EP0414581B1 - Textile bleaching compositions effective at low temperatures - Google Patents

Abstract

Detergent compositions which have a bleaching effect on textiles, adapted so as to contain a bleaching system based on peroxide compounds and of complexes of divalent metals of an atomic number of between 25 and 29 (or of their precursors) which, under the washing conditions, have a nett positive charge and act as catalysts for the decomposition of the peroxides, increasing the bleaching efficiency of the detergent compositions at low temperatures.

Description

The present invention relates to detergent compositions having a bleaching effect on textiles, suitable for containing a bleaching system based on peroxide compounds and divalent metal complexes with atomic number between 25 and 29 (or their precursors), which have, under washing conditions, a positive net charge and act as catalysts for the decomposition of peroxides, increasing the bleaching efficiency of detergent compositions at low temperatures.

BACKGROUND OF THE INVENTION

The use of peroxide compounds in compositions for washing clothes and other compositions intended for domestic or industrial use has been known for a long time, these compounds being particularly useful for removing stains having a significant content of colored materials, such as stains from coffee, tea, fruit, wine and cosmetics.

For this purpose, a wide variety of peroxides are used, such as hydrogen peroxide, mineral persalts such as perborates, percarbonates, persulfates, perphosphates and the like, and organic percarboxylic acids.

Among these compounds, those which produce hydrogen peroxide in solution are very effective at high temperatures, but their efficiency decreases very markedly when the temperature drops, which makes them ill-suited to the current practice of domestic washing, which involves relatively low temperatures. In addition, the need to work at high temperatures in industrial washing operations which employ this type of bleaching agent involves a high energy expenditure, which has repercussions on the cost of operations.

To solve this problem, it has been proposed to add organic compounds containing, for example, ester, nitrile and / or amide groups, to the detergent compositions containing bleaches based on peroxides, these compounds making it possible to improve the effectiveness of bleaching at low temperatures, producing peracids. However, these compounds, which are known in the art as bleach activators, must be added in relatively high proportions to be effective. Consequently, the cost of the product increases, with, in addition, the possibility for the bleach activator to hinder the action of the other constituents of the finished formulations.

Another solution described for improving the behavior of detergents with peroxidized bleaching agents consists in incorporating into the formulation of small quantities of metal cations in the form of coordination complexes, so that the intrinsic capacity of the metal cations to decompose the peroxides remains controlled, which makes it possible to obtain a beneficial effect on the efficiency of the bleaching of the peroxides, as described, for example, British patent n _° 984,459, the US patents n 3 3 156 654 and n 3 352 634, the application EP Patent No. 0 272 030 and DE-An Patent Application _No. 30 02 271.

In our Spanish patent application number 8803242, it is proposed to use certain divalent heavy metal complexes which, under the usual alkaline pH conditions of bleaching operations, have a positive net charge and are very effective in bleaching with peroxides at low temperatures.

Said complexes do not act by regulating the amount of free metal so that the latter is that which effectively catalyzes the decomposition; instead, it is the complexes themselves, or the complex species which they produce in solution, which catalyze this decomposition on the substrates to be bleached, so that a bleaching efficiency can be obtained at low temperatures. higher than that obtained with a catalysis by free metal.

However, it was observed that the effectiveness of the bleaching compositions described in the Spanish application _No. 8803242 shows a strong dependence with respect to the water hardness, as well as additional components constituting the detergent composition.

This dependence is manifested by a lower efficiency of compositions containing peroxides and catalysts described in patent application n _° 8803242 when working in hard water compared to that obtained in deionized water. In addition, the incorporation of the bleaching system described in the usual detergent compositions also causes a reduction in the effectiveness of said system.

This behavior is not unexpected, since the inclusion, in finished compositions, of additives having a high reactivity, such as the bleaching catalysts used in the compositions described in the present invention, generally creates considerable difficulties, because the stability , both additives and of the remaining constituents of the formulation, must be ensured.

