EP2346973B1 - Washing, cleaning, post-treating or auxiliary washing agent containing silver - Google Patents

Washing, cleaning, post-treating or auxiliary washing agent containing silver Download PDF

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Publication number
EP2346973B1
EP2346973B1 EP09740095.6A EP09740095A EP2346973B1 EP 2346973 B1 EP2346973 B1 EP 2346973B1 EP 09740095 A EP09740095 A EP 09740095A EP 2346973 B1 EP2346973 B1 EP 2346973B1
Authority
EP
European Patent Office
Prior art keywords
silver
washing
cleaning
post
treatment
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.)
Not-in-force
Application number
EP09740095.6A
Other languages
German (de)
French (fr)
Other versions
EP2346973A1 (en
Inventor
Georg Meine
Ralf Bunn
Andrea Eutebach
Frank Sonnenschein
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
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL09740095T priority Critical patent/PL2346973T3/en
Publication of EP2346973A1 publication Critical patent/EP2346973A1/en
Application granted granted Critical
Publication of EP2346973B1 publication Critical patent/EP2346973B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C11D3/048—Nitrates or nitrites
    • 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
    • C11D3/168—Organometallic compounds or orgometallic complexes
    • 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

Definitions

  • the present invention relates to a washing, cleaning, aftertreatment or washing aid containing surfactant (s), silver and / or a silver compound and other conventional ingredients of detergents, cleaners, aftertreatment or washing aids. Furthermore, the invention relates to a process for the preparation of a washing, cleaning, aftertreatment or washing aid.
  • Antimicrobially active compositions and their use in washing, cleaning, aftertreatment or washing aids are known in the art.
  • 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.
  • Natural ingredients are also desirable.
  • Silver or silver ions have a blocking effect on thiol enzymes in microorganisms and thus have a high bactericidal and fungicidal action. In addition, silver has a germicidal effect.
  • washing, cleaning, aftertreatment or washing aids containing silver and / or silver ions are not stable, because the silver ions contained in the agents can be mixed with impurities, such as chloride ions to photosensitive silver chloride salts or sulfide to poorly soluble silver sulfide. Salts react. In a (strongly) alkaline medium, soluble silver ions can first react to AgOH and then further to sparingly soluble Ag 2 O. In addition to the poor solubility of these silver salts, in particular the silver oxides and silver sulfides cause considerable color changes despite small amounts, in particular a brown or black color, the liquid washing, cleaning, aftertreatment or washing aids.
  • the silver compound is selected from the group consisting of silver acetate, silver citrate, silver diamine chloride complex, silver cyclodextrin complex, silver dicyanokalium complex, silver phthalimide, silver phenylcyanamide, silver (ethylene thiourea) complex, silver imidazolate, transition metal NHC-calix [4] arene Complexes, silver crown ethers, silver nitrate and mixtures thereof.
  • the liquid washing, cleaning, after-treatment or washing aid particularly preferably contains silver nitrate.
  • silver compounds have a sufficiently high solubility and do not fall out of the liquid washing, cleaning, aftertreatment or washing aids.
  • the amount of elemental silver and / or silver compound is from 0.0001 to 1% by weight, based on the total liquid washing, cleaning, after-treatment or washing aid.
  • the ratio of unneutralized fatty acid to elemental silver and / or the amount of silver cation is greater than or equal to 8 to 1. When setting this ratio, a particularly effective stabilization of the silver or the silver cation is achieved.
  • the amount of non-neutralized fatty acid is between 0.01 and 10 wt .-%, based on the total liquid washing, cleaning, aftertreatment or washing aid. This amount of unneutralized fatty acid achieves effective stabilization of the silver or silver cation. Excessive amounts of unneutralized fatty acid can result in undesirable clouding of the liquid agent since not all of the non-neutralized fatty acid in the agent can be dissolved.
  • the liquid washing, cleaning, aftertreatment or washing aid additionally contains 0.01 to 3 wt .-%, based on the total liquid washing, cleaning, aftertreatment or washing aid, ammonium hydroxide. Surprisingly, it has been found that particularly clear and thus aesthetically pleasing washing, cleaning, aftertreatment or washing aids are obtained by adding even small amounts of ammonium hydroxide.
  • Preferred liquid washing, cleaning, aftertreatment or washing aids contain the neutralized and unneutralized form of a fatty acid. With the help of the pH of the liquid washing, cleaning, aftertreatment or washing aid or by adding a pH adjuster can be prepared in a simple and fast way a stable, fatty acid soap and silver-containing washing, cleaning, aftertreatment or washing aid become.
  • liquid washing, cleaning, aftertreatment or washing aid is formulated as a fabric softener containing 0.5 to 50 wt .-% cationic surfactant.
  • Such fabric softeners according to the invention have the advantage that the items of laundry come into contact with the germ-reducing silver in a final treatment cycle of the washing machine, which further reduces the number of seeds on the surface of the items of laundry.
  • the agent itself reduces germs and prevents in this way the contamination of the fabric softener, which often manifests itself in unsightly black discoloration and deposit formation that arouses displeasure at the consumer.
  • the invention relates to the use of non-neutralized fatty acid for stabilizing silver-containing liquid washing, cleaning, aftertreatment or washing aids.
  • the liquid washing, cleaning, aftertreatment or washing aid contains silver and / or a silver compound.
  • silver is used either in elemental form or in the form of its compounds. If the silver used in elemental form, it preferably has particle sizes of 0.1 to 100 microns. Even finer particle sizes of silver can be achieved by using the elemental silver in colloidal form, wherein the silver has particle sizes of 0.001 to 0.1 microns.
  • the agent contains a silver compound and that silver compound is selected from the group consisting of silver acetate, silver citrate, silver diamine chloride complex, silver cyclodextrin complex, silver dicyanokalium complex, silver phthalimide, silver phenylcyanamide, silver (ethylene thiourea) complex, silver imidazolate, Transition metal NHC-calix [4] arene complexes, silver crown ethers, silver nitrate and mixtures thereof.
  • the silver compounds are preferably added in the form of solutions, suspensions or dispersions.
  • the liquid washing, cleaning, after-treatment or washing aid particularly preferably contains silver nitrate, which is used in the form of an aqueous solution.
  • the amount of elemental silver and / or silver compound is preferably from 0.0001 to 1% by weight, and more preferably from 0.001 to 0.25% by weight, based on the total washing, cleaning, after-treatment or washing aid.
  • Very particularly preferred liquid washing, cleaning, after-treatment or washing aids contain from 0.01 to 0.1% by weight of elemental silver and / or of a silver compound, based on the total washing, cleaning, after-treatment or washing aid.
  • the liquid washing, cleaning, aftertreatment or washing aid contains non-neutralized fatty acid.
  • the amount of non-neutralized fatty acid in the washing, cleaning, aftertreatment or auxiliary washing agent also depends on the amount of silver or silver compound used. In general, the amount of non-neutralized fatty acid is in the range of 0.01% to 10%, preferably 0.1% to 5%, and more preferably 0.5 to 3% to obtain optimum stabilization at a minimum cost.
  • the ratio of unneutralized fatty acid to elemental silver and / or the amount of silver cation be greater than or equal to 8 to 1.
  • Suitable fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid, linoleic acid, linolenic acid, oleic acid and behenic acid and in particular natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
  • the determination of the content or the content of non-neutralized fatty acid in a liquid, fatty acid soap-containing detergent or cleaner can on the one hand experimentally (for example by titration) or with knowledge of the pKa value of the fatty acid used with the aid of Henderson-Hasselbalch Equation.
  • the washing, cleaning, after-treatment or washing assistant contains from 2 to 60% by weight of a surfactant selected from the group consisting of anionic, nonionic, cationic and zwitterionic surfactants and mixtures thereof.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • 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.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO, 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 7 EO.
  • the stated degrees of ethoxylation represent statistical averages, which for a particular product a whole or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention.
  • a linear, ethoxylated compound having 8 to 18 carbon atoms and, on average, 1 to 12 moles of ethylene oxide (EO) per mole of alcohol.
  • Nonionic surfactants are amine oxide type surfactants such as N-cocoalkyl N, N-dimethyl amine oxide and N-tallow alkyl N, N-dihydroxyethyl amine oxide. These are preferably used in particular in laundry detergents because they have a particularly high cleaning performance of special stains, such as engine oil.
  • the content of nonionic surfactants in the washing, cleaning, after treatment or auxiliary washing agent is preferably from 2 to 40% by weight, preferably from 4 to 30% by weight and in particular from 5 to 15% by weight, in each case based on the total Washing, cleaning, aftertreatment or washing aids.
  • the surfactant mixture of the washing, cleaning, aftertreatment or auxiliary washing agent may also be an anionic surfactant.
  • the anionic surfactant used is preferably sulfonates, sulfates, soaps and mixtures thereof.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Alk (en) yl sulfates are the alkali and especially the sodium salts of Schwefelklareschester the C 12- C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C 10- C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. From washing technical Of interest are the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates preferred. 2,3-alkyl sulfates are also suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable.
  • 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 including the soaps may be in the form of their sodium, potassium or magnesium salts.
  • the anionic surfactants are in the form of their sodium salts.
  • Further preferred counterions for the anionic surfactants are also the protonated forms of choline, triethylamine or methylethylamine.
