WO2021083642A1

WO2021083642A1 - Use of surfactants from renewable raw materials

Info

Publication number: WO2021083642A1
Application number: PCT/EP2020/078546
Authority: WO
Inventors: Christian Kropf; Nadine BLUHM; Daniela HERBST; Ketan Patil; Mareile Job; Marianne Schmeling; Frank Janssen; Annika Gueldner; Marc-Steffen Schiedel; Anna KLEMMER
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2019-10-29
Filing date: 2020-10-12
Publication date: 2021-05-06
Also published as: DE102019216681A1

Abstract

Surfactants according to the general formula (I) can be used in detergents and cleaning products with an especially advantageous result if these detergents and cleaning products contain certain other ingredients in specific amounts.

Description

Use of surfactants from renewable raw materials

From the patent application DE 102016 009 798 A1 are surfactants of the general formula (I),

in which n and m, independently of one another, stand for numbers from 0 to 17, preferably n for a number from 0 to 3 and m for a number from 5 to 14, and 2 <n + m <20, preferably 6 <n + m < 16, and X ^{+ stands} for a charge-balancing cation, is known. X ⁺ is preferably selected from the group comprising the proton, alkali metal cations and the grouping N ⁺ R ¹ R ² R ³ R ⁴ , in which R ¹ , R ^2, R ³ and R ⁴ independently represent hydrogen, an alkyl group with 1 to 6 C atoms or a hydroxyalkyl group with 2 to 6 C atoms. Detergents and cleaning agents which contain surfactants of the general formula (I) are also known from this document.

Surfactants of the general formula (I) can be obtained by sulfating a compound of the general formula (II),

in which n and m have the meanings given above, with a sulphating agent, for example chlorosulphonic acid or sulfur trioxide pyridine, and optionally neutralization by subsequent reaction with X ⁺ OH ^· , where X ^{+ has} the meaning indicated above. Compounds of the general formula (II) can be obtained by monoalkylating 2,5-bis (hydroxymethyl) tetrahydrofuran, in particular by reacting it with alkenes. 2,5-bis (hydroxymethyl) tetrahydrofuran can be obtained by hydrogenation of hydroxymethylfurfural, an intermediate from the conversion of cellulose, n and m cannot be analytically determined parameters, especially when alkene mixtures are used in the production of the surfactants according to the invention -Assume whole numbers.

It has now been found that such surfactants can be used with particularly advantageous results in detergents and cleaning agents specified below if they are agreed to contain other ingredients in certain quantities. In addition, the surfactants of the general formula (I) have particularly good washing and cleaning results against soiling that is conventionally removed using enzymes (so-called “enzymatic soiling”), such as blood, egg or chocolate. The present invention therefore relates to the use of anionic surfactant of the general formula (I) to increase the performance of detergents or cleaning agents when washing laundry or cleaning hard surfaces with respect to enzymatic soiling.

Further objects of the invention are particularly composite detergents and cleaning agents. In Tables 1 to 6 below, compositions of agents according to the invention are given; There and in the following, the quantitative data for “anionic surfactant” relate to those anionic surfactants which do not correspond to those of the formula (I) given. The quantities given relate to the entire agent.

Table 1: Composition of special detergents (data in% by weight)

Table 2: Composition of solid particulate detergents (data in% by weight); P1 and P2 are powder, C1 and C1 are compacts

Table 3: Composition of hand dishwashing detergents (data in% by weight)

* to adjust the viscosity to values in the range from 1000 mPa.s to 7000 mPa.s ** to adjust the pH value to values in the range from pH 4 to pH 9

Table 3 (continued)

Table 4: Composition of liquid detergents (data in% by weight)

Table 5: Composition of liquid detergent concentrates (data in% by weight)

Table 6: Compositions of single-portion detergents

The following applies to the specified ingredients:

An agent according to the invention can contain nonionic surfactants. Suitable nonionic surfactants include alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof.

The alkoxylated fatty alcohols used are preferably ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear. In particular, fatty alkyl ethoxylates with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, Ci ₂ -i ₄ alcohols with 4 EO or 7 EO, Cg-n alcohol with 7 EO, Ci2-is alcohols with 5 EO or 7 EO and mixtures of these. The stated degrees of ethoxylation represent statistical mean values which, for a specific product, can be an integer or a fraction. 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 are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Also suitable are a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as, for example, a mixture of a C 6-18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO. Any anionic surfactants present additionally or instead of them include alkylbenzenesulfonic _{acid salts, olefin sulfonic acid salts, C 2} -C 8 alkanesulfonic acid salts, salts of sulfuric acid monoesters with a fatty alcohol, a fatty acid soap, salts of sulfuric acid monoesters with an ethoxylated fatty alcohol or a mixture of two or more of these anionic surfactants.

Suitable surfactants of the sulfonate type are, for example, come C9-i3 alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example ₂ -i8 monoolefins making phone from C terminal or internal double bond by sulfonic with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. Also suitable are Ci ₂ -18 alkanesulfonates and 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.

The alk (en) yl sulfates are the salts of the sulfuric acid _{half esters of the Ci 2} -Cis fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Cio-C ₂ o-oxo alcohols and those half esters of secondary use Alcohols of these chain lengths are preferred. From the point of view of washing technology, the _{C 2} -C 6 -alkyl sulfates and C ₁₂ _{-C 15} -alkyl sulfates and Cn-Cis-alkyl sulfates are preferred.

Also fatty alcohol ether sulfates, such as the Schwefelsäuremonoester containing on average 3.5 moles of ethylene oxide (EO) or C 1 to 6 moles of ethylene oxide ethoxylated linear or branched C7 _2i alcohols such as 2-methyl-branched Cg-n-alcohols hole ₂ -i8 fatty alcohols with 1 to 4 EO are suitable.

Other suitable anionic surfactants are fatty acid soaps. 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, are suitable.

