KR930007850B1 - Detergent compounds for use in bleaching systems - Google Patents

Abstract

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Description

Bleach composition

The present invention relates to detergent compositions containing novel quaternary ammonium substituted peroxycarboxylic acid precursors for use in bleaching systems. The bleaching system of the present invention is used in combination with a detergent active system. It is well known that free radical releasing peroxide is an effective bleach. This compound is often mixed in detergent compositions to remove stains and dirt. However, these compounds have significant limitations. That is, its activity depends significantly on temperature. Therefore, free radical releasing bleach is only practical when the bleach solution is heated above about 60 ° C. If the temperature of the bleach solution is about 60 ℃, very high amount of active oxygen-releasing compound should be added to get the bleaching effect. This is undesirable both economically and practically. If the temperature of the bleach solution is below 60 ° C, the peroxide (eg sodium perborate) becomes ineffective regardless of the amount of peroxide added to the bleach system. The temperature dependence of peroxides is important because these bleaching compounds are generally used as textile laundry detergent additives using domestic automatic washing machines operating in wash water below 60 ° C. This washing temperature is useful for fabric protection and energy. As a result, there is a continuing need for materials that provide more effective peroxide bleach compounds at temperatures below 60 ° C. Such materials are generally referred to in the art as bleach precursors, bleach promoters or bleach activators.

Bleach precursors are usually used in combination with peroxides (eg peracids) that can release hydrogen peroxide in aqueous solutions. Perborates are the most widely used perates.

In general, bleaching precursors are reactive compounds such as carboxylic acid esters which produce the peroxy acid in an alkaline solution containing a hydrogen peroxide source (e.g. a persulfate such as sodium perborate). This reaction is a nucleophilic substitution reaction to a precursor by hydroperoxyanion (HOO ⁻ ), which is facilitated by a precursor with good leaving group. This reaction is often referred to as perhydrolysis.

Examples of bleaching precursors are the carboxylic acid esters described in British Patent Nos. 836, 988, European Patent Nos. EP-A-0098129 and EP-A-012059, and the organic compounds of British Patent No. 907 356. Acylamides, and the organic carbonates described in US Pat. Nos. 3256198 and 3232.750. Quaternary ammonium peroxycarboxylic acid precursors are also known from British Patent 1382 594. Such prior art compounds have the following general formula.

In the formula,-(CnH ₂ n)-is an optionally branched chain where n is at least 3 and preferably 3-25, and R ₁ is an optionally substituted alkyl group, an alkaryl group, an optional group of C ₁ -C ₂₀ Is a substituted aryl group or a polyoxyalkylene group, R ₂ and R ₃ are C ₁ -C ₄ lower alkyl groups or hydroxy alkyl groups or at least two of R ₁ , R ₂ and R ₃ are optionally together with N-atoms; To form a substituted N-containing heterocyclic system, R ₄ is an optionally substituted phenyl group and X is chlorine or bromine.

Representative quaternary ammonium compounds according to the above references are as follows.

N-octyl, N, N-dimethyl N-10 carbophenoxydecyl ammonium chloride (ODC), N-octyl, N, N-dimethyl N-10 carbophenoxydecyl ammonium chloride (ODB) N-10 carbophenoxydecyl A disadvantage of the prior art quaternary ammonium compounds, such as pyridinium bromide (PDB) or chloride (PDC), is that their performance in washing / bleaching solutions is not constant. This is due to the fact that peroxycarboxylic acids produced from these compounds are sensitive to temperature and compositional components.

It is an object of the present invention to provide novel quaternary ammonium substituted peroxycarboxylic acid precursors in which the peracids produced from these precursors are more safe for the compositional components and temperatures present in the wash / bleach solution.

It is a further object of the present invention to provide a detergent bleaching composition containing a precursor which allows for very good bleaching over a wide range of temperatures including temperatures of up to 40 ° C.

The novel quaternary ammonium substituted peroxy carboxylic acid precursors of the present invention have the general formula:

Wherein R ₁ , R ₂ and R ₃ are each selected from optionally substituted alkyl, alkenyl, hydroxyalkyl and polyoxyalkylene groups of C ₁ -C ₁₈ , or of R ₁ , R ₂ and R ₃ Two form an optionally substituted N-containing heterocyclic system together with R ₄ and N-atoms, or two or more of R ₁ , R ₂ and R ₃ are optionally substituted with N-atoms Forms a containing heterocyclic system, and R ₄ (when not forming an N-containing heterocyclic system together with R ₁ and / or R ₂ and / or R ₃ ) is a bridging group selected from

(Where n is 0, 1, or 2, respectively) L is a leaving group, the conjugate acid having a pKa (acid halide number) in the range of 4-13, preferably about 8-10, Z ⁻ is chloride, bromide, Hydroxide, nitrate, methosulfate, bisulfate, acetate, sulfate, citrate, borate or phosphate anion.

