EP2411496A1 - Gentle bleaching agent - Google Patents

Abstract

The aim of the invention is reduce the damage to material containing cellulose during the bleaching thereof, by using bleaching catalysts, without significantly affecting the bleaching performance. This is achieved essentially by a method for the bleach treatment of material containing cellulose in the presence of a bleaching agent containing peroxygen and a bleach-enhancing transition metal complex, said method being carried out in the presence of a saccharide polymer carrying carboxy groups.

Description

 Gentle bleach

The present invention relates to the use of carboxy-group carrying saccharide polymer for reducing the damage of bleach-enhancing transition metal complexes in treating cellulosic material, particularly in the washing of textiles, a gentle process for treating cellulosic material in the presence of a pers oxygen-containing bleaching agent and a bleach-enhancing transition metal complex and agents which oxygen-containing bleaching agent, bleach-enhancing transition metal complex and carboxy-group-carrying saccharide polymer.

Inorganic peroxygen compounds, particularly hydrogen peroxide, and solid persompound 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 disinfection 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 ⁰ 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 ⁰ C substantially the same effects as with the peroxide solution alone at 95 ⁰ C. The damage to the tissue remains in a frame acceptable to the consumer.

In the pursuit of energy-saving washing and bleaching win in recent years, application temperatures well below 60 ⁰ C, especially below 45 ⁰ C down to the cold water temperature in importance.

At these low temperatures, the effect of the previously known activator compounds usually decreases noticeably. There was therefore no lack of ambition for this development of more effective bleaching systems. A starting point for this is the use of hydrogen peroxide-yielding compounds together with transition metal salts and complexes as so-called bleach catalysts. These, however, presumably because of the high reactivity of the resulting from them and the peroxygen compound oxidizing intermediates, but the risk of oxidative textile damage. The use of such transition metal catalysts in detergents has been hitherto difficult in practice, because then the damage to the tissue is significantly higher than in a peracid-forming conventional system of bleach and bleach activator. The same applies mutatis mutandis to bleaching operations that are carried out in the production of cellulosic material, such as pulp or paper.

The present invention aims at the bleaching treatment of cellulose-containing material, for example when washing cotton-containing textiles, to reduce the damage to the cellulose-containing material, for example a cotton-containing textile, when using bleach-active catalysts, without significantly influencing the bleaching performance.

The invention in a first aspect is a process for the bleaching treatment of cellulose-containing material, in particular in the production of pulp or paper or in the washing of cotton-containing textiles, in the presence of a persoxy-containing bleaching agent and a bleach-enhancing transition metal complex, which is characterized in that Presence of carboxy-group carrying saccharide polymer is performed.

Preferably, the carboxy-group carrying saccharide polymer is selected from alginate, pectin, pectinate and mixtures of at least two of these.

Alginic acid or its salts are naturally occurring ingredients of brown algae (Phaeophycea) in which they are present as cell wall components. Alginic acids are acidic, carboxy group-containing polysaccharides having a relative molecular weight M _R of about 200,000, consisting of d-mannuronic acid and I-guluronic acid in different ratios, which are linked via 1, 4-glycosidic bonds. Alginates which can be used according to the invention are, in particular, the alkali metal and alkaline earth metal salts of alginic acid, it not being necessary for all the carboxy groups of the alginic acid to be present in salt form. The sodium, potassium, ammonium and magnesium alginates are readily soluble in water. The viscosity of alginate solutions depends inter alia on the molecular weight and on the counterion. For example, calcium alginates form thermo-reversible gels at certain proportions. Sodium alginates give more or less highly viscous solutions in water. Pectins are naturally occurring polysaccharides whose main constituent (usually at least 65% by weight) is α-D-galactonic acid. The galacturonic acid monomers are connected to one another via α-1, 4, usually also to a small extent via β-1,4-glycosidic bonds, and thus form the backbone of the pectin molecule. The linear backbone is periodically interrupted by 1, 2 bonds with α-L-rhamnose. The rhamnose units in natural pectins carry oligomeric side chains from the sugars arabinose, galactose and / or xylose. The neutral sugar side chains can in turn be subdivided into arabinans, galactans and arabinogalactan-I and arabinogalactan-II, which is linked to proteins. The lengths of the side chains are usually between one and 50 sugar units. In industrial extraction of pectins, these side chains are largely lost. The hydroxyl groups on C2 and / or C3 of the galacturonic acid units are acetylated to a small extent or substituted by further neutral sugars, such as D-galactose, D-xylose, L-arabinose, L-rhamnose. A portion of the carboxyl groups of Polygalactu ronsäure is usually esterified with methanol. The degree of esterification and acetylation varies with the origin of the pectin. The action of aqueous alkaline solutions or pectinase on pectin gives rise to pectosic acid and then pectinic acid. Pectic acid forms a colorless mass, hardly in cold water, in hot, heavy, in alcohol not soluble in the solutions of neutral salts; It reacts and tastes sour and forms with the alkalis soluble, with other metals insoluble, gelatinous salts. By addition of calcium ions to the galacturonic acid units, the largely water-insoluble calcium pectinate is formed. Pectinates which can be used according to the invention are, in particular, the alkali metal salts and alkaline earth metal salts of pectinic acid, the alkali metal salts being particularly preferred and not all carboxy groups of the pectic acid having to be present in salt form.