The additional anionic surfactants, including the fatty acid soaps, can be in the form of their sodium, potassium or magnesium or ammonium salts. The anionic surfactants are preferably in the form of their sodium salts or ammonium salts. Amines which can be used for neutralization are preferably choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine or a mixture thereof, monoethanolamine being preferred. In a particularly preferred embodiment, the agent, especially when it is in liquid form, contains monoethanolamine-neutralized alkylbenzenesulfonic acid, in particular C9-13-alkylbenzenesulfonic acid, and / or fatty acid neutralized with monoethanolamine. An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular glycine diacetic acid, methyl glycine diacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-dibuccinic acid, as well as ethylenediamine-N, N'-dibuccinic acid, and hydroxy-dibuccinic acid, poly-dibuccinic acid and hydroxy-dibuccinic acid, hydroxy-dibuccinic acid, and hydroxy-dibuccinic acid, hydroxy-dibuccinic acid, hydroxy-dibuccinic acid, and hydroxy-dibuccinic acid and polymeric (poly) carboxylic acids, in particular polycarboxylates accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which can also contain small amounts of polymerizable substances without carboxylic acid functionality in polymerized form. The relative average molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, each based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid makes up at least 50% by weight. Terpolymers which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as a third monomer can also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C3-C8-carboxylic acid and preferably from a C3-C4-M0- nocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C 8 dicarboxylic acid, maleic acid being particularly preferred. In this case, the third monomeric unit is formed by vinyl alcohol and / or, preferably, an esterified vinyl alcohol. In particular, vinyl alcohol derivatives are preferred which represent an ester of short-chain carboxylic acids, for example of Ci-C ₄ carboxylic acids, with vinyl alcohol. Preferred polymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleate and 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, vinyl alcohol and / or vinyl acetate. Polymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1, are very particularly preferred and 2.5: 1. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is substituted in the 2-position with an alkyl radical, preferably with a Ci-C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives is. Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or wise acrylate, 10 wt .-% to 30 wt .-%, preferably 15 wt .-% to 25 wt .-% methallylsulphonic acid or methallylsulphonate and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 % To 40% by weight of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Sucrose is particularly preferred. The use of the third monomer presumably builds predetermined breaking points into the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol. Further preferred copolymers are those which have acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. The organic builder substances can, in particular for the production of liquid agents, be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali salts.

Particularly suitable water-soluble inorganic builder materials are polyphosphates, preferably sodium triphosphate. In particular, crystalline or amorphous, water-dispersible alkali metal aluminosilicates are used as water-insoluble inorganic builder materials. Among these, the crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, zeolite P and zeolite MAP and optionally zeolite X, are preferred. Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular have no particles with a particle size of more than 30 μm and preferably consist of at least 80% by weight of particles with a size of less than 10 μm. Their calcium binding capacity is usually in the range of 100 to 200 mg CaO per gram.

In addition or as an alternative to the mentioned water-insoluble aluminosilicate and alkali metal carbonate, further water-soluble inorganic builder materials can be contained. In addition to the polyphosphates such as sodium triphosphate, these include, in particular, the water-soluble crystalline and / or amorphous alkali silicate builders. The alkali metal silicates which can be used as builder materials preferably have a molar ratio of alkali metal oxide to S1O2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na ₂ O: Si0 ₂ of 1: 2 to 1: 2.8. The crystalline silicates used alone or in a mixture with amorphous silicates are preferably crystalline sheet silicates of the general formula Na ₂ Si _x 0 _{2x + i} y H2O, in which x, the so-called module, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline sheet silicates are those in which x in the general formula mentioned assumes the values 2 or 3. Both β- and α-sodium disilicates (Na ₂ Si ₂ Os y H2O) are particularly preferred. Also, practically anhydrous crystalline alkali silicates produced from amorphous alkali silicates The above general formula, in which x is a number from 1.9 to 2.1, can be used in the agents. In a further preferred embodiment, a crystalline layered sodium silicate with a module of 2 to 3, as can be produced from sand and soda, is used. Sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further embodiment. In a preferred embodiment of such agents, a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.

Another class of substances with builder properties, which are called chelating agents because of their pronounced heavy metal binding capacity, are the phosphonates. These are the salts of, in particular, hydroxyalkanoic or aminoalkane phosphonic acids. Among the hydroxyalkanephosphonic acids, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) is of particular importance. It is used in particular as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt reacting alkaline. Particularly suitable aminoalkanephosphonic acids are ethylenediamine tetramethylene phosphonic acid (EDTMP), diethylenetriamine penta methylene phosphonic acid (DTPMP) and their higher homologues. They are used in particular in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP. Mixtures of the phosphonates mentioned can also be used.

Suitable peroxidic bleaching agents are, in particular, organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid, monoperoxyphthalic acid, and diperdodecanedioic acid, and salts thereof such as magnesium monoperoxyphthalate, diacyl peroxides, hydrogen peroxide and, under the conditions of use, inorganic salt peroxide, such as hydrogen peroxide releasing alkali peroxide / or alkali persilicate and hydrogen peroxide inclusion compounds, such as H ₂ 0 ₂ -Harnstoffaddukte, and mixtures thereof into consideration. Hydrogen peroxide can also be generated with the help of an enzymatic system, i.e. an oxidase and its substrate. If solid peroxygen compounds are to be used, these can be used in the form of powders or granules, which can also be coated in a manner known in principle. Alkali percarbonate, alkali perborate monohydrate or hydrogen peroxide are particularly preferably used, hydrogen peroxide being the particularly preferred peroxidic bleaching agent in liquid agents and sodium percarbonate in solid agents. Peroxidic bleach particles preferably have a particle size in the range from 10 μm to 5000 μm, in particular from 50 μm to 1000 μm and / or a density from 0.85 g / cm ³ to 4.9 g / cm ³ , in particular from 0, 91 g / cm ³ to 2.7 g / cm ³ .

