KR19990028547A - Peroxygen Bleach-Containing Pretreatment Composition with Polyamine Stabilizers to Improve Fabric / Color Safety - Google Patents

Abstract

The present invention relates to liquid compositions comprising peroxygen bleach and certain polyamines or mixtures thereof. The invention further includes a method of pretreatment of contaminated colored fabrics to reduce color damage of the colored fabrics and / or to reduce the tensile strength loss of the fabrics.

Description

Peroxygen Bleach-Containing Pretreatment Composition with Polyamine Stabilizers to Improve Fabric / Color Safety

Peroxygen bleach-containing compositions have been widely described in laundry applications as laundry detergents, laundry additives or laundry pretreatments.

Indeed, liquid peroxygen bleach-containing compositions may be used in laundry pretreatment applications to assist in the removal of stains / dirts on surfaces that are particularly difficult to remove by other methods such as fats, coffee, tea, grass and mud / clay-containing dirt. It is known to use. However, a drawback associated with liquid peroxygen bleach-containing compositions is the relative instability of the compositions. Indeed, when packaged in containers made of deformable materials (typically thermoplastics), the liquid peroxide bleach-containing compositions can cause so-called swelling problems. Peroxygen bleach in the composition decomposes over time to generate oxygen in the composition. The released oxygen builds up pressure in the vessel, which eventually deforms, i.e., expands. The rate of degradation of the peroxygen bleach depends on different parameters such as temperature, pH and / or presence of metal ions.

A known solution to this problem is to reduce the degradation of peroxygen bleach in the metal ion chelating agents (eg polyaminocarboxylates) and / or phosphonate chelating agents and / or peroxygen bleach-containing compositions. Stabilizing radical scavengers are used in these compositions.

Representative techniques are described, for example, in EP-B-209 228, which discloses metal ion chelating agents such as amino polyphosphonates, and radicals such as hydroxybenzene compounds (butylated hydroxy toluene). A scavenger is used to stabilize liquid hydrogen peroxide bleaching compositions.

However, such liquid peroxygen bleach-containing compositions are not completely satisfactory from the manufacturer's point of view because they are chemically somewhat unstable and consequently easily expand the container for packaging them. That is, it was found that there is still room for further improving the chemical stability of the liquid peroxygen bleach-containing composition.

It is therefore an object of the present invention to formulate liquid peroxygen bleach-containing compositions which exhibit improved chemical stability, especially over a long period of time.

In addition, peroxygen bleach-containing compositions suitable for use as pretreatment agents should be stable to the fabric treated with the composition when formulated. Indeed, a drawback associated with the peroxygen bleach-containing composition is that when the composition is used under stress conditions, for example, it is applied directly to the fabric, leaving it to work on the fabric for a long time, ie, several hours, before cleaning the fabric. And / or damage the fabric when the fabric to be pretreated is contaminated with metal ions such as copper and / or iron and / or manganese and / or chromium, resulting in loss of tensile strength and / or color damage of the fabric fiber. This was found. Indeed, the presence of metal ions such as copper and / or iron and / or manganese and / or chromium on fabric surfaces, in particular cellulose fibers, is believed to promote radical decomposition of peroxygen bleach such as hydrogen peroxide. Thus, a radical reaction occurs on the fabric surface while generating free radicals, which results in a loss of tensile strength. It is also contemplated that the generation of such free radicals can aggressively decompose certain dyes present in the fabric, resulting in chemical damage of visible dye molecules such as decolorization and / or color change. Dyes generally present in colored fabrics include metal-containing dyes such as copper-formazan dyes or metal-azo dyes.

Accordingly, the inventors have found that it is essential to improve the safety for fabrics and colors by inhibiting the surface reactions that generate free radicals in a pretreatment environment.

It has recently been known that this can be done by adding certain polyamines or mixtures thereof to the peroxygen bleach-containing composition. Indeed, it is unexpectedly possible that the addition of polyamines or mixtures thereof, defined later, can significantly reduce the decomposition of peroxygen bleach, such as hydrogen peroxide, even under stress conditions such as prolonged exposure at elevated temperatures (eg, 20 days at 50 ° C.). Found. More specifically, the use of polyamines or mixtures thereof in peroxygen bleach-containing compositions alone or in combination with other bleach stabilizers, such as chelating agents and / or radical scavengers, impart chemical stability to the composition in both cases. But it is known to impart improved fabric safety and / or improved color safety to fabrics pretreated with the composition. Indeed, the stabilizing effect and fabric safety appear to be independent of the matrix.

Indeed, there is an optimal concentration for each of the chelating agents and / or radical scavengers used in the peroxygen bleach-containing composition, which gives the greatest effect in terms of peroxygen bleach stability. For example, in a peroxygen bleach-containing composition comprising less than about 10 weight percent peroxygen bleach, a well known chelating agent such as s, s-ethylenediamine N, N'-disuccinic acid (ssEDDS) or di The optimal concentration of ethylene triamine pentamethylene phosphonate or diethylene triamine pentaacetate (DTPA) is about 0.01 to 0.3 weight percent chelating agent in the total composition. That is, it was observed that increasing the optimal concentration further for the peroxygen bleach stability of the chelating agent in the peroxygen bleach-containing composition resulted in less chemically stable compositions and increased degradation of the peroxygen bleach. In addition, when different chelating agents are mixed at the optimal concentration for peroxygen bleach stability, the peroxygen stability does not increase, in contrast to the mixing which generally contributes to reducing peroxygen stability. It is unexpectedly recently known in the present invention that certain polyamines or mixtures thereof may be used in combination with other bleach stabilizers, such as chelating agents and / or radical scavengers, thereby providing peroxygen bleach compositions with improved chemical stability.

An advantage of the present invention is good washability against a wide range of stains and dirt such as bleachable stains and / or oil stains.

In addition, another advantage of the present invention is that the composition of the present invention provides excellent performance even when used in applications other than laundry pretreatment applications, such as other laundry applications as laundry detergents or laundry additives, or hard surface laundry applications or carpet laundry applications. It is.

Summary of the Invention

The present invention includes a liquid composition comprising a peroxygen bleach and a polyamine, or mixture thereof, as defined hereinafter.

The present invention also includes a method of pretreatment of a contaminated fabric using a liquid composition comprising a peroxygen bleach and a polyamine or mixture thereof defined therein, the method comprising the composition without mixing water on the fabric. Leaving the composition in contact with the fabric before applying to wash the fabric.

The present invention relates to a stable peroxygen bleach-containing composition suitable for use as a pretreatment agent.

The present invention is a liquid composition comprising a peroxygen bleach and a specific polyamine or mixture thereof.