Since the presence of (Z ⁻ ) as a counter ion is not essential here, a compound containing no counter ion is possible and is within the scope of the present invention.

The L group must be sufficiently responsive to the reaction occurring within the appropriate time period (ie, the wash cycle). However, if the L group is overly reactive, the precursors may be unstable for use in the composition. These characteristics correspond to pKa of the conjugate acid of the leaving group, with exceptions. Typically, leaving groups exhibiting sufficient reactivity are those in which the conjugate acid has a pKa in the range of about 4-13, preferably 8-10.

Many different leaving group structures are described in particular in the literature and are useful for the purposes of the present invention. For example, US Pat. Nos. 4 412 934 and 4 486 327, EP 170 368 and 166 571 describe examples of preferred leaving groups.

The leaving group L is selected from the following groups.

In gastroesophageal, X ₁ and X ₂ are each H, or ^{_{-SO 3 - M +, -COO -}} M -, -SO 4 - M +, (-N + R 1 R 2 R 3) Z -, -NO _Is a substituent selected from ₂ and a C ₁ -C ₈ alkyl group, R ₅ is a C ₁ -C ₁₂ alkyl group, R ₆ is H or R ₅ , Y is H or -SO ₃ ^- M ⁺ , -COO ^- M ⁺ , -SO ₄ ^- M ⁺ , (N ⁺ R ₁ R ₂ R ₃ ) Z ^- or -NO ₂ , M may or may be present as hydrogen, an alkali metal, ammonium or an alkyl- or hydroxyalkyl-substituted ammonium cation You may not.

The most preferred leaving group among the leaving groups Therefore, the novel peroxycarboxylic acid precursor of the present invention preferably has the following structural formula.

The precursor preferably has the following structural formula.

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , X ₁ , X ₂ and Z are as defined above.)

The preferred compounds have R _1, R ₂ and R ₃ is C ₁ -C ₄ alkyl group, preferably a methyl group, X ₁ is hydrogen X ₂ is -SO ₃ ^- M ⁺ or - COO ^- N ⁺ are those compounds.

The quaternary ammonium peroxycarboxylic acid may also have the following structural formula.

(Wherein R ₁ , R ₂ , R ₃ , R ₄ and Z ⁻ are as defined above.)

The following classes of compounds are representative precursors within the scope of this invention.

Preferred of these compounds are the compounds of classes I, II and III and representative examples thereof are as follows.

Particularly preferred compounds are (iii), (ii), (iii) and (iii) compounds. This is because realistic mass production is easy.

Quaternary ammonium peroxy acids, produced from these new precursors with hydrogen peroxide or persulfate, have a higher bleaching effect on fabrics than would be expected on the basis of their hydrophobicity (log P) and are often several times higher than the peracetic acid. Has a constant. Furthermore, the precursors of the present invention are peroxycarboxylic acids that are more stable to temperature and composition (e.g., borate) than those produced from quaternary ammonium peroxycarboxylic acid precursors of the prior art, ie

Create

The precursor is added to a bleaching composition which requires as an essential component a peroxide (bleaching compound) capable of producing hydrogen peroxide in an aqueous solution.

The molar ratio of hydrogen peroxide (or peroxide that produces an equivalent amount of hydrogen peroxide) in such compositions is generally in the range of about 0.5: 1 to about 25: 1. In a preferred embodiment of the present invention the molar ratio is in the range of 1: 1: 1 to about 15: 1. Hydrogen peroxide sources are well known in the art. Examples thereof include alkali peroxides and organic peroxides such as oxides and urea peroxides, and inorganic persulfate bleaching compounds such as alkali metal salts of perboric acid, percarbonate, perphosphate and persulfate. Also suitable are mixtures of two or more of these compounds. Particularly preferred compounds are sodium perborate tetrahydrate and especially sodium perborate monohydrate. Sodium perborate monohydrate is preferably used because it has excellent storage stability and dissolves very quickly in an aqueous bleach solution. Rapid dissolution is believed to increase the surface bleaching effect as it allows the production of large amounts of peroxycarboxylic acid.

