservation: Germ Identification - Company Hygiene” (5th ed. Stuttgart, New York: Thieme, 1995) as antimicrobial agents.
  • Particularly preferred cationic surfactants are the quaternary ammonium compounds (QAV, INCI Quaternary Ammonium Compounds) according to the general formula (R ') (R ") (R"') (R IV ) N + X ⁇ , in which R 1 to R ⁇ v are identical or different Ci_ 22 alkyl radicals, C 7 . 28 -Aralkylreste or heterocyclic radicals, wherein two or in the case of an aromatic inclusion as in pyridine even three radicals together with the nitrogen atom, the heterocycle, for example a pyridinium or imidazolinium compound, form, and X ⁇ halide ions, sulfate ions, hydroxide ions or the like Anions are.
  • at least one of the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
  • QACs are prepared by reacting tertiary amines with alkylating agents, e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. 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 succeeds particularly easily, and the quatern
  • Suitable QACs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (mp-dichlorobenzyl-dimethyl-C 1-4 -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- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0
  • dialkyldimethylammonium chlorides such as N-decyl dimethyl ammonium chloride (CAS No. 7173-51-5-5), didecyldimethyl ammonium bromide (CAS No. 2390-68-3), dioctyl dimethyl ammonium chloride, 1-cetyl pyridinium chloride (CAS No. 123-03-5 ) and thiazoline iodide (CAS No.
  • Preferred QUATS are the benzalkonium koniumchloride with C 8 -C 18 alkyl radicals, in particular C 2 -C 14 -Aklyl-benzyl-dimethylammonium chloride.
  • a particularly preferred QAC is the Kokospentaethoxymethylammoniummethosulfat (INCI PEG-5 Cocomonium Methosulfate; Rewoquat CPEM ®).
  • compositions contain cationic surfactants in amounts, based on the composition, of 0 to 10 wt .-%.
  • anionic surfactant compatible and / or cationic surfactant as little as possible are used or omitted in a particular embodiment of the invention entirely on cationic surfactants.
  • the total surfactant content of a detergent is preferably below 65% by weight, preferably below 40% by weight and more preferably below 35% by weight, based on the total washing or cleaning agent.
  • the total surfactant content is preferably below 30% by weight, preferably below 15% by weight and more preferably below 12% by weight.
  • Suitable builders which may be present in the detergents or cleaners are in particular silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + I • H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred. Particularly preferred densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ) marketed by the company SASOL under the brand name VEGOBOND AX® and by the formula
  • the zeolite can be used as a spray-dried powder or else as an undried, stabilized suspension which is still moist from its preparation.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 -FeK- alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain from 18 to 22% by weight, in particular from 20 to 22% by weight, of bound water.
  • phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
  • Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.
  • the washing or cleaning agent according to the invention is free of phosphates.
  • Organic builders which may be present in the detergent or cleaning agent include polycarboxylate polymers such as polyacrylates and acrylic acid / maleic acid copolymers, poly-aspartates and monomeric polycarboxylates such as citrates, gluconates, succinates or malonates, which are preferably used as sodium salts.
  • polycarboxylate polymers such as polyacrylates and acrylic acid / maleic acid copolymers
  • poly-aspartates and monomeric polycarboxylates
  • citrates gluconates, succinates or malonates
  • malonates which are preferably used as sodium salts.
  • citrates are particularly preferred.
  • the content of builder in the detergents or cleaners according to the invention is up to 40% by weight.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or organic peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, diperdodecanedioic acid, 4-phthalimidoperoxobutanoic acid, 5-phthalimidoperoxopentanoic acid, 6-phthalimidoperoxohexanoic acid, 7-phthalimidoperoxoheptanoic acid , N, N'-terephthaloyl-di-6-aminoperoxohexanoic acid and mixtures thereof.
  • Preferred peracids include the phthalimidoperoxoalkanoic acids, especially 6-phthalimidoperoxohexanoic acid (PAP). It may be preferred that the bleaching agent has an envelope which dissolves only in the actual washing process and then releases the bleaching agent, especially when the washing or cleaning agent is formulated as a liquid or gel agent or the bleaching component spatially separated from the base formulation is.