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 manganese, iron, cobalt, ruthenium or molybdenum-salene complexes, manganese , Iron, cobalt, ruthenium or molybdenum carbonyl complexes, manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, cobalt, iron, , Copper and ruthenium ammine complexes, and iron or manganese complexes with polyazacycloalkane ligands such as TACN.

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 in Oxidation state II, III, IV or V may be present, or in mixtures thereof, n and m are independently integers having a value of 1 to 4, X represents a coordinating or bridging 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

D - (CR ¹ R ² ) _t -t D * ~ (CR ¹ R ² ) £ τ4 "

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 coordinating ion or bridging molecule or 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 of these. When the charge z is positive, Y is an anion such as chloride, bromide, iodide, nitrate, perchlorate, rhodanide, hexafluorophosphate, sulfate, alkyl sulfate, alkyl sulfonate or acetate; when the charge z is negative, Y is a cation, such as an alkali ion, ammonium ion or alkaline earth metal ion. The 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 a further preferred embodiment, the bleach-enhancing transition metal complex compound corresponds to the general formula (II),

(H) in the R ¹⁰ and R ¹¹ are each independently hydrogen, a C- _M s-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 Ci_i ₈ alkyl group, R ^13, R X is ¹⁴ and R ¹⁵ independently represents halogen, hydrogen, an alkyl or hydroxyalkyl group and CI_ ₄ and A is a charge-compensating anion ligand is, which depending on its charge and the nature and number of other charges, in particular the charge of the manganese central atom, also missing or may be present several times. Manganese in it as well as in the complexes according to formula (I) can have the oxidation state II, IM, IV or V. 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.

If desired, the process according to the invention can be carried out at temperatures in the range from 10 ^° C. to 95 ^° C. The temperature is preferably in the range from 20 ^° C. to 40 ^° C.

If desired, the process according to the invention can be carried out at pH values in the weakly acidic to alkaline range, in particular in the range from pH 5 to pH 12, preferably pH 8 to pH 11.

In a method according to the invention, preferably concentrations of 0.0001 g / l to 2 g / l, in particular 0.01 g / l to 1 g / l carboxy group-carrying saccharidic polymer in the aqueous treatment solution.

In a textile washing process according to the invention preferred peroxygen concentrations (calculated as H ₂ O ₂ ) in the wash liquor are in the range of 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 0.5 μmol / l to 25 μmol / l.

The process according to the invention can be implemented, for example, by mixing peroxygen-containing bleach, bleach-enhancing transition-metal complex and the carboxy-group-carrying saccharidic polymer separately from a treatment solution for each cellulose-containing material, for example a washing solution, which may contain a conventional detergent added. It is also possible not to use the final bleach-enhancing transition metal complex but separately one or more ligands which can form a bleach-enhancing transition metal complex in situ with a transition metal; The transition metal can then also be metered separately in the form of a salt or non-bleach-enhancing complex, or it is in the process as part of the process water used for this purpose or on the cellulosic material to be treated, in textiles to be cleaned, for example as part of the soiling to be removed in introduced the process. It is possible and preferred, the bleach-enhancing transition metal complex and the carboxy-group-carrying saccharidic polymer at the same time, in particular preferably present as a water-containing or aqueous solution present as premix together.

A second aspect of the invention is the use of carboxy-group carrying saccharide polymer to reduce damage to cellulosic material, such as cotton-containing textiles, by the presence of bleach-enhancing transition metal complexes in the bleaching treatment of cellulosic material, for example, in the washing of cotton-containing textiles.