  • the washing, cleaning, after-treatment or washing aid contains the neutralized and unneutralized form of a fatty acid. This is particularly advantageous in fatty acid soap-containing liquid washing, cleaning, aftertreatment or washing aids, since there simply by the pH, for example by adding pH adjusting agents, the necessary for a stabilization of the silver or the silver cation amount can be adjusted to non-neutralized fatty acid.
  • the fatty acid soap may be derived from a different fatty acid than the fatty acid used to stabilize the elemental silver and / or the silver cation.
  • Conditioners in the form of fabric softeners contain cationic surfactants which have a softening effect.
  • the cationic surfactants include, for example, quaternary ammonium compounds such as monoalk (en) yltrimethylammonium compounds, dialk (en) yldimethylammonium compounds, mono-, di- or triesters of fatty acids with alkanolamines.
  • quaternary ammonium compounds are shown, for example, in the formulas (I) to (III): wherein in (I) R is an acyclic alkyl radical having 12 to 24 carbon atoms, R 1 is a saturated C 1 -C 4 alkyl or hydroxyalkyl radical, R 2 and R 3 are either R or R 1 or are an aromatic radical , X - is either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof.
  • Examples of cationic compounds of the formula (I) are monotaltrimethylammonium chloride, monostearyltrimethylammonium chloride, didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.
  • R 4 is an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds and / or optionally with substituents
  • R 5 is H, OH or O (CO) R 7
  • R 6 is, independently of R 5, H, OH or O (CO) R 8
  • R 7 and R 8 are each independently an aliphatic alk (ene) ylrest having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.
  • m, n and p can each independently be 1, 2 or 3.
  • X - may be either a halide, methosulfate, methophosphate or phosphate ion as well as mixtures of these anions.
  • R 5 represents the group O (CO) R 7 .
  • R 5 is the group O (CO) R 7 and R 4 and R 7 are alk (en) yl radicals having 16 to 18 carbon atoms.
  • R 6 is also OH.
  • R 12 , R 13 and R 14 independently represent a C 1-4 alkyl, alkenyl or hydroxyalkyl group
  • R 15 and R 16 each independently is a C 8-28 alkyl group
  • X - An anion and r is a number between 0 and 5.
  • Examples include methyl N- (2-hydroxyethyl) -N, N-di (tallowacyloxyethyl) ammonium methosulfate, bis (palmitoyloxyethyl) hydroxyethyl methyl ammonium methosulfate, 1,2-bis [tallowacyloxy] -3- trimethylammonium, Methyl-N, N-bis (stearoyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate or N, N-dimethyl-N, N-di (tallowacyloxyethyl) ammonium methosulfate.
  • ester group O (CO) R where R is a long-chain alk (en) yl radical
  • softening compounds which have the following groups: RO (CO), N (CO) R or RN (CO) of these groups, N (CO) R groups are preferred.
  • Another advantageous ingredient of the washing, cleaning, aftertreatment or washing aids may be ammonium hydroxide. It has been shown that even small amounts of 0.01 wt .-% ammonium hydroxide, based on the total washing, cleaning, aftertreatment or washing aid, lead to very clear and thus aesthetically very appealing agents.
  • the washing, cleaning, aftertreatment or washing aid may contain other ingredients that the performance and / or aesthetic properties of the washing, cleaning, NacANs- or detergency further improve.
  • the washing, cleaning, after-treatment or washing assistant preferably additionally contains one or more substances from the group of builders, bleaching agents, bleach catalysts, bleach activators, enzymes, electrolytes, nonaqueous solvents, pH adjusters, perfume oil, perfume carriers, Fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, anti redeposition agents, grayness inhibitors, anti-shrinkage agents, crease inhibitors, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatics, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, emollients Components as well as UV absorbers.
  • perfume oil perfume carriers
  • Fluorescent agents dyes, hydrotropes, foam inhibitors, silicone oils, anti redeposition agents, grayness inhibitors, anti-shrinkage agents, crease inhibitors, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidant
  • soluble organic builders are preferred.
  • Organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) and derivatives thereof and mixtures thereof.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of an acidifying component. As builders further polymeric polycarboxylates are suitable.
  • Citric acid or its salts, are preferably used as soluble, organic builders in liquid washing, cleaning, aftertreatment or washing aids.
  • the liquid washing, cleaning, aftertreatment or washing aid may also contain an enzyme or a mixture of enzymes.
  • Particularly suitable are those from the classes of hydrolases such as proteases, (poly) esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases, hemicellulases, cutinases, ⁇ -glucanases, oxidases, peroxidases, mannanases, tannanases, esterases / Polyesterases, perhydrolases, oxireductases and / or laccases.
  • hydrolases such as proteases, (poly) esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases, hemicellulases, cutinases, ⁇ -glucanases, oxidases, peroxidases, mannanases, tannanases, esterases / Polyesterases
  • the washing, cleaning, after-treatment or washing aids according to the invention may contain stabilizing agents, such as boric acid or borates, boric acid derivatives or amino alcohols.
  • pH adjusters In order to bring the pH of the washing, cleaning, aftertreatment or washing aid in the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis. Preferred pH adjusters are NaOH or citric acid.
  • the pH of the washing, cleaning, after-treatment or auxiliary washing agent is preferably between 5 and 8.5 and more preferably between 7.5 and 8.5.
  • the washing, cleaning, aftertreatment or washing aid preferably contains a perfume.
  • perfume oils individual fragrance compounds, for example, the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be 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.
  • washing, cleaning, after-treatment or washing aids according to the invention can be used for washing and / or cleaning and / or conditioning textile fabrics.
  • One way of preparing the washing, cleaning, aftertreatment or washing aids according to the invention is to add silver to the finished liquid agent, using it both in solid, preferably finely divided form, and as a solution, suspension or dispersion of silver in suitable solvents. Also silver compounds and solutions, suspensions or dispersions of silver compounds can be used according to the invention.
  • a liquid detergent or cleaning agent by means of conventional and known methods and methods.
  • the ingredients of detergents, cleaners can be simply mixed in stirred tanks, water, the acidic components, if present, such as the alkylarylsulfonates, citric acid, boric acid, phosphonic acid, the fatty alcohol ether sulfates, etc., and the nonionic surfactants suitably presented become.
  • the nonaqueous solvents, if present, are preferably also added at this time, but the addition may be made at a later time. Subsequently, the non-neutralized fatty acid is added and then the other ingredients, preferably in portions, are added.
  • liquid washing, cleaning, after-treatment or washing aid also contains neutralized fatty acid
  • the preparation of a conditioning agent in the form of a fabric conditioner can be obtained by techniques familiar to the person skilled in the art for the preparation of fabric conditioners. This can be done for example by mixing the raw materials, optionally using high-shear mixing equipment. It is recommended to melt the cationic surfactant and then to disperse the melt in a solvent, preferably water. The other ingredients, including the non-neutralized fatty acid, can be incorporated into the fabric softener by simple admixing.
  • the silver or silver compound is added as the last step.
  • colloidal silver in the washing, cleaning, aftertreatment or washing aid by homogenization in a colloid mill or by arc sputtering of a silver wire.
  • Table 1 shows the compositions of a comparative formulation V1 and the compositions of five detergents or cleaners E1 to E5 according to the invention (all amounts are given in% by weight of active compound, based on the composition): Table 1 V1 E1 E2 E3 E4 E5 C 12-18 fatty alcohol with 7 EO 12 12 12 12 12 12 N-coco-N, N-dimethylamine 2 2 2 2 2 2 2 AgNO 3 0,017 0,017 0,017 0,017 0,017 0,017 farnesol 0.02 0.02 0.02 0.02 0.02 0.02 C 14 fatty acid 1.61 1.61 1.61 1.61 1.61 citric acid 0.1 0.1 0.1 0.1 0.1 0.1 0.22 NaOH 0.38 0.32 0.23 0.18 0.13 0.13 NH 4 OH 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 water Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 PH value 11.5 10.04
  • the washing, cleaning, aftertreatment or washing aid V1 showed a noticeable change in color already several hours after the preparation.
  • the washing, cleaning, after-treatment or washing aids E2 to E4 were still clear formulations after 4 weeks, which showed no color change.
  • the washing, cleaning, aftertreatment or washing aid E6 although after 4 weeks and no color change, but was slightly cloudy from the beginning.
  • the washing, cleaning, aftertreatment or washing aid E1 also showed a change in color, but this occurred much later and weaker than the washing or cleaning agent V1.
  • Table 2 shows the compositions of another three washing, cleaning, after-treatment or washing aids E6 to E8 according to the invention (all amounts are given in% by weight of active compound, based on the composition): Table 2 E6 E7 E8 C 13-15 oxo alcohol with 7 EO 12 12 5 Linear C 11-13 alkyl benzoic acid - - 12 AgNO 3 0,017 0,017 0,017 farnesol 0.05 0.05 0.05 coconut fatty acid 5.13 5 2.0 citric acid 1 0.15 1 NaOH - 1.99 0.48 NH 4 OH 3.05 0.01 0.4 water Ad 100 Ad 100 Ad 100 PH value 8.6 11.4 8.7
  • the washing, cleaning, aftertreatment or washing aids E6 to E8 were still clear formulations after 4 weeks, which showed no or only very slight color changes.
  • the washing, cleaning, aftertreatment or washing aids E1 to E 8 showed good activity against Gram-positive test bacteria ( Staphylococcus aureus, Staphylococcus epidermidis ) as well as against yeast ( Candida albicans ).

Description

Die vorliegende Erfindung betrifft ein Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel, enthaltend Tensid(e), Silber und/oder eine Silberverbindung sowie weitere übliche Inhaltsstoffe von Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmitteln. Desweiteren betrifft die Erfindung ein Verfahren zur Herstellung eines Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittels.The present invention relates to a washing, cleaning, aftertreatment or washing aid containing surfactant (s), silver and / or a silver compound and other conventional ingredients of detergents, cleaners, aftertreatment or washing aids. Furthermore, the invention relates to a process for the preparation of a washing, cleaning, aftertreatment or washing aid.