  • PAP 6-phthalimidoperoxohexanoic acid
  • the amount of bleaching agent is preferably between 0.5 and 25 wt .-% based on the total washing or cleaning agent.
  • bleach activators can be incorporated into the detergents or cleaning agents.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2, 5-diacetoxy-2,5-dihydrofuran.
  • TAED tetraacety
  • bleach catalysts can be incorporated into the detergents or cleaning agents.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • photo-bleaches based on modified TiO 2 , which are activated by the action of light.
  • a liquid or gel detergent or cleanser may contain a thickener.
  • the thickener may include, for example, a polyacrylate thickener, xanthan gum, gellan gum, guar gum, alginate, carrageenan, carboxymethyl cellulose, bentonites, wellan gum, locust bean gum, agar, tragacanth, gum arabic, pectins, polyoses, starch, dextrins, gelatin and casein include.
  • modified natural substances such as modified starches and celluloses, examples which may be mentioned here include carboxymethylcellulose and other cellulose ethers, hydroxyethyl and -propylcellulose and core flour ethers, can be used as thickeners.
  • the polyacrylic and polymethacrylic thickeners 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 (INCI: Carbomer), which are also referred to as carboxyvinyl polymers.
  • a polyalkenyl polyether in particular an allyl ether of sucrose, pentaerythritol or propylene
  • carboxyvinyl polymers Such polyacrylic acids are available, inter alia, from 3V Sigma under the trade name Polygel®, for example Polygel DA, and from Noveon under the trade name Carbopol®, for example Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 (molecular weight approx 1,250,000) or Carbopol 934 (molecular weight about 3,000,000).
  • acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C
  • Carbopol® Noveon under the trade name Carbopol®, for example, the hydrophobic Carbopol ETD 2623 and Carbopol 1382 (INCI Acrylates / Cio 3O alkyl acrylate crosspolymer) and Carbopol Aqua 30 (formerly Carbopol EX 473).
  • xanthan gum a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of from 2 to 15 million daltons.
  • Xanthan is formed from a chain of ⁇ -1,4-linked glucose (cellulose) with side chains.
  • the structure of the subgroups consists of glucose, mannose, glucuronan acid, acetate and pyruvate, where the number of pyruvate units determines the viscosity of the xanthan gum.
  • a fatty alcohol is also suitable as thickener.
  • Fatty alcohols may be branched or unbranched, of native origin or of petrochemical origin.
  • Preferred fatty alcohols have a C chain length of 10 to 20 C atoms, preferably 12 to 18. Preference is given to using mixtures of different C chain lengths, such as tallow fatty alcohol or coconut fatty alcohol. Examples are Lorol® Spezial (C12-14-ROH) or Lorol® Technical (C12-18-ROH) (both ex Cognis).
  • paraffins and related hydrocarbons are also suitable as paraffins and related hydrocarbons.
  • Preferred liquid or gel detergents or cleaners contain from 0.01 to 3% by weight, and preferably from 0.1 to 1% by weight, of thickener, based on the total washing or cleaning agent.
  • the amount of thickener used depends on the type of thickener and the desired degree of thickening.
  • the viscosity of the liquid detergent, softener or detergent can be measured using standard methods (for example Brookfield viscometer LVT-II at 20 U / min and 2O 0 C, spindle 3) and is preferably in the range of 10 to 100,000 mPas.
  • Preferred detergents or cleaners have viscosities of 100 to 5000 mPas, with values between 100 and 2000 mPas being particularly preferred.
  • the washing or cleaning agent according to the invention may also contain agents for the hydrophilization of surfaces.
  • Colloidal silica sols in which the silicon dioxide is preferably nanoparticulate are particularly suitable for hydrophilization.
  • Colloidal nanoparticulate silica sols for the purposes of this invention are stable dispersions of amorphous particulate silicon dioxide SiO 2 having particle sizes in the range from 1 to 100 nm. The particle sizes are preferably in the range from 3 to 50 nm, more preferably from 4 to 40 nm a silica sol, which is suitable to be used for the purposes of this invention is that available under the trade name Bindzif ® 30/360 from Akzo silica sol having a particle size of 9 nm.