Furthermore, the problem of making reactive additives compatible in finished formulations is not limited to ensuring the stability of the formulations; it is also a question of obtaining the stability of the various constituents in the washing bath, where they are in much more intimate contact because they are dissolved there.

DESCRIPTION OF THE INVENTION

The object of the present invention is thus to produce a stable detergent and bleaching composition which contains a bleaching system consisting of a peroxidized compound and a soluble salt of a divalent heavy metal cation with atomic number between 25 and 29 and a sequestering agent capable of forming, with the metal salt, in the washing bath, a catalytic complex comprising a positive residual charge, and which is capable of providing maximum bleaching efficiency in hard water and at low temperatures. The metal cation salt and the sequestering agent can be incorporated into the detergent and bleaching compositions as such or in the form of the preformed complex.

According to the present invention, detergent compositions are described which contain a bleaching system based on a peroxide compound and a catalytic metal complex or its precursors, according to what has been described in the above paragraph, and which are suitable for enhancing the efficiency of the bleaching system in the washing operation.

The main problem posed by the incorporation of the above-mentioned bleaching systems in the detergent compositions currently in use is the fact that the mineral phosphates inactivate the bleaching catalysts described above, which significantly reduces their bleaching power.

This represents a serious disadvantage, because mineral phosphates are used in a generalized manner as detergency builders in the usual detergent compositions.

In addition, it has been observed that anionic surfactants, which are another of the key ingredients in the majority of detergent formulations, can also impede the catalytic activity of the bleaching catalysts described above.

In addition, the content of alkaline earth cations in the washing bath, which is usually designated by the term "hardness", also has a negative influence on the catalytic bleaching activity. This fact worsens because of the impossibility of adding large quantities of powerful sequestering agents to the detergent compositions in question, because said sequestering agents destroy the catalytic complexes by competing with the ligands of which they are made up.

We have now discovered detergent compositions, which are effective in hard water, in which it is possible to incorporate the catalysts described above, not only without loss of catalytic activity of the latter, but also, surprisingly, with an improvement in the efficiency of the catalysts compared to that presented in hard water.

• Elles contiennent une quantité réduite de phosphates minéraux, spécifiquement moins de 1% en poids de la composition. Ces quantités de phosphates minéraux assurent que, dans les concentrations de détergent que l'on emploie habituellement dans le lavage, la concentration en phosphate du bain ne dépasse pas 10-⁴ molaire. Des concentrations en phosphates supérieures dans le bain de lavage inhibent en partie l'effet de renforcement du blanchiment qu'ont les catalyseurs.

The detergent compositions which are suitable for containing the catalysts described above, and which improve the behavior of the latter in hard water, have a combination of characteristics which make them suitable for ensuring the effectiveness of the catalysts which they contain. These characteristics are described below:

• They contain a reduced amount of mineral phosphates, specifically less than 1% by weight of the composition. These quantities of inorganic phosphates ensure that, in the concentrations of the detergent that is usually employed in washing, the phosphate concentration of the bath is not more than 10- ⁴ molar. Higher phosphate concentrations in the wash bath partially inhibit the whitening enhancement effect of the catalysts.

They contain zeolites, replacing mineral phosphates, as detergency builders. Zeolites have a good detergency builder power without having a sequestering power which would allow them to compete with the ligands of the catalytic complex, inactivating the latter.

In addition, zeolites have the additional beneficial effect, when used to absorb the bleaching catalyst on themselves, thereby incorporating it into detergent compositions. Said additional beneficial effect consists in a reduction in the rate of decomposition of the bleaching peroxides, so that one takes advantage of their bleaching power in a more effective manner.

The use of zeolites as a support for bleaching catalysts of the type of salts of free metal cations is described in European patent applications Nos _. 224 952 and 224 953, where compositions containing manganese (+2) absorbed on are described. zeolites, so that the oxidation of manganese to manganese oxide is avoided, which can cause stains on fabrics, by further improving the storage stability of the bleaching compositions which contain said system.

In the compositions described in the present invention, said drawbacks are not encountered, since the metal catalysts used do not undergo transformation by oxidation into species capable of causing stains on the washed fabrics.