As bleach-activating compounds which produce peroxocarboxylic acid under perhydrolysis conditions, in particular compounds which contain perbenzoic acid and / or aliphatic peroxocarboxylic acids with 1 to 12 carbon atoms, which may be substituted under perhydrolysis conditions, in particular 2 to 4 carbon atoms, alone or in mixtures, can be used. Suitable bleach activators which carry O- and / or N-acyl groups, in particular the number of carbon atoms mentioned, and / or optionally substituted benzoyl groups. Polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dio-xohexahydro-1,3,5-triazine (DADHT), are preferred, N-acylimides, in particular N-nonanoyl succinimide (NOSI), acylated phenol sulfonates or carboxylates or the sulfonic or carboxylic acids of these, in particular nonanoyl or isononanoyl or lauroyloxybenzenesulfonate (NOBS or iso-NOBS or LOBS) or decanoyloxybenzoate (DOBAbenzoate) formal carbonic acid ester derivatives such as 4- (2-decanoyloxyethoxycarbonyloxy) -benzenesulfonate (DE-COBS), acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-di-acetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol and their mixtures (SORMAN ), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose, acety lated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl caprolactam.

In addition to the compounds which form peroxocarboxylic acids under perhydrolysis conditions, or instead of them, further bleach-activating compounds, such as, for example, nitriles, from which perimidic acids are formed under perhydrolysis conditions, may be present. These include in particular aminoacetonitrile derivatives with a quaternized nitrogen atom according to the formula

in which R ^{1 stands} for -H, -Chh, a C _2-24 -alkyl or -alkenyl radical, a substituted Ci-24-alkyl or C _2-24 -alkenyl radical with at least one substituent from the group -CI, -Br , -OH, -NH2, -CN and -N ⁽⁺⁾ -CH2-CN, an alkyl or alkenylaryl radical with a Ci-24-alkyl group, or for a substituted alkyl or alkenylaryl radical with at least one, preferably two, optionally substituted Ci- ₂₄ -alkyl group (s) and optionally further substituents on the aromatic ring, R ² and R ^{3 are} independently selected from -CH2-CN, -CH3, -CH2-CH ₃ , CH2-CH2-CH3, -CH ( CH ₃ ) -CH3, -CH ₂ -OH, -CH2-CH2-OH, -CH (OH) -CH ₃ , -CH2-CH2-CH2-OH, -CH ₂ -CH (OH) -CH ₃ , - CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -0) nH with n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another one above for R ¹ , R ² or R ³ have the meaning given, where at least 2 of the radicals mentioned, in particular R ² and R ³ , including the nitrogen atom and optionally further he heteroatoms can be linked to one another in a ring-closing manner and then preferably form a morpholino ring, and X is a charge discharge The same anion, preferably selected from benzenesulfonate, toluenesulfonate, cumene sulfonate, the Cg-is-alkylbenzenesulphonates, the Ci-20-alkylsulphates, the C8-22-carboxylic acid methyl ester sulphonates, sulphate, hydrogen sulphate and mixtures thereof can be used. Bleach activator particles preferably have a particle size in the range from 10 gm to 5000 gm, in particular from 50 gm to 1000 gm and / or a density of 0.85 g / cm ³ to 4.9 g / cm ³ , in particular 0.91 g / cm ³ to 2.7 g / cm ³ .

The presence of bleach-catalyzing transition metal complexes, in addition to or instead of the bleach activators mentioned, is possible. These are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes. Both inorganic and organic compounds are suitable as ligands in such transition metal complexes, including, in addition to carboxylates, in particular compounds with primary, secondary and / or tertiary amine and / or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole , triazole, 2,2 ^{'-bispyridylamine,} tris (2-pyridylme- thyl) amine, 1, 4,7-triazacyclononane, 1, 4,7-trimethyl-1, 4,7-triazacyclononane, 1, 5.9 -Trimethyl- 1, 5,9-triazacyclododecane, (bis- ((1-methylimidazol-2-yl) -methyl)) - (2-pyridylmethyl) -amine, N, N ^' - (bis- (1-methylimidazole- 2-yl) methyl) ethylenediamine, N-bis (2-benzimidazolylmethyl) aminoethanol, 2,6-bis (bis (2-benzimidazolylmethyl) aminomethyl) -4-methylphenol, N, N, N ^' , N ^' -Tetrakis- (2-benzimidazolylmethyl) -2-hydroxy-1,3-diaminopropane, 2,6-bis- (bis- (2-pyridylmethyl) aminomethyl) -4-methylphenol, 1,3 Bis- (bis- (2-benzimidazolyl-methyl) aminomethyl) -benzene, sorbitol, mannitol, erythritol, adonitol, inositol, lactose, and given Also include substituted salenes, porphins and porphyrins. The inorganic neutral ligands include in particular ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, the complex contains further, preferably anionic, and among these in particular monodentate or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NC> 2) group, that is to say a nitro ligand or a nitrito ligand. The (N0 ₂ ) group can also be bonded to a transition metal in a chelating manner, or it can bridge two transition metal atoms asymmetrically or pI-O-bridges. In addition to the ligands mentioned, the transition metal complexes can also carry further ligands, generally of a simpler structure, in particular monovalent or polyvalent anion ligands. For example, nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, oxalate, perchlorate and complex anions such as hexafluorophosphate are possible. The anion ligands should ensure the charge balance between the transition metal central atom and the ligand system. The presence of oxo ligands, peroxo ligands and imino ligands is also possible. Such ligands in particular can also have a bridging effect, so that polynuclear complexes are formed. In the case of bridged, binuclear complexes, both metal atoms in the complex do not have to be the same. The use of binuclear complexes in which the two central transition metal atoms have different oxidation numbers is also possible. If anion ligands are absent or the presence of anion ligands does not lead to charge equalization in the complex, the transition metal complex compounds to be used according to the invention gene anionic counterions present, which neutralize the cationic transition metal complex. These anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, oxalate, benzoate or citrate. Examples of transition metal complex compounds that can be used are [N, N'-bis [(2-hydroxy-5-vinylphenyl) methylene] -1, 2-diamino-cyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-nitrophenyl) methylene] -1, 2-diamino-cyclohexane] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) -methylene] -1, 2-phenylenediamine] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1, 2-diaminocyclohexane] manganese (III) chloride , [N, N'-bis [(2-hydroxyphenyl) methylene] -1, 2-diaminoethane] manganese (III) chloride, [N, N'-bis [(2-hydroxy-5- sulfonatophenyl) methylene] -1, 2-diaminoethane] manganese (III) chloride, manganese oxalato complexes, nitropentammine cobalt (III) chloride, nitritopentammine cobalt (III) chloride, hexammine cobalt (III ) chloride, chloropentammine cobalt (III) chloride and the peroxo complex [(NH3) sCo-0-0- CO (NH ₃ ) 5] CI ₄ .

