DE102008045297A1 - Method for washing textiles in the presence of a peroxygenated bleaching agent and a bleach boosting transition metal complex - Google Patents

Abstract

Method for washing textiles in the presence of a peroxygenated bleaching agent and a bleach boosting transition metal complex, is claimed, where the method is carried out in a water hardness of 0-3[deg] dH (degree of hardness). An independent claim is included for a textile care detergent comprising peroxygenated bleaching agent, bleach boosting transition metal complex or one or more ligands, which form the bleach boosting transition metal complex with transition metal complex in the washing process, and cation complexing-, cation exchange- or cation carrying substances.

Description

The The present invention relates to a textile-sparing process for Washing textiles in the presence of a persoxy-containing Bleaching agent and a bleach-enhancing transition metal complex and the use of cation-complexing, cation-exchanging or cation-precipitating substances to reduce textile damage of bleach-enhancing transition metal complexes in the washing of textiles and products containing peroxygen Bleaching agent, bleach-enhancing transition metal complex and cation-complexing, cation-exchanging or cation-precipitating Contain substances.

Inorganic peroxygen compounds, particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes. The oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H ₂ O ₂ or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N- acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfururamides and cyanurates, in addition carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetylglucose, have become known in the literature , By adding these substances, the bleaching effect of aqueous peroxide liquors can be increased so much that even at temperatures around 60 ° C substantially the same effects as with the peroxide solution alone at 95 ° C occur. The damage to the tissue remains in a frame acceptable to the consumer.

in the Strive for energy-saving washing and bleaching processes Application temperatures significantly lower in recent years 60 ° C, especially below 45 ° C down to to the cold water temperature in importance.

at these low temperatures leaves the effect the previously known activator compounds usually recognizable to. There was therefore no lack of aspirations for develop this temperature range more effective bleaching systems. A starting point for this results from the use of hydrogen peroxide-supplying Compounds together with transition metal salts and complexes as so-called bleach catalysts. These are, presumably because of the high reactivity of them and the peroxygen compound resulting oxidizing intermediates, but the risk of oxidative textile damage. The use of such transition metal catalysts in detergents has been difficult in practice so far, because then the damage to the tissue significantly higher is than in a peracid-forming conventional system bleach and bleach activator.

The The present invention is aimed at washing textiles the damage of the textile when using bleach-active Catalysts lower, without the bleaching power is essential to influence.

object The invention in a first aspect is a method for washing of textiles in the presence of a persoxy bleach and a bleach-enhancing transition metal complex, which is characterized in that it is at a water hardness from 0 ° dH to 3 ° dH, in particular 0 ° dH, is carried out.

Suitable bleach-activating transition metal complex compounds are, in particular, those of the metals Fe, Mn, Co, V, Ru, Ti, Mo, W, Cu and / or Cr, for example those from the German patent application DE 195 29 905 A1 known manganese, iron, cobalt, ruthenium or molybdenum-salene complexes and their from the German patent application DE 196 20 267 A1 known N-analogues known from the German patent application DE 195 36 082 A1 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes described in the German patent application DE 196 05 688 A1 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which are known from the German patent application DE 196 20 411 A1 known cobalt, iron, copper and ruthenium-amine complexes described in the German patent application DE 44 16 438 A1 described manganese, copper and cobalt complexes described in the European patent application EP 0 272 030 A2 beschrie include cobalt complexes resulting from the European patent application EP 0 693 550 A2 known manganese complexes resulting from the European patent application EP 0 392 592 A2 known manganese, iron, cobalt and copper complexes and / or in the European patent application EP 0 443 651 A2 or the European patent applications EP 0 458 397 A2 . EP 0 458 398 A2 . EP 0 549 271 A1 . EP 0 549 272 A1 . EP 0 544 490 A1 and EP 0 544 519 A2 described manganese complexes.

ist, worin jeder der Reste R¹ und R² Null, H, Alkyl oder Aryl, gegebenenfalls substituiert, sein kann; t und t' unabhängig voneinander 2 oder 3 sind; D und D¹ unabhängig voneinander N, NR, PR, O oder S sind, worin R H, Alkyl oder Aryl, gegebenenfalls substituiert, bedeutet; und s eine ganze Zahl mit einem Wert von 2 bis 5 ist, worin, falls D = N ist, eine der daran gebundenen Heterocarbonbindungen ungesättigt ist, was zur Herbeiführung eines N = CR¹-Teilstückes führt. Bevorzugtes Metall M ist Mangan. Die koordinierende oder überbrückende Spezies X ist vorzugsweise ein kleines koordinierendes Ion oder überbrückendes Molekül oder eine Mischung derselben, beispielsweise Wasser, OH^–, O^2–, S^2-, -S(=O)-, N^3–, HOO^–, O₂ ^2–, O₂ ^–, Amin, Cl^–, SCN^–, N₃ ^–, und Carboxylat wie zum Beispiel Acetat oder Mischungen aus diesen. Wenn die Ladung z positiv ist, ist Y ein Anion, wie beispielsweise Chlorid, Bromid, Iodid, Nitrat, Perchlorat, Rhodanid, Hexafluorphosphat, Sulfat, Alkylsulfat, Alkylsulfonat oder Acetat; wenn die Ladung z negativ ist, ist Y ein Kation, wie beispielsweise ein Alkaliion, Ammoniumion oder Erdalkaliion. Zu den bevorzugten Liganden L gehören 1,4,7-Triazacyclononan, 1,4,7-Trimethyl-1,4,7-triazacyclononan, 1,5,9-Trimethyl-1,5,9-triazacyclododecan und 1,2,4,7-Tetramethyl-1,4,7-triazacyclononan.Preferred bleach-enhancing transition metal complex compounds include metal complexes of the formula (I), [L _n M _m X _p ] ^z Y _q (I) wherein M means manganese or iron or mixtures of these metals, which may be in the oxidation state II, III, IV or V, or in mixtures thereof, n and m are independently integers having a value of 1 to 4, X is a coordinating or bridging Represents species, p is an integer from 0 to 12, Y is a counterion whose type depends on the charge z of the complex, which may be positive, zero or negative, q = z / [charge Y], and L is a ligand which is a macrocyclic organic molecule of the general formula