As an essential component, the compositions of the present invention include peroxygen bleach. Preferred peroxygen bleach is hydrogen peroxide or its water-soluble source or mixtures thereof. Hydrogen peroxide is most preferred for use in the compositions of the present invention. Indeed, the presence of peroxygen bleach, preferably hydrogen peroxide, provides a strong washing effect that is particularly recognizable in laundry applications. As used herein, a hydrogen peroxide source refers to any compound that produces hydrogen peroxide when in contact with water.

Suitable water-soluble sources of hydrogen peroxide for use herein include percarbonates, persilicates, persulfates (e.g. monopersulfates), perborates, peroxy acids (e.g. diperoxydodecanedioic acid (DPDA), magnesium perphthalic acid, per Benzoic acid and alkylperbenzoic acid) and mixtures thereof.

Typically, the composition of the present invention comprises 0.01 to 90% by weight, preferably 2 to 20% by weight and most preferably 3 to 10% by weight of the peroxygen bleach in the total composition.

As a second essential ingredient, the composition of the present invention comprises a polyamine or mixture thereof having one of the following general structural formulas:

NH _2- (CH ₂ -CH ₂ -NH) _n -CH ₂ -CH ₂ -NH ₂ , where n is an integer from 0 to 15, preferably 0 to 10, more preferably 0 to 5 ,

NH ₂ -[(CH ₂ -CH ₂ -NH) _n (CH ₂ -CH ₂ -CH ₂ -NH) _m ] CH ₂ -CH ₂ -NH ₂ , where n is 0 to 8, preferably 0 Is an integer of 3 to 3, m is 0 to 8, preferably an integer of 0 to 3),

C _n H _{2n + 2-m} (NH ₂ ) _m (where n is an integer from 2 to 20, preferably 2 to 10, more preferably 2 to 5, m is 2 to 4, preferably Is an integer of 2),

C _n H _2n-m (NH ₂ ) _m where n is an integer from 2 to 20, preferably from 2 to 10, more preferably from 2 to 6, and m is from 2 to 4, preferably from 2 Is an integer),

C _n H _2n-2-m (NH ₂ ) _m where n is an integer from 3 to 20, preferably from 3 to 10, more preferably from 3 to 5, m is from 2 to 4, preferably Is an integer of 2),

C _n H _2n-4-m (NH ₂ ) _m , where n is an integer from 4 to 20, preferably from 4 to 10, more preferably from 4 to 6, m is from 2 to 4, preferably Is an integer of 2), or

C _n H _2n-6-m (NH ₂ ) _m (where n is an integer from 5 to 20, preferably 5 to 10, more preferably 5 to 7, and m is 2 to 4, preferably Is an integer of two).

Formula _{NH 2 - [(CH 2 -CH} 2 -NH) n (CH 2 -CH 2 -CH 2 -NH) m] CH 2 -CH 2 from _{-NH 2 (CH 2 -CH 2 -NH} ) n group and It should be understood that the (CH ₂ -CH ₂ -CH ₂ -NH) _m groups can appear in any order within the molecule.

Thus, suitable polyamines or mixtures thereof for use in the present invention are generally 1,2 alkyl diamines (eg 1,2 propyl diamine), 1,3 alkyl diamines (eg 1,3 propyl-diamine), 1,4 Alkyl diamines such as 1,4 butyl-diamine, propylene diamine, isopropylene diamine, ethylene diamine. A very preferred polyamine for use herein is ethylene diamine (EDA).

Suitable polyamines for use herein can be purchased from Union Carbide. For example, ethylene diamine can be purchased from Union Carbide under the EDA® trade name.

Typically, the composition of the present invention comprises 0.01 to 5.0% by weight, preferably 0.1 to 3.0% by weight, most preferably 0.4 to 1.5% by weight of the polyamine or mixture thereof in the total composition.

The peroxygen bleach-containing composition of the present invention is chemically stable. The term "chemically stable" means that the compositions of the present invention comprising peroxygen bleach do not lose more than 10% oxygen available at 50 ° C. for two weeks. The concentration of available oxygen can be measured by chemical titration methods known in the art, such as iodine titration, permanganese titration and celium sulfate titration. Selection criteria for this and appropriate methods are described, for example, in "Hydrogen Peroxide", W. C. Schub, C. N. Satterfield and R. L. Wentworth, Reinhold Publishing Corporation, New York, 1955; "Organic Peroxides", Daniel Swern, Editor Wiley Int. Science, 1970.

Alternatively, the stability of the composition can be assessed by expansion test as described herein later in the experimental data.

The present invention compares the present compositions with the same compositions that do not contain polyamines or mixtures thereof by reducing peroxygen bleach degradation in the peroxygen bleach-containing compositions of the present invention comprising polyamines or mixtures thereof as defined herein. It is based on the discovery that it prevents expansion of the deformable container contained therein. As used herein, “modified container” means any hermetically sealed container that is generally used in the art to package detergent compositions such as pretreatment agents and is capable of expanding under internally generated pressure. Such containers include thin metal materials and / or new materials, such as aluminum sheets, recycled materials and mixtures thereof, vinyl chloride resins, polymers and copolymers derived from olefins, acrylic polymers and copolymers, polyethylene, polypropylene, polystyrene, polyethylene And those made of thermoplastics (single layer or multilayer materials) including terephthalates or mixtures thereof.

Accordingly, the peroxygen bleach-containing composition of the present invention can be packaged in a given container / bottle without prolonging the stability of the container / bottle containing the composition upon long-term standing, provided that The same composition which does not contain a polyamine or mixtures thereof as defined in can be packaged in the given container / bottle.

In addition, the present invention, in addition to the enhanced peroxygen stability imparted by the peroxygen bleach-containing compositions of the present invention comprising polyamines or mixtures thereof as defined herein, may be used when the composition is used to pretreat contaminated fabrics. It is based on the finding that the same mixture, which does not contain polyamines or mixtures thereof, gives improved fabric safety as compared to the use for pretreating the fabric. Indeed, using peroxygen bleach-containing compositions comprising polyamines or mixtures thereof as defined herein, the composition is left on the fabric for a prolonged period of time (ie, about 24 hours or more) before the fabric is washed, Example: At least 30 ppm copper per gram of fabric), even when contaminated with metal ions such as copper and / or iron and / or manganese, the loss of tensile strength of the pretreated fabric can be significantly reduced.

The tensile strength loss of the fabric can be measured using the Tensile Strength method, as can be seen later in the Examples herein. This method consists in measuring the tensile strength of the fabric by stretching it until the desired fabric breaks. The force (kg) required to break the fabric is "Ultimate Tensile Stress" and can be measured using a "Stress Deform Instron Machine". "Tensile strength loss" is understood as the difference when comparing the tensile strength of a fabric provided as a reference (eg, a non-pretreated fabric) with the tensile strength of the same fabric pretreated according to the invention. Zero tensile strength loss means that no fabric damage was observed.

