MXPA00004748A

MXPA00004748A - Laundry bleaching compositions

Info

Publication number: MXPA00004748A
Application number: MXPA/A/2000/004748A
Authority: MX
Inventors: Duca Valerio Del; Stefano Giunti; Roberto Scaramella
Original assignee: The Procter & Gamble Company
Priority date: 1997-11-12
Filing date: 2000-05-12
Publication date: 2001-05-07

Abstract

The present invention relates to a liquid composition suitable for pretreating fabrics having a pH up to 7, and comprising a peroxygen bleach, from 0.1%to 10%by weight of the total composition of a pH buffering means, and from 0.0001%to 5%by weight of a perfume. These compositions are suitable for bleaching soiled fabrics, and especially pretreating fabrics while being safe to the fabric colors.

Description

BLEACHING COMPOSITIONS FOR LAUNDRY TECHNICAL FIELD The present invention relates to the bleaching of soiled fabrics and to compositions suitable for use as a laundry detergent and especially as pre-treatment compositions for laundry.

BACKGROUND OF THE INVENTION Compositions containing peroxygen bleach have been widely described in laundry applications such as laundry detergents, laundry additives or even as pre-treatment compositions for laundry. Indeed, it is known to use peroxygen bleach-containing compositions which have an acidic to neutral pH (typically up to 7, preferably from 1 to 6, and more preferred around 5) in laundry treatment applications to promote removal. of encrusted stains / soils which are usually particularly difficult to remove, such as grease, coffee, tea, grass, dirt containing mud / clay and the like. However, it has been found that a drawback associated with such peroxygen bleach-containing compositions is that said compositions can damage the colors of the fabrics, especially when used in a pretreatment application, i.e. when applied directly (undiluted) on The fabrics are allowed to act on said fabrics for prolonged periods before rinsing the fabrics or washing and then rinsing the fabrics. It is therefore an object of the present invention to provide improved protection to the whitening colors, especially in pretreatment applications in which the undiluted compositions are left in contact with the fabrics for prolonged periods before rinsing the fabrics or washing and then rinse the fabrics. Indeed, when a fabric is subjected to pretreatment with a composition comprising a peroxygen bleach such as hydrogen peroxide formulated at a pH of up to 7, applying the undiluted composition to the fabric and letting it act on it before it is rinsed, the composition has a tendency to evaporate in the fabric. It has been observed that after evaporation of such peroxygenated bleach-containing compositions, the water contained in said compositions evaporates faster than the peroxygen bleach. In other words, the evaporation of the water contributes to increasing the concentration of the peroxygen bleach in the liquid composition that has been poured onto the surface of the fabric. This much higher concentration accelerates the production of free radicals and, as a consequence, the damage of the fabric and its colors. It is also speculated that an auto-oxidation reaction occurs after the evaporation of water when the compositions are allowed to dry on the fabrics. This auto-oxidation reaction generates peroxyl radicals which contribute to the degradation of cellulose and certain dyes present in the fabrics which results in chemical damage of the dye molecules which is visible as discoloration and / or change of hue . Therefore, in the instructions for use of such commercially available peroxygen bleach-containing compositions it is highly recommended not to allow the liquid bleaching compositions to dry on the fabric, in a pretreatment process for soiled fabrics. More surprisingly, it has now been observed that this evaporation process also results in a pH drop in addition to an increase in the concentration of bleaching agent. It is speculated that the pH drop towards strong acid values, typically below pH 2, accelerates color damage when a colorful fabric is subjected to pretreatment. It has now been found that improved color protection can be achieved by formulating a liquid bleaching composition having a pH of up to 7 and comprising a peroxygen bleach, from 0.1% to 10% by weight of the total composition of pH regulating means and from 0.0001% up to 5% by weight of a perfume. More particularly, it has been found that the use, in a composition containing peroxygen bleach having a pH of up to 7, of pH regulating means, for the pretreatment of a soiled colored fabric, considerably reduces the color damage in the fabric pretreated with said composition. Advantageously, the compositions according to the invention also provide effective protection to the fabric in addition to effective color protection. Another advantage of the present invention is that excellent bleaching performance is provided over a wide variety of stains and soils such as bleaching stains. and / or grease stains. Another advantage of the present invention is that the compositions according to the present invention provide excellent performance not only when used in a laundry pretreatment application but also when used in any laundry application, for example when used as laundry detergent or laundry additive, or even in other applications such as hard surface cleaning applications. Even a further advantage is that the compositions herein are physically and chemically stable after prolonged periods of storage. In a preferred embodiment, the compositions according to the present invention further comprise a surfactant or a mixture thereof, for example a zwitterionic betaine surfactant in combination with an alkoxylated nonionic surfactant. Indeed, it has been found that a surfactant system as such further increases the bleaching performance and contributes to the effective performance of stain removal on various types of stains including greasy stains such as mayonnaise, vegetable oil, sebum, makeup and the like, of the compositions of the present invention. In a highly preferred embodiment in the present invention, the compositions of the present invention comprise a salt-free zwitterionic zwitterionic surfactant. Indeed, using such salt-free zwitterionic zwitterionic surfactants in place of the conventional zwitterionic surfactants further contributes to the benefits of the present compositions, i.e., improved color and fabric protection.

BRIEF DESCRIPTION OF THE INVENTION The present invention encompasses a liquid composition suitable for pretreatment of fabrics having a pH of up to 7 and comprising a peroxygen bleach, from 0.1% to 10% by weight of the total composition of pH regulating media and from 0.0001% to 5% in weight of a perfume. The present invention also encompasses fabric bleaching processes, starting from a liquid composition as defined herein. The methods include the steps of contacting said fabrics with the liquid bleaching composition, undiluted or diluted, and subsequently rinsing said fabrics. In the preferred embodiment, when the fabrics are "subjected to pretreatment", the undiluted composition is applied to the fabrics, and these are rinsed, or washed in a normal washing cycle and then rinsed with water.

DETAILED DESCRIPTION OF THE INVENTION Liquid compositions The compositions according to the present invention are liquid compositions as opposed to a solid or a gas. As used herein, "liquid" includes "pasty" compositions. The liquid compositions of the present invention are preferably aqueous compositions. The liquid compositions according to the present invention preferably have a pH of up to 7, more preferred of 1 to 6 and more preferred still of 1.5 to 5.5. Formulating the compositions according to the present invention in the acid pH range contributes to the chemical stability of the compositions and to the stain removal performance of the compositions.

Peroxygen bleach As an essential element, the compositions according to the present invention comprise a peroxygen bleach or a mixture thereof. In fact, the presence of peroxygen bleach provides excellent bleaching and cleaning benefits. Peroxygen bleach suitable for use in the present invention are hydrogen peroxide, water soluble sources thereof or mixtures thereof. As used herein, a source of hydrogen peroxide refers to any compound that produces perhydroxyls when said compound is in contact with water. Water-soluble sources of hydrogen peroxide suitable for use herein include percarbonates, persilicates, perborates, peroxyacids such as diperoxydecanedioic acid (DPDA), magnesium peri-alic acid, perluric acid, perbenzoic and alkylperbenzoic acids, hydroperoxides, peroxides. of aliphatic and aromatic diacyl, and mixtures thereof. Preferred peroxygen bleaches in the present invention are hydrogen peroxide, hydroperoxide and / or diacyl peroxide. Hydrogen peroxide is the most preferred peroxygen bleach in the present invention. Hydroperoxides suitable for use herein are tert-butyl hydroperoxide, cumyl hydroperoxide, 2,4,4-trimethylpentyl 2-hydroperoxide, diisopropylbenzene monohydroperoxide, ter-amyl hydroperoxide and 2,5-dihydroperoxide 2, 5-dimethyl-hexane. Such hydroperoxides have the advantage of being particularly innocuous to fabrics and color while at the same time providing excellent bleaching performance. The aliphatic diacyl peroxides suitable for use in the present invention are dilauroyl peroxide, didecanoyl peroxide, dimyristoyl peroxide or mixtures thereof. The aromatic diacyl peroxide suitable for use in the present invention is for example benzoyl peroxide. Such diacyl peroxides have the advantage of being particularly innocuous to fabrics and color while at the same time providing excellent bleaching performance. Typically, the compositions herein comprise from 0.1% to 20% by weight of the total composition of said peroxygen bleach or mixtures thereof, preferably from 1% to 15% and more preferably from 2% to 10%.

PH regulating means As an essential element the compositions according to the present invention comprise pH regulating means or a mixture thereof at a level from 0.1% to 10% by weight of the total composition. Preferably, the compositions of the present invention comprise from 0.2% to 8% by weight of the total composition of a pH regulating medium or mixture thereof, preferably from 0.3% to 5%, more preferably from 0.3% to 3% and more preferred still from 0.3% to 2%. By "pH regulating means", it is meant herein any compound that when added to a solution causes the solution to resist a change in the concentration of hydrogen ions by adding an acid or a base.