Detergent compositions containing bleaching systems composed of the novel compounds of the present invention and active oxygen-releasing materials generally contain surfactants, detergent building materials and other known ingredients used in such compositions.

In such compositions the quaternary ammonium substituted peroxycarboxylic acid precursors of the present invention are about 0.1-20% by weight, preferably 0.5-10, with a peroxide (e.g. sodium perborate monohydrate or tetrahydrate) which is a bleaching compound. It is present in an amount of 1% by weight, in particular 1-7.5% by weight. The amount of this peroxide is usually in the range of about 2-40% by weight, preferably about 4-30% by weight, in particular about 10-30% by weight.

Surfactants are natural derivatives such as soap or synthetic materials selected from anionic, nonionic, amphoteric, zwitterionic, cationic surfactants and mixtures thereof. Many suitable surfactants are commercially available and described in detail in, for example, "Surface Active Agents and Detergents", Vol. I and II, by Schwartz, Perry and Berch. The total amount of surfactant is up to 50% by weight of the composition, preferably about 1-40% by weight, in particular about 4-25% by weight.

Synthetic anionic surfactants are usually water soluble alkaline metal salts of organosulfuric acid and sulfonic acid having an alkyl group of about C ₈ -C ₂₂ . The term alkyl is used herein to include the alkyl portion of the higher alkyl group.

Examples of suitable synthetic anionic detergent compounds are sodium sulfate and ammonium alkyls, in particular sodium sulfate and ammonium: alkyl (C ₉ ), for example obtained by the sulfidation of higher (C ₈ -C ₁₈ ) alcohols produced from tallow or coconut oil. -C ₂₀₎ benzene sulfonate and linear alkyl, especially as a second-class ammonium (C ₁₀ -C ₁₅₎ benzene sulfonate: alkyl glyceryl ether sulfate, especially as tallow or coco units and the higher alcohol derived from synthetic oil derived from the flow path The above ethers of alcohols: coconut oil fatty acid monoglyceride sulfuric acid and sulfonic acid natrum: sodium and ammonium salts of sulfuric esters of higher (C ₉ -C ₁₈ ) fatty alcohol-alkylene oxides (especially ethylene oxide): fatty acids such as coconut fat Reaction product esterified with isethionic acid and neutralized with sodium hydroxide: fatty acid amide of methyl taurine Thrium and ammonium salts: substances induced by reaction of alpha-olefins (C ₈ -C ₂₀ ) and sodium bisulfite, or hydrolyzed to bases to produce random sulfonates after the reaction of paraffins with SO ₂ and Cl ₂ Alkanes monosulfonates, such as those derived from: C ₇ -C ₁₂ dialkyl sulfosuccinate sodium and ammonium: Neutralization and hydrolysis of the reaction product after reaction of olefins (especially C ₁₀ -C ₂₀ alpha-olefins) with SO ₃ Olefin sulfonates meaning the substances obtained by Preferred anionic detergent compounds are sodium (C ₁₁ -C ₁₅ ) alkylbenzemsulfonate, sodium (C ₁₆ -C ₁₈ ) alkyl sulfate and sodium (C ₁₆ -C ₁₈ ) alkylether sulfate.

Suitable nonionic surfactants preferably used with anionic surfactants are especially alkylene oxides (usually ethylene oxide) -alkyl (C ₆ -C ₂₂ ) phenols (generally ethylene oxide 5: 25 units per molecule, i.e. 5-25 EO). ): Condensation product of aliphatic (C ₈ -C ₁₈ ) primary or secondary linear or branched alcohol and ethylene oxide (usually 6-30EO): Product of condensation reaction of propylene oxide with ethylenediamine and ethylene oxide. . Other so-called nonionic surfactants include alkyl poly glycosides, long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl-sulfoxides.

Amphoteric or zwitterionic surfactant compounds may be used in the compositions of the present invention but are not preferred because they are relatively expensive. If amphoteric or zwitterionic surfactant compounds are used, they are added in small amounts to compositions based on synthetic anions and nonionic surfactants that are more commonly used than usual.

As mentioned above, soaps may also be incorporated into the compositions of the invention, preferably in amounts of up to 30% by weight. Soap in particular is advantageous when used in low content in mixtures of binary systems (soaps / anions) or tertiary systems (including nonionic or mixed synthetic anions and nonionic compounds).