wherein each of R ¹ and R ^{2 may be} zero, H, alkyl or aryl, optionally substituted; t and t 'are independently 2 or 3; D and D ^{1 are} independently N, NR, PR, O or S, wherein R is H, alkyl or aryl, optionally substituted; and s is an integer having a value of 2 to 5, wherein, when D = N, one of the heterocarbon bonds bonded thereto is unsaturated, resulting in the formation of an N = CR ¹ portion. Preferred metal M is manganese. The coordinating or bridging species X is preferably a small co-ordinating ion or bridging molecule or a mixture thereof, for example water, OH ^-, O ^2-, S ^2-, -S (= O) -, N ^3-, HOO ^-, O ₂ ^2- , O ₂ ^- , amine, Cl ^- , SCN ^- , N ₃ ^- , and carboxylate such as acetate or mixtures thereof. When the charge z is positive, Y is an anion such as chloride, bromide, iodide, nitrate, perchlorate, rhodanide, hexafluorophosphate, sulfate, alkylsulfate, alkylsulfonate or acetate; when the charge z is negative, Y is a cation, such as an alkali ion, ammonium ion or alkaline earth metal ion. Preferred ligands L include 1,4,7-triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl-1,5,9-triazacyclododecane and 1,2, 4,7-tetramethyl-1,4,7-triazacyclononane.

in der R¹⁰ und R¹¹ unabhängig voneinander für Wasserstoff, eine C_1-18-Alkylgruppe, eine Gruppe NR¹³R¹⁴, eine Gruppe -N⁺R¹³R¹⁴R¹⁵ oder eine Gruppe

R¹² für Wasserstoff, -OH, oder eine C_1-18-Alkylgruppe, R¹³, R¹⁴ und R¹⁵ unabhängig voneinander für Wasserstoff, eine C_1-4-Alkyl- oder -Hydroxyalkylgruppe und X für Halogen stehen sowie A für einen ladungsausgleichenden Anionliganden steht, der je nach seiner Ladung und der Art und Anzahl der sonstigen Ladungen, insbesondere der Ladung des Mangan-Zentralatoms, auch fehlen oder mehrfach vorhanden sein kann. Mangan kann darin wie auch in den Komplexen gemäß Formel (I) die Oxidationsstufe II, III, IV oder V aufweisen. Gewünschtenfalls, wenn auch weniger bevorzugt, können in derartigen Komplexverbindungen anstelle des Mn-Zentralatoms auch andere Übergangsmetalle, wie beispielsweise Fe, Co, Ni, V, Ru, Ti, Mo, W, Cu und/oder Cr, vorhanden sein.In a further preferred embodiment, the bleach-enhancing transition metal complex compound corresponds to the general formula (II),

in R ¹⁰ and R ¹¹ independently of one another represent hydrogen, a C _1-18 -alkyl group, a group NR ¹³ R ¹⁴ , a group -N ⁺ R ¹³ R ¹⁴ R ¹⁵ or a group

R ^{12 is} hydrogen, -OH, or a C _1-18 alkyl group, R ¹³ , R ¹⁴ and R ^{15 are} independently hydrogen, a C _1-4 alkyl or hydroxyalkyl group and X is halogen and A is a charge-balancing anion ligands, depending on its charge and the type and number of other charges, ins special of the charge of the central manganese atom, also missing or may be present several times. Manganese can have the oxidation state II, III, IV or V therein as well as in the complexes according to formula (I). If desired, though less preferred, other transition metals such as Fe, Co, Ni, V, Ru, Ti, Mo, W, Cu and / or Cr may be present in such complex compounds instead of the Mn central atom.

The if desired at temperatures in the range of 10 ° C to 95 ° C be performed. Preferably, the temperature is in the Range from 20 ° C to 40 ° C.