The compositions in question can contain any type of cationic, amphoteric, zwitterionic, nonionic and anionic surfactants. However, anionic surfactants have a negative effect on catalysis, as indicated above.

However, it has been discovered that, if the formulation simultaneously contains anionic and nonionic surfactants, such that the ratio of the quantity of the former to the quantity of the latter is less than or equal to 2.0, the negative effect can be eliminated. anionic surfactants on the catalysts.

Finally, as already indicated, strong sequestering agents can only be included in detergent compositions which contain bleaching catalysts in very small quantities, less than 0.2% by weight of the composition, since they enter in competition with the ligands which form the catalytic complex, inhibiting the activity of the latter.

• A. De 0,001% à 1,5%, exprimé en poids du cation métallique, d'un complexe catalytique formé de sels de métaux divalents de numéro atomique compris entre 25 et 29 et d'agents séquestrants qui forment des complexes catalytiques chargés positivement avec lesdits cations métalliques dans le bain de lavage, ledit catalyseur étant présent sous forme du complexe ou de ses précurseurs.
• B. De 1 à 30% d'agents de blanchiment peroxydés.
• C. De 0% à 1 % d'adjuvants de détergence du type phosphate ou polyphosphate minéral.
• D. De 5% à 40% d'aluminosilicates alcalins, également connus sous le nom de zéolithes.
• E. De 3% à 25% de tensioactifs non ioniques et/ou anioniques, de façon que le rapport en poids des tensioactifs anioniques aux tensioactifs non ioniques soit inférieur à 2,0.
• F. De 0% à 0,2% d'agents séquestrants puissants.

According to the present invention, bleaching detergents are proposed having the following composition, expressed as a percentage by weight:

• A. From 0.001% to 1.5%, expressed by weight of the metal cation, of a catalytic complex formed from divalent metal salts with atomic number between 25 and 29 and sequestering agents which form positively charged catalytic complexes with said metal cations in the washing bath, said catalyst being present in the form of the complex or of its precursors.
• B. From 1 to 30% of peroxide bleaches.
• C. From 0% to 1% of detergency builders of the mineral phosphate or polyphosphate type.
• D. From 5% to 40% of alkaline aluminosilicates, also known as zeolites.
• E. From 3% to 25% of nonionic and / or anionic surfactants, so that the weight ratio of anionic surfactants to nonionic surfactants is less than 2.0.
• F. From 0% to 0.2% of strong sequestering agents.

The compositions according to the invention may contain, in addition, constituents such as surfactants from other categories, foaming regulators, bleaching activators of the peroxide precursor type, polymers which inhibit encrustation and redeposition, structuring and / or alkaline salts, optical brighteners, photoactivators, tinting agents, colorants, perfumes and, in general, any type of additive that is commonly used in detergents.

The various constituents which can be incorporated into the detergents described in the present invention are detailed below.

The bleaching catalysts suitable for practicing the present invention are those formed from the salts of divalent metal cations having an atomic number between 25 and 29 with sequestering agents which form with said cations complexes which, at the usual alkaline pH in the washing, have a positive residual charge and have free coordination positions, or may undergo transformation, in the washing bath, into species which have said free coordination positions.

Said catalysts can be incorporated into the formulations which are the subject of the present invention, either in the form of the preformed complexes, or in the form of the precursors of the said complexes, in which case the latter are formed when the compositions are placed in aqueous solution. The term “precursors of catalytic complexes” should be understood to mean the salts of divalent cations with atomic number between 25 and 29 and the sequestering agents which form with said salts the complexes described in the above paragraph.

Examples of these complexes are those formed by the salts of divalent metals with atomic number between 25 and 29 with diamines in which the nitrogen atoms are separated by a chain of at most five atoms, these diamines may or may not be substituted substituted, the substituents possibly comprising functional groups by means of which the diamines may or may not establish additional attachment points with the divalent metal with which they form the complexes.