Enzymes that can be used in the agents are those from the class of the proteases, amylases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof. Enzymes obtained from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus are particularly suitable. The enzymes can be adsorbed on carrier substances and / or embedded in coating substances in order to protect them against premature inactivation. If the agent according to the invention contains protease, it preferably has a proteolytic activity in the range from about 100 PU / g to about 10,000 PU / g, in particular 300 PU / g to 8000 PU / g. If several enzymes are to be used in the agent according to the invention, this can be carried out by incorporating the two or more separate or separately packaged enzymes in a known manner or by two or more enzymes packaged together in a granulate.

To set a desired pH value that does not result from the mixture of the other components, the agents according to the invention can contain systemic and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also contain mineral acids, especially sulfuric acid, or bases, especially ammonium or alkali hydroxides.

Dyes contained in solid agents can give the entire agent the same homogeneous color or are preferably used to color only part of the solid ingredients of the agent, so that so-called speckles or "speckles" result. The use of several different colored speckles is also possible. It is also possible to color different layers or parts of agents that are present as molded bodies. The task of graying inhibitors is to keep the dirt detached from the textile fiber suspended in the liquor. Water-soluble colloids of mostly organic nature are suitable for this, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acid sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. It is also possible to use starch derivatives other than those mentioned above, for example aldehyde starches. Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used.

Polymers with the ability to release dirt, which are often referred to as "soil release" polymers or because of their ability to make the treated surface, for example the fiber, dirt-repellent, as "soil repellents", are, for example, nonionic or cationic cellulose derivatives. The especially polyester-active soil-releasing polymers include copolyesters made from dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol. The preferably used dirt-releasing polyesters include those compounds which are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR ¹¹ -) _a OH, which is also known as a polymer Diol H- (0- (CHR ¹¹ -) _a ) bOH may be present. Ph therein denotes an o-, m- or p-phenylene radical, which can carry 1 to 4 substituents selected from alkyl radicals with 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ^{11 is} hydrogen or an alkyl radical 1 to 22 carbon atoms and their mixtures, a a number from 2 to 6 and b a number from 1 to 300. The polyesters obtainable from these preferably contain both monomer diol units -0- (CHR ¹¹ -) _a O- and polymer diol units - (0- (CHR ¹¹ -) _a ) b0- before. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. In the polymer diol units, the degree of polymerization b is preferably in the range from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum molecular weight distribution of preferred soil-releasing polyesters is in the range from 250 to 100,000, in particular from 500 to 50,000 The acid on which the remainder Ph is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as an alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferred. If desired, small proportions, in particular not more than 10 mol% based on the proportion of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be contained in the soil-releasing polyester instead of the HOOC-Ph-COOH monomer. These include, for example, AI Cylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. The preferred diols HO- (CHR ¹¹ -) _a OH include those in which R ^{11 is} hydrogen and a is a number from 2 to 6, and those in which a has the value 2 and R ¹¹ is hydrogen and the alkyl radicals with 1 to 10, in particular 1 to 3 carbon atoms is selected. Among the last-mentioned diols, those of the formula HO-CH2-CHR ¹¹ -OH, in which R ^{11 has} the abovementioned meaning, are particularly preferred. Examples of diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol , 1, 2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol with an average molecular weight in the range from 1000 to 6000. If desired, these polyesters can also be end-capped, with possible end groups being alkyl groups with 1 to 22 carbon atoms and esters of monocarboxylic acids. The end groups bonded via ester bonds can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, lineal acidic acid, elaboric acid, petroselenic acid, linostearic acid, linealic acid, petroselic acid, linostearic acid , Arachidic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which can carry 1 to 5 substituents with a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid. The end groups can also be based on hydroxymonocarboxylic acids with 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids can for their part be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. The number of hydroxymonocarboxylic acid units per end group, that is, their degree of oligomerization, is preferably in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate, in which the polyethylene glycol -Units have molecular weights from 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used alone or in combination with cellulose derivatives.

If desired, the agents can contain a customary color transfer inhibitor which, in a preferred embodiment, is selected from the polymers of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or the copolymers of these. Both polyvinylpyrrolidones with molar weights of 15,000 g / mol to 50,000 g / mol and polyvinylpyrrolidones with higher molar weights of, for example, up to over 1,000,000 g / mol, in particular from 1,500,000 g / mol to 4, can be used 000 000 g / mol, N-vinylimidazole / N-vinylpyrrolidone copolymers, polyvinyl oxazolidones, copolymers based on vinyl monomers and carboxamides, pyrro- polyesters and polyamides containing lidone groups, grafted polyamidoamines and polyethyleneimines, polyamine-N-oxide polymers and polyvinyl alcohols. However, it is also possible to use enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which supplies hydrogen peroxide in water. The addition of a mediator compound for the peroxidase, for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, and the aforementioned polymeric dye transfer inhibitor active ingredients can also be used. Polyvinylpyrrolidone preferably has an average molar mass in the range from 10,000 g / mol to 60,000 g / mol, in particular in the range from 25,000 g / mol to 50,000 g / mol. Among the copolymers, those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 with an average molar mass in the range from 5,000 g / mol to 50,000 g / mol, in particular 10,000 g / mol to 20,000 g / mol, are preferred .

Preservatives can be used to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistats and fungicides and so on. Substances from these groups are, for example, benzalkonium chlorides, alkylarlyl sulfonates, halophenols and phenol mercuriacetate, and these compounds can also be dispensed with entirely.

Detergents can contain, for example, derivatives of diaminostilbene disulphonic acid or their alkali metal salts as optical brighteners, although they are preferably free from optical brighteners for use as color detergents. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly structured compounds which, instead of morpholino -Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type can be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Mixtures of the aforementioned optical brighteners can also be used.