The preferred pH regulating means for use in the present invention comprises a weak acid having its pKa (if only one exists) or at least one of its pKa in the range of 1.5 to 6.5, preferably from 2 to 6 and most preferred from 4 to 6, and its conjugate base. The pKa is defined according to the following equation: pKa = -log Ka in which Ka is the Dissociation Constant of the weak acid in water and corresponds to the following equation: [Al [H +] / [HA] = Ka in the which HA is the acid and A "is the conjugate base" By "conjugate base" it is meant in the present invention that (A ") is the corresponding base of the weak acid (HA) of the present invention. This conjugate base can be obtained by adding a source of alkalinity in the compositions according to the present invention comprising a weak acid as described in the present invention. Suitable alkalinity sources to be used herein are caustic alkalies such as sodium hydroxide, potassium hydroxide and / or lithium hydroxide and / or alkali metal oxides such as sodium and / or potassium oxide. A preferred source of alkalinity is a caustic alkali, more preferred sodium hydroxide and / or potassium hydroxide. Alternatively, the conjugate base can be commercially available as such and added directly to the weak acid of the present invention.

Typically, according to the invention, the weak acid (HA) and its conjugate base (A ") are in equilibrium in the compositions of the present invention according to the equation: HA <? > A" + H + (ions) hydrogen) Preferably the pH regulating means in the present invention consist of the weak acid as defined herein and its conjugate base in a weight ratio of the weak acid to its conjugate base preferably from 0.1: 1 to 10.1, more preferred 0.2: 1 to 5: 1. The ratio of weak acid to its conjugate base which is most preferred is 1 since this is the best combination to achieve the optimum pH regulation capacity. Preferably, pH regulating means for regulating the pH of compositions having a pH between pH = pKa-1 and pH = pKa +1 of each of their pKa will be used herein. For example, the citric acid / citrate pair is particularly suitable for regulating the pH of compositions having a pH between 3.74 and 5.74 (pKa 2 = 4.74) and between 2.06 and 4.06 (pKa 1 = 3.06). Weak acids having at least one of their pKa of 1.5 to 6 suitable for use in the present invention include citric acid (pKa 1 = 3.06, pKa 2 = 4.74), oxalic acid (pKa 2 = 2.49), tartaric acid (pKa 1 = 2.99, pKa 2 = 4.34), phthalic acid (pKa 1 = 2.89, pKa 2 = 5.41), acetic acid (pKa = 4.74), benzoic acid (pKa = 4.20), formic acid (pKa = 3.76) and salicylic acid (pKa 1 = 2.97). The pH regulating means particularly suitable for use in the present invention are citric acid / sodium citrate, citric acid / potassium citrate, oxalic acid / sodium oxalate, tartaric acid / potassium bitartrate, oxalic acid / potassium tetraoxalate dihydrate , phthalic acid / potassium phthalate, acetic acid / sodium acetate, formic acid / sodium formate, benzoic acid / sodium benzoate and / or salicylic acid / sodium salicylate. The preferred pH regulating means for use in the present invention are citric acid / sodium citrate, citric acid / potassium citrate, oxalic acid / sodium oxalate, tartaric acid / potassium bitartrate, oxalic acid / potassium tetraoxalate dihydrate and most preferred are citric acid / sodium citrate and / or citric acid / potassium citrate. The highly preferred pH regulating means for use in the present invention are citric acid and sodium citrate. Citric acid is commercially available from Sigma Aldrich and Flucka Chemicals under its chemical name.

The perfume As an essential element, the compositions according to the present invention contain a perfume or a mixture thereof at a level of from 0.0001% to 5% by weight of the total composition. Preferably, the compositions of the present invention comprise from 0.0001% to 1% by weight of the total composition of a perfume or a mixture thereof, more preferred from 0.001% to 1%, and more preferred still from 0.1% to 0.5% . Naturally, for the purpose of the present invention the perfumes to be used herein are stable to peroxygen bleach. By "stable" to peroxygen bleach, it is meant in the present invention a perfume that exhibits odor stability after days of storage at 50 ° C and that does not affect the stability of the product. The perfumes suitable for use herein include materials that provide an olfactory aesthetic benefit and / or help to cover any "chemical" odor that the product may have. The main function of a small fraction of the highly volatile, low boiling perfume components (which have low boiling points) in such perfumes is to improve the fragrance odor of the product itself rather than having an impact on the subsequent surface odor that is being cleaned. However, some of the less volatile, high boiling perfume ingredients provide a fresh and clean impression to the surfaces, and it is desirable that said ingredients are deposited and presented on the dry surface. The perfume ingredients can be easily solubilized in the compositions, for example, by nonionic detergent surfactants. The ingredients and perfume compositions suitable for use herein are those conventional known in the art. The selection of any perfume component, or amount of perfume, is based primarily on aesthetic considerations. Suitable perfume compositions and compositions can be found in the art including U.S. Pat. Nos. 4,145,184, Brain and Cummins, issued March 20, 1979; 4,209,417, Whyte, issued June 24, 1980; 4,515,705, Moeddel, issued May 7, 1985; and 4,152,272, Young, issued May 1, 1979, said patents being incorporated herein by reference. In general, the degree of substantivity of a perfume is almost proportional to the percentages of the substantive perfume material used. Relatively substantive perfumes contain at least about 1%, preferably at least about 10%, of substantive perfume materials. Substantive perfume materials are those odoriferous compounds that are deposited on the surface by the cleaning procedure and that can be detected by people with normal olfactory acuity. Such materials typically have lower vapor pressures than the average perfume material. Likewise, they typically have molecular weights of about 200 and more and can be detected at levels below those of the average perfume material. The perfume ingredients useful herein, together with their odor character, and their physical and chemical properties, such as boiling point and molecular weight, are given in "Perfume and Flavor Chemicals (Aroma Chemicals)," Steffen Arctander, published by the author, 1969, incorporated herein by reference. Examples of highly volatile, low boiling perfume ingredients are: anethole, benzyl acetate, benzyl alcohol, iso-bornyl acetate, camphene, citronellol, citronellyl acetate, para-cymene, dihydrolinalool, dihydromyrcenol, dimethylphenylcarbinol, eucalyptol, geraniol , geranyl acetate, geranylnitrile, cis-3-hexenyl acetate, d-limonene, linalool, linalool oxide, linalyl acetate, linalyl propionate, methyl anthranilate, alpha-metilylonone, methylnonylacetaldehyde, methylphenylcarbinyl acetate, levo-menthyl acetate, menthone, iso-menthone, myrcene, myrcenyl acetate, mircenol, nerol, neryl acetate, nonyl acetate, phenylethyl alcohol, alpha-pinene, beta-pinene, gamma-terpinene, alpha-terpineol, beta-terpineol, terpinyl acetate, and vertenex (para-tert-butylcyclohexyl acetate). Some natural oils also contain large percentages of highly volatile perfume ingredients. For example, the bleach contains as major components: linalool; linalyl acetate; geraniol; and citronellol. Lemon oil and orange terpenes contain about 95% d-limonene. Examples of moderately volatile perfume ingredients are: amylcinnamic aldehyde, iso-amyl salicylate, beta-caryophyllene, cedrene, cinnamic alcohol, dimentylbenzylcarbinyl acetate, ethylvanillin, eugenol, iso-eugenol, florescetate, heliotropin, 3-cis-hexenyl salicylate , hexyl salicylate, lilial (para-tert-butyl-alpha-methylhydrocinnamic aldehyde), gamma-metilyonone, nerolidol, patchouli alcohol, phenylhexanol, beta-selinose, triethyl citrate, vanillin and veratraldehyde. Cedarwood terpenes are mainly composed of alpha-cedrene, beta-cedrene and other sesquiterpenes of C15H24. Examples of the less volatile, high boiling perfume ingredients are: benzophenone, benzyl salicylate, ethylene brasylate, hexyl cinnamic aldehyde, lyral, (4- (4-hydroxyl-4-methylphenyl) -3-cyclohexen- 10-carboxaldehyde), methyledrilone, methyldihydrojasmonate, methyl-beta-naphthyl ketone and phenylethylphenyl acetate. The selection of any particular perfume ingredient is dictated primarily by aesthetic considerations. The present invention is based on the discovery that the pH regulating means reduces the pH drop that normally occurs when applying an undiluted composition containing peroxygen bleach having a pH up to 7 on the fabrics to be subjected to pretreatment and let it act (and therefore evaporate) before rinsing the fabrics, or washing the fabrics and then rinsing them. In other words, the color damage of some types of dyes (for example, blue and / or green dyes found especially in colored fabrics made from silks), that is, the change in color and / or discoloration, observed when whiten such dirty colored fabrics with a composition containing peroxygen bleach having pH up to 7 and pH regulating means, is reduced, compared to the color change and / or discoloration observed when the same composition is used but without any regulating medium of pH. This reduction of color change and / or discoloration is especially observed in a pretreatment application in which the composition is allowed to dry, or only partially, on the dirty colored fabrics (this means to allow drying typically for a period ranging from 5 to 60 minutes). Damage to the color of a colorful fabric can be assessed by visual scoring and / or by an instrumental method with the HunterLab MINISCAN® Tristimulus apparatus by comparing side by side bleached colorful fabrics according to the present invention and bleached colorful fabrics with a reference composition which is for example free of any pH regulating medium. Advantageously, the loss of tensile strength caused by the presence of copper and / or iron and / or manganese and / or chromium on the surface of the fabric and / or by exposure to UV radiation from sunlight is also it reduces when bleaching, and especially when a soiled fabric is subjected to pre-treatment, with the compositions according to the present invention. The loss of tensile strength of a fabric can be measured using the tensile strength method. This method consists of measuring the tensile strength of a given fabric by stretching said fabric until it breaks. The force, expressed in kg, needed to break the fabric is the "final stress effort" and can be measured with an INSTRON® stress strain machine, which can be obtained from INSTRON. The loss of tensile strength is the difference between the tensile strength of a fabric taken as a reference, for example a fabric that has not been bleached, and the tensile strength of the same fabric after being bleached. A loss of tensile strength of zero means no damage to the fabric is observed. In addition, the reduction of loss of tensile strength and / or reduction of damage to the color of a fabric are obtained according to the invention., without compromising bleaching performance or stain removal performance. Also an advantage of the compositions of the present invention is that they are physically and chemically stable after prolonged periods of storage. More particularly, the pH regulating means, in the compositions according to the present invention, contribute to the excellent chemical stability of said compositions after prolonged periods of storage. More particularly a secondary benefit of the pH regulating means especially citric acid / citrate, used in the compositions of the present invention is that they act as an antioxidant, ie they absorb the oxygen present in the bleaching environment and thus reduce the oxidative decomposition of the oxidizable materials present in the bleaching compositions, ie peroxygen bleach, perfumes, colorants and the like. The chemical stability of the compositions herein can be evaluated by measuring the concentration of available oxygen (often abbreviated as AvO2) in a given storage time, after the compositions have been manufactured. The concentration of available oxygen can be measured by chemical titration methods known in the art, such as the iodometric method, the thiosulfatimetric method, the permanganometric method and the cerimetric method. These methods and the criteria for the choice of the appropriate method are described, for example in "Hydrogen Peroxide", W.C. Schumb, C.N. Satterfield and RL Wentworth, Reinhold Publishing Corporation, New York, 1995 and "Organic Peroxides", Daniel Swern, Editor Wiley Int. Science, 1970. By "physically stable", it is hereby implied that no separation of phases in the compositions over a period of 14 days at 50 ° C.