Examples of these complexes are those formed by divalent copper or divalent manganese with polyamines such as ethylenediamine, diethylenetriamine, 1,3-propylenediamine, 1,2-propylenediamine and 1,2-cyclohexylenediamine.

Additional examples are the complexes formed by macrocyclic compounds such as 1,4,8,11-tetraaza-2,3,9,10-tetramethylcyclotetradeca-1,3,8,10-tetraene and the salts of divalent copper and divalent manganese.

The peroxidized bleaching agents suitable for practicing the present invention are mineral persalts, both those which are real persalts and those which are compounds of addition of mineral salts and of hydrogen peroxide. Examples of this type of bleach are alkaline perborates, such as sodium perborate, mono- or tetrahydrate, and alkaline percarbonates.

The mineral phosphates mentioned in the description include orthophosphates, pyrophosphates and polyphosphates of alkali metals, and in particular sodium and potassium tripolyphosphates in their different degrees of hydration.

As regards the alkaline aluminosilicates ion exchangers or zeolites, it is possible to use both the crystallines and the amorphous ones or that amorphous / crystalline mixtures, both of natural origin and of synthetic origin.

Those which are particularly suitable are the finely divided synthetic zeolites of formula (Na20) P ,,, (AI203) y, (SiO2) ,, WH20, in which x is equal to 1, y has a value of 0.6 to 1 , 3 and is preferably about 1, za a value from 1 to 4 and preferably from 2 to 3 or about 2, and wa a value from 0 to 9 and preferably from 2.5 to 6. The aluminosilicates of this type are commercially available products and are usually called zeolites A and X or their mixtures.

The surfactant system includes different types of compounds. First, synthetic anionic surfactants, those suitable for use in the present invention including the soluble salts of alkylbenzenesulfonates, alkylsulfates, alkyl (polyether) sulfates, a-olefinesulfonates, paraffin sulfonates, alkylglyceryl ether sulfonates, a-sulfocarboxylates and their esters, sulfates and sulfonates of fatty acid monoglycerides, alkylphenol (polyether) sulfates and the like. Among them, alkali metal alkylbenzenesulfonates are preferred, the alkyl chain of which is essentially linear and contains a number of carbon atoms between 10 and 14.

Another category of surfactants used are nonionic surfactants, among which can be used those of the polyoxyalkylenated fatty alcohol type with a number of moles of alkylene oxide per mole of fatty alcohol of between 2 and 20, and preferably between 3 and 15, and said fatty alcohols having straight or partially branched chains having a number of carbon atoms between 8 and 22. Examples of said surfactants are the products of the oxyethylenation of lauryl alcohol and the products of l oxyethylenation of synthetic alcohols found on the market under brands such as Dobanol ^R , Synperonic ^R , Lutensol ^R or LiaI ^R.

Also suitable as nonionic surfactants are reaction products of alkylene oxides with alkylphenols in which the alkyl radical contains a number of carbon atoms between 7 and 11, so that the number of moles of oxide d alkylene per mole of alkylphenol is between 3 and 20, and preferably between 5 and 12.

It is also possible to use as surfactants soaps of fatty acids, saturated or unsaturated, comprising a number of carbon atoms between 8 and 24. As examples of said soaps, there may be mentioned the alkaline salts of fatty acids, mainly saturated, which preferably contain between 10 and 20 carbon atoms, the alkali salts of mixtures of fatty acids derived from tallow and coconut and palm oils being particularly preferred.

Aminopolycarboxylic acids or their salts, such as ethylenediaminetetraacetic or nitrilotriacetic acid, and the like, are suitable for use as potent sequestering agents. Organic phosphonic acids or their salts and hydroxycarboxylates or their salts are also suitable.

In addition to the essential constituents already mentioned, it may prove advantageous to supplement the detergent compositions of the invention with another type of optional constituents.

Among this type of optional constituents, mention may be made of proteolytic or amylolytic enzymes such as those found on the market under the brands Maxatase ^R and Alcalase ^R.