Durch die veränderten Waschgewohnheiten der Verbraucher kann es bei der Textilwäsche heutzutage zu einem Hygieneproblem kommen. Ein großer Teil der Wäsche wird mittlerweile bei 40 °C oder weniger gewaschen, einerseits wegen der Energiekosten, andererseits aber auch, um das Material und die Farben zu schonen. Viele moderne Textilarten sind tatsächlich nur bis 30 °C waschbar.Due to the changing washing habits of consumers, it can nowadays lead to a hygiene problem in textile laundry. A large part of the laundry is now washed at 40 ° C or less, on the one hand because of the energy costs, on the other hand, however, in order to protect the material and the colors. Many modern textile types are actually only washable up to 30 ° C.

Bei einer 60 °C-Wäsche, wie sie früher die Regel war, wurden zuverlässig nahezu alle Keime vernichtet, zum einen durch die höhere Temperatur, zum anderen durch die in den üblicherweise verwendeten Universalwaschmitteln enthaltenen Bleichmittel.In a 60 ° C wash, as was the rule in the past, almost all germs were reliably destroyed, on the one hand by the higher temperature, and on the other by the bleach contained in the commonly used universal detergents.

Neben der niedrigeren Waschtemperatur ist jedoch heutzutage auch die Verwendung flüssiger Waschmittel üblich, die in der Regel frei von Bleichmitteln sind.In addition to the lower washing temperature, however, the use of liquid detergents which are generally free of bleaching agents is customary today.

Somit können mit Bakterien, Schimmel- oder Hefepilzen verunreinigte Textilien nicht im erforderlichen Maße keimfrei gemacht werden, so dass unter Umständen eine (Re-) Infektion beim erneuten Kontakt des Verbrauchers mit der vermeintlich reinen Wäsche erfolgen kann.Thus, contaminated with bacteria, mold or yeast fungi textiles can not be made germ-free to the extent necessary, so that under certain circumstances, a (re) infection can be done on renewed contact of the consumer with the supposedly pure laundry.

Antimikrobiell wirksame Zusammensetzungen und ihr Einsatz in Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmitteln sind im Stand der Technik bekannt. Häufig handelt es sich bei den eingesetzten Desinfektionsmitteln um halogenhaltige Stoffe oder Phenolderivate oder andere aromatische Kohlenwasserstoffe, die aus Gründen der Umweltverträglichkeit als problematisch angesehen werden können. Andere, verträglichere Mikrobiozide haben nur ein eingeschränktes Wirkungsspektrum oder sind nur unter bestimmten physikalischen Bedingungen wirksam. Für Anwendungen im Haushalt besteht aber ein hoher Bedarf an antimikrobiellen Zusammensetzungen, die gegen ein breites Spektrum an Mikroorganismen wirksam und dabei umweltschonend sind; natürliche Bestandteile sind ebenfalls wünschenswert.Antimicrobially active compositions and their use in washing, cleaning, aftertreatment or washing aids 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.

Silber bzw. Silberionen üben eine blockierende Wirkung auf Thiol-Enzyme in Mikroorganismen aus und besitzen so eine hohe bakterizide und fungizide Wirkung. Darüber hinaus wirkt Silber keimtötend. Im Stand der Technik sind deshalb, beispielsweise aus der EP 1670885 A1 und US 2006/0051430 , bereits keimreduzierende Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel, enthaltend Silber und/oder Silberionen bekannt.Silver or silver ions have a blocking effect on thiol enzymes in microorganisms and thus have a high bactericidal and fungicidal action. In addition, silver has a germicidal effect. In the prior art, therefore, for example, from the EP 1670885 A1 and US 2006/0051430 , already germ-reducing washing, cleaning, aftertreatment or washing aids, containing silver and / or silver ions known.

Oftmals sind Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel, enthaltend Silber und/oder Silberionen nicht stabil, denn die in den Mitteln enthaltenen Silberionen können mit Verunreinigungen, wie Chlorid-Ionen zu lichtempfindlichen Silberchlorid-Salzen oder wie Sulfid zu schlecht löslichen Silbersulfid-Salzen reagieren. In einem (stark) alkalischen Medium können lösliche Silberionen zunächst zu AgOH und dann weiter zu schwerlöslichem Ag2O reagieren. Neben der Schwerlöslichkeit dieser Silbersalze bewirken insbesondere die Silberoxide und Silbersulfide trotz geringer Mengen erhebliche Farbveränderungen, insbesondere eine Braun- oder Schwarzfärbung, der flüssigen Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel.Often, washing, cleaning, aftertreatment or washing aids containing silver and / or silver ions are not stable, because the silver ions contained in the agents can be mixed with impurities, such as chloride ions to photosensitive silver chloride salts or sulfide to poorly soluble silver sulfide. Salts react. In a (strongly) alkaline medium, soluble silver ions can first react to AgOH and then further to sparingly soluble Ag 2 O. In addition to the poor solubility of these silver salts, in particular the silver oxides and silver sulfides cause considerable color changes despite small amounts, in particular a brown or black color, the liquid washing, cleaning, aftertreatment or washing aids.

Es ist deshalb eine Aufgabe der Erfindung, ein stabiles Silber- und/oder Silberionen-haltiges keimreduzierendes flüssiges Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel bereitzustellen.It is therefore an object of the invention to provide a stable silver and / or silver ion-containing germ-reducing liquid washing, cleaning, aftertreatment or washing aid.

Diese Aufgabe wird gelöst durch ein flüssiges Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel, enthaltend

  1. (a) 2 bis 60 Gew.-% eines Tensids ausgewählt aus der Gruppe bestehend aus anionischen, nichtionischen, kationischen und zwitterionischen Tensiden sowie Mischungen daraus,
  2. (b) Silber in elementarer und/oder oxidierter Form,
  3. (c) 0,01 bis 10 Gew.-% nicht-neutralisierte Fettsäure
  4. (d) Ammoniumhydroxid,
  5. (e) sowie weitere übliche Inhaltsstoffe von Wasch- und Reinigungsmitteln.
This object is achieved by a liquid washing, cleaning, aftertreatment or washing aid containing
  1. (a) 2 to 60% by weight of a surfactant selected from the group consisting of anionic, nonionic, cationic and zwitterionic surfactants and mixtures thereof,
  2. (b) silver in elemental and / or oxidized form,
  3. (c) 0.01 to 10% by weight of unneutralized fatty acid
  4. (d) ammonium hydroxide,
  5. (e) and other common ingredients of detergents and cleaners.

Überraschenderweise hat sich gezeigt, dass durch die Gegenwart von nicht-neutralisierter Fettsäure eine Stabilisierung des elementaren Silbers und/oder des Silberkations erreicht werden kann, ohne dass eine Beeinträchtigung der keimtötenden Wirkung des flüssigen Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel auftritt.Surprisingly, it has been found that by the presence of non-neutralized fatty acid stabilization of the elemental silver and / or the silver cation can be achieved without affecting the germicidal effect of the liquid washing, cleaning, aftertreatment or washing aid occurs.

Es ist bevorzugt, dass die Silberverbindung aus der Gruppe bestehend aus Silberacetat, Silbercitrat, Silberdiaminchlorid-Komplex, Silbercyclodextrin-Komplex, Silberdicyanokalium-Komplex, Silberphthalimid, Silberphenylcyanamid, Silber(ethylenthioharnstoff)-Komplex, Silberimidazolat, Übergangsmetall-NHC-Calix[4]aren-Komplexe, Silber-Kronenether, Silbernitrat und Mischungen daraus ausgewählt ist. Besonders bevorzugt enthält das flüssige Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel Silbernitrat.It is preferable that the silver compound is selected from the group consisting of silver acetate, silver citrate, silver diamine chloride complex, silver cyclodextrin complex, silver dicyanokalium complex, silver phthalimide, silver phenylcyanamide, silver (ethylene thiourea) complex, silver imidazolate, transition metal NHC-calix [4] arene Complexes, silver crown ethers, silver nitrate and mixtures thereof. The liquid washing, cleaning, after-treatment or washing aid particularly preferably contains silver nitrate.

Diese Silberverbindungen weisen eine ausreichend hohe Löslichkeit aus und fallen nicht aus den flüssigen Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmitteln aus.These silver compounds have a sufficiently high solubility and do not fall out of the liquid washing, cleaning, aftertreatment or washing aids.

Es ist ferner bevorzugt, dass die Menge an elementarem Silber und/oder Silberverbindung 0,0001 bis 1 Gew.-%, bezogen auf das gesamte flüssige Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel, beträgt.It is further preferred that the amount of elemental silver and / or silver compound is from 0.0001 to 1% by weight, based on the total liquid washing, cleaning, after-treatment or washing aid.

Es ist insbesondere bevorzugt, dass das Verhältnis nicht-neutralisierte Fettsäure zu elementarem Silber und/oder der Menge an Silberkation größer gleich 8 zu 1 beträgt. Bei Einstellung dieses Verhältnisses wird eine besonders effektive Stabilisierung des Silbers bzw. des Silberkations erzielt.It is particularly preferred that the ratio of unneutralized fatty acid to elemental silver and / or the amount of silver cation is greater than or equal to 8 to 1. When setting this ratio, a particularly effective stabilization of the silver or the silver cation is achieved.