The present invention also provides polyamines when the composition is used for pretreatment of contaminated colored fabrics, in addition to the enhanced peroxygen stability imparted by the peroxygen bleach-containing compositions of the present invention comprising polyamines or mixtures thereof as defined herein. Or based on the discovery that the same composition, except without containing a mixture thereof, confers improved color safety compared to when used to pretreat the fabric. Indeed, the use of peroxygen bleach-containing compositions comprising polyamines or mixtures thereof as defined herein results in color change of the pretreated colored fabrics even if the composition is left on the colored fabrics for an extended period of time (about 24 hours or more) prior to washing the colored fabrics. And / or discoloration is significantly reduced.

The composition according to the invention is an aqueous liquid wash composition. The aqueous composition should be formulated at an acidic pH, preferably at a pH of 0-6, more preferably at a pH of 2-5. Formulation of the composition of the present invention in the acidic pH range contributes to the stability of the composition. The pH of the composition of the present invention can be adjusted by using an organic acid, an inorganic acid or an alkalizing reagent.

The present invention includes, for example, raw material compositions essentially containing peroxy bleach and comprising polyamines or mixtures thereof as defined herein, other stabilizers, chelating agents, radical scavengers, surfactants, bleach activators, reinforcing agents, dirt suspensions. Agents, solvents, varnishes, perfumes, foaming inhibitors, dyes or mixtures thereof, including fully formulated detergent compositions incorporating additional ingredients commonly used in the field of detergents.

Peroxygen bleach-containing compositions of the invention may comprise chelating agents or mixtures thereof as very preferred optional ingredients. Chelating agents suitable for use herein are additional agents such as phosphonate chelating agents, amino carboxylate chelating agents, polyfunctional-substituted aromatic chelating agents, and glycine, salicylic acid, aspartic acid, glutamic acid, malonic acid or mixtures thereof. Chelating agents selected from the group consisting of chelating agents.

Suitable phosphonate chelating agents for use herein are etidronic acid, and amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonate, ethylene diamine Amino phosphonate compounds, including tetramethylene phosphonate and diethylene triamine penta methylene phosphonate. The phosphonate compound may exist in its acid form or in a different cation salt form for some or all of the acid functionality. Preferred phosphonate chelating agent for use herein is diethylene triamine penta methylene phosphonate. Such phosphonate chelating agents can be purchased from Monsanto under the DEQUEST® trade name.

Multifunctional-substituted aromatic chelating agents may also be useful in the present compositions. See US Pat. No. 3,812,044 to Connor et al. On May 21, 1974. Preferred compounds of this kind in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

Preferred biodegradable chelating agents for use herein are ethylene diamine N, N'-disuccinic acid, or alkali metal, alkaline earth metal, ammonium or substituted ammonium salts or mixtures thereof. Ethylenediamine N, N'-disuccinic acid, in particular (S, S) isomers, is described extensively in US Pat. No. 4,704,233, issued November 3, 1987 to Hartman and Perkins. Ethylenediamine N, N'-disuccinic acid is commercially available, for example, under the ssEDDS trade name from Palmer Research Laboratories.

Suitable amino carboxylates for use herein include ethylene diamine tetra acetate, diethylene triamine pentaacetate, diethylene triamine pentaacetate (DTPA), N-hydroxyethylethylenediamine triacetate, nitrilotriacetate, ethylenediamine tetraprop Cypionate, triethylenetetraamine hexaacetate, ethanol diglycine, propylene diamine tetraacetic acid (PDTA) and methyl glycine di-acetic acid (MGDA) are included in acid form, or both in their alkali metal, ammonium and substituted ammonium salt forms. Particularly suitable amino carboxylates for use herein are diethylene triamine penta acetic acid, propylene diamine tetraacetic acid (PDTA; e.g., commercially available from BASF under the Trilon FS® trade name) and methyl glycine di-acetic acid (MGDA )to be.

Particularly preferred chelating agents for use herein are diethylene triamine methylene phosphonate, ethylene N, N'-disuccinic acid, diethylene triamine pentaacetate, glycine, salicylic acid, aspartic acid, glutamic acid, malonic acid or mixtures thereof Salicylic acid is very preferred. Salicylic acid is available from Rhone-Poulenc under the Salicylic Acid tradename.

The peroxygen bleach-containing composition of the present invention may further comprise a radical scavenger or a mixture thereof as a very preferred optional ingredient. Suitable radical scavengers for use herein include substituted monohydroxybenzenes, substituted dihydroxybenzenes and their analogs, alkyl carboxylates, aryl carboxylates and mixtures thereof well known. Preferred radical scavengers for use herein are di-tert-butyl hydroxy toluene (BHT), hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone, tert-butyl-hydroxy anisole , Benzoic acid, toluic acid, tert-butyl catechol, benzylamine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, n-propyl-gallate or Di-tert-butyl hydroxy toluene, including mixtures thereof, is very preferred.

The peroxygen-bleach containing composition of the present invention may add any surfactant known to those skilled in the art, including nonionic, anionic, cationic, zwitterionic or zwitterionic surfactants or mixtures thereof. It can be included as.

In addition, the peroxygen-bleach containing composition of the present invention may comprise a liquid hydrophobic bleach activator as a very preferred optional ingredient. By “bleach activator” is meant herein a compound that reacts with hydrogen peroxide to form peracids. The peracids thus formed constitute an activating bleach. By "hydrophobic bleach activator" is meant an active agent that is not substantially stably miscible with water. Typically, the hydrophobic bleach activator has an HLB of less than 11. Suitable liquid hydrophobic bleach activators typically belong to the ester, amide, imide or anhydride class. Particularly interesting groups of bleach activators are described in EP 624 154, with particular preference being given to acetyl triethyl citrate (ATC). ATC eventually breaks down into citric acid and alcohol, which has other environmentally friendly benefits. In addition, ATC has sufficient hydrolytic stability in the present compositions and is an efficient bleach activator. As a result, ATC provides sufficient reinforcement to the composition. It is also possible here to use mixtures of liquid hydrophobic bleach activators. The present composition in which the bleach activator is present should comprise from 0.5 to 20% by weight, preferably from 2 to 10% by weight and most preferably from 3 to 7% by weight of the total composition.

When the peroxygen bleach-containing composition according to the invention further comprises a liquid hydrophobic bleaching activator, an aqueous emulsion comprising a liquid hydrophobic bleaching activator, or hydrophilic including water, peroxygen bleach and anionic and nonionic surfactants. It is highly desirable for stability to blend the composition as a microemulsion of liquid hydrophobic bleach activator in a matrix comprising a surfactant system.