When used in machine processes in particular, it can be advantageous to add customary foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps are natural or synthetic origin which have a high proportion of CI8-C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkylene diamides. Mixtures of various foam inhibitors are also advantageously used, for example those made from silicones, paraffins or waxes. The foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors, are preferably attached to a granular, water-soluble or dispersible carrier substance bound. Mixtures of paraffins and bistearyl ethylene diamide are particularly preferred.

Water-miscible solvents include, for example, monohydric alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert. -Butanol, diols and triols with 2 to 4 carbon atoms, in particular ethylene glycol, propylene glycol and glycerol, and mixtures thereof and the ethers which can be derived from the classes of compounds mentioned.

A perfume or scent is a chemical substance that stimulates the sense of smell. In order to be able to stimulate the sense of smell, the chemical substance should be at least partially dispersible in the air, ie the fragrance should be at least slightly volatile at 25 ° C. If the fragrance is now very volatile, the odor intensity will then quickly subside again. With a lower volatility, however, the odor impression is more lasting, i.e. it does not disappear as quickly. In one embodiment, the fragrance therefore has a melting point which is in the range from -100 ° C to 100 ° C, preferably from -80 ° C to 80 ° C, even more preferably from -20 ° C to 50 ° C, in particular from - 30 ° C to 20 ° C. In a further embodiment, the fragrance has a boiling point in the range from 25 ° C. to 400 ° C., preferably from 50 ° C. to 380 ° C., more preferably from 75 ° C. to 350 ° C., in particular from 100 ° C. to 330 ° C. Overall, a chemical substance should not exceed a certain molecular weight in order to function as a fragrance, since if the molecular weight is too high, the required volatility can no longer be guaranteed. In one embodiment, the fragrance has a molecular weight of 40 to 700 g / mol, more preferably 60 to 400 g / mol. The smell of a fragrance is perceived as pleasant by most people and often corresponds to the smell of, for example, flowers, fruits, spices, bark, resin, leaves, grasses, mosses and roots. For example, fragrances can also be used to mask unpleasant odors or to provide a non-odorous substance with a desired odor. Individual fragrance compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type can be used as fragrances. Fragrance compounds of the aldehyde type are, for example, adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methoxybenzaldehyde), cymal (3- (4-isopropyl-phenyl) -2-methylpropanal), Ethylvanillin, Florhydral (3- (3-isopropylphenyl) butanal), Helional (3- (3,4-Methylenedioxyphenyl) -2-methylpropanal), Heliotropin, Hydroxycitronellal, Lauraldehyde, Lyral (3- and 4- (4-Hydroxy -4-methylpentyl) -3- cyclohexene-1-carboxaldehyde), methylnonylacetaldehyde, Lilial (3- (4- tert-butylphenyl) -2-methylpropanal), phenylacetaldehyde, undecylenealdehyde, vanillin, 2,6,10-trimethyl- 9-undecenal, 3-dodecen-1-al, alpha-n-amylcinnamaldehyde, melonal (2,6-dimethyl-5-heptenal), 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (Triplal ), 4-ethoxybenzaldehyde, benzaldehyde, 3- (4-tert-butylphenyl) propanal, 2-methyl-3- (para-ethoxyphenyl) propanal, 2-methyl-4- (2,6,6-timethyl-2 ( 1) -cyclohexen-1-yl) butanal, 3-phenyl-2-propenal, cis- / trans-3,7-dimethyl-2,6-octadien-1-al, 3,7-dimethyl-6- octen-1-al, [(3,7-dimethyl-6-octenyl) oxy] acetaldehyde, 4-isopropylbenzylaldehyde, 1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde, 2,4-dimethyl-3-cyclo- hexene-1-carboxaldehyde, 2-methyl-3- (isopropylphenyl) propanal, 1-decanal, 2,6-dimethyl-5-heptenal, 4- (tricyclo [5.2.1 0 (2,6)] decylidene -8) -butanal, octahydro-4,7-methane-1 H-indenecarboxaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, para-ethyl-alpha, alpha-dimethylhydrocinnamaldehyde, alpha-methyl-3,4- (methylenedioxy) -hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, alpha-n-hexylcinnamaldehyde, m-cymene-7-carboxaldehyde, alpha-methylphenylacetaldehyde, 7-hydroxy-3,7-dimethyloctanal, undecenal, 2,4,6-trimethyl -3-cyclohexene-1-carboxaldehyde, 4- (3) (4-methyl-3-pentenyl) -3-cyclohexenecarboxaldehyde, 1 -dodecanal, 2,4-dimethylcyclohexene-3-carboxaldehyde, 4- (4-hydroxy-4 -methylpentyl) -3-cyclohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al, 2-methyl-undecanal, 2-methyldecanal, 1-nonanal, 1-octanal, 2,6,10- Trimethyl-5, 9-undecadienal, 2-methyl-3- (4-tert-butyl) propanal, dihydrocinnamaldehyde, 1-methyl-4- (4-methyl-3-pentenyl) -3-cyclohexene-1-carboxaldehyde , 5- or 6-methoxyhexahydro-4,7-methanindan-1-ode r-2-carboxaldehyde, 3,7-dimethyloctan-1-al, 1-undecanal, 10-undecen-1-al, 4-hydroxy-3-methoxybenzaldehyde, 1-methyl-3- (4-methylpentyl ) -3-cyclohexenecarboxaldehyde, 7-hydroxy-3J-dimethyl-octanal, trans-4-decenal, 2,6-nonadienal, para-tolylacetaldehyde, 4-methylphenylacetaldehyde, 2-methyl-4- (2,6,6-trimethyl -1-cyclohexen-1-yl) -2-butenal, ortho-methoxycinnamaldehyde, 3,5,6-trimethyl-3-cyclohexene-carboxaldehyde, 3J-dimethyl-2-methylen-6-octenal, phenoxyacetaldehyde, 5,9- Dimethyl-4,8-decadienal, peony aldehyde (6,10-dimethyl-3-oxa-5,9-undecadien-1-al), hexahydro-4, 7-methanindane-1-carboxaldehyde, 2-methyloctanal, alpha - methyl-4- (1-methylethyl) benzene-acetaldehyde, 6,6-dimethyl-2-norpinene-2-propionaldehyde, para-methylphenoxyacetaldehyde, 2- methyl-3-phenyl-2-propen-1-al, 3, 5,5-trimethylhexanal, hexahydro-8,8-dimethyl-2-naphthaldehyde, 3-propyl-bicyclo- [2.2.1] -hept-5-en-2-carbaldehyde, 9-decenal, 3-methyl- 5-phenyl-1-pentanal, methylnonylacetaldehyde, hexanal and trans-2-hexenal. Fragrance compounds of the ketone type are, for example, methyl-beta-naphthyl ketone, musk indanone (1, 2,3,5,6,7-hexahydro-1, 1, 2, 3, 3-pentamethyl-4H-inden-4-one), Tonalid (6-acetyl-1, 1, 2,4,4, 7-hexamethyltetralin), alpha-damascone, beta-damascone, delta-damascone, iso-damascone, damascenone, methyldihydrojasmon, menthone, carvone, camphor, coavone (3,4,5,6,6-pentamethylhept-3-en-2-one), fenchone, alpha-ionone, beta-ionone, gamma-methyl-ionone, fleuramone (2-heptylcyclopen-tanone), dihydrojas - mon, cis-jasmon, iso-E-Super (1- (1, 2,3,4,5,6J, 8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl) -ethane-1 -one (and isomers)), methyl cedrenyl