Es ist weiterhin bevorzugt, dass die Menge an nicht-neutralisierter Fettsäure zwischen 0,01 und 10 Gew.-%, bezogen auf das gesamte flüssige Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel, beträgt. Mit Hilfe dieser Menge an nicht-neutralisierter Fettsäure wird eine effektive Stabilisierung des Silbers bzw. des Silberkations erreicht. Zu hohe Mengen an nicht-neutralisierter Fettsäure können zu einer unerwünschten Eintrübung des flüssigen Mittels führen, da nicht die gesamte Menge an nicht-neutralisierter Fettsäure in dem jeweiligen Mittel gelöst werden kann.It is further preferred that the amount of non-neutralized fatty acid is between 0.01 and 10 wt .-%, based on the total liquid washing, cleaning, aftertreatment or washing aid. This amount of unneutralized fatty acid achieves effective stabilization of the silver or silver cation. Excessive amounts of unneutralized fatty acid can result in undesirable clouding of the liquid agent since not all of the non-neutralized fatty acid in the agent can be dissolved.

Es kann bevorzugt sein, dass das flüssige Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel zusätzlich 0,01 bis 3 Gew.-%, bezogen auf das flüssige gesamte Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel, Ammoniumhydroxid enthält. Überraschenderweise hat sich gezeigt, dass besonders klare und somit ästhetisch ansprechende Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel durch Zugabe bereits geringer Mengen an Ammoniumhydroxid erhalten werden.It may be preferred that the liquid washing, cleaning, aftertreatment or washing aid additionally contains 0.01 to 3 wt .-%, based on the total liquid washing, cleaning, aftertreatment or washing aid, ammonium hydroxide. Surprisingly, it has been found that particularly clear and thus aesthetically pleasing washing, cleaning, aftertreatment or washing aids are obtained by adding even small amounts of ammonium hydroxide.

Bevorzugte flüssige Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel enthalten die neutralisierte und die nicht-neutralisierte Form einer Fettsäure. Mit Hilfe des pH-Wertes des flüssigen Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittels bzw. durch Zugabe eines pH-Stellmittels kann auf einfache und schnelle Weise ein stabiles, Fettsäureseife- und Silberhaltiges Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel hergestellt werden.Preferred liquid washing, cleaning, aftertreatment or washing aids contain the neutralized and unneutralized form of a fatty acid. With the help of the pH of the liquid washing, cleaning, aftertreatment or washing aid or by adding a pH adjuster can be prepared in a simple and fast way a stable, fatty acid soap and silver-containing washing, cleaning, aftertreatment or washing aid become.

Es kann bevorzugt sein, dass das flüssige Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel als Weichspüler konfektioniert ist, der 0,5 bis 50 Gew.-% kationisches Tensid enthält.It may be preferred that the liquid washing, cleaning, aftertreatment or washing aid is formulated as a fabric softener containing 0.5 to 50 wt .-% cationic surfactant.

Solche erfindungsgemäßen Weichspüler weisen den Vorteil auf, dass die Wäschestücke in einem abschließenden Behandlungsgang der Waschmaschine mit dem keimreduzierenden Silber in Berührung kommen, wodurch die Keimanzahl auf der Oberfläche der Wäschestücke nochmals reduziert wird. Darüber hinaus wirkt das Mittel an sich keimreduzierend und verhindert auf diese Weise die Verkeimung des Weichspülerdosierfaches, die sich oftmals in unansehnlicher schwarzer Verfärbung und Belagsbildung äußert, die Missfallen beim Verbraucher erregt.Such fabric softeners according to the invention have the advantage that the items of laundry come into contact with the germ-reducing silver in a final treatment cycle of the washing machine, which further reduces the number of seeds on the surface of the items of laundry. In addition, the agent itself reduces germs and prevents in this way the contamination of the fabric softener, which often manifests itself in unsightly black discoloration and deposit formation that arouses displeasure at the consumer.

Die Erfindung betrifft auch ein Verfahren zur Herstellung eines flüssigen Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel, enthaltend

  1. (a) 2 bis 60 Gew.-% eines Tensids ausgewählt aus der Gruppe bestehend aus anionischen, nichtionischen, kationischen und zwitterionischen Tensiden sowie Mischungen daraus
  2. (b) Silber und/oder eine Silberverbindung und
  3. (c) weitere übliche Inhaltsstoffe von Wasch- und Reinigungsmitteln,
wobei dem Mittel ferner 0,01 bis 10 Gew.-% nicht-neutralisierte Fettsäure, bezogen auf das gesamte Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel, zugesetzt werden.The invention also relates to a process for the preparation of a liquid washing, cleaning, aftertreatment or washing aid containing
  1. (A) 2 to 60 wt .-% of a surfactant selected from the group consisting of anionic, nonionic, cationic and zwitterionic surfactants and mixtures thereof
  2. (b) silver and / or a silver compound and
  3. (c) other common ingredients of detergents and cleaners,
wherein the agent further 0.01 to 10 wt .-% of unneutralized fatty acid, based on the total washing, cleaning, aftertreatment or washing aid, are added.

Ferner betrifft die Erfindung die Verwendung von nicht-neutralisierter Fettsäure zur Stabilisierung silberhaltiger flüssiger Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel.Furthermore, the invention relates to the use of non-neutralized fatty acid for stabilizing silver-containing liquid washing, cleaning, aftertreatment or washing aids.

Im Folgenden soll die Erfindung, unter anderem anhand von Beispielen, detaillierter beschrieben werden.In the following, the invention will be described in more detail, inter alia, by way of examples.

Als essentiellen Bestandteil enthält das flüssige Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel Silber und/oder eine Silberverbindung.As an essential ingredient, the liquid washing, cleaning, aftertreatment or washing aid contains silver and / or a silver compound.

Erfindungsgemäß wird Silber entweder in elementarer Form oder in Form seiner Verbindungen eingesetzt. Wird das Silber in elementarer Form eingesetzt, so weist es vorzugsweise Partikelgrößen von 0,1 bis 100 µm auf. Noch feinere Partikelgrößen des Silbers lassen sich durch Einsatz des elementaren Silbers in kolloidaler Form erreichen, wobei das Silber Partikelgrößen von 0,001 bis 0,1 µm aufweist.According to the invention, silver is used either in elemental form or in the form of its compounds. If the silver used in elemental form, it preferably has particle sizes of 0.1 to 100 microns. Even finer particle sizes of silver can be achieved by using the elemental silver in colloidal form, wherein the silver has particle sizes of 0.001 to 0.1 microns.

Es ist allerdings bevorzugt, dass das Mittel eine Silberverbindung enthält und diese Silberverbindung ausgewählt ist aus der Gruppe bestehend aus Silberacetat, Silbercitrat, Silberdiaminchlorid-Komplex, Silbercyclodextrin-Komplex, Silberdicyanokalium-Komplex, Silberphthalimid, Silberphenylcyanamid, Silber(ethylenthioharnstoff)-Komplex, Silberimidazolat, Übergangsmetall-NHC-Calix[4]aren-Komplexe, Silber-Kronenether, Silbernitrat und Mischungen daraus. Die Silberverbindungen werden vorzugsweise in Form von Lösungen, Suspensionen oder Dispersionen zugesetzt. Besonders bevorzugt enthält das flüssige Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel Silbernitrat, welches in Form einer wässrigen Lösung eingesetzt wird.However, it is preferred that the agent contains a silver compound and that silver compound is selected from the group consisting of silver acetate, silver citrate, silver diamine chloride complex, silver cyclodextrin complex, silver dicyanokalium complex, silver phthalimide, silver phenylcyanamide, silver (ethylene thiourea) complex, silver imidazolate, Transition metal NHC-calix [4] arene complexes, silver crown ethers, silver nitrate and mixtures thereof. The silver compounds are preferably added in the form of solutions, suspensions or dispersions. The liquid washing, cleaning, after-treatment or washing aid particularly preferably contains silver nitrate, which is used in the form of an aqueous solution.

Die Menge an elementarem Silber und/oder Silberverbindung beträgt vorzugsweise 0,0001 bis 1 Gew.-% und mehr bevorzugt zwischen 0,001 und 0,25 Gew.-%, bezogen auf das gesamte Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel. Ganz besonders bevorzugte flüssige Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel enthalten 0,01 bis 0,1 Gew.-% an elementarem Silber und/oder einer Silberverbindung, bezogen auf das gesamte Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel.The amount of elemental silver and / or silver compound is preferably from 0.0001 to 1% by weight, and more preferably from 0.001 to 0.25% by weight, based on the total washing, cleaning, after-treatment or washing aid. Very particularly preferred liquid washing, cleaning, after-treatment or washing aids contain from 0.01 to 0.1% by weight of elemental silver and / or of a silver compound, based on the total washing, cleaning, after-treatment or washing aid.

Als weiteren essentiellen Bestandteil enthält das flüssige Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel nicht-neutralisierte Fettsäure.As a further essential ingredient, the liquid washing, cleaning, aftertreatment or washing aid contains non-neutralized fatty acid.

Die Menge an nicht-neutralisierter Fettsäure in dem Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel hängt auch von der Menge an eingesetztem Silber bzw. an eingesetzter Silberverbindung ab. Im Allgemeinen liegt die Menge an nicht-neutralisierter Fettsäure in dem Bereich von 0,01 % bis 10 %, bevorzugt 0,1 % bis 5 % und stärker bevorzugt 0,5 bis 3 %, um eine optimale Stabilisierung bei minimalen Kosten zu erhalten.The amount of non-neutralized fatty acid in the washing, cleaning, aftertreatment or auxiliary washing agent also depends on the amount of silver or silver compound used. In general, the amount of non-neutralized fatty acid is in the range of 0.01% to 10%, preferably 0.1% to 5%, and more preferably 0.5 to 3% to obtain optimum stabilization at a minimum cost.