  • silica sols are BindziP 15 / 500, 30/220, 40/200 ⁇ Akzo), NyacoP 215, 830, 1430, 2034DI and NyacoP DP5820, DP5480, DP5540 etc.
  • LevasiP 100/30, 100F / 30, 100S / 30, 200 / 30, 200F / 30, 300F / 30, VP 4038, VP 4055 (HC Starck / Bayer) or CAB-O-SPERSE ® PG 001, PG 002 (aqueous dispersion of CAB-O-SIL ®, Cabot), Quartron PL-1, PL-3 (Fuso Chemical Co.), Köstrosol 0830, 1030, 1430 (Chemiewerk Bad Köstritz).
  • the silica sols used may also be surface-modified silica treated with sodium aluminate (alumina-modified silica).
  • hydrophilizing polymers are amphoteric polymers, for example copolymers of acrylic or methacrylic acid and MAPTAC, DADMAC or another polymerizable quaternary ammonium compound.
  • copolymers with AMPS (2-acrylamido-2-methylpropanesulfonic acid).
  • Polyethersiloxanes, ie copolymers of polymethylsiloxanes with ethylene oxide or propylene oxide segments are further suitable polymers.
  • acrylic polymers, maleic acid copolymers and polyurethanes with PEG (polyethylene glycol) units are also usable.
  • Suitable polymers are, for example, under the trade names Mirapol Surf-S 100, 110, 200, 210, 400, 410, A 300, A 400 (Rhodia), Tegopren 5843 (Goldschmidt), Sokalan CP 9 (BASF) or Polyquart Ampho 149 (Cognis ) commercially available.
  • the washing or cleaning agent may contain enzymes in encapsulated form and / or directly in the washing or cleaning agent.
  • Suitable enzymes include in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases, hemicellulases, mannanases, cutinases, ⁇ -glucanases, oxidases, peroxidases, tannases, perhydrolases and / or laccases and mixtures of said enzymes in question. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying.
  • cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils.
  • Oxireductases can also be used for bleaching or inhibiting color transfer.
  • Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and ß-glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes may be adsorbed to carriers to protect against premature degradation.
  • the proportion of the enzymes, the enzyme liquid formulation (s) or the enzyme granules directly in the washing or cleaning agent may be for example about 0.01 to 5 wt .-%, preferably 0.12 to about 2.5 wt .-%.
  • the detergent or cleaning agent contains no enzymes.
  • electrolyte from the group of inorganic salts a wide number of different salts can be used.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates.
  • NaCl or MgCl 2 in the washing or cleaning agents is preferred.
  • organic salts is also possible.
  • the proportion of electrolytes in the washing or cleaning agents is usually 0.1 to 10 wt .-%.
  • Non-aqueous solvents which can be used in liquid detergents or cleaners, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether , Diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or
  • hard surface cleaners are preferably formulated as aqueous agents.
  • the water content in these compositions is usually more than 50 wt .-%, preferably more than 70 wt .-%, more preferably more than 80 wt .-%, in particular more than 85 wt .-%.
  • pH adjusters In order to bring the pH of a liquid detergent or cleaning agent in the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, as well as electrolyte systems, unless their use for technical application or environmental reasons or for reasons of consumer protection prohibits. Usually, the amount of these adjusting agents does not exceed 7% by weight of the total formulation.
  • the agents according to the invention may contain volatile alkali.
  • ammonia and / or alkanolamines which may contain up to 9 C atoms in the molecule, are used.
  • alkanolamines the ethanolamines are preferred and of these in turn the monoethanolamine.
  • the content of ammonia and / or alkanolamine is preferably 0.01 to 0.5 wt .-%; ammonia is particularly preferably used.
  • the detergents according to the invention may also contain small amounts of bases.
  • bases are selected from the group of the alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is particularly preferred.
  • bases are used in amounts of not more than 1% by weight, preferably 0.01 to 0.1% by weight.
  • Alkaline agents may additionally contain carboxylic acids in addition to the volatile alkali, the equivalent ratio of amine and / or ammonia to carboxylic acid preferably being between 1: 0.9 and 1: 0.1.
  • carboxylic acids having up to 6 carbon atoms, which may be mono-, di- or polycarboxylic acids.