In an embodiment of the invention wherein the peroxygen bleach-containing composition of the invention is formulated as an aqueous emulsion, the peroxygen bleach-containing emulsion has two or more different surfactants, i.e. up to 9 HLB, to emulsify the liquid hydrophobic bleaching agent. Surfactant systems of at least one hydrophobic surfactant and at least one hydrophilic surfactant having an HLB greater than 10. Indeed, the two different surfactants for forming a stable emulsion should have different HLB values (hydrophilic lipophilic equilibrium values) and preferably the difference in the HLB values should be at least 1, preferably at least 3. That is, by properly mixing two or more surfactants with different HLB in water, a stable emulsion is formed that does not substantially separate into separate layers upon standing at 50 ° C. for at least two weeks.

Emulsions according to the invention comprise from 2 to 50% by weight, preferably from 5 to 40% by weight, more preferably from 8 to 30% by weight of hydrophilic and hydrophobic surfactants in the total composition. The emulsion according to the invention is at least 0.1% by weight, preferably at least 3% by weight, more preferably at least 5% by weight, and at least 0.1% by weight of hydrophilic surfactant or mixture thereof in the total emulsion. Or more, preferably 3% by weight or more, and more preferably 6% by weight or more.

Hydrophobic nonionic surfactants and hydrophilic nonionic surfactants are preferred for use herein. Hydrophobic nonionic surfactants as used herein have an HLB of 9 or less, preferably less than 9, more preferably less than 8, and the hydrophilic surfactant is an HLB greater than 10, preferably an HLB greater than 11, more preferably. Preferably has an HLB greater than 12. Indeed, the hydrophobic nonionic surfactants used herein have good oily cleavage properties and therefore have a solvent effect that contributes to hydrophobic dirt removal. The hydrophobic surfactant acts as a carrier of the hydrophobic varnish on the fabric, whereby the varnish acts near the fabric surface after initiation of the wash.

Suitable nonionic surfactants for use herein include alkoxylated fatty alcohols, preferably fatty alcohol ethoxylates and / or propoxylates. Indeed, many different alkoxylated fatty alcohols with very different HLB values (hydrophilic lipophilic equilibrium) are commercially available. The HLB value of the alkoxylated nonionic surfactant depends essentially on the chain length of the fatty alcohol, the nature of the alkoxylation reaction and the degree of alkoxylation. Hydrophilic nonionic surfactants are likely to have high alkoxylation reactivity and short chain fatty alcohols, while hydrophobic surfactants are likely to have low alkoxylation reactivity and long chain fatty alcohols. Each HLB can be purchased with a list of surfactants describing many surfactants, including nonionics.

Suitable chemical processes for preparing nonionic surfactants for use herein include condensation reactions of the corresponding alcohols and alkylene oxides in the desired ratios. Such processes are well known to those skilled in the art and have been described extensively in the art. Optionally, many different alkoxylated alcohols suitable for use herein are commercially available from various suppliers.

Preferred hydrophobic nonionic surfactants for use in the emulsions according to the invention are surfactants according to the formula RO- (C ₂ H ₄ O) _n (C ₃ H ₆ O) _m H, having an HLB of 9 or less, wherein Wherein R is a C ₆ to C ₂₂ alkyl chain or a C ₆ to C ₂₈ alkyl benzene chain, n + m is 0.5 to 5, n is 0.5 to 5, m is 0 to 5, preferably n + m is 0.5 to 4, n and m are 0-4. Preferred R chains for use herein are C ₈ to C ₂₂ alkyl chains. Accordingly, suitable hydrophobic nonionic surfactants for use herein include Dobanol® 91-2.5 (HLB = 8.1; R is a mixture of C ₉ and C ₁₁ alkyl chains, n is 2.5, m is 0), Lutensol® TO3 (HLB = 8; R is a mixture of C ₁₃ and C ₁₅ alkyl chains, n is 3, m is 0), Tergitol® 25L3 (HLB = 7.7; R is C ₁₂ to C ₁₅ alkyl chain length, n is 3, m is 0, Dobanol® 23-3 (HLB = 8.1; R is a mixture of C ₁₂ and C ₁₃ alkyl chains, n is 3, m is 0 ), Dobanol® 23-2 (HLB = 6.2; R is a mixture of C ₁₂ and C ₁₃ alkyl chains, n is 2, m is 0) or mixtures thereof. Preferred herein are Dobanol® 23-3, Dobanol® 23-2, Lutensol® TO3 or mixtures thereof. The Dobanol® surfactant is commercially available from SHELL. The Lutensol® surfactants are commercially available from BASF, and Tergitol® surfactants are commercially available from Union Carbide. Other suitable hydrophobic nonionic surfactants used herein are nonalkoxylated surfactants. An example is Dobanol® 23 (HLB <3).

Preferred hydrophilic nonionic surfactants used in the emulsions according to the invention are surfactants which have an HLB greater than 10 and according to the formula RO- (C ₂ H ₄ O) _n (C ₃ H ₆ O) _m H, wherein R is C ₆ to C ₂₂ alkyl chain or C ₆ to C ₂₈ alkyl benzene chain, n + m is 5 to 11, n is 0 to 11, m is 0 to 11, preferably n + m is 6 to 10 , n and m are 0 to 10. N and m throughout this specification refer to the average reactivity of ethoxylation / propoxylation. Preferred R chains for use herein are C ₈ -C ₂₂ alkyl chains. Thus, suitable hydrophilic nonionic surfactants for use herein include Dobanol® 23-6.5 (HLB = 11.9; R is a mixture of C ₁₂ to C ₁₃ alkyl chains, n is 6.5, m is 0), Dobanol® 25-7 (HLB = 12; R is a mixture of C ₁₂ to C ₁₅ alkyl chains, n is 7, m is 0), Dobanol® 45-7 (HLB = 11.6; R is A mixture of C ₁₄ and C ₁₅ alkyl chains, n is 7, m is 0), Dobanol® 91-5 (HLB = 11.6; R is a mixture of C ₉ to C ₁₁ alkyl chains, n is 5, m Is 0), Dobanol® 91-6 (HLB = 12.5; R is a mixture of C ₉ to C ₁₁ alkyl chains, n is 6, m is 0), Dobanol® 91-8 (HLB = 13.7; R is a mixture of C ₉ to C ₁₁ alkyl chains, n is 8, m is 0), Dobanol® 91-10 (HLB = 14.2; R is a mixture of C ₉ to C ₁₁ alkyl chains, n is 10, m is 0) or a mixture thereof. Preference is given here to Dobanol® 91-10, Dobanol® 45-7, Dobanol® 23-6.5 or mixtures thereof. These Dobanol® surfactants are commercially available from Shell. Apart from hydrophilic nonionic surfactants, other hydrophilic surfactants, such as the anionic surfactants described herein below, may further be used in the emulsions of the present invention.