Dabei ist es ferner bevorzugt, dass das Verhältnis nicht-neutralisierte Fettsäure zu elementarem Silber und/oder der Menge an Silberkation größer gleich 8 zu 1 beträgt. Um eine effektive Stabilisierung des Silbers und/oder Silberverbindung zu erzielen, ist es notwendig, die nicht-neutralisierte Fettsäure in großem Überschuß einzusetzen. Es hat sich gezeigt, dass bei einem Verhältnis nicht-neutralisierte Fettsäure zu elementarem Silber und/oder der Menge an Silberkation kleiner 8 zu 1 oftmals keine ausreichende Stabilisierung erreicht wird und es zu unerwünschten Ausfällung und/oder Farbveränderungen kommen kann.It is further preferred that the ratio of unneutralized fatty acid to elemental silver and / or the amount of silver cation be greater than or equal to 8 to 1. In order to achieve effective stabilization of the silver and / or silver compound, it is necessary to use the unneutralized fatty acid in large excess. It has been found that at a ratio of unneutralized fatty acid to elemental silver and / or the amount of silver cation less than 8 to 1 often insufficient stabilization is achieved and can lead to undesirable precipitation and / or color changes.

Geeignete Fettsäuren umfassen Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, (hydrierten) Erucasäure, Linolsäure, Linolensäure, Ölsäure und Behensäure sowie insbesondere natürliche Fettsäuren, zum Beispiel Kokos-, Palmkern-, Olivenöl- oder Talgfettsäuren.Suitable fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid, linoleic acid, linolenic acid, oleic acid and behenic acid and in particular natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.

Die Bestimmung des Gehalts bzw. die Einstellung des Gehalts an nicht-neutralisierter Fettsäure in einem flüssigen, Fettsäureseife-haltigen Wasch- oder Reinigungsmittel kann einerseits experimentell (beispielsweise mittels Titration) oder bei Kenntnis des pKa-Wertes der eingesetzten Fettsäure mit Hilfe der Henderson-Hasselbalch-Gleichung erfolgen.The determination of the content or the content of non-neutralized fatty acid in a liquid, fatty acid soap-containing detergent or cleaner can on the one hand experimentally (for example by titration) or with knowledge of the pKa value of the fatty acid used with the aid of Henderson-Hasselbalch Equation.

Das Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel enthält 2 bis 60 Gew.-% eines oberflächenaktiven Mittels ausgewählt aus der Gruppe bestehend aus anionischen, nichtionischen, kationischen und zwitterionischen Tenside sowie Mischungen daraus.The washing, cleaning, after-treatment or washing assistant contains from 2 to 60% by weight of a surfactant selected from the group consisting of anionic, nonionic, cationic and zwitterionic surfactants and mixtures thereof.

Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, zum Beispiel aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-14-Alkohole mit 3 EO, 4 EO oder 7 EO, C9-11-Alkohol mit 7 EO, C13-15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-14-Alkohol mit 3 EO und C12-18-Alkohol mit 7 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO. Auch nichtionische Tenside, die EO- und PO-Gruppen zusammen im Molekül enthalten, sind erfindungsgemäß einsetzbar.The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, 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. The preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO, 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 7 EO. The stated degrees of ethoxylation represent statistical averages, which for a particular product a whole or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention.

Aus leistungstechnischer Sicht und im Hinblick auf die biologische Abbaubarkeit wird besonders bevorzugt ein linearer, ethoxylierte mit 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt.From a performance point of view and with regard to biodegradability, it is particularly preferable to use a linear, ethoxylated compound having 8 to 18 carbon atoms and, on average, 1 to 12 moles of ethylene oxide (EO) per mole of alcohol.

Eine weitere Klasse bevorzugter nichtionischer Tenside sind Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid. Diese werden insbesondere in Textilwaschmitteln bevorzugt eingesetzt, da sie eine besonders hohe Reinigungsleistung an speziellen Flecken, wie beispielsweise Motorenöl, besitzen.Another class of preferred nonionic surfactants are amine oxide type surfactants such as N-cocoalkyl N, N-dimethyl amine oxide and N-tallow alkyl N, N-dihydroxyethyl amine oxide. These are preferably used in particular in laundry detergents because they have a particularly high cleaning performance of special stains, such as engine oil.

Der Gehalt an nichtionischen Tensiden beträgt in dem Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel bevorzugt 2 bis 40 Gew.-%, vorzugsweise 4 bis 30 Gew.-% und insbesondere 5 bis 15 Gew.-%, jeweils bezogen auf das gesamte Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel.The content of nonionic surfactants in the washing, cleaning, after treatment or auxiliary washing agent is preferably from 2 to 40% by weight, preferably from 4 to 30% by weight and in particular from 5 to 15% by weight, in each case based on the total Washing, cleaning, aftertreatment or washing aids.

Neben dem/den nichtionischen Tensid(en) kann die Tensidmischung des Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittels auch ein anionisches Tensid. Als anionisches Tensid werden vorzugsweise Sulfonate, Sulfate, Seifen und Mischungen daraus eingesetzt.In addition to the nonionic surfactant (s), the surfactant mixture of the washing, cleaning, aftertreatment or auxiliary washing agent may also be an anionic surfactant. The anionic surfactant used is preferably sulfonates, sulfates, soaps and mixtures thereof.

Als Tenside vom Sulfonat-Typ kommen dabei vorzugsweise C9-13-Alkylbenzolsulfonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C12-18-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Alkansulfonate, die aus C12-18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden. Ebenso sind auch die Ester von α-Sulfofettsäuren (Estersulfonate), zum Beispiel die α-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren geeignet.The surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettalkohole, beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der C10-C20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlängen bevorzugt. Aus waschtechnischem Interesse sind die C12-C16-Alkylsulfate und C12-C15-Alkylsulfate sowie C14-C15-Alkylsulfate bevorzugt. Auch 2,3-Alkylsulfate sind geeignete Aniontenside.Alk (en) yl sulfates are the alkali and especially the sodium salts of Schwefelsäurehalbester the C 12- C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C 10- C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. From washing technical Of interest are the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates preferred. 2,3-alkyl sulfates are also suitable anionic surfactants.

Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-21-Alkohole, wie 2-Methyl-verzweigte C9-11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12-18-Fettalkohole mit 1 bis 4 EO, sind geeignet.The sulfuric acid monoesters of straight-chain or branched C 7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12-18 . Fatty alcohols with 1 to 4 EO are suitable.

Auch bevorzugte anionische Tenside sind Seifen. Geeignet sind gesättigte und ungesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, (hydrierten) Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, zum Beispiel Kokos-, Palmkern-, Olivenöl- oder Talgfettsäuren, abgeleitete Seifengemische.Also 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.

Die anionischen Tenside einschließlich der Seifen können in Form ihrer Natrium-, Kalium- oder Magnesiumsalze vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natriumsalze vor. Weitere bevorzugte Gegenionen für die anionischen Tenside sind auch die protonierten Formen von Cholin, Triethylamin oder Methylethylamin.The anionic surfactants including the soaps may be in the form of their sodium, potassium or magnesium salts. Preferably, the anionic surfactants are in the form of their sodium salts. Further preferred counterions for the anionic surfactants are also the protonated forms of choline, triethylamine or methylethylamine.

Es kann bevorzugt sein, dass das Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel die neutralisierte und die nicht-neutralisierte Form einer Fettsäure enthält. Dies ist insbesondere bei Fettsäureseifen-haltigen flüssigen Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel vorteilhaft, da dort ganz einfach über den pH-Wert, beispielsweise mittels Zugabe von pH-Stellmitteln, die für eine Stabilisierung des Silbers bzw. des Silberkations notwendige Menge an nicht-neutralisierter Fettsäure eingestellt werden kann.It may be preferred that the washing, cleaning, after-treatment or washing aid contains the neutralized and unneutralized form of a fatty acid. This is particularly advantageous in fatty acid soap-containing liquid washing, cleaning, aftertreatment or washing aids, since there simply by the pH, for example by adding pH adjusting agents, the necessary for a stabilization of the silver or the silver cation amount can be adjusted to non-neutralized fatty acid.

Alternativ kann sich die Fettsäureseife von einer anderen Fettsäure ableiten als die Fettsäure, die zur Stabilisierung des elementaren Silbers und/oder dem Silberkation eingesetzt wird.Alternatively, the fatty acid soap may be derived from a different fatty acid than the fatty acid used to stabilize the elemental silver and / or the silver cation.

Es hat sich gezeigt, dass besonders stabile und ästhetisch ansprechende Wasch- oder reinigungsmittel, die Silber und/oder eine Silberverbindung sowie Fettsäureseife enthalten, erhalten werden, wenn das Verhältnis nicht-neutralisierte Fettsäure zu Fettsäureseife zwischen 5 : 95 und 60 : 40, mehr bevorzugt zwischen 10 : 90 und 40 : 60, beträgt.It has been found that particularly stable and aesthetically pleasing detergents or cleaners containing silver and / or a silver compound and fatty acid soap are obtained when the ratio of unneutralized fatty acid to fatty acid soap is between 5:95 and 60:40, more preferably between 10: 90 and 40: 60.

Nachbehandlungsmittel in Form von Weichspülern enthalten kationische Tenside, die einen weichmachenden Effekt besitzen.Conditioners in the form of fabric softeners contain cationic surfactants which have a softening effect.

Die kationischen Tenside umfassen beispielsweise quaternäre Ammoniumverbindungen wie Monoalk(en)yltrimethylammonium-Verbindungen, Dialk(en)yldimethylammonium-Verbindungen, Mono-, Di- oder Triester von Fettsäuren mit Alkanolaminen.The cationic surfactants include, for example, quaternary ammonium compounds such as monoalk (en) yltrimethylammonium compounds, dialk (en) yldimethylammonium compounds, mono-, di- or triesters of fatty acids with alkanolamines.