Soaps which are preferably used are sodium or potassium (less preferred) salts of saturated or unsaturated C ₁₀ -C ₂₄ fatty acids or mixtures thereof. The amount of such soap is about 0.5-20% by weight, and generally about 0.5- about 5% by weight is sufficient for foam control. Soap is used in an amount of about 2 to about 20% by weight, in particular about 5 to about 15% by weight, in order to obtain a good effect in terms of cleaning power. This is especially valuable for compositions used in hard water when soap acts as an assistant builder.

Detergent compositions of the present invention usually also contain a cleaning power builder. The builder material is selected from 1) calcium blockers, 2) precipitated materials, 3) calcium ion exchangers, and 4) mixtures thereof.

Examples of calcium-blockable builder materials include alkali metal salts of polyphosphoric acid such as sodium tripolyphosphate: nitrilotriacetic acid and its water-soluble salts: carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid, oxysuccinic acid, melitric acid, benzene polycarboxyl Alkali metal salts of acids, citric acid, polyacetal carboxylic acids (see US Pat. Nos. 4,144,226 and 4,146,495).

Examples of precipitating builder materials include several types of insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known.

In particular, the compositions of the present invention may contain any organic or inorganic builder material, such as sodium tripolyphosphate and potassium, sodium pyrophosphate and potassium, sodium orthophosphate and potassium, sodium carbonate, sodium salt of nitrilotriacetic acid, sodium citrate, Carboxymethyl malonate, carboxymethyloxysuccinate and insoluble crystalline or amorphous aluminosilicate material, or mixtures thereof.

Such builder materials are present in amounts of, for example, 5-80% by weight, preferably 10-60% by weight.

In addition to the above-mentioned components, the detergent composition of the present invention contains the usual adducts in the amounts commonly used in the detergent composition for fabric washing. Such additives include foaming accelerators (e.g. methanolamides derived from alkanolamides, in particular palm nucleofatty acids and coconut fats), foaming agents (e.g. alkyl phosphates and silicones), anti-deposition agents (e.g. carboxymethylcellulose And alkyl or substituted alkyl cellulose ethers), other stabilizers (e.g. ethylenediaminetetraacetic acid), fabric softeners, inorganic salts (e.g. sodium sulfate) and the like as fluorescent ingredients, flavoring agents, enzymes (e.g. Proteases, cellulases, lipases and amylases), fungicides and coloring agents and the like are also added.

Bleaching precursors and their peroxycarboxylic acid derivatives described herein are useful in many types of cleaning products. Such cleaning products include laundry detergents, laundry bleaches, hard surface cleaners, toilet bowl cleaners, automatic dishwashing compositions, and tooth cleaners. The precursors of the present invention can be used in various forms of products, including non-aqueous liquids such as powders, sheets or other materials, bag forms, tablets or liquid nonionic detergents.

In general, the bleaching precursor is preferably present in the form of particles consisting of this precursor and a binder or flocculant. Many different industries for producing such precursor particle bodies have been described in various patent documents.

For example, Canadian Patent No. 1 102966, British Patent No. 1 561333, US Patent No. 4 087 369, European Patent No. 0 240057, 0 No. 241 962, No. 0 101 634, and No. 0 062 523. have. Each of these methods can be selectively applied to the bleach material of the present invention.

Particle bodies containing the bleaching precursor of the present invention are usually added to the spray-dried portion of the cleaning composition together with other dry mixing components such as enzymes, inorganic peroxygen bleaching compounds and foam control agents. However, the detergent composition itself to which the bleaching precursor particles are applied is prepared by various methods such as dry mixing, coagulation extrusion, flaking and the like, and this manufacturing method is well known to those skilled in the art and the method itself is It does not form part.

The peroxy acid precursors of the present invention may also be mixed into detergent additive products.

Such additive products are usually intended to supplement or enhance the performance of the detergent composition. This additive product may not contain all of the components present in the fully formulated detergent composition but may contain any of the components of such a composition. Additive products according to the features of the present invention may contain alkaline hydrogen peroxide sources under certain conditions, but are usually added to aqueous solutions containing (alkaline) hydrogen peroxide sources.

The additive product according to the features of the present invention may contain the compound alone, together with a carrier such as a compatible particulate substrate, soft particulate matter or container. Examples of compatible particulate substrates include inerts such as clays and other natural and synthetic aluminosilicates (including zeolites). Other compatible particulate carrier substrates are water soluble inorganic salts such as phosphates, carbonates and sulfates.