  • the content of carboxylic acid is preferably between 0.01 and 6 wt .-%, in particular between 0.01 and 1 wt .-%.
  • carboxylic acids examples include acetic acid, glycolic acid, lactic acid, citric acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid, of which preferably acetic acid, citric acid and lactic acid are used.
  • Optically active carboxylic acids can be used in the form of their racemates or enantiomerically pure. Particular preference is given to using acetic acid.
  • Acid detergents according to the invention may also contain acids instead of volatile alkali.
  • Suitable acids are, in particular, organic acids such as the abovementioned carboxylic acids acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid.
  • organic acids such as the abovementioned carboxylic acids acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid.
  • mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof Particular preference is given to acids selected from the group comprising amidosulfonic acid, citric acid and formic acid. They are preferably used in amounts of 0.1 to 8 wt .-%, more preferably 0.5 to 6 wt .-%, in particular 1 to 5 wt .-
  • the washing or cleaning agent optionally contains one or more perfumes in an amount of usually up to 20 wt .-%, preferably 0.001 to 10 wt .-%, in particular 0.05 to 3 wt .-%, particularly preferably 0 , 1 to 2.5 wt .-% and most preferably 0.2 to 2 wt .-%.
  • the amount of perfume used is also dependent on the type of detergent or cleaning agent.
  • perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures as are available from plant sources.
  • Components of the perfume oil can have antimicrobial properties or inhibit or reduce the growth of germs. This applies, for example, to the aldehydes. But even labile alkyl cyanides can have effects against bacteria, fungi or viruses.
  • dyes can be dyed with suitable dyes.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of detergents and cleaning agents and to light and no pronounced substantivity to textile fibers or hard surfaces, so as not to stain them.
  • the dyes can be selected to form complexes and / or addition compounds with nuclei. These can serve as indicators of effective hygienic cleaning. However, such indicator function can also exercise other excipients, such as suitable DNA fragments.
  • Suitable defoamers which can be used in the detergents or cleaners are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials. Also used may be sodium carbonate (Na 2 CO 3 ), alone or in combination with hydrogen peroxide, in encapsulated form.
  • Suitable soil release polymers also referred to as "anti-redeposition agents” include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose having a methoxy group content of 15 to 30 wt% and hydroxypropyl groups of 1 to 15 wt%, respectively based on the nonionic cellulose ether and the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene and / or polypropylene glycol terephthalates or anionic and / or nonionic modified derivatives of this.
  • Suitable derivatives include the sulfonated derivatives of the phthalic and terephthalic acid polymers.
  • Optical brighteners may be added to detergents to eliminate graying and yellowing of the treated fabrics which will attract the fiber and cause lightening and fake bleaching by turning invisible ultraviolet radiation into visible longer wavelength convert light, wherein the absorbed from sunlight ultraviolet light is radiated as a pale blue fluorescence and the yellow shade of the grayed or yellowed laundry to yield pure white Suitable compounds originate for example from the substance classes of 4.4.
  • optical brighteners are usually e in amounts between 0% and 0.3 wt .-%, based on the final detergent or cleaning agent used.
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the detergents or cleaners used.
  • the wash or cleaning agent may contain a dye transfer inhibitor.
  • the color transfer inhibitor is a polymer or copolymer of cyclic amines such as vinylpyrrolidone and / or vinylimidazole.
  • Suitable color transfer inhibiting polymers include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride, and mixtures thereof.
  • polyvinylpyrrolidone PVP
  • polyvinylimidazole PVI
  • copolymers of vinylpyrrolidone and vinylimidazole PVP / PVI
  • the polyvinylpyrrolidones (PVP) used preferably have an average molecular weight of 2,500 to 400,000 and are commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or available from BASF as Sokalan® HP 50 or Sokalan® HP 53.
  • the copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) used preferably have a molecular weight in the range from 5,000 to 100,000.
  • a PVP / PVI copolymer for example from BASF under the name Sokalan® HP 56th
  • the amount of dye transfer inhibitor based on the total amount of the detergent or cleaning agent is preferably from 0.01 to 2% by weight, preferably from 0.05 to 1% by weight, and more preferably from 0.1 to 0.5% by weight. -%.
  • enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which removes hydrogen peroxide in water as a color transfer inhibitor.
  • a mediator compound for the peroxidase for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, wherein additionally the above-mentioned polymeric Farbü can bertrag ungs inhibitors can be used.
  • the detergents or cleaning agents may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
  • the detergents or cleaners according to the invention may contain preservatives, it being preferred to use only those which have no or only a slight skin-sensitizing potential.
  • preservatives examples are sorbic acid and its salts, benzoic acid and its salts, salicylic acid and its salts, phenoxyethanol, 3-iodo-2-propynyl butylcarbamate, sodium N- (hydroxymethyl) glycinate, biphenyl-2-ol and mixtures thereof.
  • isothiazolinone derivatives for example that available under the trade name Kathon ® CG mixture of methylchloroisothiazolinone and methylisothiazolinone, or under the trade name Bronopol ® available 2-bromo-2-nitropropane-1, 3-diol, used as a preservative.
  • the detergents or cleaners may contain antioxidants.
  • antioxidants include, for example, substituted phenols, hydroquinones, catechols and aromatic amines as well as phosphites, phosphonates, ascorbic acid and vitamin E.
  • Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges.
  • External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
  • Lauryl (or stearyl) -dimethylbenzylammonium- chlorides are suitable as antistatic agents for textile fabrics or as an additive to detergents or cleaners, wherein additionally a softening effect is achieved.
  • silicone derivatives can be used in the detergents or cleaners. These additionally improve the rinsing behavior of the washing or cleaning agents by their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
  • the viscosities of the preferred silicones at 25 0 C in the range between 100 and 100,000 mPas, wherein the silicones can be added in amounts between 0.2 and 5 wt .-%, based on the total detergent or cleaning agent.
  • Suitable heavy metal complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • anionic polyelectrolytes such as polymaleates and polysulfonates.
  • a preferred class of complexing agents are the phosphonates, which in preferred detergents or cleaners in amounts of 0.01 to 3.5 wt .-%, preferably 0.02 to 2 wt .-% and in particular from 0.03 to 1, 5 wt .-% are included.
  • These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane -1, 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.
  • the washing or cleaning agent may further contain one or more plant extracts. These are, for example, vegetable oils, essential oils, extracts of chamomile, aloe vera and / or echinacea or a mixture thereof.
  • Suitable vegetable oils that can be used include, for example, avocado oil, olive oil, palm oil, palm kernel oil, rapeseed oil, linseed oil, soybean oil, peanut oil, coriander oil, castor oil, poppy seed oil, cocoa oil, coconut oil, pumpkin seed oil, wheat germ oil, sesame oil, sunflower oil, almond oil, macadamia nut oil, apricot kernel oil, Hazelnut oil, jojoba oil and / or canola oil.
  • Preferred vegetable oils include almond oil and / or jojoba oil and / or avocado oil, but especially almond oil.
  • essential oils are extracted from flowers, spices, herbs, woods or fibers and are complex mixtures of various organic molecules such as terpenes, ethers, coumarins, esters, aldehydes, phenyl esters, monoterpenols, phenols, monoterpenes, oxides, sesquiterpene ketones, sesquiterpenes and sesquiterpenols. Due to their small molecular structure, essential oils pass through the skin and / or the mucous membrane into the bloodstream and tissue. In this way they can influence the entire organism.
  • Suitable essential oils include, for example, oils of Abies Sibirica, Amyris balsamifera, anise (Illicium verum), lemon balm (Melissa officinalis), basil (Ocimum basilicum), pimenta acre, bee balm (Monarda didyma), bergamot (citrus aurantium bergamia), birch (betula Aba), Bitter Orange (Citrus Aurantium Amara), Hibiscus, Hundred Rose (Rosa Centifolia), Calendula Officinalis, Californian Nusseibe (Torreya Californica), Camellia Sinensis, Capsicum Frutescers Oleoresin, Carum Carvi, Cardamom (Elettaria Cardamomum), Cedar ( Cedrus Atlantica), Chamaecyparis obtusa, Chamomile (Anthemis nobilis), Cinnamon (Cinnamomum cassia),
  • the detergents or cleaners may also contain UV absorbers which are applied to the treated fabrics and improve the light fastness of the fibers.