Optional ingredients The compositions herein may further comprise a variety of other optional ingredients such as surfactants, chelating agents, radical scavengers, antioxidants, builders, stabilizers, bleach activators, soil suspending agents, polyamine polymers, soil suspending agents. , polymeric agents releasing dirt, catalysts, dye transfer agents, solvents, brighteners, perfumes, pigments and dyes.

The surfactant The compositions according to the present invention may comprise a surfactant or a mixture thereof as a highly preferred optional ingredient. Naturally, for the purpose of the present invention the surfactants are stable to the peroxygen bleach. Typically, the compositions of the present invention comprise up to 60% by weight of the total composition of a surfactant or a mixture thereof, preferably from 0.1 % until %, more preferred from 0.5% to 15% and even more preferred from 1% to 10%. Suitable surfactants for use in the present invention include any of the nonionic, anionic, zwitterionic, cationic and / or amphoteric surfactants. Surfactants particularly suitable for use in the present invention are nonionic surfactants such as the agents non-ionic alkoxylated surfactants and / or polyhydroxy fatty acid amide surfactants and / or amine oxide surfactants and / or zwitterionic surfactants such as the zwitterionic betaine surfactants described below in the present invention. The non-ionic alkoxylated surfactants suitable for use herein are ethoxylated nonionic surfactants according to the formula RO- (C2H4O) nH, wherein R is an alkyl chain of Ce to C22 or an alkyl benzene chain of Ce to C2a, and wherein n is from 0 to 20, preferably from 1 to 15, more preferably from 2 to 15 and most preferably from 2 to 12. Preferred R chains for use herein are C8 alkyl chains to C22 Non-propoxylated and ethoxy-propoxylated nonionic surfactants can also be used herein in place of the ethoxylated nonionic surfactants as defined hereinbefore or together with said surfactants. Preferred ethoxylated nonionic surfactants are according to the above formula and have an HLB (hydrophilic-lipophilic balance) below 16, preferably below 15 and more preferably below 14. These ethoxylated nonionic surfactants have been found to provide good fat cutting properties. Accordingly, ethoxylated nonionic surfactants suitable for use herein are Dobanol® 91-2.5 (HBL = 8.1, R is a mixture of Cg and Cu alkyl chains, n is 2.5), or Lutensol® TO3 (HLB = 8, R is a mixture of C? 3 alkyl chains, n is 3), or Lutensol? AO3 (HLB = 8; R is an alkyl chain of C? 3 and C? 5, n is 3) , or Tergitol® 25L3 (HBL = 7.7, R is in the length range of the alkyl chain of C? 2 to C15, n is 3), or Dobanol® 23-3 (HBL = 8.1; R is a mixture of alkyl chains of C-? 2 and C13, n is 3), or Dobanol® 23-2 (HBL = 6.2, R is a mixture of alkyl chains of d_ and C? 3, n is 2), or Dobanol® 45-7 (HBL = 1 1.6, R is an alkyl chain mixture of C and C? 5, n is 7), or Dobanol® 23-6.5 (HBL = 11.9; R is a mixture of C12 alkyl chains and C13, n is 6.5), or Dobanol® 25-7 (HBL = 12, R is a mixture of alkyl chains of C12 and C-? 5, n is 7), or Dobanol® 91-5 (HBL = 11.6; R is a mixture of alkyl chains of Cg and Cu, n is 5), or Dobanol ® 91-6 (HBL = 12.5; R is a mixture of Cg and Cu alkyl chains, n is 6), or Dobanol® 91-8 (HBL = 13.7, R is a mixture of Cg and Cu alkyl chains, n is 8), Dobanol® 91- 10 (HBL = 14.2; R is a mixture of alkyl chains from Cg to Cu, n is 10), or mixtures thereof. Preferred herein are Dobanol® 91-2.5, or Lutensol® TO3, or Lutensol® AO3, or Tergitol® 25L3, or Dobanol® 23-3, or Dobanol® 23-2, or mixtures thereof. These Dobanol® surfactants are commercially available from SHELL. These Lutensol® surfactants are commercially available from BASF and these Tergitol® surfactants are commercially available from UNION CARBIDE. Suitable chemical processes for preparing the ethoxylated nonionic surfactants for use herein include the condensation of the corresponding alcohols with alkylene oxide, in the desired proportions. Such procedures are well known to those skilled in the art and have been extensively described in the art. The compositions herein may desirably comprise one of those ethoxylated nonionic surfactants or a mixture of those ethoxylated nonionic surfactants having different HLB (hydrophilic-lipophilic balance). In a preferred embodiment, the compositions herein comprise an ethoxylated nonionic surfactant according to the above formula and having an HLB of up to 10 (ie, a so-called hydrophobic ethoxylated nonionic surfactant), preferably below 10. , more preferably below 9, and an ethoxylated nonionic surfactant according to the above formula and having an HLB above 10 and up to 16 (ie, a so-called hydrophilic ethoxylated nonionic surfactant), preferably from 11 to 14 Indeed, in this preferred embodiment, the compositions of the present invention typically comprise from 0.01% to 15% by weight of the total composition of said hydrophobic ethoxylated nonionic surfactant, preferably from 0.5% to 10% and from 0.01% to 15% by weight of said hydrophilic ethoxylated nonionic surfactant, preferably from 0.5% to 10%. Such mixtures of ethoxylated nonionic surfactants with different HLBs could be desired, since they allow the optimum cleaning performance of grease removal on a wider variety of greasy soils having different hydrophobic / hydrophilic characters. Other nonionic surfactants particularly suitable for use herein include polyhydroxy fatty acid amide surfactants, or mixtures thereof, according to the formula: R2-C (O) -N (R1) -Z, in where R1 is H, or CrC4 alkyl, C? -C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R2 is a C5-C3-? hydrocarbyl and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R1 is C? -C alkyl, more preferably Ci or C2 alkyl and most preferably methyl, R2 is a straight chain C -C? Alkyl or alkenyl, preferably an alkyl or alkenyl of Cg-C-? 8 straight chain, more preferably straight chain Cn-C 8 8 alkyl or alkenyl and most preferably straight chain Cu-Cu alkyl or alkenyl or mixtures thereof. Z will be derived preferably from a reducing sugar in reductive amination reaction; more preferably Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup and high maltose corn syrup as well as the individual sugars listed above can be used. These corn syrups can provide a mixture of sugar components for Z. It should be understood that it is not intended in any way to exclude other suitable raw materials. Z will preferably be selected from the group consisting of -CH2- (CHOH) n -CH2OH, -CH (CH2OH) - (CHOH) n -? - CH2OH, -CH2- (CHOH) 2- (CHOR ') (CHOH) - CH2OH, wherein n is an integer from 3 to 5, inclusive, and R 'is H or a cyclic or aliphatic monosaccharide and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly CH2- (CHOH) 4-CH2OH. In the formula R2-C (O) -N (R1) -Z, R1 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl. R2-C (O) -N <; it can be, for example, cocoamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, seboamide and the like. Z can be 1-deoxyglucityl, 2-deoxyfructile, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxyanityl, 1-deoxymalototriotityl and the like. The polyhydroxy fatty acid amide surfactants suitable for use herein can be commercially available under the trade name HOE® from Hoechst. Methods for making polyhydroxy fatty acid amide surfactants are known in the art. In general, they can be made by reacting an alkylamine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine and then reacting the N-alkyl polyhydroxyamine with a triglyceride or fatty aliphatic ester in a condensation / amidation step to form the N-alkyl, N-polyhydroxylic acid amide product. Methods for making compositions containing polyhydroxy fatty acid amide are discussed, for example in Great Britain Patent Specification 809,060 published February 18, 1959, by Thomas Hedley & Co., Ltd., the patent of E.U.A. 2,965,576, issued December 20, 1960 to E. R. Wilson, the patent of E.U.A. 2,703,798, Anthony M. Schwartz, issued March 8, 1955, the patent of E.U.A. 1, 985,424, issued December 25, 1934 to Piggott and WO92 / 06070, each of which is hereby incorporated by reference. Other suitable nonionic surfactants for use herein include amine oxides having the following formula R? R2R3NO wherein each Ri, R2 and R3 is independently a saturated or unsubstituted, straight or branched, hydrocarbon chain of 1 to 30 carbon atoms. Preferred amine oxide surfactants for use in accordance with the present invention are amine oxides having the following formula R-? R2R3NO wherein Ri is a hydrocarbon chain comprising from 1 to 30 carbon atoms, preferably from 6 to 20, more preferably from 8 to 16, most preferably from 8 to 12, and wherein R 2 and R 3 are independently substituted or unsubstituted, straight or branched hydrocarbon chains, comprising from 1 to 4 carbon atoms, preferably from 1 to 3 atoms and most preferably methyl groups. Ri can be a saturated, substituted or unsubstituted, straight or branched hydrocarbon chain. Amine oxides suitable for use herein are for example amine oxide of Cs-C? 0 of natural mixture as well as C12-Ci6 amine oxides commercially obtainable from Hoechst. Another class of surfactants particularly suitable for use in the present invention include zwitterionic betaine surfactants which contain both a cationic hydrophilic group, ie a quaternary ammonium group, and an anionic hydrophilic group on the same molecule in a relatively broad range of pH. Typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups such as sulfates, phosphonates and the like can be used. A generic formula for zwitterionic betaine surfactants to be used herein is: R? -N + (R2) R3R4X 'where Ri is a hydrophobic group; R 2 is hydrogen, C 1 -C 2 alkyl, hydroxyalkyl or another substituted C 1 -C 6 alkyl group; R3 is C-alkyl, hydroxyalkyl or another substituted C1-C6 alkyl group which can also be attached to R2 to form ring structures with the N, or a C6-C6 carboxylic acid group or a CrC6 sulfonate group; R4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically an alkylene, hydroxyalkylene or polyalkoxy group containing from 1 to 10 carbon atoms; and X is the hydrophilic group which is a carboxylate or sulfonate group. Preferred hydrophobic groups R1 are aliphatic or aromatic hydrocarbon chains, saturated or unsaturated, substituted or unsubstituted, which may contain linking groups such as amido groups, ester groups. The most preferred R1 is an alkyl group containing from 1 to 24 carbon atoms, preferably from 8 to 18 and more preferably from 10 to 16. These simple alkyl groups are preferred for reasons of cost and stability. However, the hydrophobic