ketone, acetophenone, methylacetophenone, para-methoxyacetophenone, methyl-beta-naphthyl ketone, benzylacetone, benzophenone, para-hydroxyphenylbutanone, celery ketone (3-methyl-5-propyl-2- cyclohexenone), 6-isopropyldecahydro-2-naphthone, dimethyloctenone, Frescomenthe (2-butan-2-yl-cyclohexan-1-one), 4- (1-ethoxyvinyl) -3, 3,5,5-tetramethylcyclohexanone, Methylheptene one, 2- (2- (4-methyl-3-cyclohexen-1-yl) propyl) cyclopentanone, 1- (p-menthen-6 (2) yl) -1-propanone, 4- (4-hydroxy -3-methoxyphenyl) -2-butanone, 2-acetyl-3,3-dimethylnorbornane, 6,7-dihydro-1, 1, 2,3,3-pentamethyl-4 (5H) -indanone, 4-damascol, dulcinyl (4- (1,3-benzodioxol-5-yl) butan-2-one), hexalone (1- (2,6,6-trimethyl-2-cyclohexene-1-yl) -1,6-heptadiene -3-one), isocyclemonE (2-acetonaphthon-1, 2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl), methylnonyl ketone, methylcyclocitron, methyl lavender ketone, orivon (4-tert-amyl-cyclohexanone), 4- tert-butylcyclohexanone, Delphon (2-pentyl-cyclopentanone), muscon (CAS 541-91-3), neobutene (1- (5,5-dimethyl-1- cyclohexenyl) pent-4-en-1-one), Plicaton (CAS 41724-19-0), Velouton (2,2,5-trimethyl-5-pentylcyclopentan-1-one), 2,4,4,7-tetramethyl-oct-6-en-3-one and tetrameran (6,10-dimethylundecen-2-one) . Fragrance compounds of the alcohol type are, for example, 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol, 2-tert.-butycyclohexanol, 3,5,5-trimethylcyclohexanol, 3-hexanol, 3-methyl-5-phenyl-pentanol, 3-octanol, 3-phenyl-propanol, 4-heptenol, 4-isopropyl-cyclohexanol, 4-tert-butycyclohexanol , 6,8-dimethyl-2-nonanol, 6-nonen-1-ol, 9-decen-1-ol, α-methylbenzyl alcohol, terpineol, amyl salicylate, benzyl alcohol, benzyl salicylate, β-terpineol, butyl salicylate, citro - nellol, cyclohexyl salicylate, decanol, dihydromyrcenol, dimethylbenzylcarbinol, dimethylheptanol, dimethyloctanol, ethyl salicylate, ethylvaniline, eugenol, farnesol, geraniol, heptanol, hexyl salicylate, n-ol, hexyl salicylate, isobomeol, isopyrtenanol, isopyrulugenol, isobomeol, isopyrtenol , Nerol, nonanol, octanol, p-menthan-7-ol, phenylethyl alcohol, phenol, phenyl salicylate, tetrahydrogeraniol, tetrahydrolinalool, thymol, trans-2-cis-6-nonadicnol, trans-2-nonene-1-o l, trans-2-octenol, undecanol, vanillin, champiniol, hexenol and cinnamon alcohol. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenylglycinate, allyl methylphenyl glycinate, allyl cyclohexylate, allylcyclohexyl propionyl, allyl cyclohexyl propionate, allyl cyclohexylate, allyl cyclohexyl propionyl, allylcyclohexyl propionyl, allylcyclohexyl propionyl, allyl cyclohexyl propionyl, allylcyclohexyl propionyl, allyl cyclohexyl propionyl, allylcyclohexyl propionyl, allylcyclohexyl propionyl, allylcyclohexylpropionate, allylcyclohexyl propionyl, allylcyclohexyl propionyl, allylcyclohexyl propionate, p-tert-butylcyclohexyl propionate, The ethers include, for example, benzyl ethyl ether and ambroxan. The hydrocarbons mainly include terpenes such as limonene and pinene. Mixtures of different fragrances are preferably used, which together produce an appealing fragrance note. Such a mixture of fragrances can also be referred to as perfume oil. Such perfume oils can also contain natural fragrance mixtures, such as are available from vegetable sources. The fragrances of vegetable origin include essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, champaca flower oil, citrus oil, noble fir oil, noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, guajun oil, gourd oil, gherkin oil, galbanum oil, gherkin oil, gjajun oil , Ginger oil, iris oil, jasmine oil, kajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, copaiva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, labdanum oil, lavender oil, lemon linden oil, mandarin flower oil, lavender oil , Muscatel oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, orange blossom oil, orange peel oil, origanum oil, palmarosa oil, patchouli oil, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, allspice oil, celery oil, sage oil, starch oil, rosemary oil, sandstone oil, rosemary oil , Turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, We rmut oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, citronella oil, lemon oil and cypress oil as well as ambrettolide, ambroxan, alpha-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, anthranilic acid methyl ester, benzyl acetone, Benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerianate, borneol, bornyl acetate, boisambrene forte, alpha-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, gerucalyptyl acetate, geranium, farnesia formol, eucalyptyl acetate, geranium formol , Heptine carboxylic acid methyl ester, hept aldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamic alcohol, indole, Iran, Isoeugenol, isoeugenol methyl ether, isosafrol, jasmone, camphor, carvakrole, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl-n-amyl ketone, methylanthranilic acid methyl ester, p-methylacetophenoline, methyl chavikol, p-methylquinoline naphthyl ketone, methyl n-nonylacetaldehyde, methyl n-nonyl ketone, muscon, beta-naphthol ethyl ether, beta-naphthol methyl ether, nerol, n-nonyl aldehyde, nonyl alcohol, n-octyl aldehyde, p-oxy acetophenone, pentadecanolide, beta-phenylethyl alcohol, phenylacetic acid, pulegon, safrol, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester, salicylic acid cyclohexyl ester, santalol, sandelice, skatol, terpineol, thymen, thymol, troenan, cinnamic acid, cinnamic acid, gamma aldehyde-undelated alcohol Cinnamic acid benzyl ester, diphenyl oxide, limonene, linalool, linalyl acetate and propionate, melusate, menthol, menthone, methyl-n-heptenone, pinene, phenyl acetaldehyde, terpinylacetate, citral, lemon llal, as well as mixtures thereof. In one embodiment it can be preferred that at least part of the perfume is used as a fragrance precursor or in encapsulated form (fragrance capsules), in particular in microcapsules. However, the entire fragrance can also be used in encapsulated or non-encapsulated form. The microcapsules can be water-soluble and / or water-insoluble microcapsules. For example, melamine-urea-formaldehyde microcapsules, melamine-formaldehyde microcapsules, urea-formaldehyde microcapsules or starch microcapsules can be used. “Fragrance precursors” refers to compounds that only release the actual fragrance after chemical conversion / cleavage, typically through exposure to light or other environmental conditions such as pH, temperature, etc. Such compounds are often referred to as fragrance storage substances or "pro-fragrance".