Surprisingly, it has been found that the use of the carboxy-group-carrying saccharidic polymer not only reduces the damage to the cellulose-containing material, but also improves the bleaching performance of the bleaching agent-containing bleaching agent and bleaching-enhancing transition metal complex. Another object of the invention is therefore the use of carboxy-group-carrying saccharide polymer for improving the bleaching performance of bleach-enhancing transition metal complex in aqueous solutions containing bleach containing peroxygen.

In a further preferred embodiment of the invention, an agent comprising peroxygen-containing bleach, bleach-enhancing transition metal complex, or a ligand capable of forming a bleach-enhancing transition metal complex in situ with a transition metal in situ and carboxy-containing saccharide polymer is employed. Such a textile-sparing detergent is a further object of the invention.

Detergents according to the invention, which may be present in solid form or as liquids or pastes, can be used as such in mechanical or manual washing processes, but can also be used as detergent additives and / or as laundry or textile pretreatment agents. 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 A further field of application of such agents is the removal of local soiling from otherwise clean surfaces, so that a more complex washing or cleaning process of the corresponding overall structure, be it a piece of clothing or a carpet or a piece of furniture upholstery, can be avoided can be in a simple manner an inventive means, optionally together with an amount of water which is insufficient for complete dissolution of the agent, apply to the textile surface or its part to be cleaned, optionally mechanical energy, for example by friction with a cloth or a sponge, and after a period of time to be determined by the user, remove the agent and the oxidatively broken stain by washing with water, for example with the help of a moistened cloth or sponge.

The agents according to the invention preferably comprise from 0.01% by weight to 0.5% by weight, in particular from 0.02% by weight to 0.3% by weight, of bleach-enhancing transition metal complex. Alternatively or optionally in addition, the agent according to the invention can also contain only one or more ligands which can form a bleach-enhancing transition metal complex in situ in the washing process with a transition metal. The transition metal can also be present in the detergent in the form of a salt or non-bleach-enhancing complex or is introduced into the washing process as part of the process water used for this purpose or via the textile to be cleaned, for example as part of the soiling to be removed.

The detergents and cleaners according to the invention can, in addition to the peroxygen-containing bleach, the bleach-enhancing transition metal complex or the ligand, which can form the bleach-enhancing transition metal complex in situ, and carboxy-group-carrying saccharide polymer in principle contain all known ingredients customary in such agents. The detergents and cleaners according to the invention may in particular be builders, surface-active surfactants, enzymes, sequestering agents, electrolyte regulators, pH regulators, polymers with special effects, such as soil release polymers, dye transfer inhibitors, grayness inhibitors, crease-reducing active ingredients and shape-retaining active substances, and further auxiliaries, such as optical Brightener, foam regulators, additional peroxygen activators, dyes and fragrances included. Suitable peroxygen compounds for use in the process according to the invention, in the use according to the invention and in agents according to the invention are in particular organic peracids or persistent salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing conditions, including alkali metal perborate , Alkali percarbonate, persilicate and / or persulfate such as caroate include, into consideration. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. The addition of small amounts of known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful. An agent according to the invention preferably contains 15% by weight to 50% by weight, in particular 18% by weight to 35% by weight, of peroxygen-containing bleaching agent, in particular alkali percarbonate. Alternatively or optionally additionally, in the process according to the invention, hydrogen peroxide can also be produced by an enzymatic system, namely an oxidase in combination with its substrate, which in a preferred embodiment of the invention is a constituent of the agent according to the invention and partially or preferably entirely replaces the persoxy-containing bleaching agent therein can.

In addition to the bleach-enhancing transition metal complex compound, further compounds known as bleach-activating agents, in particular conventional bleach activators, that is to say compounds which are optionally substituted perbenzoic acid under perhydrolysis conditions and / or peroxocarboxylic acids having 1 to 10 carbon atoms, in particular 2 to 4, may be present in the compositions according to the invention C atoms arise, are used. Suitable are customary bleach activators which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonates , in particular nonanoyloxy or isononanoyloxybenzenesulfonate, N-acylated capro- or valerolactams, in particular N-acetylcaprolactam, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose, as well as acetylated, optionally N-alkylated glucamine and gluconolactone. It is also possible to use peritrile-forming nitriles, such as 4-morpholinecarbonitrile or acetonitriles bearing ammonium groups, under perhydrolysis conditions. Preferably, however, the agents according to the invention are free from such conventional bleach activators. The compositions of the invention may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof come into question. Suitable nonionic surfactants are, in particular, alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols having in each case 12 to 18 C atoms in the alkyl moiety and 3 to 20, preferably 4 to 10, alkyl ether groups. Furthermore, corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which, with regard to the alkyl moiety, correspond to the long-chain alcohol derivatives mentioned, and of alkylphenols having from 5 to 12 carbon atoms in the alkyl group rest usable.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form. Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation. Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.