group R1 can also be an amido radical of the formula Ra-C (O) -NH- (C (Rb) 2.m, where Ra is an aliphatic or aromatic hydrocarbon chain, saturated or unsaturated, substituted or unsubstituted, preferably an alkyl group containing from 8 to 20 carbon atoms, preferably up to 18, more preferably up to 16, Rb is selected from the group consisting of hydrogen and hydroxy groups, and m is from 1 to 4, preferably from 2 to 3, more preferably 3, with not more than one hydroxy group in any portion (C (Rb) 2) - The preferred R 2 is hydrogen or C 1 -C 3 alkyl and more preferably methyl The preferred R 3 is the acid group C1-C4 carboxylic acid or the C1-C4 sulfonate group or a C- [alpha] -C3 alkyl and more preferably methyl.The preferred R is (CH2) n wherein n is an integer from 1 to 10, preferably from 1 to 6, more preferably from 1 to 3. Some common examples of betaine / sulfobetaine are described in the E patents U.S.A. 2,082,275, 2,702,279 and 2,255,082, incorporated herein by reference. Examples of particularly suitable alkyldimethylbetaines include cocodimethylbetaine, lauryl dimethylbetaine, decyl dimethyl betaine, 2- (N-decyl, N-dimethylammonium) acetate, 2- (N-coco-N, N-dimethylammonium) acetate, myristyldimethylbetaine, palmityldimethylbetaine, cetyldimethylbetaine, stearyldimethylbetaine. For example, cocodimethylbetaine can be commercially available from Seppic under the trade name of Amonyl 265®. Laurylbetaine can be purchased commercially from Albright & amp;; Wilson under the trade name Empigen BB / L®. Examples of amidobetaines include cocoamidoethylbetaine, cocoamidopropylbetaine or acylamidopropylene (hydropropylene) sulfobetaine C10-C14 fat. For example, acylamidopropylene (hydropropylene) sulfobetaine C10-C14 fat can be commercially available from Sherex Company under the tradename "Varion CAS® sulfobetaine". A further example of betaine is lauryl imino dipropionate commercially available from Rhone-Poulenc under the trade name Mirataine H2C-HA®. Particularly preferred zwitterionic betaine surfactants for use herein are salt-free, ie, the raw material of the zwitterionic betaine surfactant contains less than 5% by weight of salts, preferably less than 2%, more preferably less of 1%, more preferably still less than 0.01% to 0.5%. By "salts" is meant herein any material having a base unit, a pair made of positive on (or positive molecular) and negative on (or negative molecular) containing one or more atoms of halogen Such salts include sodium chloride, potassium chloride, sodium bromide and the like. Such salt-free zwitterionic betaine surfactants can be obtained by conventional manufacturing processes such as reverse osmosis or fractional precipitation. For example, reverse osmosis is based on the principle of contacting the raw material of the zwitterionic betaine surfactant (commercially available) with a polar solvent (it is understood that said solvent is free of salts) separated by a semipermeable membrane, for example acetate-cellulose. Appropriate pressure is applied on the system to allow the salts to move from the raw material of the surfactant into the polar solvent phase. In this way the raw material of zwitterionic betaine surfactant is purified, ie the salts are removed from the raw material. Advantageously, it has now been found that the use of such salt-free zwitterionic betaine surfactants provides improved protection to the fabric and / or color when bleaching fabrics with a composition containing peroxy bleach containing them, as compared to the use of the same zwitterionic betaine surfactants with larger amounts of salts. Therefore, in its broadest aspect, the present invention also encompasses the use of a composition comprising a salt-free zwitterionic zwitterionic surfactant, a peroxygen bleach and pH regulating means for bleaching soiled fabrics, especially pretreatment of soiled fabrics, whereby color protection is improved (ie color damage / discoloration is reduced) and / or cloth protection is improved. In a preferred embodiment herein, the surfactants present in the composition of the present invention are a mixture of ethoxylated nonionic surfactants and zwitterionic betaine surfactants. Indeed, such zwitterionic betaine surfactants and ethoxylated nonionic surfactants act together to provide excellent stain removal on greasy stains (e.g., lipstick, olive oil, mayonnaise, vegetable oil, sebum, make-up), while At the same time they provide improved bleaching performance to the liquid peroxygen bleach-containing compositions of the present invention which contain them. Indeed, a significant cooperation between these ingredients has been observed to obtain an optimum performance of stain removal on a variety of soils, from particulate soils to non-particulate soils, from hydrophobic soils to hydrophilic soils under any domestic application and especially application of laundry on both hydrophilic and hydrophobic fabrics. Optimal stain removal performance and bleaching performance are obtained when the ethoxylated nonionic agent and the zwitterionic betaine agent are present in the compositions of the present invention comprising a peroxygen bleach (pH below 7), in a weight ratio of the non-ionic ethoxylated agent to the zwitterionic betaine agent from 0.01 to 20, preferably from 0.1 to 15, more preferred from 0.5 to 5, and even more preferred from 0.6 to 3. Importantly, the Improved bleaching benefit and bleaching benefit are supplied with a liquid composition which is a clear and transparent composition like water. The appearance of a composition can be evaluated by turbidimetric analysis. For example, the transparency of a composition can be evaluated by measuring its absorbance by a spectrophotometer at a wavelength of 800 nm. Although less desirable than the aforementioned surfactants in terms of their stain removal properties, other surfactants may be used in the compositions of the present invention. Suitable anionic surfactants to be used in the compositions herein include water soluble salts or acids of the formula ROSO 3 M wherein R is preferably C 0 -C 2 hydrocarbyl, preferably an alkyl or hydroxyalkyl having an alkyl component of C? 0-C20, more preferably a C12-C18 alkyl or hydroxyalkyl, and M is H or a cation, for example an alkali metal cation (eg, sodium, potassium, lithium), or ammonium or substituted ammonium ( for example, methyl-, dimethyl- and trimethylammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like) . Typically, C12-16 alkyl chains are preferred for low wash temperatures (eg, below about 50 ° C) and C12-18 alkyl chains are preferred for higher wash temperatures (eg, above of approximately 50 ° C). Other anionic surfactants suitable for use herein are water soluble salts or acids in the formula RO (A) mSO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component , preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C- | 2-Ciß alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which may be, for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium cation or substituted ammonium cation. Alkylethoxylated sulfates as well as alkyl-propoxylated sulfates are contemplated herein. Some specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium, and quaternary ammonium cations, such as tetramethylammonium, dimethylpiperidinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Exemplary surfactants include alkylpolyethoxylate- (1.0) -C 2 -C 8 -sulfate (E (1.0) M C 12 -C 8), alkyl polyethoxylate- (2.25) -C 2-C 18 sulfate, E ( 2.25) M of C12-C18), alkyl polyethoxylate- (3.0) -C12-C18 sulfate, C12-C15 alkylethyloxylate (C12-C15), alkylethylethoxylate- (4.0) -C12-C-sulfate, E (4.0) M of C12-C18, wherein M is conveniently selected from sodium and potassium. Other anionic surfactants useful for other detersive purposes may also be used herein. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di- and triethanolamine salts) of soap, linear Cg-C2o alkylbenzenesulfonates, primary or secondary C8-alkan sulfonates. C22, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, for example, as described in British patent specification No. 1, 082,179, Cs-C24 alkyl polyglycol ether sulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as Cu-C 6 methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, ethylene oxide ether sulfates of alkylphenol, paraffinsulfonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyltaurates, alkylsuccinamates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C? 2-C18 monoesters) , sulfosuccinate diesters (especially saturated and unsaturated CT-CU diesters), alkylpolysaccharide sulfates such as alkyl polyglycoside sulfates (non-sulphonated nonionic compounds are described below), branched primary alkyl sulphates, alkylpolyethoxycarboxylates such as those of the formula RO ( CH2CH2O)? CH2COO-M + wherein R is C8-C22 alkyl, k is an integer from 0 to 10 and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and hydrogenated resin acids and resin acids present in the wood oil or derivatives thereof. Other examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in the US patent. A. 3,929,678, issued December 30, 1975, to Laughiin, et al., In column 23, line 58 to column 29, line 23 (incorporated herein by reference). Other suitable anionic surfactants which are to be used in the present invention also include acyl sarcosinates or mixtures thereof, in their acid and / or salt form, preferably long chain acyl sarcosinates having the following formula: wherein M is hydrogen or a cationic portion and wherein R is an alkyl group of 1 to 15 carbon atoms, preferably 1 to 13 carbon atoms. The preferred M is hydrogen and alkali metal salts, especially sodium and potassium. Said acyl sarcosinate surfactants are derived from natural fatty acids and the amino acid is sarcosine (N-methyl glycine). They are suitable for use as an aqueous solution of their salt or in acid form as a powder. Being derivatives of natural fatty acids, said acyl sarcosinates are rapidly and completely biodegradable and have good compatibility with the skin. Accordingly, long chain acyl sarcosinates suitable for use in the present invention include C ?2 acyl sarcosinate (ie, an acyl sarcosinate according to the above formula wherein M is hydrogen and R is an alkyl group of 1 1 carbon atoms ) and Cu acyl sarcosinate (ie, an acyl sarcosinate according to the above formula wherein M is hydrogen and R is an alkyl group of 13 carbon atoms). C12 acyl sarcosinate can be obtained commercially, for example, as Hamposyl L-30R supplied by Hampshire, Cu acyl sarcosinate can be obtained commercially, for example, as Hamposyl M-30R supplied by Hampshire.