Emulsions according to the present invention may further comprise other surfactants which do not significantly change the weighed average HLB of the total emulsion.

In a preferred embodiment of the emulsion of the invention comprising a liquid hydrophobic bleach activator, the emulsification system satisfies the following equation:

In the above,

X refers to the hydrophobic component to emulsify, and, if several hydrophobic components are present, all of them,

A refers to one of the nonionic surfactants (hydrophilic or hydrophobic),

B refers to one of the other nonionic surfactants (hydrophilic or hydrophobic),

The sum of% A and% B is 100%.

In a particularly preferred embodiment of the emulsion of the invention wherein the emulsion comprises acetyl triethyl citrate as the bleaching agent, suitable nonionic surfactant systems are for example hydrophobic nonionic surfactants having a HLB of 6 (e.g., Dobanol (registered) 23-2) and, for example, hydrophilic nonionic surfactants having an HLB of 15 (e.g., Dobanol® 91-10). Other suitable nonionic surfactant systems include, for example, Dobanol® 23-6.5 (about 12 HLB) and Dobanol® 23 (less than 6 HLB) or Dobanol® 45-7 ( HLB 11.6) and Lutensol® TO3 (HLB 8).

In an embodiment of the invention wherein the peroxygen bleach-containing composition of the invention is formulated as a microemulsion, the peroxygen bleach-containing microemulsion according to the invention comprises a hydrophilic surfactant system comprising an anionic surfactant and a nonionic surfactant. It includes. A key element for the stable incorporation of hydrophobic actives is that one or more surfactants must have an HLB value that is significantly different from the HLB value of the hydrophobic active agent. Indeed, if all surfactants have an HLB value equal to the HLB value of the hydrophobic active agent, a continuous single phase will form which will lower the chemical stability of the bleach / bleach activator system. Preferably, the at least one surfactant has an HLB that differs from the bleach activator and at least 1.0 HLB units, preferably at least 2.0 HLB units.

Suitable anionic surfactants herein include a water soluble salt of formula ROSO ₃ M or an acid thereof, wherein R is preferably an alkyl having a C ₁₀ -C ₂₄ hydrocarbyl, preferably a C ₁₀ -C ₂₀ alkyl component. Or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, M is H or a cation such as an alkali metal cation (eg sodium, potassium, lithium) or ammonium or substituted ammonium (eg 4, such as quaternary ammonium cations derived from tetramethyl ammonium and dimethyl pipedinium cations, and alkylamines such as ethylamine, diethylamino, triethylamine and mixtures thereof, and the like. Quaternary ammonium cation). Typically, C ₁₂ -C ₁₆ alkyl chains are preferred for low wash temperatures (eg below about 50 ° C.), and C ₁₆ -C ₁₈ alkyl chains are preferred for high wash temperatures (eg above about 50 ° C.). .

Other anionic surfactants suitable for use herein are water soluble salts or acids of the formula RO (A) _m SO ₃ M, wherein R represents an unsubstituted C ₁₀ -C ₂₄ alkyl or C ₁₀ -C ₂₄ alkyl component. Having a hydroxyalkyl group, preferably C ₁₂ -C ₂₀ alkyl or hydroxy alkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxy alkyl, A is an ethoxy or propoxy unit, m is greater than 0 Large, typically from about 0.5 to about 6, more preferably from about 0.5 to about 3, M is H or, for example, metal cations (eg sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted Cation, which may be an ammonium cation. Alkyl ethoxylated sulfates and alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethylammonium; And quaternary ammonium cations which are cations derived from tetramethyl-ammonium and dimethyl piperidinium and alkanolamines such as ethyl amine, diethyl amine, triethyl amine and mixtures thereof and the like. Exemplary surfactants include C ₁₂ -C ₁₈ alkyl polyethoxylate (1.0) sulfate, C ₁₂ -C ₁₈ (1.0) M, C ₁₂ -C ₁₈ alkyl polyethoxylate (2.25) sulfate, C ₁₂ -C ₁₈ E (2.25) M, C ₁₂ -C ₁₈ alkyl polyethoxylate (3.0) sulfate C ₁₂ -C ₁₈ E (3.0) and C ₁₂ -C ₁₈ alkyl polyethoxylate (4.0) sulfate C ₁₂ -C ₁₈ E (4.0) M, where M is conveniently selected from sodium and potassium.

In addition, other anionic surfactants useful for detergent purposes can be used herein. These include salts of soaps (eg, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts), C ₉ -C ₂₀ linear alkylbenzenesulfonates, C ₈ -C Sulfonated polycarboxylic acids prepared by sulfonation of pyrrolation products of alkaline earth metal citrates as described in ₂₂ primary or secondary alkanesulfonates, C ₈ -C ₂₄ olefinsulfonates, British Patent No. 1,082,179, C ₈ -C ₂₄ Alkyl polyglycol ether sulfate (containing up to 10 moles of ethylene oxide); Alkyl ester sulfonates such as C ₁₄ -C ₁₆ methyl ester sulfonates; Acyl glycerol sulfonate, fatty oleyl glycerol sulfate, alkyl phenol ethylene oxide ether sulfate, paraffin sulfonate, alkyl phosphate, isethionate (e.g. acyl isethionate, N-acyl taurate, alkyl succinate and sulfosuccisine ), Monoesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinates (especially saturated and unsaturated C ₆ -C ₁₄ diesters), acyl sacosylates Sulfates of alkylpolysaccharides such as sulfates of alkylates, alkylpolyglucosides (nonionic nonsulfated compounds are described below), branched primary alkyl sulfates, formula RO (CH ₂ CH ₂ O) _k CH ₂ COO ^- M Alkyl polyethoxy carboxylates, such as compounds of ⁺ , wherein R is C ₈ -C ₂₂ alkyl, k is an integer from 0 to 10, and M is soluble salt-forming It is a cation. Also suitable are resinous acids and hydrogenated resinous acids, such as resinic acids and hydrogenated resinous acids present in or derived from rosin, hydrogenated rosin, and tol oils. Further examples are provided in "Surface Active Agents and Detergents", Vol I and II, Schwartz, Perry and Berch. In addition, various surfactants are generally described in US Pat. No. 3,929,678, column 23, line 58 to column 29, line 23, issued December 30, 1975 to Laughlin et al. Used as a reference in.