  • Compounds which have these desired properties are, for example, the compounds which are active by radiationless deactivation and derivatives of benzophenone with substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, titanium dioxide (if appropriate modified), organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.
  • Solid washing or cleaning agents may additionally contain fillers such as sodium sulfate or sodium bicarbonate.
  • the antimicrobial active composition can be applied at the end of the production process to the finished washing or cleaning agent ("post-addition", for example analogously to the introduction of perfume), for example by means of spraying Detergents but liquid.
  • the antimicrobial composition according to the invention or the detergents or cleaners according to the invention can be used for inhibiting the growth of microorganisms on textiles and on hard surfaces such as tiles, kitchen work surfaces, stainless steel or plastic in the household, the washing or cleaning agents according to the invention also for cleaning and / or conditioning said substrates.
  • the antimicrobially active composition according to the invention or the washing or cleaning agents according to the invention can furthermore be used in a process for the treatment and cleaning of germinated surfaces in the household, in which they are brought into contact with the correspondingly contaminated surface, if necessary act and subsequently within the usual range Washing or cleaning process are removed again.
  • a liquid detergent or cleaning agent by means of conventional methods and methods in which, for example, the components are simply mixed in stirred tanks, water, non-aqueous solvents and surfactants are conveniently presented. Subsequently, if present, the saponification of the fatty acid portion at 50 to 60 0 C. Then, the other ingredients, including the antimicrobial composition, added in portions.
  • Antimicrobial compositions A1 to A5 according to the invention and a comparison formulation V1 were formulated and their effect on various microorganisms after incorporation in a commercially available liquid detergent was investigated.
  • compositions were each incorporated in a commercial, liquid detergent.
  • WA1 0.017 wt% farnesol, 0.017 wt% silver nitrate, 0.33 wt% MGDA, and 0.0496 wt% sodium thiosulfate.
  • WA2 0.034 wt% farnesol, 0.008 wt% silver nitrate, 0.17 wt% MGDA and 0.0233 wt% sodium thiosulfate.
  • WA3 0.00% by weight of farnesol, 0.025% by weight of silver nitrate, 0.5% by weight of MGDA and 0.0729% by weight of sodium thiosulfate.
  • WA4 0.00% by weight of farnesol, 0.05% by weight of silver nitrate, 0.00% by weight of MGDA and 0.1459% by weight of sodium thiosulfate.
  • WA5 0.025 wt% farnesol, 0.025 wt% silver nitrate, 0.00 wt% MGDA and 0.0729 wt% sodium thiosulfate.
  • WV1 0.025 wt% farnesol, 0.00 wt% silver nitrate, 0.5 wt% MGDA and 0.00 wt% sodium thiosulfate.
  • Detergents WA1 to WA5 according to the invention showed good activity both against gram-positive test organisms (Staphylococcus aureus, Staphylococcus epidermidis) and against yeast (Candida albicans). The inhibitory effect on S. aureus was very good for all detergents WA1 to WA5 (> 5 LOG).
  • the two detergents WA1 and WA2 showed a germicidal or germ-inhibiting effect on a broader spectrum of germs.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
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Abstract

L'invention décrit un agent de lavage ou de nettoyage, associé à une composition exerçant un effet antibactérien. Cette composition exerçant un effet antibactérien est formée à partir d'un sel d'argent soluble dans l'eau et d'un agent complexant. L'agent de lavage ou de nettoyage ainsi que la composition exerçant un effet antibactérien peuvent être utilisés dans les tâches ménagères pour freiner la croissance de micro-organismes sur des textiles et sur des surfaces dures, et peuvent être employés lors des tâches ménagères pour le traitement et le nettoyage de surfaces contaminées par des germes.