Chelating agents: Thus, the compositions of the present invention may comprise a chelating agent as a preferred optional ingredient. Suitable chelating agents can be any of those known to those skilled in the art, such as those selected from the group comprising phosphonate chelating agents, aminocarboxylate chelating agents, other carboxylate chelating agents, polyfunctionally substituted aromatic chelating agents, ethylenediamine- N, N'-disuccinic, or mixtures thereof. A chelating agent may be desired in the compositions of the present invention as it allows reducing the loss of fabric tensile strength and / or color damage, especially in a laundry pre-treatment application. Indeed, the chelating agents inactivate the metal ions present on the surface of the fabrics and / or in the cleaning compositions (without mixing or diluted) which would otherwise contribute to the radical decomposition of the peroxygen bleach. Phosphonate chelating agents suitable for use herein include alkali metal ethane-1-hydroxy diphosphonates (HEDP) alkylene poly (alkylene phosphonate), as well as amine phosphonate compounds, including amino-aminotrimethylene phosphonic acid (ATMP), nitrimethylene phosphonates (NTP) ), ethylenediaminetetramethylenephosphonates and diethylenetriaminpentamethylenephosphonates (DTPMP). The phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities. Preferred phosphonate chelating agents that have been used herein are diethylenetriaminpentamethylenephosphonate (DTPMP) and ethane-1-hydroxy diphosphonate (HEDP). Such phosphonate chelating agents can be obtained commercially from Monsanto under the trade name DEQUEST®. Polyfunctionally substituted aromatic chelating agents may also be useful in the compositions herein. See the patent of E.U.A. 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelating agent for use herein is ethylene diamine-N'-disuccinic acid, or alkali metal, or alkaline earth, ammonium or substituted ammonium salts thereof or mixtures thereof. Ethylenediamine-N, N'-disuccinic acids, especially the (S, S) isomer, have been extensively described in the U.S. patent. 4,704,233, issued November 3, 1987, by Hartman and Perkins. Ethylene diamine-N-disuccinic acids can be obtained commercially, for example, under the trade name ssEDDS® of Palmer Research Laboratories. Aminocarboxylates suitable for use herein include ethylenediaminetetraacetates, diethylenetriaminpentaacetates, diethylenetriamine pentaacetate (DTPA), N-hydroxyethylenediaminetriacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetraminehexaacetates, ethanol diglycine, propylenediaminetetraacetic acid (PDTA) and methylglycine-di-acetic acid (MGDA), both in its acid form, as in its forms of alkali metal, ammonium and substituted ammonium salts. Particularly suitable aminocarboxylates to be used herein are diethylenetriaminpentaacetic acid, propylenediaminetetraacetic acid (PDTA) which is commercially available, for example, from BASF under the tradename of Triion FS® and methylglycliciacic acid (MGDA). Other carboxylate chelating agents that have been used herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof. Another chelating agent for use herein is of the formula: wherein Ri, R2, R3 and R4 are independently selected from the group consisting of -H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -NO2, -C (O) R \ and SO2R "; R 'is selected from the group consisting of -H, -OH, alkyl, alkoxy, aryl, and aryloxy; R "is selected from the group consisting of alkyl, alkoxy, aryl, and aryloxy; and R5, R6, R and s are independently selected from the group consisting of -H and alkyl. Particularly preferred chelating agents to be used herein are aminoaminotrimethylene phosphonic acid, diethylenetriaminepentaacetic acid, diethylenetriaminepentamethylenephosphonate, 1-hydroxy-ethanediphosphonate, ethylene diamine-N-disuccinic acid, and mixtures thereof. Typically, the compositions according to the present invention comprise up to 5% by weight of the total composition of a chelating agent or mixtures thereof, preferably from 0.01% to 1.5% by weight and more preferably from 0.01% to 0.5%.