Such surfactants are present in the detergents or detergents according to the invention in amounts of preferably from 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 methylglycine diacetic 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, especially the accessible by oxidation of polysaccharides or dextrins polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. 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, each 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 acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight. As water-soluble organic builders, it is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer. 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 alkylsulfonic 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.

If desired, such organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight 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. As water-insoluble, water-dispersible inorganic builder materials are in particular crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40 wt .-% and in liquid agents, in particular from 1 wt .-% to 5 wt .-%, used. 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, which can be determined according to the specifications of the German patent DE 24 12 837, is generally 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 of} less than 0.95, in particular of 1: 1, 1 to 1: 12, and may be amorphous or crystalline. 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 y are used _{2x + 1} H ₂ O, in which x, known as the modulus, an integer of 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 y H ₂ O) are preferred. Also prepared from amorphous alkali silicates, practically anhydrous crystalline alkali 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 of 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention. In a preferred embodiment of compositions according to the invention, a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, in each case based 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 preferably present in the detergents or cleaners according to the invention in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight, while the disinfectants according to the invention are preferably free from the complexing only of the components of the water hardness Builders are and preferably not more than 20 wt .-%, in particular from 0.1 wt .-% to 5 wt .-%, of heavy metal complexing substances, preferably from the group comprising aminopolycarboxylic, Aminopolyphosphonsäuren and hydroxy polyphosphonic and their water-soluble salts and their Mixtures, included.

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 Excluding substances are, which may be commercially available as impurities or stabilizing additives in small amounts in the other ingredients of the agent. 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 of the agent containing it under the usual conditions, preferably at least 15% by weight and up to 55% by weight in the agents according to the invention, which preferably consists of the components a) 5% by weight to 35% by weight of citric acid, alkali citrate and, in particular, 25% by weight to 50% by weight of water-soluble builder block b) up to 10% by weight of alkali metal silicate with a modulus in the range from 1.8 to 2.5, c) up to 2% by weight of phosphonic acid and / or alkali metal carbonate, which may also be replaced at least proportionally by alkali metal bicarbonate or Alkaliphosphonat, d) up to 50 wt .-% alkali phosphate, and e) up to 10 wt .-% of polymeric polycarboxylate, wherein the amounts are based on the total detergent or cleaning agent .This also applies to all other Mengenanga unless expressly stated otherwise.

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

With regard to component a), in a preferred embodiment of the composition according to the invention, 15% by weight to 25% by weight of alkali carbonate, which may at least partly be replaced by alkali metal hydrogencarbonate, and up to 5% by weight, in particular 0.5% by weight. % to 2.5% by weight of citric acid and / or alkali citrate. In an alternative embodiment of compositions according to the invention 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 wt .-%, in particular 1% by weight to 5% by weight of alkali metal carbonate, which may at least partly be replaced by alkali metal bicarbonate. If both alkali metal carbonate and alkali metal bicarbonate are present, the component comprises a) alkali carbonate and alkali metal bicarbonate, preferably in a weight ratio of 10: 1 to 1: 1.

With regard to component b), in a preferred embodiment of the composition according to the invention 1 wt .-% to 5 wt .-% alkali metal silicate with a modulus in the range of 1, 8 to 2.5 included.

With regard to component c), in a preferred embodiment, agents according to the invention contain from 0.05% by weight to 1% by weight of phosphonic acids and / or alkali metal phosphonate. Phosphonic acids also include optionally substituted alkyl and aryl phosphonic acids, such as phenylphosphonic understood, which may also have several phosphonic acid groups (so-called polyphosphonic acids). They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali salts, for example dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1 -Hydroxyethane-1, 1-diphosphonic acid (HEDP), amino-tris (methylenephosphonic acid), and acylated derivatives of phosphorous acid, which can also be used in any mixtures.