In order to achieve an optimal reduction of textile damage by the method according to the invention, it is usually not sufficient to operate a washing machine with demineralized or ion-exchanged water or to use appropriate handwashing water, since so before the actual beginning of the washing process, a water hardness of 0 ° dH However, in the course of the washing program, Ca and / or Mg ions, which are presumably present in small amounts in the ingredients of the detergent necessarily used for washing or in the soiling on the fabric to be washed, release and increase the water hardness. In order to avoid this, it is preferable to additionally use cation-complexing, cation-exchanging and / or cation-precipitating substances in the process according to the invention; It is preferred to introduce a larger amount of these substances in the wash liquor than would be necessary to bring the water hardness in the wash liquor to a value in the range of 0 ° dH to 3 ° dH, and in particular cation-complexing substances even at a water hardness of 0 ° dH in addition to use. In particular, it is preferred to use cation-complexing, cation-exchanging and / or cation-precipitating substances in at least amounts such that the water hardness remains within that range for at least the time period during which the system of peroxygen-containing bleach and bleach-enhancing transition metal complex is to exhibit its bleaching performance. These additives are further elaborated below in connection with the builders or surfactants which can be used in detergents. Examples of such additives are phosphonates (such as HEDP or DPTMP), complexing polymers, especially polycarboxylates (for example Sokalan ^® CP 5), ion exchanging substances, such as zeolite A (Sasil ^®), zeolite P and zeolite X or complexing surfactants, in particular anionic surfactants (such as, for example, linear alkylbenzenesulfonates), which if desired can also be used in any desired combination. Another object of the invention is therefore the use of cation-complexing, cation-exchanging or cation-precipitating substances for reducing the textile damage of bleach-enhancing transition metal complexes in the washing of textiles. In this embodiment of the invention, the use of common service water, which usually has a water hardness above 0 ° dH, possible. In a preferred embodiment of the invention, more cation-complexing, cation-exchanging and / or cation-precipitating substance is used than would be necessary to achieve a water hardness of 0 ° dH, although it may also be possible to use less cation-complexing, cation-exchanging and / or Cation precipitating substance, as would be necessary to reach a water hardness of 3 ° dH.

If Phosphonates in the process of the invention are to be used, the concentration of Phosphonate in the wash liquor preferably 0.01 mmol / l to 10 mmol / l, in particular 0.1 mmol / l to 2 mmol / l.

If Complexing polymers in the invention Procedures to be used, is the concentration of complexing polymer in the wash liquor preferably 0.001 g / l to 5 g / l, in particular 0.01 g / l to 1 g / l.

If ion-exchanging substances in the inventive Procedures to be used, is the concentration of ion-exchanging substance in the wash liquor preferably 0.01 g / l to 100 g / l, in particular 0.1 g / l to 10 g / l.

If Complexing surfactants in the inventive Procedures to be used, is the concentration of complexing surfactant in the wash liquor preferably 0.01 g / l to 50 g / l, in particular 0.02 g / l to 10 g / l.

Preferred peroxygen concentrations (calculated as H ₂ O ₂ ) in the wash liquor are in the range from 0.001 g / l to 10 g / l, in particular 0.1 g / l to 1 g / l. The concentration of bleach-enhancing transition metal complex in the wash liquor is preferably in the range from 0.1 μmol / to 100 μmol / l, in particular from 1 μmol / l to 20 μmol / l.

The inventive method leaves For example, realize that by pers oxygen-containing Bleaching agent, bleach-enhancing transition metal complex and optionally cation-complexing, cation-exchanging and / or cation-precipitating substances each separately from a washing solution, which may contain a conventional detergent added. It is also possible, not the final bleach-enhancing transition metal complex, but separately one or more ligands, which in the washing process with a transition metal in situ, a bleach-enhancing transition metal complex can insert; the transition metal can then also separately in the form of a salt or not bleach-enhancing Complex be dosed, or it will be in the washing process as Part of the service water used for this or over the textile to be cleaned, for example as part of removing stain, introduced into the washing process. there For example, it is possible and preferred to use the bleach-enhancing transition metal complex and the cation-complexing, cation-exchanging and / or cation-precipitating Substance simultaneously, in particular as preferably hydrous or present as an aqueous solution Premix, together in the washing process.

Especially the premixing of a bleach-enhancing transition metal complex with phosphonates (such as HEDP or DPTMP), respectively may be present as a water-containing preparation is preferred probably the phosphonate as Coligand, optionally under Loss of other ligands (X in formulas I and II) to the transition metal central atom complex binds. It is preferred, if appropriate, by addition system-compatible acids or bases, the pH the hydrous mixture of transition metal complex and phosphonate to values in the range of pH 5 to pH 12, in particular of Adjust pH 7 to pH 11 and more preferably from pH 8 to pH 10. The water hardness in this hydrous mixture can if desired, 0 ° dH to 30 ° dH, in particular 0 ° dH to 10 ° dH. Preferably, bleach-enhancing transition metal complex and phosphonate in molar ratios of 10: 1 to 1:10, in particular 1: 1 to 1: 2 used. The so at temperatures in the Range of preferably 10 ° C to 100 ° C, in particular Mixture complex formed at 30 ° C to 80 ° C can either be added as a solution to the wash liquor or, if desired by adding salts such as alkali metal or ammonium sulfate, hydrogen sulfate, carbonate, bicarbonate, phosphate, hydrogen phosphate, dihydrogen phosphate or the like to the aqueous system, in particular in concentrations of 0.01 mol / l to 1 mol / l, in particular 0.1 mol / l to 0.7 mol / l, previously isolated and as a separate substance be incorporated into a detergent or cleaning agent formulation or in the context of the invention Use or a method according to the invention be used.

Also it is preferred, in a washing process, first the cation-complexing, cation-exchanging and / or cation-precipitating substance and then, for example after a few minutes, the bleach-enhancing transition metal complex or the ligand, which in the washing process with a transition metal in situ a bleach-enhancing transition metal complex can form into the washing process. In another preferred embodiment of the invention is used Detergent containing peroxygen bleach, bleach-enhancing transition metal complex or a ligand which is in the washing process with a transition metal in situ a bleach-enhancing transition metal complex can form, and cation-complexing, cation-exchanging and / or contains cation-precipitating substance. Such a textile-friendly Detergent is another object of the invention.

invention Detergents in solid form or as liquids or pastes may be present as such used in machine or manual washing processes, but also as detergent additives and / or as laundry or Textile pretreatment are used.