Radical scavengers The compositions of the present invention may comprise a radical scavenger or a mixture thereof. Radical scavengers suitable for use herein include the already known mono- and dihydroxybenzene substituted and their analogs, alkyl- and arylcarboxylates and mixtures thereof. Preferred radical scavengers of this type for use herein include di-tert-butylhydroxytoluene (BHT), hydroquinone, di-tert-butylhydroquinone, mono-tert-butylhydroquinone, tert-butyl-hydroxyanisole, benzoic acid, toluic acid, catechol, t-butylcatechol, benzylamine, 1, 1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-propylgalate or mixtures thereof, and especially preferred is the tert-butylhydroxytoluene. Such radical scavengers such as N-propyl gallate can be obtained commercially from Nipa Laboratories under the trade name Nipanox S1®. Radical scavengers when used, in the present invention typically are found in amounts ranging up to 10% by weight of the total composition, preferably from 0.01% to 2% and most preferably from 0.001% to 0.5% by weight. The presence of radical scavengers can contribute to the reduction of the loss of tensile strength of the fabrics and / or the color damage when the compositions of the present invention are used in any laundry application, especially in an application of laundry pre-treatment.

Antioxidants The compositions according to the present invention may further comprise an antioxidant or a mixture thereof.

Typically, the compositions herein comprise up to 10% by weight of the total composition of an antioxidant or mixture thereof, preferably from 0.002% to 5%, most preferably from 0.005% to 2% and most preferably from 0.01% to 1%. %. Suitable antioxidants for use herein include organic acids such as ascorbic acid, adipic acid and sorbic acid, or amines such as lecithin or amino acids such as aglutamine, methionine and cysteine, or esters such as ascorbyl palmitate, ascorbyl stearate and tri eti I citrate, or mixtures thereof. the same. Preferred antioxidants for use herein are, ascorbic acid, ascorbic palmitate, lecithin or mixtures thereof.

Bleach activators As an optional ingredient, the compositions of the present invention may comprise a bleach activator or mixtures thereof. By "bleach activator", it is meant herein a compound that reacts with hydrogen peroxide to form a peracid. The peracid thus formed constitutes the activated bleach. Bleach activators suitable for use herein include those belonging to the class of esters, amides, imides or anhydrides. Examples of suitable compounds of this type are set forth in British patents GB 1 586 769 and GB 2 143 231 and a method for forming them into pellets is described in European published patent application EP-A-62 523. Some suitable examples of such compounds to be used herein are tetracetylethylene amine (TAED)Sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate, diperoxydodecanoic acid as described, for example, in US Pat. No. 4,818,425 and peroxyadipic acid nonyl amide as described, for example, in US 4 259 201 and n-nonanoyloxybenzenesulfonate ( NOBS). N-acylcaprolactams selected from the group consisting of benzoylcaprolactam, octanoylcaprolactam, nonanoylcaprolactam, hexanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, formylcaprolactam, acetylcaprolactam, propanoylcaprolactam, butanoylcaprolactam, substituted or unsubstituted pentanoylcaprolactam, or mixtures thereof are also suitable. A particular family of bleach activators of interest is described in EP 624 154, and acetyltriethyl citrate (ATC) is particularly preferred in that family. Acetyltriethyl citrate has the advantage that it does not harm the environment and is finally degraded in citric acid and alcohol. In addition, acetyltriethyl citrate has good hydrolytic stability in the product during storage and is an effective bleach activator. Finally, it provides good capacity for detergency improvement to the composition. The compositions according to the present invention may comprise from 0.01% to 20% by weight of the total composition of said bleach activator, or mixtures thereof, preferably from 1% to 10% and more preferably from 3% to 7% .

Foaming reducing system: The compositions according to the present invention may comprise a foam reducing agent or a mixture thereof. Any foam reducing agents known to those skilled in the art are suitable for use herein. In a preferred embodiment a foam system comprises a fatty acid together with a non-ionic alkoxylated surfactant of blocked ends, as defined herein below and / or silicone is used. Typically, the compositions herein can comprise from% to 10% by weight of the total composition of a fatty acid or a mixture thereof, preferably from% to 5% and most preferably from% to 5%. Typically, the compositions herein may comprise from% to 20% by weight of the total composition of a blocked end alkoxylated nonionic surfactant as defined herein or a mixture thereof, preferably from% to 10% and very preferably from% to 5%. Typically, the compositions herein may comprise from% to 5% by weight of the total composition of a silicone or a mixture thereof, preferably from% to 1% and most preferably from% to 0.5%. Suitable fatty acids for use herein are alkaline salts of C8-C24 fatty acid. Said alkaline salts include the fully saturated metal salts such as the sodium, potassium and / or lithium salts, as well as the ammonium and / or alkylammonium salts of fatty acids, preferably the sodium salt. The fatty acids which are preferred for use herein contain from 8 to 22 carbon atoms, preferably from 8 to 20 and most preferably from 8 to 18. Suitable fatty acids can be chosen from caprylic acid, capric acid, lauric acid, acid myristic, palmitic acid, stearic acid and mixtures of suitably hardened fatty acids, derived from natural sources such as plant or animal esters (eg palm oil, coconut oil, soybean oil, castor oil, bait, peanut oil of whale and fish and / or babassu oil For example, coconut fatty acid is commercially available from UNICHEMA under the name PRIFAC 5900. The non-ionic alkoxylated surfactants of blocked ends suitable for use in the present invention are in accordance with US Pat. formula: wherein Ri is a linear or branched C8-C2 alkyl or alkenyl group, aryl group, alkaryl group, preferably Ri e s an alkyl or alkenyl group of C-C-is, most preferably an alkyl or alkenyl group of C-io-C-I5, very much preferably a C10-C15 alkyl group; wherein R2 is a linear or branched C1-C10 alkyl group, preferably a linear or branched C2-C10 alkyl group, preferably a C3 group; wherein R3 is an alkyl or alkenyl group of C-i-C-, preferably a C1-C5 alkyl group, most preferably methyl; and wherein n and m are integers that vary independently on a scale of 1 to 20, preferably 1 to 10, most preferably 1 to 5 or mixtures thereof. These surfactants are commercially available from BASF under the tradename Plurafac®, from HOECHST under the trade name Genepol®, or from ICI under the trade name Symperonic®. The blocked end nonionic alkoxylated surfactants of the above formula are those which are commercially available under the tradename Genepol® L 2.5 NR from Hoechst, and Plurafac® from BASF. Silicones suitable for use herein include any mixture of silicone and silica-silicone. Silicones can generally be represented by alkylated polysiloxane materials, while silica is normally used in finely divided forms exemplified by silica aerogels and hydrophobic xerogels of various types. These materials can be incorporated as particles wherein the silicone is incorporated so that it can be usefully released in a waterproof non-surfactant detergent impermeable vehicle soluble in water or dispersible in water. Alternatively, the silicone can be dissolved or dispersed in a liquid vehicle and applied by sprinkling on one or more other components. In reality in industrial practice, the term "silicone" has become a generic term that includes a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl groups of various types. In fact, silicone compounds have been extensively described in the art, for example see US 4076648, US 4021365, US 4749740, US 4983316, EP 150872, EP 217501 and EP 499364. The silicone compounds described herein are suitable in the context of the present invention. Generally, the silicone compounds can be described as siloxanes having the general structure: RI - (YES? -) n - R where n is from 20 to 2000, and wherein each R can independently be an alkyl radical or an aryl radical . Examples of such substituents are methyl, ethyl, propyl, butyl and phenyl. Preferred polydiorganosiloxanes are polydimethylsiloxanes having blocking units at their trimethylsilyl end and having a viscosity of 25 ° C of 5 x 10"5 m2 / s to 0.1 m2 / s, ie a value of n on a scale of 40 to 1500. These are preferred because they can be easily accessed and their cost is relatively low.