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 the 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 like ^'3 , melting point 60 °) and monohydrate (density 2.04 like ^{' 3} ). Both salts are white powders which are very slightly soluble in water and which lose the 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 primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt of density 2.33 ^{'' 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 like ^'3 , water loss at 95 °), 7 moles (density 1, 68 like ^{' 3} , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1, 52 like ^"3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and goes on stronger heating in the diphosphate Na ₄ P ₂ O _7. Disodium hydrogen phosphate is by neutralization of phosphoric acid with sodium carbonate solution under Use of 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, sodium tertiary phosphate, Na ₃ PO ₄ , are colorless crystals, which are soluble in water as dodecahydrate a density of 1, 62 like ^'3 and a melting point of 73-76 ⁰ C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) has a melting point of 100 ⁰ C and in anhydrous form (corresponding to 39 -40% P ₂ O ₅ ) like a density of 2.536 ^'3 Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporation of a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. tripotassium (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56, preferably ³ , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for 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 like ^"3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1, 815-1, 836 like ^'3 , melting point 94 ° Substances are colorless crystals which are soluble in water with an alkaline reaction Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying. the decahydrate complexes heavy metal salts and hardness salts 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 represents ^{gcm -3} , which is soluble in water, wherein the pH of the 1% solution at 25 ° is 10.4 By condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ arise higher molecular sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphatem and chain types, the sodium or Kaliumpolyphosphate. In particular, for the latter are a variety of names in use: fused or annealed 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:

(NaPOs) ₃ + 2 KOH ^ Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O These are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; 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 also be used according to the invention.

With regard to component e), in a preferred embodiment of the composition according to the invention 1.5 to 5 wt .-% polymeric polycarboxylate, in particular selected from the polymerization or copolymerization of acrylic acid, methacrylic acid and / or maleic acid. Among these, particularly preferred are the homopolymers of acrylic acid and, among these, those having an average molecular weight in the range from 5,000 D to 15,000 D (PA standard).

As enzymes which can be used in the compositions, apart from the abovementioned oxidase, those from the class of the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof are suitable, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Alcalase®, Esperase®, Savinase®, Durazym® and / or Purafect® OxP, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such 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 contains 5% by weight to 50% by weight, in particular 8-30% by weight of anionic and / or nonionic surfactant, up to 60% by weight, in particular 5-40% by weight. % Builder and 0.2% to 2% by weight of enzyme selected from the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, oxidases and peroxidases, and mixtures thereof.

For setting a desired, by the mixture of the other components in the addition of water not automatically resulting pH value, the compositions of the invention system and environmentally friendly acids, especially 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 wt .-%, in particular from 1, 2 wt .-% to 17 wt .-%, contained in the inventive compositions.

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. 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 has the value 2 and R ^{11 is selected} from hydrogen and the alkyl radicals having 1 to 10, in particular 1 to 3, carbon atoms. 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. Polyethylene glycol having an average molecular weight in the range from 1000 to 6000 is particularly preferred among the polymeric diols. If desired, these polyesters may also be end-capped, alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups. The ester groups bonded via end groups 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, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linoleic acid, linolenic acid , Elaeostearic 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 polyethylene glycol units have molecular weights of 750 to 5,000 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.

Polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers belong to the color transfer inhibitors which are suitable for use in laundry detergents according to the invention.

The compositions according to the invention for use in textile washing may contain anti-crease agents since textile fabrics, in particular of rayon, wool, cotton and their mixtures, may tend to wrinkle because the individual fibers are resistant to bending, buckling, pressing and squeezing across the fiber direction. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, -alkylol esters, -alkenylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

Graying inhibitors have the task of keeping suspended from the hard surface and in particular from the textile fiber suspended dirt in the fleet. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions ,

The agents may contain optical brighteners, among these in particular derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or similarly constructed compounds which are substituted for the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Further, brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl). 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. Suitable 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. Preferably, the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and Bistearylethylenediamide preferred.

In agents according to the invention it is also possible to use active substances for avoiding the tarnishing of silver objects, 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 Metals in one of the oxidation states II, IM, IV, V or VI are present.

An agent according to the invention may comprise customary antimicrobial agents in addition to the ingredients mentioned above in order to enhance the disinfecting action against specific germs. Such antimicrobial additives are preferably present in compositions according to the invention in amounts of not more than 10% by weight, in particular from 0.1% by weight to 5% by weight.