Geeignete Beispiele für quaternäre Ammoniumverbindungen sind beispielsweise in den Formeln (I) bis (III) gezeigt:

Figure imgb0001
Figure imgb0002
 wobei in (I) R für einen acyclischen Alkylrest mit 12 bis 24 Kohlenstoffatomen, R1 für einen gesättigten C1-C4 Alkyl- oder Hydroxyalkylrest steht, R2 und R3 entweder gleich R oder R1 sind oder für einen aromatischen Rest stehen. X- steht entweder für ein Halogenid-, Methosulfat-, Methophosphat- oder Phosphation sowie Mischungen aus diesen. Beispiele für kationische Verbindungen der Formel (I) sind Monotalgtrimethylammoniumchlorid, Monostearyltrimethylammoniumchlorid, Didecyldimethylammoniumchlorid, Ditalgdimethylammoniumchlorid oder Dihexadecylammoniumchlorid.Suitable examples of quaternary ammonium compounds are shown, for example, in the formulas (I) to (III):
Figure imgb0001
Figure imgb0002
 wherein in (I) R is an acyclic alkyl radical having 12 to 24 carbon atoms, R 1 is a saturated C 1 -C 4 alkyl or hydroxyalkyl radical, R 2 and R 3 are either R or R 1 or are an aromatic radical , X - is either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof. Examples of cationic compounds of the formula (I) are monotaltrimethylammonium chloride, monostearyltrimethylammonium chloride, didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.

Verbindungen der Formel (II) und (III) sind so genannte Esterquats. Esterquats zeichnen sich durch eine hervorragende biologische Abbaubarkeit aus. In Formel (II) steht R4 für einen aliphatischen Alk(en)ylrest mit 12 bis 22 Kohlenstoffatomen mit 0, 1, 2 oder 3 Doppelbindungen und/oder gegebenenfalls mit Substituenten; R5 steht für H, OH oder O(CO)R7, R6 steht unabhängig von R5 für H, OH oder O(CO)R8, wobei R7 und R8 unabhängig voneinander jeweils für einen aliphatischen Alk(en)ylrest mit 12 bis 22 Kohlenstoffatomen mit 0, 1, 2 oder 3 Doppelbindungen steht. m, n und p können jeweils unabhängig voneinander den Wert 1, 2 oder 3 haben. X- kann entweder ein Halogenid-, Methosulfat-, Methophosphat- oder Phosphation sowie Mischungen aus diesen Anionen sein. Bevorzugt sind Verbindungen, bei denen R5 die Gruppe O(CO)R7 darstellt. Besonders bevorzugt sind Verbindungen, bei denen R5 die Gruppe O(CO)R7 darstellt und R4 und R7 Alk(en)ylreste mit 16 bis 18 Kohlenstoffatomen sind. Insbesondere bevorzugt sind Verbindungen, bei denen R6 zudem für OH steht. In Formel (III) steht R12, R13 und R14 unabhängig voneinander für eine C1-4-Alkyl-, Alkenyl- oder Hydroxyalkylgruppe, R15 und R16 jeweils unabhängig ausgewählt eine C8-28-Alkylgruppe, X- ist ein Anion und r ist eine Zahl zwischen 0 und 5 ist. Beispiele umfassen Methyl-N-(2-hydroxyethyl)-N,N-di(talgacyloxyethyl)ammonium-methosulfat, Bis-(palmitoyloxyethyl)-hydroxyethyl-methyl-ammonium-methosulfat, 1,2-Bis-[talgacyloxy]-3-trimethylammoniumpropanchlorid, Methyl-N,N-bis(stearoyloxyethyl)-N-(2-hydroxyethyl)ammoniummethosulfat oder N,N-Dimethyl-N,N-di(talgacyloxyethyl)ammoniummethosulfat.Compounds of formula (II) and (III) are so-called ester quats. Esterquats are characterized by excellent biodegradability. In formula (II) R 4 is an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds and / or optionally with substituents; R 5 is H, OH or O (CO) R 7 , R 6 is, independently of R 5, H, OH or O (CO) R 8 , where R 7 and R 8 are each independently an aliphatic alk (ene) ylrest having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. m, n and p can each independently be 1, 2 or 3. X - may be either a halide, methosulfate, methophosphate or phosphate ion as well as mixtures of these anions. Preference is given to compounds in which R 5 represents the group O (CO) R 7 . Particular preference is given to compounds in which R 5 is the group O (CO) R 7 and R 4 and R 7 are alk (en) yl radicals having 16 to 18 carbon atoms. Particularly preferred are compounds in which R 6 is also OH. In formula (III), R 12 , R 13 and R 14 independently represent a C 1-4 alkyl, alkenyl or hydroxyalkyl group, R 15 and R 16 each independently is a C 8-28 alkyl group, X - An anion and r is a number between 0 and 5. Examples include methyl N- (2-hydroxyethyl) -N, N-di (tallowacyloxyethyl) ammonium methosulfate, bis (palmitoyloxyethyl) hydroxyethyl methyl ammonium methosulfate, 1,2-bis [tallowacyloxy] -3- trimethylammonium, Methyl-N, N-bis (stearoyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate or N, N-dimethyl-N, N-di (tallowacyloxyethyl) ammonium methosulfate.

Anstelle der Estergruppe O(CO)R, wobei R für einen langkettigen Alk(en)ylrest steht, können weichmachende Verbindungen eingesetzt werden, die folgende Gruppen aufweisen: RO(CO), N(CO)R oder RN(CO) weisen, wobei von diesen Gruppen N(CO)R-Gruppen bevorzugt sind.Instead of the ester group O (CO) R, where R is a long-chain alk (en) yl radical, it is possible to use softening compounds which have the following groups: RO (CO), N (CO) R or RN (CO) of these groups, N (CO) R groups are preferred.

Ein weiterer vorteilhafter Inhaltsstoff der Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel kann Ammoniumhydroxid sein. Es hat sich gezeigt, dass bereits geringe Mengen von 0,01 Gew.-% Ammoniumhydroxid, bezogen auf das gesamte Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel, zu sehr klaren und somit ästhetisch sehr ansprechenden Mitteln führen.Another advantageous ingredient of the washing, cleaning, aftertreatment or washing aids may be ammonium hydroxide. It has been shown that even small amounts of 0.01 wt .-% ammonium hydroxide, based on the total washing, cleaning, aftertreatment or washing aid, lead to very clear and thus aesthetically very appealing agents.

Zusätzlich zu den Tensiden, dem Silber bzw. der Silberverbindung und der nicht-neutralisierten Fettsäure kann das Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel weitere Inhaltsstoffe enthalten, die die anwendungstechnischen und/oder ästhetischen Eigenschaften des Wasch-, Reinigungs-, Nacbehandlungs- oder Waschhilfsmittels weiter verbessern. Im Rahmen der vorliegenden Erfindung enthält das Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel vorzugsweise zusätzlich einen oder mehrere Stoffe aus der Gruppe der Gerüststoffe, Bleichmittel, Bleichkatalysatoren, Bleichaktivatoren, Enzyme, Elektrolyte, nichtwässrigen Lösungsmittel, pH-Stellmittel, Parfümöl, Parfümträger, Fluoreszenzmittel, Farbstoffe, Hydrotope, Schauminhibitoren, Silikonöle, Antiredepositionsmittel, Vergrauungsinhibitoren, Einlaufverhinderer, Knitterschutzmittel, Farbübertragungsinhibitoren, antimikrobiellen Wirkstoffe, Germizide, Fungizide, Antioxidantien, Konservierungsmittel, Korrosionsinhibitoren, Antistatika, Bittermittel, Bügelhilfsmittel, Phobier- und Imprägniermittel, Quell- und Schiebefestmittel, weichmachenden Komponenten sowie UV-Absorber.In addition to the surfactants, the silver or the silver compound and the non-neutralized fatty acid, the washing, cleaning, aftertreatment or washing aid may contain other ingredients that the performance and / or aesthetic properties of the washing, cleaning, Nacbehandlungs- or detergency further improve. In the context of the present invention, the washing, cleaning, after-treatment or washing assistant preferably additionally contains one or more substances from the group of builders, bleaching agents, bleach catalysts, bleach activators, enzymes, electrolytes, nonaqueous solvents, pH adjusters, perfume oil, perfume carriers, Fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, anti redeposition agents, grayness inhibitors, anti-shrinkage agents, crease inhibitors, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatics, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, emollients Components as well as UV absorbers.

Als Gerüststoffe, die in dem Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel enthalten sein können, sind aus Gründen der Ästhetik lösliche, organische Gerüststoffe bevorzugt.As builders which may be included in the washing, cleaning, after-treatment or washing aid, for reasons of aesthetics, soluble organic builders are preferred.

Organische Gerüststoffe sind beispielsweise die in Form ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wobei unter Polycarbonsäuren solche Carbonsäuren verstanden werden, die mehr als eine Säurefunktion tragen. Beispielsweise sind dies Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), Methylglycindiessigsäure (MGDA) und deren Abkömmlinge sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren und Mischungen aus diesen. Auch die Säuren an sich können eingesetzt werden. Die Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente. Als Gerüststoffe sind weiter polymere Polycarboxylate geeignet.Organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) and derivatives thereof and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of an acidifying component. As builders further polymeric polycarboxylates are suitable.