Preferred surfactants for use in microemulsions herein are alkyl benzene sulfonates, alkyl sulfates, alkyl alkoxylated sulfates and mixtures thereof. As mentioned above, anionic surfactants provide improved washability. In addition, the anionic surfactants of the present application appear to improve the physical stability of the microemulsion of the present invention even at high temperatures (less than 50 ℃) in a small amount.

Suitable nonionic surfactants for use in the microemulsions herein include hydrophilic nonionic surfactants as described above for the emulsion.

Preferred preparations of the microemulsions of the present invention comprising liquid hydrophobic bleaching activators include premixing the surfactant with water followed by addition of other components including hydrogen peroxide and hydrophobic bleaching activators. Regardless of this preferred order of addition, during the mixing of the constituents it is important to constantly stir the microemulsion under a relatively high stirring energy, preferably at 750 rpm for 30 minutes, most preferably at 1000 rpm for 30 minutes.

In an embodiment of the invention wherein the composition is formulated into a microemulsion, the composition is transparent to the naked eye in the absence of opaques and pigments. In the centrifugation test, the microemulsion of the present application was observed to show no phase separation after 15 minutes at 6000 rpm. On microscopic examination, the microemulsion appeared as droplet dispersion in the matrix. The matrix is the hydrophilic matrix described above, and the droplets are composed of liquid hydrophobic bleach activators. We have observed that the particles typically have a size of about 3 microns or less in diameter.

The peroxygen bleach-containing composition of the present invention may further comprise an amine oxide surfactant according to the formula R1R2R3NO, wherein each of R1, R2 and R3 is independently C ₆ -C ₃₀ , preferably C ₁₀ -C ₃₀ , most preferably a C ₁₂ -C ₁₆ hydrocarbon chain. Indeed, the inventors have observed that improved chemical stability, ie, where bleach and bleach activator are present, degrades less by the addition of amine oxides. This stability appears to be due to the ability of the amine-oxide to limit the interaction through emulsification between bleach and bleach activator, if present. This stabilization effect appears to be independent of the matrix. It was further observed that the presence of amine oxides in the pretreatment process improves washability for particulates and / or oily stains. This improvement in washability appears to be independent of the matrix. In order to obtain this effect, the amine oxide should preferably be present at 0.1 to 10% by weight, more preferably 1 to 3% by weight of the total composition.

The peroxygen bleach-containing composition of the present invention may further comprise up to 10% by weight, preferably 2 to 4% by weight of alcohol according to the formula HO-CR'R "-OH in the total composition, wherein R ' And R ″ are independently H or C ₂ -C ₁₀ hydrocarbon chains and / or cycles. Preferred alcohols according to the above formula are propanediol. Indeed, the inventors have observed that these common alcohols, and in particular propanediol, also improve the chemical stability of the composition to reduce their degradation to amine oxides when bleach and bleach activator are present. In addition, the alcohol lowers the surface tension of the product to prevent the formation of surface films or gels. Thus, the alcohol improves the appearance of the present composition. The chemical stabilizing effect of the alcohol appears to be a two factor. Firstly, the alcohol can act as a radical scavenger, and secondly, interact with the hydrogen peroxide while preventing or limiting hydrolysis to reduce the rate of decomposition of the peroxide. The improvement in chemical stability obtained by alcohol appears to be independent of the matrix.

The peroxygen bleach-containing composition according to the present invention may further comprise a blowing inhibitor such as 2-alkyl alkanol or mixtures thereof as an optional component. Particularly suitable for use in the present invention are 2-alkyl alkanols having alkyl chains having 6 to 16 carbon atoms, preferably 8 to 12 carbon atoms and terminal hydroxy groups, wherein the alkyl chain is in the α position. Substituted by an alkyl chain containing 1 to 10, preferably 2 to 8, more preferably 3 to 6 carbon atoms. Such suitable compounds are commercially available, for example, in the Isofol series such as Isofol® 12 (2-butyl octanol) or Isofol® 16 (2-hexyl decanol). Typically, the compositions of the present invention comprise up to 2% by weight, preferably 0.05 to 1.5%, most preferably 0.1 to 0.8% by weight of 2-alkyl alkanols or mixtures thereof in the total composition.

The present invention includes a process for pretreatment of a contaminated fabric using a liquid composition comprising a peroxygen bleach and a polyamine or mixtures thereof as defined herein, wherein the process is preferably applied to the fabric in a form that is not mixed with water. Preferably, prior to washing the fabric, leaving the composition in contact with the fabric while preventing the composition from drying on the fabric. The composition can typically be left in contact with the fabric for 1 minute to 24 hours, preferably 1 minute to 1 hour, more preferably 5 minutes to 30 minutes. Alternatively, if the fabric is contaminated with stains / dirts on the surface that are relatively difficult to remove, the composition according to the invention may be rubbed and / or brushed somewhat strongly, for example by using a sponge, a brush or simply by rubbing the two parts of the fabric together. can do.

The term "washing" herein means using a washing machine or simply rinsing the fabric with water by hand or washing the fabric with a conventional composition comprising one or more surfactants.

By "mixed with water" herein is meant that the composition described herein is added directly onto the fabric to be pretreated without dilution, ie the composition is applied as described herein.

According to the process of pretreatment of the contaminated fabric of the present invention, the liquid composition used in the process should preferably not be left to dry on the fabric. Indeed, water evaporation is known to increase the concentration of free radicals on the fabric surface and consequently increase the rate of the chain reaction. It is also assumed that the liquid composition is left to dry on the fabric so that an automatic oxidation reaction occurs when the water evaporates. The auto-oxidation reaction generates peroxygen-radicals that can contribute to cellulose degradation. Thus, in the pretreatment process of the contaminated fabric of the present invention, as described herein, the liquid composition does not allow it to dry on the fabric, thereby contributing to the effects of the present invention to pretreat the fabric using a liquid peroxygen-bleach containing composition. Can reduce the tensile strength loss.

Preferred uses of the compositions described herein are laundry pretreatments, but the compositions according to the invention can also be used as laundry detergents or laundry detergent promoters and lobster cleaners in bathrooms and kitchens for washing dishes and carpets.

The invention can be further illustrated by the following examples.

A) Stability Test Method

The following compositions were prepared by mixing the described components in the stated proportions (% by weight unless otherwise indicated).