The additive product enclosed in a bag or container is present in a form suitable for releasing the contents when the container is dried, preventing the contents from escaping outwards and submerged in an aqueous solution.

In certain embodiments, the quaternary ammonium-substituted peroxycarboxylic acid precursors of the present invention are peroxides, which are bleaching compounds in so-called non-aqueous liquid laundry detergent compositions, in order to give effective cleaning and degreasing capabilities, particularly for textile and textile products. Suitable for mixing with (eg sodium perborate).

Non-aqueous liquid compositions, including pasty and gelatinous detergent compositions, into which bleaching precursors can be mixed, are known in the art and various compositions are described, for example, in US Pat. Nos. 2,864,770,938,938. Suggested in 772 412, 3 368977 British Patents 1 205711, 1270040, 1292352, 1370 377, 2194536, German Patent 2233771, and European Patent EP-B-0028849 It is.

Usually such a composition is a composition containing a non-aqueous liquid medium with or without a dispersed solid phase. The non-aqueous liquid medium may be a liquid surfactant, preferably a liquid nonionic surfactant: a nonpolar liquid medium, such as liquid paraffin: a polar solvent, such as, optionally, a low molecular weight monohydric alcohol such as ethanol or isopropanol. Blended polyhydric alcohols such as glycerol, sorbitol, ethylene glycol: or mixtures thereof.

Solid phases are builders, alkalines, abrasives, polymers, clays, other solid ionic surfactants, bleaches, hyogo, fluorescents and other common solid detergent components.

The bleaching precursor of the present invention is synthesized by the following compounding process.

Learn 1

m- and p-isomers

This is a two step process with starting material with suitable chloromethyl benzoic acid. The quaternization gives a high yield (90-95%) and the product precipitates by coupling of acid chloride in water, which also provides a good yield of about 85%.

Process Description

α-chloro-P-toluic acid (60 g, 0.35 m) was heated with reflux with trimethylamine (35% solution, 200 ml) in methanol for 4 hours. The product was concentrated under reduced pressure, acidified with hydrochloric acid 5 m (pH 2) and then concentrated to dryness. Thionyl chloride (100 ml) was added to the solid and the mixture was heated to reflux for 30 minutes. Excess thionyl chloride was removed under reduced pressure to give an acid chloride.

This acid chloride (100 g) was used in a 2x50 g batch containing sodium phenol sulfonic acid salt (56 g: excess) with sodium hydroxide (9.2 g: excess) in water (500 ml) without further purification.

The product separated from the solution was filtered and washed with water. Total dry yield was 73 g (60%).

This material was crystallized from water 2: 1 isopropanol to give 65 g. This material was 92% pure by 'H NMR analysis.

Learn 2

This process uses an amino acid as the starting material to quaternize it with dimethyl sulfuric acid and convert it to the appropriate acid chloride using thionyl chloride. The esterification reaction is carried out in dimethylformamide using triethylamine and phenolsulfuric acid as bases. The product is insoluble and thus obtained at leisure. The yield is not constant but is usually above 60%.

Process Description

3-N, N-dimethylaminobenzoic acid (16.5 g, 0.1 m) was dissolved in acetonitrile (100 ml) heated under reflux with dimethyl sulfuric acid (12.6 g, 0.1 m) for 6 hours. The quaternized salt obtained was crystallized and separated by filtration (25 g, 86%), this salt (5 g, 0.017 ml) was dissolved in thionyl chloride (15 ml) and heated with reflux for 2 hours. The thionyl chloride was removed under reduced pressure, and the acid chloride was added to a dry DMF containing phenolsulfonic acid triethyl ammonium salt (7.7 g) and triethylamine (2.5 g). The mixture was cooled with stirring. The product precipitated from the solution was collected by filtration and washed with methanol. This solid (3.3 g, 58%) was dried.

Learn 3

This process is similar to Process 2, which uses amino acids as starting material, which yields inconsistent yields but usually yields of 60% or more.

Process Description

Nicotinic acid (36.9 g, 0.3 m) was added to 'spectrosil' acetonitrile (200 ml) containing dimethyl sulfuric acid (37.8 g, 0.3 m) and the mixture was heated to reflux for 8 hours. After cooling, the crystallized product from the solution was separated by filtration and washed with acetonitrile. Yield was 56 g (75%).