Cationic surfactants of the quaternary ammonium salt type, in which at least one or two of the alkyl radicals are linear or partially branched C _s -C _is carbon chains, can also be incorporated.

Among the amphoteric surfactants, which can also be used, are the water-soluble derivatives of secondary and tertiary aliphatic amines in which the aliphatic radical may comprise a straight or branched chain, and, among the water-soluble derivatives, one of the substituents contains from 8 to 18 carbon atoms and another consists of an anionic group such as, for example, a carboxy, sulfonate, phosphate or phosphonate group.

It is also possible to use the surfactants known as surfactants with hybrid or zwitterionic ions, such as the water-soluble derivatives of cationic aliphatic compounds with the quaternary ammonium, phosphoric and sulphonic groups, in which the radicals can comprise a linear or branched chain and in which one aliphatic substituents contains 8 to 18 carbon atoms and another contains an anionic group which is soluble in water.

Substances that help prevent redeposition of soiling on fabrics during the washing process can also be added. Examples are cellulose derivatives like its carboxyalkylated or hydroxyalkylated compounds.

Another optional constituent in the compositions of the present invention is the structuring salts, among which there are a large number of mineral salts which are neutral to hydrolysis and which have a high solubility in water. Among the preferred salts, mention may be made of sodium sulfate.

Alkalizing agents suitable for these compositions are the alkali metal salts derived from carbonic, orthosilicic, metasilicic acids and the like.

Anionic fluorescent brighteners, also known as optical brighteners, can also be used. Among this type of products, those which are most suitable are the water-soluble sulfonated derivatives of stilbenes and the water-soluble sulfonated derivatives of distyrylbiphenyl. There is a wide variety of these products sold by Ciba-Geigy, among which we can cite those of the brands Tinopal ^R 5BMS, Tinopal ^R DMS, Tinopal ^R LMS-X and Tinopal ^R CBS-X.

Other advantageous constituents are the polymers which produce a better appearance of the washed linen, because they manifest an inhibiting action on the incrustation, that is to say that they prevent the insoluble mineral salts which form in the bath. washing to settle on fabrics, producing a phenomenon of graying and cumulative hardening. Said polymers are the water-soluble salts of polycarboxylic homo- or copolymers having a configuration such that the carboxylic radicals are separated from one another by one or two carbon atoms. Products of this type are homo or copolymers of monomer units such as, for example, maleic anhydride, maleic acid, methylvinyl ether, acrylic acid, methacrylic acid, and the like. These products are found on the market under names such as Sokalan ^R , Gantrez ^R , Primal ^R and the like.

It is also possible to incorporate foam regulators other than soaps or nonionic surfactants having a high degree of oxyethylenation, such as, for example, waxes, saturated hydrocarbons, esters of phosphoric acid and silicones. In this context, we prefer silicones such as combinations of dialkylpolysiloxanes with finely divided silica and silane silicas or, alternatively, copolymers of dialkylpolysiloxanes with glycol or ethylene oxide radicals. Said special silicones are marketed by the firm Dow Corning under the references Q2-3092, DB-100, DC-190, DC-193, DC-198. Said silicones can be used as presented by the supplier, or else protected by granulation and coating with inert materials to avoid their interaction with the constituents of the detergent composition.

Finally, it is useful to note that, as constituents present only in very small quantities and the sole role of which is to improve the presentation of the product, perfumes, dyes, opacifiers and the like are added to the composition.

DESCRIPTION OF EXAMPLES OF EMBODIMENT

By way of examples, and without it being possible to consider them as limiting the scope of the present invention, various compositions according to the invention are indicated and the reflectance results of EMPA-114 fabrics of 10 × 10 cm washed with said compositions bleaching detergents.

It should be explained that the designation EMPA-114 corresponds to standard cotton fabrics stained with red wine according to the standards of the Eidgenôssiche Materialprüfungsamt of Switzerland.