As a detergent additive agents of the invention are used together with a conventional detergent. This is especially useful if the user wants to improve the usual detergent in its bleaching performance. In the laundry pretreatment, the agents according to the invention are used to improve the removal of encrusted dirt or stains, in particular "problem spots" such as coffee, tea, red wine, grass or fruit juice, which are difficult to remove by washing with conventional textile detergents, but are accessible to an oxidative attack. Another application of such means is the removal of local stains on otherwise clean surfaces, so that a more complex washing or cleaning process of the corresponding overall structure, be it now a piece of clothing or a carpet or furniture upholstery, avoid. For this purpose, it is possible in a simple manner to apply an agent according to the invention, optionally together with an amount of water which is insufficient for complete dissolution of the agent, to the textile surface or its part to be cleaned, optionally mechanical energy, for example by rubbing with a cloth or a sponge. and after a time to be determined by the user, the agent and the oxidative rupture soiling by washing with water, for example with the help of a moistened cloth or sponge.

Preferably the agents according to the invention contain 0.01% by weight to 0.5 wt .-%, in particular 0.02 wt .-% to 0.3 wt .-% of bleach-enhancing transition metal complex. Alternatively or possibly additionally, the inventive means also only one or contain several ligands, which in the washing process with a transition metal in situ a bleach-enhancing transition metal complex can form. The transition metal can thereby in the form of a salt or non-bleach-enhancing complex also be present in the detergent or will be in the washing process as part of the process water used for this purpose or over the textile to be cleaned, for example as part of removing stain, be introduced into the washing process.

The Detergents and cleaning agents according to the invention can in addition to the pers oxygen bleach, the bleach-enhancing transition metal complex or the ligand which in situ the bleach-enhancing transition metal complex and the cation-complexing, cation-exchanging and / or cation-precipitating substance in principle all known and contain conventional ingredients in such agents. The washing and cleaning agents according to the invention In particular builders, surface-active Surfactants, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, dye transfer inhibitors, Grayness inhibitors, crease-reducing agents and form-retaining Active ingredients, and other excipients, such as optical brighteners, foam regulators, additional peroxygen activators, dyes and fragrances containing the cation-complexing, cation-exchanging and / or cation-precipitating agent among the builders, Surfactants or sequestering agents as mentioned above cation-complexing, cation-exchanging or cation-precipitating Substances for the process according to the invention, the use according to the invention and the use come in question in inventive compositions.

When for use in the invention Method in the use according to the invention and peroxygen compounds useful in compositions of this invention come in particular organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, Perbenzoic acid or salts of diperdodecanedioic acid, Hydrogen peroxide and hydrogen peroxide under the washing conditions donating inorganic salts, which include alkali metal perborate, alkali metal percarbonate, -persilikat and / or -persulfat such as Caroat belong, in Consideration. If solid peroxygen compounds are used should, in the form of powders or granules be used, which are also wrapped in a manner known in principle can. The addition of small amounts of known bleach stabilizers such as phosphonates, bristles or metaborates and metasilicates and magnesium salts such as magnesium sulfate be expedient. An inventive agent preferably contains 15% by weight to 50% by weight, in particular From 18% by weight to 35% by weight of peroxygen bleach, in particular Alkali percarbonate. Alternatively or optionally in addition can in the process according to the invention hydrogen peroxide also by an enzymatic system, namely an oxidase in combination with its substrate, produced in one preferred embodiment of the invention, components of the invention Means are and in these the persoxy bleach partially or preferably completely replace.

additionally to the bleach-enhancing transition metal complex compound can in the inventive compositions if desired, further as bleach-activating agents known compounds, in particular conventional bleach activators, that is, compounds that are under perhydrolysis conditions optionally substituted perbenzoic acid and / or peroxycarboxylic acids with 1 to 10 C-atoms, in particular 2 to 4 C-atoms, used become. Suitable bleach activators are conventional, the O- and / or N-acyl groups of said C atom number and / or optionally bear substituted benzoyl groups. Preference is given to multiple acylated Alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated Glycolurils, especially tetraacetylglycoluril (TAGU), acylated Triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonates, especially nonanoyloxy or isononanoyloxybenzenesulfonate, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetylglucose (PAG), Pentaacetylfruktose, tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone. Also under perhydrolysis conditions forming perimic acids Nitriles, for example acetonitriles bearing ammonium groups, can be used be used. Preferably, the invention However, means free of such conventional bleach activators.

The compositions of the invention may contain one or more surfactants, in particular anio niche surfactants, nonionic surfactants and mixtures thereof come into question. Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Furthermore, corresponding ethoxylation and / or propoxylation of N-alkyl-amines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to said long-chain alcohol derivatives with respect to the alkyl part, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.

suitable anionic surfactants are in particular soaps and those containing or sulfonate groups with preferably alkali ions as cations. Useful soaps are preferably the alkali salts of the saturated ones or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids may also be incomplete neutralized form can be used. Among the useful surfactants of the sulfate type include the salts of sulfuric acid half esters of fatty alcohols containing 12 to 18 carbon atoms and the sulfation products of mentioned nonionic surfactants with a low degree of ethoxylation. Suitable surfactants of the sulfonate type include linear ones Alkylbenzenesulfonates with 9 to 14 C atoms in the alkyl moiety, alkanesulfonates with 12 to 18 carbon atoms, as well as olefinsulfonates with 12 to 18 carbon atoms, in the implementation of corresponding monoolefins with sulfur trioxide arise as well as alpha-sulfo fatty acid esters, which in the Sulfonation of fatty acid methyl or ethyl esters arise.

such Surfactants are present in the cleaning or detergents in amounts of preferably 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight.