PCT/EP2008/054210 2007-05-31 2008-04-08 Agent de lavage ou de nettoyage à effet antibactérien Ceased WO2008145446A1 (fr)

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DE102007025561.8 2007-05-31
DE102007025561A DE102007025561A1 (de) 2007-05-31 2007-05-31 Wasch- oder Reinigungsmittel mit antibakterieller Wirkung

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Cited By (6)

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WO2010057723A1 (fr) * 2008-11-21 2010-05-27 Henkel Ag & Co. Kgaa Produit de lavage, de nettoyage, de traitement ultérieur ou produit auxiliaire de lavage contenant de l'argent
WO2010084057A1 (fr) * 2009-01-22 2010-07-29 Henkel Ag & Co. Kgaa Détergent pour vaisselle à la main ayant une action antibactérienne
US20150044298A1 (en) * 2011-09-16 2015-02-12 Robert White Disinfectant compositions and uses thereof
US9745543B2 (en) 2012-09-10 2017-08-29 Ecolab Usa Inc. Stable liquid manual dishwashing compositions containing enzymes
US20230189813A1 (en) * 2020-05-20 2023-06-22 Ancor Tecnologica Canaria, S.L. Disinfectant and protective composition for textiles or similar
CN120836568A (zh) * 2025-07-14 2025-10-28 广东中科鸿泰新材料有限公司 一种复合新型杀菌剂、其制备方法及应用

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PL2604298T3 (pl) * 2011-12-15 2016-11-30 Płyny uniwersalne do pielęgnacji soczewek kontaktowych zawierające rumianek
DE102012209168A1 (de) 2012-05-31 2013-12-05 Henkel Ag & Co. Kgaa Verbindungen und Mittel zur Verminderung von Schlechtgerüchen
DE102012221619A1 (de) 2012-11-27 2014-05-28 Henkel Ag & Co. Kgaa Salicylate
DE102020111465A1 (de) 2020-04-27 2021-10-28 Linden Chemie Hellenthal GmbH & Co. KG Desinfektionsmittel und Verfahren zur Herstellung eines Desinfektonsmittels
CN115466652A (zh) * 2022-09-21 2022-12-13 云南水星生物科技有限公司 一种抗菌护色剂及其制备方法与应用

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US4267168A (en) * 1977-03-11 1981-05-12 Aquatain Partnership Method of reducing bacteria on human tissue using liquid biocidal compositions comprising a mixture of silver ions and sodium pectate
US5651978A (en) * 1993-05-18 1997-07-29 Matsushita Electric Industrial Co., Ltd. Silver thiosulfate silica gel antibacterial compositions
EP0695501A1 (fr) * 1994-08-01 1996-02-07 Kawasumi Laboratories, Inc. Article en matière synthétique contenant un agent bactéricide métallique
US6726936B1 (en) * 1998-06-19 2004-04-27 Sumitomo Metal Mining Co., Ltd. Antimicrobial agents
WO2004028461A2 (fr) * 2002-09-25 2004-04-08 Edwin Odell Miner Solutions antiseptiques contenant de l'argent chelate par un polypectate et de l'edta
WO2004083352A1 (fr) * 2003-03-21 2004-09-30 Henkel Kommanditgesellschaft Auf Aktien Produit de lavage ou de nettoyage reduisant les germes et procede de preparation dudit produit
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010057723A1 (fr) * 2008-11-21 2010-05-27 Henkel Ag & Co. Kgaa Produit de lavage, de nettoyage, de traitement ultérieur ou produit auxiliaire de lavage contenant de l'argent
WO2010084057A1 (fr) * 2009-01-22 2010-07-29 Henkel Ag & Co. Kgaa Détergent pour vaisselle à la main ayant une action antibactérienne
US20150044298A1 (en) * 2011-09-16 2015-02-12 Robert White Disinfectant compositions and uses thereof
US9745543B2 (en) 2012-09-10 2017-08-29 Ecolab Usa Inc. Stable liquid manual dishwashing compositions containing enzymes
US10723974B2 (en) 2012-09-10 2020-07-28 Ecolab Usa Inc. Stable liquid manual dishwashing compositions containing enzymes
US20230189813A1 (en) * 2020-05-20 2023-06-22 Ancor Tecnologica Canaria, S.L. Disinfectant and protective composition for textiles or similar
CN120836568A (zh) * 2025-07-14 2025-10-28 广东中科鸿泰新材料有限公司 一种复合新型杀菌剂、其制备方法及应用

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