• C1 : Perborate de sodium monohydraté.
• C2 : Chlorure cuivrique dihydraté.
• C3 : Diéthylènetétramine.
• C4 : Ethylènediamine.
• C5 : Alkyl(linéaire en C₁₂)benzènesulfonate de sodium.
• C6 : Mélange de savon de suif et de savon de poisson avec 16% de C₂₀-C₂₂.
• C7 : Alcool de suif hydrogéné avec 11 moles d'oxyde d'éthylène.
• C8 : Tripolyphosphate pentasodique préhydraté.
• C9 : Zéolithe cristalline de type A Wessalith^R de Degussa.
• C10 : Polyacrylate SOKALAN^R CP-5 de faible masse moléculaire.
• C11 : Ethylènediaminetétraacétate de sodium (EDTA).
• C12 : Nitrilotriacétate de sodium Trilon^R A sous forme pulvérisée de BASF.
• C13 : Sel hexasodique de l'acide éthylènediaminetétraméthylènephosphonique Dequest^R 2046 de Monsanto.
• C14 : Carbonate de sodium.
• C15 : Sulfate de sodium anhydre.
• C16 : Carboxyméthylcellulose sodique.
• C17 : Silicate de sodium avec un rapport Na₂0/Si0₂ = 1:2,3.
• C18 : H₂0.

Likewise, the following abbreviations will be used to denote each of the constituents present in the detergent compositions used in these examples:

• C1: Sodium perborate monohydrate.
• C2: Cupric chloride dihydrate.
• C3: Diethylenetetramine.
• C4: Ethylenediamine.
• C5: Alkyl (linear in C ₁₂ ) sodium benzenesulfonate.
• C6: Mixture of tallow soap and fish soap with 16% C ₂₀ -C ₂₂ .
• C7: Hydrogenated tallow with 11 moles of ethylene oxide.
• C8: Prehydrated pentasodium tripolyphosphate.
• C9: Wessalith ^R type A crystalline zeolite from Degussa.
• C10: SOKALAN ^R CP-5 polyacrylate of low molecular weight.
• C11: Sodium ethylenediaminetetraacetate (EDTA).
• C12: Sodium nitrilotriacetate Trilon ^R A in spray form of BASF.
• C13: Hexasodium salt of ethylenediaminetetramethylenephosphonic acid Dequest ^R 2046 from Monsanto.
• C14: Sodium carbonate.
• C15: Anhydrous sodium sulfate.
• C16: Sodium carboxymethylcellulose.
• C17: Sodium silicate with a Na ₂ 0 / Si0 ₂ ratio = 1: 2.3.
• C18: H ₂ 0.

EXAMPLES 1 TO 9

Detergent compositions are prepared according to the following formulations:

It should be explained that the components C2, C3 and C4, which including cupric chloride dihydrate, diethylenetriamine and ethylenediamine, are combined to form the catalytic bleaching complex in the washing bath.

To make the examples homogeneous, so that the reflectance measurements of the different compositions are directly comparable, all the examples were carried out using catalysts comprising copper as metal cation. Furthermore, for the same reason, ethylenediamine was used as complexing agent in all of the examples, except number 7, in which diethylenetriamine was used with a composition identical to that of Example 2, to show the influence of ligand change.

Examples 1 to 7 correspond to compositions according to what is described in the present invention and, for this reason, all these compositions provide a high bleaching efficiency in washing EMPA-114 stains, which leads to reflectance values high.

Example 8 corresponds to a detergent composition which does not fulfill the conditions of the present invention.

Finally, Example 9 corresponds to reference compositions and contains only perborate and a catalyst in the absence of any other constituent, and offers the same concentration of perborate in the bath. as the compositions of Examples 1 to 8.

The compositions of Examples 1 to 9 are studied by washing with them standard stains by means of the washing process described below.

A dose of 210 grams of the detergent composition to be studied is introduced into the detergent compartment of a Zanussi 630 stainless steel washing machine and a washing cycle is programmed at a temperature of 30 _° C for 70 minutes, after which rinse cycles, which last a total of 40 minutes.

The fabrics are removed from the washing machine and dried at room temperature.