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 methylglycinediacetic acid, nitrilotriacetic acid, ethylenediamine-N, N'-disuccinic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1 -Hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the accessible by oxidation of polysaccharides or dextrins polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which also small amounts of polymerizable substances without Carboxylic acid functionality may contain polymerized. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. It is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth) -acrylic acid. The second acidic monomer or its salt may be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical. Such polymers generally have a molecular weight between 1,000 and 200,000. Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

such If desired, organic builders may be used in amounts up to 40 wt .-%, in particular up to 25 wt .-% and preferably from 1% by weight to 8% by weight.

Suitable water-soluble inorganic builder materials are, in particular, polymeric alkali metal phosphates, which may be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of these are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid agents, in particular from 1% by weight to 5% by weight, are used as what are water-insoluble, water-dispersible inorganic builder materials. , inserted puts. Among these, preferred are the detergent grade crystalline sodium aluminosilicates, especially zeolite A, P and optionally X. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Their calcium binding capacity, according to the information of the German Patent DE 24 12 837 can be determined, is usually in the range of 100 to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na ₂ Si _x O _{2x + 1} · are used yH ₂ O, in which x, the so-called module, 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 phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred. Also prepared from amorphous alkali silicates, practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used in inventive compositions. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention. In a preferred embodiment of inventive compositions, a granular compound of alkali metal silicate and alkali, such as is available, for example under the name Nabion ^® 15 commercially. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1. In agents containing both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.

builders are in the washing or cleaning agents according to the invention preferably in amounts of up to 60% by weight, in particular of 5% by weight to 40 wt .-%, while the inventive Disinfectants preferably free from the only components water hardness complexing builder substances and preferably not more than 20% by weight, in particular of 0.1 Wt .-% to 5 wt .-%, of heavy metal complexing substances, preferably from the group comprising aminopolycarboxylic acids, aminopolyphosphonic acids and hydroxypolyphosphonic acids and their water-soluble Salts and mixtures thereof.

• a) 5 Gew.-% bis 35 Gew.-% Citronensäure, Alkalicitrat und/oder Alkalicarbonat, welches auch zumindest anteilig durch Alkalihydrogencarbonat ersetzt sein kann,
• b) bis zu 10 Gew.-% Alkalisilikat mit einem Modul im Bereich von 1,8 bis 2,5,
• c) bis zu 2 Gew.-% Phosphonsäure und/oder Alkaliphosphonat,
• d) bis zu 50 Gew.-% Alkaliphosphat, und
• e) bis zu 10 Gew.-% polymerem Polycarboxylat,

wobei die Mengenangaben sich auf das gesamte Wasch-beziehungsweise Reinigungsmittel beziehen. Dies gilt auch für alle anderen Mengenangaben, sofern nicht ausdrücklich anders angegeben.In a preferred embodiment of the invention, an agent according to the invention has a water-soluble builder block. The use of the term "builder block" is intended to express that the agents do not contain any further builder substances than those which are water-soluble, ie all builder substances contained in the agent are combined in the "block" characterized in this way, at most the amounts of Substances are excluded, which may be present as impurities or stabilizing additives in small amounts in the other ingredients of the products commercially. The term "water-soluble" is to be understood as meaning that the builder block dissolves without leaving a residue at the concentration which results from the use amount of the agent containing it in the customary conditions. Preferably, at least 15 wt .-% and up to 55 wt .-%, in particular 25 wt .-% to 50 wt .-% of water-soluble builder block in the inventive compositions. This is preferably composed of the components

• a) 5% by weight to 35% by weight of citric acid, alkali citrate and / or alkali metal carbonate, which may also be replaced at least proportionally by alkali metal bicarbonate,
• b) up to 10% by weight of alkali silicate having a modulus in the range of 1.8 to 2.5,
• c) up to 2% by weight of phosphonic acid and / or alkali phosphonate,
• d) up to 50% by weight of alkali metal phosphate, and
• e) up to 10% by weight of polymeric polycarboxylate,

wherein the quantities are based on the entire detergent or cleaning agent. This also applies to all other quantities, unless expressly stated otherwise.

In a preferred embodiment of the invention Agent contains the water-soluble builder block at least 2 of components b), c), d) and e) in quantities greater 0% by weight.

Regarding Component a) are in a preferred embodiment Inventive agent 15% by weight to 25% by weight Alkali carbonate, which at least partially by alkali metal bicarbonate may be replaced, and up to 5 wt .-%, in particular 0.5 wt .-% contain up to 2.5 wt .-% citric acid and / or alkali citrate. In an alternative embodiment according to the invention Agents are as component a) 5 wt .-% to 25 wt .-%, in particular 5 wt .-% to 15 wt .-% citric acid and / or alkali citrate and up to 5% by weight, in particular 1% by weight to 5% by weight, of alkali metal carbonate, which at least partially replaced by alkali metal bicarbonate can be included. If both alkali carbonate and alkali bicarbonate are present, the component a) alkali carbonate and alkali metal bicarbonate preferably in a weight ratio of 10: 1 to 1: 1.