N-methyl nicotinic acid methosulfate (10 g, 0.04 m) was dissolved in thionyl chloride (15 ml) and heated with reflux for 1 hour. Thionyl chloride was removed under reduced pressure. This acid chloride was dissolved in anhydrous DMF (15 ml) containing triethylamine (10 g) and triethylammonium salt (17 g) of 4-hydroxybenzene sulfonic acid. This mixture was sonicated and precipitated over 1 hour. This precipitate was separated by filtration and washed with methanol. This solid was vacuum dried. H NMR analysis showed 94% purity.

Learn 4

Processes 1 and 4 were used for mass production of about 2 kg. The total yield of the mass reactions was 86% and 67% for Process 1 and Process 4, respectively. The purity of the material obtained was 97% and 93%, respectively.

EXAMPLE

Two series of bleaching experiments were performed on cotton fabric stained with black tea on a turgotometer. The temperature of the washing was isothermal and the washing time was 30 minutes. The concentration of the bleaching precursor was 1.2 mM and the hydrogen peroxide was 12 mM.

One series of experiments was performed at 40 ° C., pH 9.3 and another series of experiments was performed at 22 ° C., pH 8.

Experiments were carried out using the five types of quaternary ammonium peroxycarboxylic acid precursors (ii), (iii), (iii) and (iii) of the present invention, which were quaternary ammonium peroxides in the art. Compared with oxycarboxylic acid precursors (A), N, N, N ', N'-tetraacetyl ethylene diamine (TAED) and sodium benzoyloxybenzene sulfonic acid (SBOBS).

Bleaching performance was measured using an Elrepho reflectometer and the results expressed as ΔR (460 mm) are shown in the following table.

[table]

From these data, it can be seen that the bleaching precursor of the present invention is clearly superior to the bleaching performance than Compound (A), TAED and SBOBS.

When these experiments were repeated in the presence of a conventional phosphate build detergent base powder, the bleaching precursors (ii), (iii), (iii), (iii) and (iii) of the present invention showed excellent bleaching performance with the same results. However, the bleaching precursor (A) was found to decrease ΔR from 16.9 to 9.0.

This suggests that there are no incompatibilities between the components of precursors (ii), (iii), (iii), (iii) and the detergent base powder. On the other hand it is apparent that there is incompatibility with the anionic component of the precursor (A) or its intermediate material and the detergent composition.

Claims (7)

(B) 2-40% by weight of a peroxide bleaching compound capable of producing hydrogen peroxide in an aqueous solution, (ii) a peroxycarboxylic acid precursor having the following structural formula: 0.1-20% by weight of substance (Wherein R ₁ , R ₂ , R ₃ are each selected from C ₁ -C ₁₈ alkyl, alkenyl, hydroxyalkyl and polyoxyalkylene groups, or two of R ₁ , R ₂ , and R ₃ are Together with R ₄ and N-atoms form a substituted or non-cyclic nitrogen-containing heterocyclic system, or at least two of R ₁ , R ₂ , and R ₃ together with the N-atom are substituted or unsubstituted nitrogen-containing heterocyclic Forming a system, R ₄ (when not forming a nitrogen-containing heterocyclic system together with R ₁ and / or R ₂ and / or R ₃ ) is a bridge group group selected from (Where n is 0, 1, or 2, respectively) L is a leaving group, the acid of which has a pKa (acid halide number) in the range 4-13, preferably about 8-10, and Z ⁻ is chloride, bromide , Anion selected from hydroxide, nitrate, methosulfate, bisulfate, acetate, sulfate, citrate, borate or phosphate anions). (Iii) 1-50% by weight of surfactant material selected from anionic, nonionic, amphoteric, zwitterionic and cationic surfactants and mixtures thereof (iii) 5-80% by weight of cleaning power builder The bleach detergent composition according to claim 1, wherein L has a structural formula as follows. (In transplantation, X _1, and X ₂ is H or -SO _3, respectively ^{- M +, -COO - M +} , -SO 4- M +, - (N + R 1 R 2 R 3) Z -, -NO ₂ and C ₁ -C ₈ alkyl) The bleach detergent composition according to claim 2, wherein the precursor has the following structural formula. The bleach detergent composition according to claim 3, wherein R ₁ , R ₂ and R ₃ are C ₁ -C ₄ alkyl groups. The bleach detergent composition according to claim 4, wherein R ₁ , R ₂ and R ₃ are methyl groups. The bleach detergent composition according to claim 2, wherein the bleaching precursor has the following structural formula. The bleach composition of claim 6 wherein R ₂ is methyl and n = 0.