Composition I II III IV V VI Na Alkyl Sulfonate 2.0 2.0 2.0 2.0 2.0 2.0 Dobanol® 45-7 8.6 8.6 8.6 8.6 8.6 8.6 Dobanol® 23-3 6.4 6.4 6.4 6.4 6.4 6.4 ATC 3.5 3.5 3.5 3.5 3.5 3.5 H ₂ O ₂ 6.0 6.0 6.0 6.0 6.0 6.0 BHT 0.05 0.05 0.05 0.05 0.05 0.05 DTPA 0.1 0.5 - - - - DETPMP - - 0.1 0.37 - - Ethylene diamine - - - - 0.5 1.2 Water and small amounts of material Up to 100% H ₂ SO ₄ up to pH 4 Time to inflate container during storage at 50 ℃ (days) 4-6 2-3 10-12 6-7 14-16 21-24 ATC is acetyl triethyl citrate. BHT is di-tert-butyl hydroxy toluene marketed by Shell Corporation under the IONOL CP tradename. DTPA is diethylene triamine pentaacetate. DETPMP is a DEQUEST® from Monsanto. Trademark: diethylene triamine pentamethylene phosphonate commercially available under the trade name.

Composition VII VIII IX X Na alkylsulfonate 2.0 2.0 2.0 2.0 Dobanol (registered trademark) 45-7 8.6 8.6 8.6 8.6 Dobanol (registered trademark) 23-3 6.4 6.4 6.4 6.4 ATC 3.5 3.5 3.5 3.5 H ₂ O ₂ 6.0 6.0 6.0 6.0 BHT 0.05 0.05 0.05 0.05 Ethylene diamine - 0.5 - 0.5 Malonic acid 1.5 1.5 - - Salicylic acid - - 2 1.5 Water and small amounts of material Up to 100% H ₂ SO ₄ up to pH 4 Number of days to inflate container at 50 ° C storage 3-4 5-6 8-10 13-15 ATC is acetyl triethyl citrate. BHT is di-tert-butyl hydroxy toluene sold by Shell Corporation under the IONOL CP® tradename.

Compounds I to IV are considered by reference and they include hydrogen peroxide and other chelating agents provided in amounts such as diethylene triamine pentaacetate or diethylene triamine penta methylene phosphonate. Compositions VII and IX are also considered to be standards, which include malonic acid and salicylic acid as hydrogen peroxide and chelating agents.

Compositions V and VI represent the present invention, which comprise hydrogen peroxide and polyamines defined herein, ie ethylene diamine (EDA), in different amounts. Compositions VIII and X also represent the present invention, which comprise chelating agents, ie hydrogen peroxide in addition to malonic acid and salicylic acid and a polyamine as defined herein, ie ethylene diamine (EDA).

Stability testing was carried out using the compositions I to X mentioned herein above. This test was performed by filling each of the compositions I-X in the same container. The vessel used was a 250 ml bottle about 200 mm high, about 50 mm deep and about 60 mm wide. The wall thickness of the bottle was 1-3 mm. The vessel was sealed with a sealed lid using screws. To ensure tightness during the test, a silicone band was added over the screws and the lid was sealed with tape. The filled closed container was then stored at 50 ° C. for a designated period. Each composition was tested in six different iterations. Expansion was assessed by visually observing the rocker bottom on the vessel.

The results are expressed as the time it takes for the vessel to expand (rocker bottom). Indeed, the first numerical value of the results indicated herein above for Compositions I-X represents the time (in days) required to observe the rocker bottom for one or more of the six containers tested for the provided compositions, The second figure of the result represents the time (in days) required to observe the rocker bottom over the entire of six containers for the composition.

The results clearly show that the peroxygen-bleach-containing composition of the present invention comprising a polyamine as defined herein, for example ethylene diamine, exhibits improved chemical stability. Indeed, the results indicate that ethylene diamine is used alone (compositions V and VI vs. I, II, III vs. IV) or in addition to chelating agents (compositions VIII vs. Compositions VII and X vs. compositions for the compositions of the present invention). IX) demonstrates an increase in the time required to observe the expansion of the donor vessel (rocker bottom) under stress conditions, i.e. at 50 ° C. storage, in comparison with the same composition except that it does not contain ethylene diamine in both cases. Apply.

B) Tensile Strength Test Method

The following compositions are prepared by mixing the described ingredients in the stated proportions (% by weight unless otherwise indicated).

Composition I II III IV V VI Na Alkyl Sulfonate 2.0 2.0 2.0 2.0 2.0 2.0 Dobanol 45-7 8.6 8.6 8.6 8.6 8.6 8.6 Dobanol 23-3 6.4 6.4 6.4 6.4 6.4 6.4 ATC 3.5 3.5 3.5 3.5 3.5 3.5 H ₂ O ₂ 6.0 6.0 6.0 6.0 6.0 6.0 BHT 0.05 0.05 0.05 0.05 0.05 0.05 DTPA 1.5 - - - - - Malonic acid - - 1.5 1.5 - - Salicylic acid - - - 1.0 1.0 Ethylene diamine - 1.5 - 0.5 - 0.5 Water and small amounts of material Up to 100% H ₂ SO ₄ up to pH 4 Tensile Strength Loss (%) 40 21 29 25 18 11 The pretreated 24-hour fabric was contaminated with 30 ppm of copper per gram of fabric. ATC is acetyl triethyl citrate. BHT is di-tert-butyl hydroxy toluene sold under the IONOL CP® brand in the shell. Diethylene triamine pentaacetate.

Composition I comprising 1.5% by weight of diethylene triamine pentaacetate was not suitable and the rocker bottom appeared within just 1 day. Composition I is considered herein as a criterion for evaluating the strength loss of the steel. Compositions III and V are also considered to be standards, which include hydrogen peroxide and chelating agents such as salicylic acid or malonic acid. Compositions II, IV and VI represent the present invention comprising hydrogen peroxide and ethylene diamine.

Tensile strength testing was performed using the compositions mentioned herein above. This test was performed on fabrics contaminated with metal. Indeed, cotton ribbons (12.5 X 5 cm 2 dimensions) having a copper concentration of 30 ppm per gram of cotton were pretreated according to the present invention. Indeed, the cotton ribbons were pretreated using 2 ml of each liquid composition referred to herein above. Before rinsing the ribbon with water, the composition was left for 24 hours to come into contact with the ribbon. The damage on the fabric (e.g. cotton ribbon) was then assessed by stretching the ribbon until the ribbon broke. The force required to break the ribbon, ie the final tensile stress, was measured in the wet state using a stress straining Instron machine, model 4411. The lower the force required to break the cotton ribbon, the more severe the damage caused to the fabric. Sufficient confidence in the results (standard deviation = 2-4 kg) is obtained by repeating each test five times.

The tensile strength loss mentioned above for the different compositions tested is expressed in%, and the tensile strength of the donor fabric (i.e., the non-pretreated fabric) to be considered as a reference and of the fabric measured after pretreatment as mentioned herein above. Obtained by comparing tensile strength.