Citronensäure, beziehungsweise deren Salze, werden bevorzugt als lösliche, organische Gerüststoffe in den flüssigen Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmitteln eingesetzt.Citric acid, or its salts, are preferably used as soluble, organic builders in liquid washing, cleaning, aftertreatment or washing aids.

Das flüssige Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel kann auch ein Enzym oder eine Mischung aus Enzymen enthalten. Geeignet sind insbesondere solche aus der Klassen der Hydrolasen wie der Proteasen, (Poly)Esterasen, Lipasen bzw. lipolytisch wirkende Enzyme, Amylasen, Cellulasen bzw. andere Glykosylhydrolasen, Hemicellulase, Cutinasen, β-Glucanasen, Oxidasen, Peroxidasen, Mannanasen, Tannanasen, Esterasen/Polyesterasen, Perhydrolasen, Oxireduktasen und/oder Laccasen.The liquid washing, cleaning, aftertreatment or washing aid may also contain an enzyme or a mixture of enzymes. Particularly suitable are those from the classes of hydrolases such as proteases, (poly) esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases, hemicellulases, cutinases, β-glucanases, oxidases, peroxidases, mannanases, tannanases, esterases / Polyesterases, perhydrolases, oxireductases and / or laccases.

Zur Stabilisierung der Enzyme können die erfindungsgemäßen Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel Stabilisierungsmittel wie Borsäure bzw. Borate, Borsäure-Derivate oder Aminoalkohole enthalten.To stabilize the enzymes, the washing, cleaning, after-treatment or washing aids according to the invention may contain stabilizing agents, such as boric acid or borates, boric acid derivatives or amino alcohols.

Um den pH-Wert des Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittels in den gewünschten Bereich zu bringen, kann der Einsatz von pH-Stellmitteln angezeigt sein. Einsetzbar sind hier sämtliche bekannten Säuren bzw. Laugen. Bevorzugte pH-Stellmittel sind NaOH oder Citronensäure.In order to bring the pH of the washing, cleaning, aftertreatment or washing aid in the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis. Preferred pH adjusters are NaOH or citric acid.

Der pH-Wert des Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittels liegt bevorzugt zwischen 5 und 8,5 und mehr bevorzugt zwischen 7,5 und 8,5.The pH of the washing, cleaning, after-treatment or auxiliary washing agent is preferably between 5 and 8.5 and more preferably between 7.5 and 8.5.

Das Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel enthält vorzugsweise ein Parfüm. Als Parfümöle können einzelne Riechstoffverbindungen, zum Beispiel die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Solche Parfümöle können auch natürliche Riechstoffgemische enthalten, wie sie aus pflanzlichen Quellen zugänglich sind.The washing, cleaning, aftertreatment or washing aid preferably contains a perfume. As perfume oils, individual fragrance compounds, for example, the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures as are available from plant sources.

Die erfindungsgemäßen Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel können zum Waschen und/oder Reinigen und/oder Konditionieren von textilen Flächengebilden verwendet werden.The washing, cleaning, after-treatment or washing aids according to the invention can be used for washing and / or cleaning and / or conditioning textile fabrics.

Ein Weg zur Herstellung der erfindungsgemäßen Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel besteht darin, dem fertigen, flüssigen Mittel Silber zuzugeben, wobei es sowohl in fester, vorzugsweise feinverteilter Form zum Einsatz kommt, als auch als Lösung, Suspension oder Dispersion von Silber in geeigneten Lösungsmitteln. Auch Silberverbindungen sowie Lösungen, Suspensionen oder Dispersionen von Silberverbindungen sind erfindungsgemäß einsetzbar.One way of preparing the washing, cleaning, aftertreatment or washing aids according to the invention is to add silver to the finished liquid agent, using it both in solid, preferably finely divided form, and as a solution, suspension or dispersion of silver in suitable solvents. Also silver compounds and solutions, suspensions or dispersions of silver compounds can be used according to the invention.

Die Herstellung eines flüssigen Wasch- oder Reinigungsmittels erfolgt mittels üblicher und bekannter Methoden und Verfahren. So können beispielsweise die Bestandteile der Wasch-, Reinigungsmittel einfach in Rührkesseln vermischt werden, wobei Wasser, die sauren Komponenten, falls jeweils vorhanden, wie beispielsweise die Alkylarylsulfonate, Citronensäure, Borsäure, Phosphonsäure, die Fettalkoholethersulfate, usw., und die nichtionischen Tenside zweckmäßigerweise vorgelegt werden. Die nicht-wässrigen Lösungsmittel, falls vorhanden, werden vorzugsweise auch zu diesem Zeitpunkt zugegeben, die Zugabe kann aber auch zu einem späteren Zeitpunkt erfolgen. Anschließend wird die nicht-neutralisierte Fettsäure zugegeben und danach werden die weiteren Bestandteile, vorzugsweise portionsweise, hinzugefügt.The preparation of a liquid detergent or cleaning agent by means of conventional and known methods and methods. Thus, for example, the ingredients of detergents, cleaners can be simply mixed in stirred tanks, water, the acidic components, if present, such as the alkylarylsulfonates, citric acid, boric acid, phosphonic acid, the fatty alcohol ether sulfates, etc., and the nonionic surfactants suitably presented become. The nonaqueous solvents, if present, are preferably also added at this time, but the addition may be made at a later time. Subsequently, the non-neutralized fatty acid is added and then the other ingredients, preferably in portions, are added.

Enthält das flüssige Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittels auch neutralisierte Fettsäure ist es zweckmäßig nach Zugabe der Tenside und der nicht-wässrigen Lösungsmittel, falls vorhanden, eine Base (einschließlich Ammoniumhydroxid, falls vorhanden) vorzulegen, dann die nicht-neutralisierte Fettsäure zugegeben und anschließend einen Teil der nicht-neutralisierten Fettsäure bei 50 bis 60 °C zu verseifen. Dann werden die weiteren Bestandteile, vorzugsweise portionsweise, hinzugefügt.If the liquid washing, cleaning, after-treatment or washing aid also contains neutralized fatty acid, it is convenient, after addition of the surfactants and non-aqueous solvents, if present, to provide a base (including ammonium hydroxide, if present), then the unneutralized fatty acid and then saponify a portion of the non-neutralized fatty acid at 50 to 60 ° C. Then the other ingredients, preferably in portions, are added.

Die Herstellung eines Nachbehandlungsmittels in Form eines Weichspülers kann nach dem Fachmann geläufigen Techniken zur Herstellung von Weichspülern erhalten werden. Dies kann beispielsweise durch Aufmischen der Rohstoffe, gegebenenfalls unter Einsatz von hochscherenden Mischapparaturen, geschehen. Es empfiehlt sich ein Aufschmelzen des kationischen Tensids und ein nachfolgendes Dispergieren der Schmelze in einem Lösungsmittel, vorzugsweise Wasser. Die weiteren Inhaltsstoffe, einschließlich der nicht-neutralisierten Fettsäure, können durch einfaches Zumischen in die Weichspüler integriert werden.The preparation of a conditioning agent in the form of a fabric conditioner can be obtained by techniques familiar to the person skilled in the art for the preparation of fabric conditioners. This can be done for example by mixing the raw materials, optionally using high-shear mixing equipment. It is recommended to melt the cationic surfactant and then to disperse the melt in a solvent, preferably water. The other ingredients, including the non-neutralized fatty acid, can be incorporated into the fabric softener by simple admixing.

In allen Fällen wird als letzter Schritt das Silber bzw. die Silberverbindung zugesetzt.In all cases, the silver or silver compound is added as the last step.

Es kann sich auch anbieten, das Silber kollidal im Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel durch Homogenisation in einer Kolloidmühle oder durch Lichtbogenzerstäubung eines Silberdrahtes zu erzeugen.It may also be advisable to produce the colloidal silver in the washing, cleaning, aftertreatment or washing aid by homogenization in a colloid mill or by arc sputtering of a silver wire.