The reflectance measurements are made in an Ultrascan device from the company Hunterlab, with a halogen lamp of the JCR type of 9.5 V and 55 W, with a light of the D65 / 10 ° type, inclusion of brightness and of a filter. ultraviolet.

The reflectances of the fabrics washed with each of the compositions in table 1 are shown in table 2 and are graphically represented in graph 1.

As shown in Table 2, and as shown more visually in Chart 1, Examples 1 to 7, which correspond to detergent bleaching compositions which meet the conditions described in the present invention, provide reflectances of the washed fabrics higher than those which is obtained by washing with a composition which contains only perborate and a catalyst (Example 9). However, the composition of Example 8, which does not meet the conditions of the present invention, provides an even lower reflectance than that obtained with the reference composition of Example 9.

Claims (8)

1. Detergent and bleaching compositions for washing textiles, which are efficacious in hard waters and at low temperatures, characterized in that they contain peroxide compounds, a catalytic bleaching complex - made up of salts of divalent metals of an atomic number of between 25 and 29 and of sequestering agents which form positively charged catalytic complexes with the said metal cations in the washing bath - present in the form of the complex or of its precursors, quantities of inorganic phosphates which are lower than 1 % by weight, zeolites and anionic and nonionic surfactants so that the ratio of the quantity of anionic surfactants to the quantity of nonionic surfactants is lower than 2.0.

2. Detergent compositions for bleaching according to the preceding claim, characterized in that they contain the following essential constituents:

A. from 0.001 % to 1.5 %, expressed as weight of the metal cation, of a catalytic complex made up of salts of divalent metals of atomic number of between 25 and 29 and of sequestering agents which form positively charged catalytic complexes with the said metal cations in the washing bath, the said catalyst being present in the form of the complex or of its precursors,

B. from 1 to 30 % of peroxide bleaching agents,

C. from 0 % to 1 % of detergency adjuvants of the inorganic phosphate or polyphosphate type,

D. from 5 % to 40 % of alkali metal aluminosilicates, also known by the name of zeolites,

E. from 3 % to 25 % of anionic and/or nonionic surfactants, so that the weight ratio of the anionic surfactants to the nonionic surfactants is lower than 2.0,

F. from 0 % to 0.2 % of powerful sequestering agents.

3. Detergent compositions for bleaching according to the preceding claims, characterized in that the sequestering agents which form part of the catalytic complexes form complexes with divalent copper which have formation constants higher than 10¹⁵.

4. Detergent compositions for bleaching according to Claims 1 and 2, characterized in that the ligands which form the catalytic complex are diamines in which the nitrogen atoms are separated by a chain of not more than five atoms, it being possible for these diamines to be substituted or unsubstituted, it being possible for the substituents to comprise functional groups by means of which the diamines may or may not establish additional points of binding with the divalent metal with which they form the complexes.

5. Compositions according to Claim 1, characterized in that the metal cation which forms part of the catalytic complexes is copper or manganese.

6. Compositions according to Claim 1, characterized in that they contain mixtures of synthetic crystalline zeolites of A and/or X types.

7. Compositions according to Claim 1, characterized in that they contain, as anionic surfactants, soluble salts of linear alkylbenzenesulphonates and, as nonionic surfactants, polyoxyalkylenated fatty alcohols with a number of moles of alkylene oxide per mole of alcohol of between 2 and 20, the said fatty alcohols having linear or partly branched chains containing a number of carbon atoms of between 8 and 22.

8. Use, for the washing and the bleaching of textile fibres at low temperatures, of detergent compositions for bleaching which are efficacious in hard waters and at low temperatures, characterized in that they contain peroxide compounds, a catalytic bleaching complex - made up of salts of divalent metals of atomic number of between 25 and 29 and of sequestering agents which form positively charged catalytic complexes with the said metal cations in the washing bath - present in the form of the complex or of its precursors, quantities of inorganic phosphates which are lower than 1 % by weight, zeolites and anionic and nonionic surfactants so that the ratio of the quantity of anionic surfactants to the quantity of nonionic surfactants is lower than 2.0.

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