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-trimethyl-1, 4,7-triazacyclononane manganese complex, Mn-Me ₃ TACN). Solutions of 0.35 g / l H ₂ O ₂ and 5 μmol / l Mn-Me ₃ TACN and in each case 0 g / l (V1) or 0.11 g / l (M 1) Na alginate or 0 were used , 11 g / l (M2) pectin in water (3 ° dH), the pH of each had been adjusted to pH 10.5 by means of NaOH.

For the measurement of the primary wash performance cotton substrates, which had been provided with a standardized tea soil were treated in the respective solutions at 30 ⁰ C for 30 minutes. The treated fabric substrate was rinsed under running water and then dried and color measured. The following table shows the brightness value of the cotton measuring pieces.

For the measurement of wet tensile strength loss, cotton strips of defined width (number of threads) were treated 20 times for 45 minutes each at 6O ⁰ C in the respective solutions. The strips were dried and dipped in a wetting solution before being torn using a constant rate tensile testing machine. The tensile strength of the treated cotton was compared with the tensile strength of the untreated cotton and the wet tensile strength loss in% was calculated.

Five-fold determinations were made for the primary and wet tensile strength. The following table shows the mean values.

Claims

claims

1. A process for the bleaching treatment of cellulose-containing material, in particular in the production of pulp or paper or in the washing of cotton-containing textiles, in the presence of a peroxygen bleaching agent and a bleach-enhancing transition metal complex, characterized in that it is carried out in the presence of carboxygruppendem saccharidischem polymer.

2. The method according to claim 1, characterized in that it is carried out at temperatures in the range of 10 ⁰ C to 95 ⁰ C, in particular in the range of 20 ⁰ C to 40 ⁰ C.

3. The method according to claim 1 or 2, characterized in that it is carried out at pH values in the range of pH 5 to pH 12, in particular from pH 8 to pH 11.

4. The method according to any one of claims 1 to 3, characterized in that one uses concentrations of 0.0001 g / l to 2 g / l, in particular 0.01 g / l to 1 g / l carboxygruppentragendes saccharidic polymer.

5. textile washing process according to one of claims 1 to 4, 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 lies.

6. textile washing process according to one of claims 1 to 5, characterized in that the concentration of bleach-enhancing transition metal complex in the wash liquor in the range of 0.1 .mu.mol / to 100 .mu.mol / l, in particular 0.5 .mu.mol / l to 25 .mu.mol / l ,

7. The method according to any one of claims 1 to 6, characterized in that one does not use the finished bleach-enhancing transition metal complex, but separately one or more ligands, which can form a bleach-enhancing transition metal complex in the process with a transition metal in situ, and the transition metal also separately in Form of a salt or non-bleach-enhancing complex added or it brings in the process as part of the process water used for this purpose or on the treated cellulosic material.

8. Use of carboxy-group-carrying saccharide polymer for reducing the damage of cellulosic material by the presence of bleach-enhancing transition metal complexes in the bleaching treatment of cellulosic material.

9. Use of carboxy-group-carrying saccharide polymer for improving the bleaching performance of bleach-enhancing transition metal complex in aqueous solutions containing peroxygen-containing bleach.

A textile-sparing detergent containing peroxygen bleaching agent, bleach-enhancing transition metal complex or one or more ligands capable of forming a bleach-enhancing transition metal complex in situ in the washing process with a transition metal, and carboxy-group carrying saccharide polymer.

11. A method, use or agent according to any one of claims 1 to 10, characterized in that the carboxy-group-carrying saccharidic polymer of alginate, pectin, pectinate and mixtures of at least two of these is selected.

12. A method, use or composition according to any one of claims 1 to 11, characterized in that the bleach-enhancing transition metal complex compound is a metal complex of 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

D - (CR ¹ R ² ) _t -f D * ~ (CR ¹ R ² ) _t T

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, where, if D = N, one of the heterocarbon bonds attached thereto is unsaturated, resulting in the production of an N = CR ¹ moiety.

13. Process, use or composition according to claim 12, 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.

14. A method, use or composition according to any one of claims 1 to 11, characterized in that the bleach-enhancing transition metal complex compound is a manganese complex of the formula (II),

in the R ¹⁰ and R ¹¹ are each independently hydrogen, a Ci_i ₈ 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- |. ₁₈ alkyl group, R ¹³ , R ¹⁴ and R ^{15 are} independently hydrogen, a C |. ₄ alkyl or hydroxyalkyl group and X is halogen and A is a charge-balancing anion, which 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 more than once.