In Tabelle 1 sind die Zusammensetzungen von einer Vergleichsrezepturen V1 sowie die Zusammensetzungen von fünf erfindungsgemäßen Wasch- oder Reinigungsmitteln E1 bis E5 gezeigt (alle Mengen sind in Gew.-% Aktivstoff, bezogen auf das Mittel, angegeben): Tabelle 1 V1 E1 E2 E3 E4 E5 C12-18-Fettalkohol mit 7 EO 12 12 12 12 12 12 N-Kokosalkyl-N,N-dimethylaminoxid 2 2 2 2 2 2 AgNO3 0,017 0,017 0,017 0,017 0,017 0,017 Farnesol 0,02 0,02 0,02 0,02 0,02 0,02 C14-Fettsäure 1,61 1,61 1,61 1,61 1,61 1,61 Citronensäure 0,1 0,1 0,1 0,1 0,1 0,22 NaOH 0,38 0,32 0,23 0,18 0,13 0,13 NH4OH 0,06 0,06 0,06 0,06 0,06 0,06 Wasser Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 pH-Wert 11,5 10,04 8,99 8,5 8,03 7,5 Nicht-neutralisierte Fettsäure [Gew.-% im Mittel] 0,0007 0,0206 0,2033 0,4970 0,9150 1,316 Fettsäureseife [Gew.-% im Mittel] 1,6093 1,5894 1,4067 1,1130 0,6950 0,2940 % nicht-neutralisierte Fettsäure 0 1,3 12,6 30,9 56,8 81,7 % Fettsäureseife 100 98,7 87,4 69,1 43,2 18,3 Nicht-neutralisierte Fettsäure / Silberkation -- 2:1 20:1 50:1 92:1 132:1 Die Bestimmung des Gehaltes an nicht-neutralisierter Fettsäure und an Fettsäureseife erfolgte unter Anwendung der Henderson-Hasselbalch-Gleichung unter Verwendung eines pKa-Wertes von 8,15 für Myristinsäure ( J. R. Kanicky, A. F. Poniatowski, N. R. Mehta, und D. Shah, Langmuir, Band 16, S. 172 -177, 2000 ).Table 1 shows the compositions of a comparative formulation V1 and the compositions of five detergents or cleaners E1 to E5 according to the invention (all amounts are given in% by weight of active compound, based on the composition): Table 1 V1 E1 E2 E3 E4 E5 C 12-18 fatty alcohol with 7 EO 12 12 12 12 12 12 N-coco-N, N-dimethylamine 2 2 2 2 2 2 AgNO 3 0,017 0,017 0,017 0,017 0,017 0,017 farnesol 0.02 0.02 0.02 0.02 0.02 0.02 C 14 fatty acid 1.61 1.61 1.61 1.61 1.61 1.61 citric acid 0.1 0.1 0.1 0.1 0.1 0.22 NaOH 0.38 0.32 0.23 0.18 0.13 0.13 NH 4 OH 0.06 0.06 0.06 0.06 0.06 0.06 water Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 PH value 11.5 10.04 8.99 8.5 8.03 7.5 Non-neutralized fatty acid [weight% on average] 0.0007 0.0206 .2033 0.4970 0.9150 1.316 Fatty acid soap [weight% on average] 1.6093 1.5894 1.4067 1.1130 .6950 .2940 % non-neutralized fatty acid 0 1.3 12.6 30.9 56.8 81.7 % Fatty acid soap 100 98.7 87.4 69.1 43.2 18.3 Non-neutralized fatty acid / silver cation - 2: 1 20: 1 50: 1 92: 1 132: 1 The non-neutralized fatty acid and fatty acid soap content was determined using the Henderson-Hasselbalch equation using a pKa of 8.15 for myristic acid ( JR Kanicky, AF Poniatowski, NR Mehta, and D. Shah, Langmuir, Volume 16, pp. 172-177, 2000 ).

Das Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel V1 zeigte bereits mehrere Stunden nach der Herstellung eine merkliche Farbveränderung. Dagegen waren die Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel E2 bis E4 auch nach 4 Wochen noch klare Formulierungen, die keinerlei Farbveränderung zeigten. Das Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel E6 zeigte zwar nach 4 Wochen auch noch keine Farbveränderung, war aber von Anfang an leicht trüb. Das Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel E1 zeigte zwar auch eine Farbveränderung, diese trat aber deutlich später und schwächer auf, als bei dem Wasch- oder Reinigungsmittel V1.The washing, cleaning, aftertreatment or washing aid V1 showed a noticeable change in color already several hours after the preparation. By contrast, the washing, cleaning, after-treatment or washing aids E2 to E4 were still clear formulations after 4 weeks, which showed no color change. The washing, cleaning, aftertreatment or washing aid E6, although after 4 weeks and no color change, but was slightly cloudy from the beginning. Although the washing, cleaning, aftertreatment or washing aid E1 also showed a change in color, but this occurred much later and weaker than the washing or cleaning agent V1.

In Tabelle 2 sind die Zusammensetzungen weiterer drei erfindungsgemäßer Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel E6 bis E8 gezeigt (alle Mengen sind in Gew.-% Aktivstoff, bezogen auf das Mittel, angegeben): Tabelle 2 E6 E7 E8 C13-15-Oxoalkohol mit 7 EO 12 12 5 Lineare C11-13-Alkylbenzolsäure -- -- 12 AgNO3 0,017 0,017 0,017 Farnesol 0,05 0,05 0,05 Kokosfettsäure 5,13 5 2,0 Citronensäure 1 0,15 1 NaOH -- 1,99 0,48 NH4OH 3,05 0,01 0,4 Wasser Ad 100 Ad 100 Ad 100 pH-Wert 8,6 11,4 8,7 Table 2 shows the compositions of another three washing, cleaning, after-treatment or washing aids E6 to E8 according to the invention (all amounts are given in% by weight of active compound, based on the composition): Table 2 E6 E7 E8 C 13-15 oxo alcohol with 7 EO 12 12 5 Linear C 11-13 alkyl benzoic acid - - 12 AgNO 3 0,017 0,017 0,017 farnesol 0.05 0.05 0.05 coconut fatty acid 5.13 5 2.0 citric acid 1 0.15 1 NaOH - 1.99 0.48 NH 4 OH 3.05 0.01 0.4 water Ad 100 Ad 100 Ad 100 PH value 8.6 11.4 8.7

Die Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel E6 bis E8 waren auch nach 4 Wochen noch klare Formulierungen, die keinerlei oder lediglich ganz geringe Farbveränderungen zeigten.The washing, cleaning, aftertreatment or washing aids E6 to E8 were still clear formulations after 4 weeks, which showed no or only very slight color changes.

Die Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel E1 bis E8 zeigten sowohl gegen gram-positive Testkeime (Staphylococcus aureus, Staphylococcus epidermidis) als auch gegen Hefe (Candida albicans) eine gute Wirksamkeit.The washing, cleaning, aftertreatment or washing aids E1 to E 8 showed good activity against Gram-positive test bacteria ( Staphylococcus aureus, Staphylococcus epidermidis ) as well as against yeast ( Candida albicans ).

Claims (8)

  1. A liquid washing, cleaning, post-treatment or auxiliary washing agent containing
    (a) from 2 to 60 wt.% of a surfactant selected from the group consisting of anionic, nonionic, cationic and zwitterionic surface-active agents, and mixtures thereof,
    (b) silver and/or a silver compound,
    (c) unneutralized fatty acid,
    (d) ammonium hydroxide,
    (e) and additional conventional ingredients of washing, cleaning, post-treatment or auxiliary washing agents.
  2. The washing, cleaning, post-treatment or auxiliary washing agent according to claim 1, characterized in that it contains a silver compound selected from the group consisting of silver acetate, silver citrate, silver diamine chloride complex, silver cyclodextrin complex, silver dicyanopotassium complex, silver phthalimide, silver phenylcyanamide, silver(ethylene thiourea) complex, silver imidazolate, transition metal NHC calix[4]arene complexes, silver crown ether, silver nitrate, and mixtures thereof.
  3. The washing, cleaning, post-treatment or auxiliary washing agent according to claim 1 or claim 2, characterized in that the amount of silver and/or silver compound is from 0.0001 to 1 wt.%, based on the total washing, cleaning, post-treatment or auxiliary washing agent.
  4. The washing, cleaning, post-treatment or auxiliary washing agent according to one of claims 1 to 3, characterized in that the ratio of unneutralized fatty acid to elementary silver and/or the amount of silver cation is greater than or equal to 8 to 1.
  5. The washing, cleaning, post-treatment or auxiliary washing agent according to one of claims 1 to 4, characterized in that the amount of unneutralized fatty acid is between 0.01 and 10 wt.%, based on the total washing, cleaning, post-treatment or auxiliary washing agent.
  6. The washing, cleaning, post-treatment or auxiliary washing agent according to one of claims 1 to 5, characterized in that it contains from 0.01 to 3 wt.% of ammonium hydroxide, based on the total washing, cleaning, post-treatment or auxiliary washing agent.
  7. The washing, cleaning, post-treatment or auxiliary washing agent according to one of claims 1 to 6, characterized in that it contains the neutralized and unneutralized form of a fatty acid.
  8. The washing, cleaning, post-treatment or auxiliary washing agent according to one of claims 1 to 6, characterized in that it is formulated as a softener which contains from 0.5 to 50 wt.% of a cationic surfactant.
EP09740095.6A 2008-11-21 2009-10-15 Washing, cleaning, post-treating or auxiliary washing agent containing silver Not-in-force EP2346973B1 (en)

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DE102008058544A DE102008058544A1 (en) 2008-11-21 2008-11-21 Silver-containing washing, cleaning, aftertreatment or washing aid
PCT/EP2009/063490 WO2010057723A1 (en) 2008-11-21 2009-10-15 Washing, cleaning, post-treating or auxiliary washing agent containing silver

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JP (1) JP2012509372A (en)
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JP6577937B2 (en) * 2013-04-16 2019-09-18 ユニリーバー・ナームローゼ・ベンノートシヤープ Bar soap with improved antibacterial activity
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EP3099773B2 (en) * 2014-01-29 2020-07-22 Unilever NV Cleansing composition containing oligodynamic metal and efficacy enhancing agent
US10093885B2 (en) * 2014-01-29 2018-10-09 Conopco, Inc. Aqueous composition containing oligodynamic metal
CA2935912C (en) * 2014-01-29 2022-05-03 Unilever Plc Cleansing compositions containing stable silver
EP3201306B1 (en) 2014-09-29 2019-11-06 Unilever NV Antimicrobial cleansing composition
US20170050870A1 (en) 2015-08-21 2017-02-23 Applied Silver, Inc. Systems And Processes For Treating Textiles With An Antimicrobial Agent
US20180303086A1 (en) * 2015-10-21 2018-10-25 Conopco, Inc., D/B/A Unilever An Antimicrobial Composition
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WO2018160708A1 (en) 2017-03-01 2018-09-07 Applied Silver, Inc. Systems and processes for treating textiles with an antimicrobial agent
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JP2012509372A (en) 2012-04-19
EP2346973A1 (en) 2011-07-27
WO2010057723A1 (en) 2010-05-27
US20110224120A1 (en) 2011-09-15
ES2657415T3 (en) 2018-03-05
DE102008058544A1 (en) 2010-05-27

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