Regarding Component b) are in a preferred embodiment Inventive agent 1 wt .-% to 5 wt .-% Alkali silicate with a modulus in the range of 1.8 to 2.5 included.

Regarding component c) are in a preferred embodiment Inventive agent 0.05% by weight to 1% by weight Phosphonic acid and / or Alkaliphosphonat included. Under Phosphonic acids are also optionally substituted Alkylphosphonic understood that also several phosphonic acid groups could have (so-called polyphosphonic acids). They are preferably selected from the hydroxy and / or Aminoalkylphosphonsäuren and / or their alkali metal salts, such as for example, dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenyl-methanediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediamine tetrakis (methylenephosphonic acid), Diethylenetriamine-penta (methylenephosphonic acid) (DPTMP) and acylated derivatives of phosphorous acid, which are also present in Any mixtures can be used.

With regard to component d), in a preferred embodiment of the composition according to the invention, 15% by weight to 35% by weight of alkali metal phosphate, in particular trisodium polyphosphate, are contained. Alkaliphosphat is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to high molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance. Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and pass on Madrell's salt. NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt of density 2.33 gcm ^-3 , has a melting point of 253 ° (decomposition to form (KPO ₃ ) _x , potassium polyphosphate) and is slightly soluble in water. Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water. Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises z. Example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry. Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , Melting point 94 ° with loss of water). For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4. Condensation of the NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher molecular weight sodium and potassium phosphates, which can be cyclic representatives, the sodium or Kaliummetaphosphatem and chain types, the sodium or potassium as potassium phosphates can distinguish. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches and Madrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates. The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are according to the invention exactly like sodium tripolyphosphate, Potassium tripolyphosphate or mixtures of these two can be used; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

Regarding component e) are in a preferred embodiment Inventive agent 1.5% by weight to 5% by weight polymeric polycarboxylate, in particular selected from the Polymerization or copolymerization of acrylic acid, Contain methacrylic acid and / or maleic acid. Under these are the homopolymers of acrylic acid and among these again those with an average molecular weight in the range of 5,000 D to 15,000 D (PA standard) is particularly preferred.

As use in the detergents enzymes other than the above oxidase are those from the class of proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and their mixtures, for example proteases such as BLAP ^®, Optimase.RTM ^®, Opticlean ^®, Maxacal ^®, Maxapem ^®, Alcalase ^®, Esperase ^®, Savinase ^®, Durazym ^® and / or Purafect ^® OxP, amylases, such as Termamyl ^®, amylase LT ^®, Maxamyl ^®, Duramyl ^® and / or Purafect ^® OxAm, lipases as Lipolase ^®, Lipomax ^®, Lumafast ^® and / or Lipozym ^®, cellulases such as Celluzyme ^® and / or Carezyme ^®. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents. The optionally used enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in the detergents, cleaners and disinfectants according to the invention in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight, particular preference being given to stabilizing enzymes which are stabilized against oxidative degradation become.

In a preferred embodiment of the invention the agent 5 wt .-% to 50 wt .-%, in particular 8-30 wt .-% anionic and / or nonionic surfactant, up to 60 wt .-%, in particular 5-40% by weight of builder substance and 0.2% by weight to 2% by weight Enzyme selected from the proteases, lipases, cutinases, Amylases, pullulanases, mannanases, cellulases, oxidases and peroxidases as well as their mixtures.

To set a desired, by mixing the other components while admitting non-self-adding pH of water which is preferably in the range from 5 to 12, in particular 7 to 11 and particularly preferably 8 to 10 (based on the wash liquor) in the process according to the invention, the agents according to the invention can be system- 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 mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight, in the compositions according to the invention.

Soil release polymers, often referred to as "soil release" agents or because of their ability to impart soil repellency to the treated surface, for example fiber, are, for example, nonionic or cationic cellulose derivatives. The particularly polyester-active soil release polymers include copolyesters of 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. Preferred soil release polyesters include those compounds which are formally accessible by esterification of two monomeric moieties, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR ²¹ -) _a OH, also known as polymeric Diol H- (O- (CHR ²¹ -) _a ) _b OH may be present. Therein, Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ^{21 is} hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, in the polyesters obtainable from these, both monomer diol units -O- (CHR ²¹ -) _a O- and also polymeric diol units ( O- (CHR ²¹ -) _a ) _b O-. 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 of 4 to 200, especially 12 to 140. The molecular weight or the average molecular weight or the maximum molecular weight distribution of preferred soil release polyester is in the range of 250 to 100,000, especially 500 to 50,000 The acid underlying the remainder Ph 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 alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable. If desired, in place of the monomer HOOC-Ph-COOH small proportions, in particular not more than 10 mol% based on the proportion of Ph having the meaning given above, of other acids having at least two carboxyl groups may be included in the soil release-capable polyester. These include, for example, alkylene 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 ²¹ -) _a OH include those in which R ^{21 is} hydrogen and a is a number from 2 to 6, and those in which a is 2 and R ¹¹ is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected. Among the latter diols, those of the formula HO-CH ₂ -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 having an average molecular weight in the range of 1000 to 6000. If desired, these polyesters may also be endgruppenverschlossen, with alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids in question as end groups. The ester groups bound by end groups alkyl, alkenyl and Arylmonocarbonsäuren with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms, based. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid, arachidic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid , The end groups may also be based on hydroxymonocarboxylic acids having 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 may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. Preferably, the number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is 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 poly ethylene glycol units have molecular weights of 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.