The result is the use of a liquid composition according to the composition of the invention comprising peroxygen bleach and a polyamine (e.g. ethylene diamine) alone (composition II vs. composition I) or in addition to chelating agents (compositions IV vs. compositions III and VI Composition V) clearly shows that an unexpected fabric stabilizing effect, i.e. a reduction in tensile strength loss, is obtained compared to using the same composition except that it does not contain a polyamine. Indeed, the tensile strength loss is reduced even in the presence of high concentrations of copper (30 ppm per gram of cotton fabric) on the fabric surface upon prolonged (ie 24 hours) contact when pretreating the fabric with the composition according to the invention.

The following compositions were prepared by mixing the substrate components in a substrate proportion (% by weight unless otherwise indicated).

Composition I II III IV V VI H ₂ O ₂ 6.0 6.0 6.0 7.0 7.0 6.0 ATC 3.5 3.5 3.5 - - 3.5 Alkylsulfonate (1) 12 12 12 2 2 2 Dobanol® 23-3 12 12 12 - 3 - Dobanol® 45-7 - - - 3 - 15 Ethylene diamine 1.0 0.5 0.5 1.0 0.5 0.5 Salicylic acid - 1.0 - - 1.0 1.0 Malonic acid - - 1.0 - - - Water and a small amount of material (dye) Up to 100% H ₂ SO ₄ up to pH 4

In an embodiment said composition is in accordance with the invention. Tensile strength loss is due to the presence of high concentrations of metal ions (e.g. about 30 ppm copper per gram of cotton fabric) on the fabric surface for a prolonged period of time (i.e. 24 hours) prior to washing the fabric when pretreated with compositions I-VI. Decrease even if left to work.

In addition, no color change and / or discoloration was observed when using the above compositions I-VI to pre-color the colored fabrics.

These compositions produce up to 3% available oxygen loss when stored at 50 ° C. for a long period of 20 days.

Claims (15)

A stable liquid composition comprising a polyamine or mixture thereof having one of the following structural formulas and a peroxygen bleach: NH _2- (CH ₂ -CH ₂ -NH) _n -CH ₂ -CH ₂ -NH ₂ , where n is an integer from 0 to 15, NH ₂ -[(CH ₂ -CH ₂ -NH) _n (CH ₂ -CH ₂ -CH ₂ -NH) _m ] CH ₂ -CH ₂ -NH ₂ , where n is an integer from 0 to 8 and m Is an integer from 0 to 8), C _n H _{2n + 2-m} (NH ₂ ) _m , where n is an integer from 2 to 20 and m is an integer from 2 to 4, C _n H _2n-m (NH ₂ ) _m , where n is an integer from 2 to 20 and m is an integer from 2 to 4, C _n H _2n-2-m (NH ₂ ) _m , where n is an integer from 3 to 20 and m is an integer from 2 to 4, C _n H _2n-4-m (NH ₂ ) _m , where n is an integer from 4 to 20 and m is an integer from 2 to 4, C _n H _2n-6-m (NH ₂ ) _m , where n is an integer from 5 to 20 and m is an integer from 2 to 4. The method of claim 1, The polyamine is selected from the group comprising ethylene diamine, propylene diamine, isopropylene diamine, 1,2-alkyl diamine, 1,3-alkyl diamine, 1,4-alkyl diamine and mixtures thereof, preferably ethylene diamine Liquid composition. The method according to claim 1 or 2, A composition comprising polyamine or a mixture thereof in an amount of 0.01 to 5.0% by weight, preferably 0.1 to 3.0% by weight, more preferably 0.4 to 1.5% by weight of the total composition. The method according to any one of claims 1 to 3, Wherein said peroxygen bleach is hydrogen peroxide or a water soluble source thereof or a mixture thereof, preferably hydrogen peroxide. The method according to any one of claims 1 to 4, A composition comprising peroxygen bleach at 0.01 to 90%, preferably 2 to 20%, more preferably 3 to 10% by weight of the total composition. The method according to any one of claims 1 to 5, A composition having a pH of 0 to 6, preferably a pH of 2 to 5. The method according to any one of claims 1 to 6, A composition further comprising a chelating agent and / or a radical scavenger or mixtures thereof. The method of claim 7, wherein The chelating agent is selected from the group comprising diethylene triamine methylene phosphonate, ethylene N, N'-disuccinic acid, diethylene triamine pentaacetate, salicylic acid, malonic acid, glutamic acid, glycine and / or a radical scavenger is substituted Monohydroxy benzene, substituted dihydroxy benzene and its homologues, alkyl carboxylates, aryl carboxylates and mixtures thereof, preferably di-tert-butyl hydroxy toluene. The method according to any one of claims 1 to 8, A liquid hydrophobic bleach activator, preferably acetyl triethyl citrate, further comprising in an amount of 0.5 to 20% by weight, preferably 2 to 10% by weight of the total composition. The method of claim 9, A composition formulated as a microemulsion of a hydrophobic liquid bleaching agent in a matrix comprising a hydrophilic surfactant system comprising water, peroxygen bleach, and anionic and nonionic surfactants. The method of claim 10, At least one surfactant in the system has an HLB value that differs from the bleach activator by at least 1 HLB units, preferably by 2 HLB units, Optionally an amine oxide according to the general formula R 1 R 2 R 3 NO, wherein R 1, R 2 and R 3 are each independently C ₆ -C ₃₀ , preferably C ₁₀ -C ₃₀ , most preferably C ₁₂ -C ₁₆ hydrocarbon chains 0.1 to 10% by weight, preferably 1 to 3% by weight of the total composition, and wherein the general formula HO-CR'R "-OH, wherein R 'and R" are independently H or C ₂ -C ₁₀ hydrocarbon Chains and / or cycles or mixtures thereof), further comprising up to 10%, preferably 2 to 4%, by weight of the total composition. The method of claim 9, At least one hydrophilic surfactant having an HLB greater than 10, preferably a hydrophilic nonionic surfactant having an HLB greater than 11, preferably greater than 12, and at least one hydrophobic nonionic surfactant having an HLB of 9 or less Formulated as an aqueous emulsion comprising an active agent, preferably a hydrophobic nonionic surfactant having an HLB of less than 9, preferably an HLB of less than 8, A composition wherein the hydrophobic bleach activator is emulsified by the surfactant. 13. The composition comprising applying the liquid composition according to any one of claims 1 to 12 in a non-mixed form with water on the fabric before washing the contaminated fabric and leaving the composition in contact with the fabric. To pretreat contaminated fabrics using Use of the liquid composition according to any one of claims 1 to 12 for pretreatment prior to washing the fabric to reduce the loss of tensile strength of the contaminated fabric. Use of the liquid composition according to any one of claims 1 to 12 for pretreatment of the colored fabric before washing to reduce color damage of the contaminated colored fabric.