A preferred type of silicone compounds useful in the compositions of the present invention comprises a mixture of an alkylated siloxane of the type mentioned as described above and solid silica. The solid silica can be fuming silica, a precipitated silica or a silica made by the gel-forming technique. The silica particles can be made hydrophobic by treatment with dialkylsilyl groups and / or trialkylsilane groups, either directly bonded to the silica or by means of silicone resin. A silicone compound which is preferred comprises a hydrophobic silanated silica, most preferably trimethylsilylated silica having a particle size in the range of 10 mm to 20 mm and a specific surface area of 50 m2 / g. The silicone compounds used in the compositions according to the present invention suitably have an amount of silica on a scale of 1 to 30% (most preferably 2.0 to 15%) by weight of the total weight of the silicone compounds resulting in compounds of silicone having an average viscosity on a scale of 2 xl O ^ m 2 / s to 1 m2 / s. Preferred silicone compounds can have a viscosity on a scale from 5 x 10"3m2 / s to 0.1 m2 / s Particularly suitable silicone compounds are those having a viscosity of 2 x 10" 2m2 / s or 4.5 x 10"2m2 / s The silicone compounds suitable for use herein are commercially available from various companies, including Rhone Poulenc, Fueller and Dow Corning Examples of silicone compounds to be used herein are Silicone DB® 100 and Silicone Emulsion 2-3597®, both commercially available from Dow Corning.Another preferred silicone silicone compound is disclosed in U.S. Patent No. 3,933,672 to Bartollota et al. Other particularly useful silicone compounds are the self-emulsifiable silicone compounds described in the German patent application DTOS 2 646 126, published on April 28, 1977. An example of such a compound is DC-544®, commercially available from Dow Corning, the al is a siloxane-glycol copolymer. Preferred silicone compounds are typically described in European patent application EP-A-57396699. Said compositions may comprise a mixture of silicon / silica in combination with vaporized non-porous silica such as Aerosil ® Method for blanching fabrics: In the present invention, the liquid bleaching composition of the present invention necessarily makes contact with the fabrics that will be bleached. This can be done either in a so-called "pretreatment mode", where the liquid composition is applied undiluted on said fabrics before the fabrics are rinsed or washed and subsequently rinsed, or in a "soaking mode", where the liquid composition is first diluted in an aqueous bath and the fabrics are soaked and soaked in the bath, before they are rinsed, or in a "washing mode", where the liquid composition is added to a washing solution formed by dissolution or dispersion of a typical detergent for laundry. It is also very important in both cases, that the fabrics are rinsed after having made contact with said composition, before said composition is completely dried. In the pretreatment mode, the method comprises the steps of applying said undiluted liquid composition on said fabrics, or at least the soiled portions thereof, and subsequently rinsing or washing and subsequently rinsing said fabrics. In this mode, the pure compositions can optionally be left to act on said fabrics for a period that varies from 1 min. at 1 hour, before rinsing the fabrics or washing them and then rinsing them, since the composition is not allowed to dry on said fabrics. For particular stains it may be suitable to carve or brush said fabrics with a sponge or brush or by rubbing two pieces of cloth against each other. In another way, generally referred to as "soaking," the method comprises the steps of diluting said undiluted liquid composition in an aqueous bath such that a dilute composition is formed. The level of dilution of the liquid composition in an aqueous bath is typically up to 1: 85, preferably up to 1: 50 and most preferably close to 1: 25 (composition: water). Subsequently the fabrics make contact with the aqueous bath containing the liquid composition, and the fabrics are finally rinsed or washed and subsequently rinsed. Preferably in such an embodiment, the fabrics are immersed in the aqueous bath containing the liquid composition, and also preferably, the fabrics are allowed to soak for a period ranging from 1 min. at 48 hours, preferably from 1 hour to 24 hours. In another additional mode that can be considered as a "soaking" submodality, generally referred to as "bleaching during washing", the liquid composition is used as a laundry additive. In such an embodiment, the aqueous bath is formed by dissolving or dispersing a conventional laundry rgent in water. The undiluted liquid composition makes contact with the aqueous bath and the fabrics subsequently make contact with the aqueous bath containing the liquid composition. Finally, the fabrics are rinsed. Depending on the end use that is desired, the compositions in the present invention can be packaged in a variety of containers including conventional containers, containers equipped with a rotating ball applicator, sponge, brush or spray. Although the preferred application of the compositions described herein is a laundry application and especially a laundry pre-treatment, the compositions in accordance with the present invention can be used for domestic cleaning on bathroom or kitchen surfaces. The invention is further illustrated with the examples below.

EXAMPLES The following compositions were made by mixing the ingredients listed in the listed proportions (% by weight unless otherwise specified).

Compositions I II III IV V VI VII VIII Dobanol® 91-10 - - - 1.6. - 2.6 - Dobanol® 45-7 - 2.0 2.6 - 2.6 1.6 - 2.0 Dobanol® 23-3 - - 1.0 2.0 1.0 2.0 1.0 - Betaine free of salts 5.0 2.4 2.4 2.4 2.4 5.0 2.4 5.0 H202 7.0 6.8 5.8 7.0 5.8 7.0 5.8 7.0 HEDP 0.16 - 0.16 - 0.16 0.16 0.16 0.16 DTPMP - 0.18 - 0.18 - - - - Propilgalato 0.1 0.1 - - - 0.1 - 0.1 BHT - - 0.1 0.1 0.1 - 0.1 - Citric acid 0.30 0.5 0.50 0.3 0.50 0.50 0.50 0.50 Perfume * 0.10 0.20 0.15 0.05 0.16 0.15 0.16 0.10 Fatty acid 0.10 0.10 0.25 0.10 0.175 0.25 0.175 0.10 Alcohol of extremes 0.10 0.10 0.10 2.0 0.10 - 0.10 0.10 blocked * Silicone DB® 100 - 0.004 0.002 - 0.002 0.004 0.002 0.004 Water and in? Up to 2% NaOH or KOH up to pH of 4 or 5 DTPMP is diethylenetriaminpentamethylenephosphanate.

Compositions IX X XI XII XIII XIV XV Dobanol® 91-10 - - 1.6 _ - 1.6 - Dobanol® 45-7 1.6 1.6 - - 1.6 - 2.0 Dobanol® 23-3 1.5 1.5 2.0 2.0 2.0 2.0 2.0 Glucosamide * 1.5 1.5 1.5 1.5 1.5 1.5 1.5 C25-AE3-S 2.0 2.0 2.0 2.0 2.0 3.0 1.0 Fatty acid 0.10 0.10 0.10 0.10 0.25 0.25 - Alcohol ends 0.10 0.10 - 2.0 - 0.25 - blocked * Silicone DB® 100 - 0.004 0.004 - 0.004 0.004 - H2Oz 7.0 6.0 7.0 6.0 7.0 6.0 7.0 HEDP - 0.16 0.16 - 0.16 0.16 - DTPMP 0.18 - - 0.18 - - - Propilgalato 0.1 0.1 0.1 0.3 0.1 0.1 - Citric acid / citrate 0.50 0.40 0.35 0.75 - - - sodium Tartaric acid / bitartrate - - - - 0.50 0.25 0.75 potassium Perfume * 0.10 0.20 0.15 0.05 0.16 0.15 0.16 Water and ingredients up to 101 n% secondary PH (undiluted product) 5 5 5 5 4 4 4 Compositions XVI XVII XVIII XIX XX XXI XXII XXIII (% by weight) Dobanol® 91 -10 - 1.6 - - - - 1.6 - Dobanol® 45-7 1.6 - 2.6 1.6 2.0 1.6 - - Dobanol® 23-3 1.5 2.0 1.0 2.0 2.0 2.0 2.0 - Glucosamide * 1.5 1.5 - 1.5 1.5 - - - C25-AE3-S 2.0 2.0 - 2.0 1.0 - - - Laurylbetaine - - 2.4 - - 5.0 5.0 - H202 6.0 7.0 6.0 7.0 7.0 7.0 7.0 7.0 HEDP 0.16 0.16 0.16 0.16 - 0.16 0.16 - DTPMP - - - - 0.18 - - BHT 0.1 0.1 0.1 0.1 0.3 0.1 0.1 - - Citric acid / citrate 0.50 0.25 0.75 1.0 - - 0.5 0.5 Oxalic acid / oxalate of - - - - 0.50 0.75 0.5 -sodium Perfume * 0.1 0.15 0.1 0.15 0.1 0.15 0.1 0.10 Water and ingredients - 100% -secondary PH (undiluted product) 5 5 5 5 4 4 4 4.5 HEDP is 1-hydroxy-ethanediphosphonate DTPMP is diethylenetriaminpentamethylenephosphonate.

BHT is di-tert-butylhydroxytoluene Betaine free of salts * is lauryldimethylbetaine containing 0.3% by weight of sodium chloride. This betaine is obtainable by purification from the Lauryl dimethylbetaine GENAGEN LAB® (Hoechst), (which contains 7.5% sodium chloride). The perfume used in the above compositions contains as main ingredients di-hydro-mircenol and hexyl cinnamic aldehyde. Compositions I to XIII, when used to bleach dirty colored fabrics, exhibit excellent security for color, as well as good security for the fabric to fabrics bleached therewith. For example, in a pre-treatment mode, undiluted compositions I to XIII are applied over the stained portion of the fabric and allowed to act thereon for 5 minutes. Subsequently the fabric is washed with a conventional detergent and rinsed. Surprisingly, excellent security for the color is obtained, as well as good security for the fabric when using these compositions, even by allowing these compositions to act on the fabric for a prolonged time, for example 1 hour, before washing the fabrics. fabrics When used in bleach mode during washing, any of compositions I to XIII are contacted with an aqueous bath formed by dissolving a conventional detergent in water.