To for use in the invention Means for the laundry of textiles eligible In particular, color transfer inhibitors belong Polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers.

The Composition according to the invention for use in textile washing may contain anti-wrinkle agents since fabrics, in particular from rayon, wool, cotton and their mixtures, for Wrinkles can tend because the individual fibers against bending, Buckling, pressing and crushing sensitive to the grain direction are. These include, for example, synthetic products based on fatty acids, fatty acid esters, Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products on the Base of lecithin or modified phosphoric acid ester.

graying have the job of the hard surface and in particular suspended from the textile fiber dirt suspended in the fleet to keep. For this purpose, water-soluble colloids are usually more organic Nature suitable, for example starch, glue, gelatin, Salts of ether carboxylic acids or ether sulfonic acids starch or cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water-soluble, Acidic group-containing polyamides are for this purpose suitable. Furthermore, other than the above-mentioned starch derivatives can be used use, for example, aldehyde levels. To be favoured Cellulose ethers, such as carboxymethyl cellulose (Na salt), methyl cellulose, Hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, Methylhydroxypropylcellulose, methylcarboxymethylcellulose and their Mixtures, for example in amounts of 0.1 to 5 wt .-%, based on the means used.

The Means can be optical brighteners, among these particular Derivatives of Diaminostilbendisulfonsäure or their alkali metal salts. For example, salts are suitable 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar compounds, instead of the morpholino group a diethanolamino group, a methylamino group, an anilino group or carry a 2-methoxyethylamino group. Furthermore you can Brighteners of the type of substituted diphenylstyrene may be present for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Mixtures of the aforementioned optical brightener can be used.

In particular, when used in automatic washing and cleaning processes, it may be advantageous to add conventional foam inhibitors to the compositions. As foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes. The foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.

In agents according to the invention can also Active ingredients to prevent the tarnishing of objects made of silver, so-called silver corrosion inhibitors. Preferred silver corrosion inhibitors are organic disulfides, dihydric phenols, trihydric phenols, optionally alkyl or aminoalkyl-substituted triazoles such as benzotriazole and cobalt-, Manganese, titanium, zirconium, hafnium, vanadium or cerium salts and / or complexes in which the said metals in one of the oxidation states II, III, IV, V or VI are present.

One Composition according to the invention can be used for reinforcement the disinfecting effect against special germs in addition to the previously mentioned ingredients usual antimicrobial Contain active ingredients. Such antimicrobial additives are in agents according to the invention, preferably in amounts not more than 10% by weight, in particular from 0.1% by weight to 5% Wt .-%, contained.

In addition, a hard surface cleaning agent according to the invention may contain abrasive constituents, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and glass microspheres and mixtures thereof. Abrasive substances are preferably not more than 20% by weight, in particular from 5% by weight to 15% by weight, in the cleaning agents according to the invention.

Examples

Primary washing power and wet tensile strength loss were tested in a miniaturized washing test. It was worked with a simplified wash liquor consisting of H ₂ O ₂ and catalyst (1,4,7-Triazacyclononan manganese complex, MnTACN). Solutions of 0.35 g / l H ₂ O ₂ and 4.1 mg / l MnTACN and in each case 0, 0.5 or 1.5 mmol / l of the complexing agent 1-hydroxyethane-1,1-diphosphonic acid (HEDP ) in distilled water (0 ° dH) whose pH values had been adjusted to pH 10 and pH 11, respectively, by means of NaOH. added.

For the primary washing performance measurements were cotton substrates, which had been provided with a standardized tea soiling, 30 minutes at 30 ° C in the respective solutions treated. The treated fabric substrate was under running Washed out water and then dried and color measurement. The following table shows the brightness value of the cotton measuring pieces specified.

For the measurement of wet tensile strength loss was cotton strips with defined width (number of threads) 20 times over each 45 minutes at 60 ° C in the respective solutions treated. The strips were dried and placed in a mesh solution immersed before using a tensile tester with constant tensile test speed were torn. The Tear strength of the treated cotton was with the tearing force compared to the untreated cotton and the wet tear strength loss calculated in%.

It were for the primary washing power and the wet tear power loss each 5-fold determinations carried out. In the following Table, the mean values are given.

pH bleaching power [Y value] Wet tensile strength loss [%] H ₂ O ₂ + MnTACN 10 58.4 49 H ₂ O ₂ + MnTACN + 0.5 mM HEDP 10 55.8 18 H ₂ O ₂ + MnTACN + 1.5 mM HEDP 10 55.8 16 H ₂ O ₂ + MnTACN 11 66.8 94 H ₂ O ₂ + MnTACN + 1.5 mM HEDP 11 65.7 55

Using instead of water at 0 ° dH at 16 ° dH, the results of the wet tensile strength loss test for H ₂ O ₂ + MnTACN and H ₂ O ₂ + MnTACN + 1.5mM HEDP were not significantly different from those obtained using Water at 0 ° dH.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• DE 19529905 A1 [0007]
• - DE 19620267 A1 [0007]
• DE 19536082 A1 [0007]
• - DE 19605688 A1 [0007]
• - DE 19620411 A1 [0007]
• - DE 4416438 A1 [0007]
• EP 0272030 A2 [0007]
• EP 0693550 A2 [0007]
• EP 0392592 A2 [0007]
• EP 0443651 A2 [0007]
• EP 0458397 A2 [0007]
• EP 0458398 A2 [0007]
• EP 0549271 A1 [0007]
• EP 0549272 A1 [0007]
• - EP 0544490 A1 [0007]
• - EP 0544519 A2 [0007]
• - DE 2412837 [0031]