According to the present invention, those bitter substances are particularly preferred which are soluble in water at 20 ° C. to an extent of at least 5 g / l. With regard to an undesirable interaction with the fragrance components possibly contained in the composition, in particular a change in the fragrance note perceived by the consumer, the ionic bitter substances have proven to be superior to the non-ionic ones. Ionic bitter substances consisting of organic cation (s) and organic anion (s) are consequently preferred for the compositions according to the invention. Quaternary ammonium compounds which contain an aromatic group both in the cation and in the anion are very suitable in the context of the present invention. In various embodiments, the bitter substance is therefore a quaternary ammonium compound. A suitable quaternary ammonium compound is, for example, benzyldiethyl ((2,6-xylylcarbamoyl) methyl) ammonium benzoate, which is commercially available under the trademarks Bitrex® and Indige-stin®. This compound is also known as Denatonium Benzoate. The bitter substance is preferably benzyl diethyl ((2,6-xylylcarbamoyl) methyl) ammonium benzoate. In particular in the case of agents packaged in portions in water-soluble wrapping material, bitter substances can preferably also be present as a component of the wrapping material and in particular be applied to the side of the wrapping material facing away from the center. Individually portioned agents can be packaged as solid moldings each corresponding to one portion or packaged in portions in water-soluble wrapping material.

In a preferred embodiment of the invention, the single-portioned agent is present in single-portioned ready-to-dose form in a chamber made of water-soluble material; then the agent preferably contains less than 15% by weight, in particular in the range from 1% by weight to 12% by weight, of water. A portion is an independent dosing unit with at least one chamber in which the material to be dosed is contained. A chamber is a space delimited by walls (for example by a film), which can also exist without the material to be dosed (possibly with a change in its shape). A surface coating or a layer of a surface coating is therefore not a wall according to the present invention.

The walls of the chamber are made of a water-soluble material. The water solubility of the material can be determined using a square film of the said material (film: 22 x 22 mm with a thickness of 76 μm) fixed in a square frame (edge length on the inside: 20 mm) according to the following measurement protocol. Said framed film is immersed in 800 ml of distilled water heated to 20 ° C in a 1 liter beaker with a circular bottom surface (Fa. Schott, Mainz, beaker 1000 ml, low shape) so that the surface of the clamped film is at right angles to The bottom surface of the beaker is arranged, the top edge of the frame is 1 cm below the water surface and the bottom edge of the frame is aligned parallel to the bottom surface of the beaker in such a way that the bottom edge of the frame runs along the radius of the bottom surface of the beaker and the center of the bottom edge of the frame is arranged over the center of the radius of the beaker bottom. The material dissolves with stirring (stirring speed, magnetic stirrer 300 rpm, stirring rod: 5 cm long) within 600 seconds in such a way that no individual solid particles are visible to the naked eye.

The walls of the chambers and thus the water-soluble envelopes of the detergents according to the invention are preferably formed by a water-soluble film material. Such water-soluble packaging can be produced either by the vertical form fill sealing or by thermoforming processes.

The thermoforming process generally includes forming a first layer of a water-soluble sheet material to form bulges for receiving a composition therein, pouring the composition into the bulges, covering the bulges filled with the composition with a second layer of a water-soluble sheet material and sealing the first and second layers with one another at least around the bulges. The water-soluble film material is preferably selected from polymers or polymer mixtures. The envelope can be formed from one or from two or more layers of water-soluble film material. The water-soluble film materials of the first layer and of the further layers, if any, can be the same or different.

It is preferred that the water-soluble cover contains polyvinyl alcohol or a polyvinyl alcohol copolymer; it is particularly preferably composed of polyvinyl alcohol or polyvinyl alcohol copolymer.

Water-soluble films for producing the water-soluble envelope are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is in the range from 10,000 to 1,000,000 gmof ¹ , preferably from 20,000 to 500,000 gmof ¹ , particularly preferably from 30,000 to 100,000 gmof ¹ and in particular from 40,000 to 80,000 gmof ¹ lies.

Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

Polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid and / or mixtures of the above polymers can also be added to a film material suitable for producing the water-soluble envelope. The copolymerization of monomers on which such polymers are based, individually or in mixtures of two or more, with vinyl acetate is also possible.

Preferred polyvinyl alcohol copolymers include vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof in addition to vinyl alcohol; the esters are Ci- ₄ alkyl or -Hydroxyal- alkyl esters are preferred. Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, ethylenically unsaturated dicarboxylic acids as further monomers. Suitable dicarboxylic acids are, for example, itaconic acid, maleic acid, fumaric acid and mixtures thereof, with itaconic acid being particularly preferred.

Suitable water-soluble films for use in the casings of the water-soluble packaging according to the invention are films that are available from MonoSol LLC, for example, under with the designation M8630, C8400 or M8900. Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.

The detergent or cleaning agent portion, comprising the washing or cleaning agent and the water-soluble casing, can have one or more chambers. The water-soluble envelopes with a chamber can have an essentially dimensionally stable spherical, ellipsoidal, cube, cuboid or cushion-shaped configuration with a circular, elliptical, square or rectangular basic shape. The agent can be contained in one or more chambers, if present, of the water-soluble envelope.

In a preferred embodiment, the water-soluble envelope has two chambers. In this embodiment, both chambers can each contain a solid partial composition or a liquid partial composition, or the first chamber contains a liquid and the second chamber a solid partial composition.

The proportions of the agents contained in the different chambers of a water-soluble envelope with two or more chambers can have the same composition. Preferably, however, the agents in a water-soluble casing with at least two chambers have partial compositions which differ in at least one ingredient and / or in the content of at least one ingredient. A partial composition of such agents according to the invention preferably has enzyme and / or bleach activator and a further partial composition present separately therefrom has peroxidic bleach, in which case the first-mentioned partial composition in particular has no peroxidic bleach and the second-mentioned partial composition in particular has no enzyme and no bleach activator.

The portion-wise packaging in a water-soluble envelope enables the user to place one or, if desired, several, preferably one, of the portions in the washing machine or dishwasher, in particular in the dispensing compartment of a washing machine, or in a container for carrying out a manual washing or cleaning process. Such portion packs meet the consumer's desire for simplified dosing. After adding water, the wrapping material dissolves so that the ingredients are released and can develop their effect in the liquor. A water-soluble coated portion preferably weighs 10 g to 35 g, in particular 12 g to 28 g and particularly preferably 12 g to 15 g, with 0.3 g to 2.5 g, in particular 0, of the water-soluble coating contained in the weight specification .7 g to 1.2 g are omitted. The production of solid agents according to the invention presents no difficulties and can be carried out in a known manner, for example by spray drying or granulation, with enzymes and any other thermally sensitive ingredients such as bleaching agents optionally being added later separately. For the production of agents with increased bulk density, in particular in the range from 650 g / l to 950 g / l, a method comprising an extrusion step is preferred.

Liquid or pasty agents according to the invention in the form of solutions containing conventional water solvents are generally produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.

Examples

The surfactant “E-surfactant” specified in the following examples is a surfactant according to formula (I) with X ⁺ = Na ⁺ , m = 11 and n = 0.

example 1

The special detergents S1 and S2 specified in the table below were produced by mixing the ingredients in the specified amounts:

Table 7: Special detergents (data in% by weight)

Example 2 The liquid detergents E1 to E8 specified in the table below were prepared by mixing the ingredients in the specified amounts. They are dosed with 50 ml per wash cycle.

Table 8: Liquid detergents (data in% by weight)

Table 8 (continued)

Example 3 The liquid detergents specified in the table below were prepared by mixing the ingredients in the specified amounts. They are dosed with 20 ml per wash cycle.

Table 9: Liquid detergents (data in% by weight)

Example 4

The single-portion detergents specified in the table below were produced by mixing the ingredients in the specified amounts and packed in films made of polyvinyl alcohol: Table 10: Individual portioned detergents (data in% by weight)

Example 5

Washing tests were carried out at 40 ° C. in Miele W1935 washing machines as a 6-fold determination with a dosage of 52.5 g of the liquid detergents composed as specified below.

Table 11: Detergents (data in% by weight)

The brightness values (Y values) after washing were determined on various standardized soils by means of colorimetric measurements. The use of the M3 resulted in higher brightness values and thus improved stain removal on enzymatic soiling (see the following table):

Table 12: Y values

Claims

1 . Use of anionic surfactant of the general formula (I),

in which n and m stand independently for numbers from 0 to 17 and 2 <n + m <20, and X ^{+ stands} for a charge-balancing cation, to increase the performance of detergents or cleaning agents when washing laundry or cleaning hard Surfaces against enzymatic soiling.

2. Washing or cleaning agents containing an anionic surfactant of the general formula

(I),

in which n and m independently of one another stand for numbers from 0 to 17 and 2 <n + m <20, and X ^{+ stands} for a charge-balancing cation, characterized in that it contains (data in% by weight)

3. Washing or cleaning agents containing an anionic surfactant of the general formula

(I),

4. Washing or cleaning agents containing an anionic surfactant of the general formula

(I),

5. Washing or cleaning agents containing an anionic surfactant of the general formula

(I),

6. Washing or cleaning agents containing an anionic surfactant of the general formula

(I), in which n and m independently of one another stand for numbers from 0 to 17 and 2 <n + m <20, and X ^{+ stands} for a charge-balancing cation, characterized in that it contains (data in% by weight)

7. Washing or cleaning agents containing an anionic surfactant of the general formula

(I),

8. Use according to claim 1 or washing or cleaning agent according to one of claims 2 to 7, characterized in that in the compounds of the general formula (I) n is a number from 0 to 3 and m is a number from 5 to 14 , and / or X ⁺ from the group comprising the proton, alkali metal cations and the grouping N ⁺ R ¹ R ² R ³ R ⁴ , in which R ¹ , R ² , R ³ and R ⁴ independently of one another represent hydrogen, an alkyl group with 1 to 6 carbon atoms or a hydroxyalkyl group with 2 to 6 carbon atoms is selected.