Claims (17)

A process for washing textiles in the presence of a persoxy-containing bleaching agent and a bleach-enhancing transition metal complex, characterized in that it is carried out at a water hardness of 0 ° dH to 3 ° dH Method according to claim 1, characterized in that that it is at temperatures in the range of 10 ° C to 95 ° C, especially in the range of 20 ° C to 40 ° C performed becomes. Method according to claim 1 or 2, characterized that cation-complexing, cation-exchanging or cation-precipitating Substances, especially in larger quantities, than would be necessary to increase the water hardness in the wash liquor to a value in the range of 0 ° dH to 3 ° dH bring, use. Method according to claim 3, characterized that phosphonates, complexing polymers, especially polycarboxylates, ion-exchanging substances and / or complexing surface-active Substances uses. Method according to claim 4, characterized in that that the concentration of phosphonate in the wash liquor is 0.01 mmol / l to 10 mmol / l, in particular 0.1 mmol / l to 2 mmol / l. Method according to claim 4 or 5, characterized that the concentration of complexing polymer in the wash liquor 0.001 g / l to 5 g / l, in particular 0.01 g / l to 1 g / l. Method according to one of claims 4 to 6, characterized in that the concentration of ion-exchanging Substance in the wash liquor 0.01 g / l to 100 g / l, in particular 0.1 g / l to 10 g / l. Method according to one of claims 4 to 7, characterized in that the concentration of complexing surfactant in the wash liquor preferably 0.01 g / l to 50 g / l, in particular 0.02 g / l to 10 g / l. Method according to one of claims 1 to 8, characterized in that the peroxygen concentrations (calculated as H ₂ O ₂ ) in the wash liquor in the range of 0.001 g / l to 10 g / l, in particular 0.1 g / l to 1 g / l is. Method according to one of claims 1 to 9, characterized in that the concentration of bleach-enhancing transition metal complex in the wash liquor in the range of 0.1 μmol / to 100 μmol / l, in particular 1 μmol / 1 to 20 μmol / l. Method according to one of claims 1 to 10, characterized in that it is not the finished bleach-enhancing transition metal complex, but separately one or more ligands, which in the washing process with a transition metal in situ, a bleach-enhancing transition metal complex can form and insert the transition metal also separately in the form of a salt or not bleach-enhancing Complex dosed or it in the washing process as a component of the service water used for this purpose or over brings the textile to be cleaned. Use of cation-complexing, cation-exchanging or cation-precipitating substances to reduce textile damage of bleach-enhancing transition metal complexes when washing textiles. Textile-friendly detergent containing pers oxygen-containing Bleaching agent, bleach-enhancing transition metal complex or one or more ligands which undergo a transition metal washing process in situ a bleach-enhancing transition metal complex and cation-complexing, cation-exchanging and / or cation-precipitating substance. A method, use or composition according to any one of claims 1 to 13, characterized in that the bleach-enhancing transition metal complex compound is a metal complex of the formula (I), [L _n M _m X _p ] ^z Y _q (I) wherein M means manganese or iron or mixtures of these metals, which may be in the oxidation state II, III, IV or V, or in mixtures thereof, n and m are independently integers having a value of 1 to 4, X is a coordinating or bridging Represents species, p is an integer from 0 to 12, Y is a counterion whose type depends on the charge z of the complex, which may be positive, zero or negative, q = z / [charge Y], and L is a ligand which is a macrocyclic organic molecule of the general formula

wherein each of R ¹ and R ^{2 may be} zero, H, alkyl or aryl, optionally substituted; t and t 'are independently 2 or 3; D and D ^{1 are} independently N, NR, PR, O or S, wherein R is H, alkyl or aryl, optionally substituted; and s is an integer having a value of 2 to 5, wherein, when D = N, one of the heterocarbon bonds bonded thereto is unsaturated, resulting in the formation of an N = CR ¹ portion. Method, use or means after Claim 14, characterized in that the complex of formula (I) with M = manganese and L = 1,4,7-triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl-1,5,9-triazacyclododecane or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane equivalent. A method, use or composition according to any one of claims 1 to 13, characterized in that the bleach-enhancing transition metal complex compound is a manganese complex of formula (II),

in R ¹⁰ and R ¹¹ independently of one another represent hydrogen, a C _1-18 -alkyl group, a group -NR ¹³ R ¹⁴ , a group -N ⁺ R ¹³ R ¹⁴ R ¹⁵ or a group

R ^{12 is} hydrogen, -OH, or a C _1-18 alkyl group, R ¹³ , R ¹⁴ and R ^{15 are} independently hydrogen, a C _1-4 alkyl or hydroxyalkyl group, and X is halogen and A is a charge-balancing anion is, depending on its charge and the nature and number of other Laungen, in particular the charge of the manganese central atom, also missing or may be present several times. Method, use or means after one of claims 1 to 13, characterized in that bleach-enhancing transition metal complex with phosphonate, each of which is present as a water-containing preparation can, premixed and optionally isolated the mixed complex as your own substance.