Subsequently the fabrics are put in contact with the aqueous bath comprising the liquid detergent and the fabrics are rinsed. The compositions can also be used in a soaking mode, wherein 100 ml of the liquid compositions are diluted in 10 liters of water. The fabrics are then put in contact with the aqueous bath containing the composition and allowed to soak therein for a period of 24 hours. Finally the fabrics are washed.

Claims

NOVELTY OF THE INVENTION CLAIMS

1. - A liquid composition suitable for pretreating fabrics having a pH of up to about 7 and comprising a peroxygen bleach, from about 0.1% to about 10% by total weight of the composition of a means for regulating the pH and of about 0.0001% to about 5% by weight of a perfume.

2. The composition according to claim 1, further characterized in that said peroxygen bleach is hydrogen peroxide or a water soluble source thereof, selected from the group consisting of percarbonates, persilicates, perborates, peroxyacids, hydroperoxides, aromatic diacyl peroxides and aliphatics and mixtures thereof, preferably is hydrogen peroxide, tertbutyl hydroperoxide, cumyl hydroperoxide, 2,4,4-trimethylphenyl-2-hydroperoxide, di-isopropylbenzene monohydroperoxide, ter-amyl hydroperoxide, 2,5- dimethylhexane-2,5-dihydroperoxide, dilauroyl peroxide, didecanoyl peroxide, dimyristoyl peroxide, benzoyl peroxide and mixtures thereof, and most preferably hydrogen peroxide.

3. The composition according to claim 1, further characterized in that it comprises from about 0.1% to about 20% by weight of the total composition of said peroxygen bleach or a mixture thereof.

4. The composition according to claim 3, further characterized in that it comprises from about 1% to about 15% of the total composition of said peroxygen bleach or a mixture thereof.

5. The composition according to claim 3, further characterized in that it comprises from about 2% to about 10% by weight of the total composition of said peroxygen bleach or a mixture thereof.

6. The composition according to claim 1, further characterized in that said means for regulating the pH comprises a weak acid having its pKa or one of its pKa about 1.5 to about 6.5 and its conjugate base.

7. The composition according to claim 6, further characterized in that said means for regulating the pH comprises a weak acid having its pKa or one of its pKa from about 2 to about 6, and its conjugate base.

8. The composition according to claim 6, further characterized in that said means for regulating the pH comprises a weak acid having its pKa or one of its pKa about 4 to about 6 and its conjugate base.

9. The composition according to claim 1, further characterized in that said means for regulating the pH is citric acid / sodium citrate, citric acid / potassium citrate, citric acid, oxalic acid / sodium oxalate, tartaric acid / bitartrate of potassium, oxalic acid / potassium tetraoxalate dihydrate, phthalic acid / potassium phthalate, acetic acid / sodium acetate, formic acid / sodium formate, benzoic acid / sodium benzoate, and / or salicylic acid / sodium salicylate and very preferably it is citric acid / sodium citrate and / or citric acid / potassium citrate.

10. The composition according to claim 1, further characterized in that it comprises from about 0.2% to about 8% by weight of the total composition of a means for regulating the pH or a mixture thereof. 1.

The composition according to claim 10, further characterized in that it comprises from about 0.3% to about 5% by weight of the total composition of a means for regulating the pH or a mixture thereof.

12. The composition according to claim 10, further characterized in that it comprises from about 0.3% to about 3% by weight of the total composition of a means for regulating the pH or a mixture thereof.

13. The composition according to claim 10, further characterized in that it comprises from about 0.3% to about 2% by weight of the total composition of a means for regulating the pH or a mixture thereof.

14. - The composition according to claim 1, further characterized in that it comprises from about 0.0001% to about 1% by weight of the total composition of a perfume or a mixture thereof.

15. The composition according to claim 14, further characterized in that it comprises from about 0.001% to about 1% by weight of the total composition of a perfume or a mixture thereof.

16. The composition according to claim 14, further characterized in that it comprises from about 0.01% to about 0.5% by weight of the total composition of a perfume or a mixture thereof.

17. The composition according to claim 1, further characterized in that said composition comprises up to about 60% by weight of the total composition of a surfactant or a mixture thereof.

18. The composition according to claim 17, further characterized in that said composition comprises from about 0.1% to about 30% by weight of the total composition of a surfactant or a mixture thereof.

19. The composition according to claim 17, further characterized in that said composition comprises from about 0.5% to about 15% by weight of the total composition of a surfactant or a mixture thereof.

20. The composition according to claim 17, further characterized in that said surfactant is a nonionic and / or zwitterionic surfactant, preferably a mixture of a non-ionic alkoxylated surfactant and a zwitterionic betaine surfactant.

21. The composition according to claim 20, further characterized in that said nonionic surfactant is a non-ionic ethoxylated surfactant according to the formula RO- (C2H4O) nH, where R is an alkyl chain of C6 to C22 or an alkylbenzene chain of C6 to C28, and wherein n is an integer from about 0 to about 20, preferably from about 1 to about 15, most preferably from about 2 to about 15 and much very preferably from about 2 to about 12, and / or an amine oxide surfactant and / or a polyhydroxy fatty acid amide surfactant.

22. The composition according to claim 20 or 21, further characterized in that said zwitterionic betaine surfactant is in accordance with the formula: R.-N + (R2) (R3) R4X-wherein R1 is a hydrocarbon chain aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted containing linking groups such as amido groups, ester groups, preferably an alkyl group containing from about 1 to about 24 carbon atoms, preferably from about 8 to about 18, and most preferably at about 10 to about 16, or an amido radical of the formula Ra-C (O) -NH- (C (Rb) 2) m. where Ra is aliphatic or aromatic hydrocarbon chain, saturated or unsaturated, substituted or unsubstituted, preferably an alkyl group containing from about 8 to about 20 carbon atoms, preferably up to about 18, most preferably up to about 16 Rb it is selected from the group consisting of hydrogen and hydroxyl groups, and m is from about 1 to about 4, preferably from about 2 to about 3, most preferably 3, without more than one hydroxyl group in any portion (C (R )2); R2 is hydrogen, Ci-Cß alkyl, hydroxyalkyl or another substituted alkyl group of C-t-C6; R3 is C6-C6 alkyl, hydroxyalkyl or another substituted C-C3 alkyl group which can also be attached to R2 to form ring structures with N, or a C-Cß carboxylic acid group or a C-I-CT sulfonate group; R4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically an alkylene, hydroxyalkyl or polyalkoxy group containing from about 1 to about 10 carbon atoms; and X is a carboxylate or sulfonate group or a mixture thereof.

23. The composition according to claim 20 or 22, further characterized in that said zwitterionic betaine surfactant is a salt-free zwitterionic betaine surfactant containing less than about 5% weight of salts.

24. The composition according to claim 23, further characterized in that said zwitterionic betaine surfactant contains less than about 3% by weight of salts.

25. The composition according to claim 23, further characterized in that said zwitterionic betaine surfactant contains less than about 2% by weight of salts.

26. The composition according to claim 23, further characterized in that said zwitterionic betaine surfactant contains less than about 1% by weight of salts.

27. The composition according to claim 23, further characterized in that said zwitterionic betaine surfactant contains from about 0.01% to about 0.5% by weight of salts.

28. The composition according to claim 1, further characterized in that said composition additionally comprises a chelating agent or a mixture thereof, up to 5% by weight of the total composition, preferably from about 0.01% to about 1.5% , wherein said chelating agent is preferably a phosphonate chelating agent, an aminocarboxylate chelating agent, another carboxylate chelating agent, a polyfunctionally substituted aromatic chelating agent, ethylene diamine N, N'-disuccinic acid or mixtures thereof, and most preferably amino aminotri (methylene phosphonic acid), di-ethylene-triamino-pentaacetic acid, diethylenetriaminepentamethylenephosphonate, 1-hydroxyethanedisofophonate, ethylene diamine N, N'-succinic acid, or a mixture thereof.

29. The composition according to claim 1, further characterized in that said composition is aqueous and is typically formulated with a pH of about 1 to about 6.

The composition according to claim 29, further characterized in that said composition is formulated with a pH of about 1.5 to about 5.5.

31. A method for bleaching fabrics that includes the steps of diluting in a water bath a liquid composition according to claims 1, 2, 3, 6, 9, 10, 14, 17, 20, 21, 28, 29, in its undiluted form, causing said fabrics to make contact with said aqueous bath containing said liquid composition, and subsequently rinsing, or washing and subsequently rinsing said fabrics.

32. A method for bleaching fabrics, including the steps of diluting in a water bath a liquid composition according to claim 22 in its undiluted form, causing said fabrics to make contact with said aqueous bath containing said liquid composition, and subsequently rinsing, and washing and subsequently rinsing said fabrics. 33.- A method for bleaching fabrics that includes the steps of diluting an aqueous composition according to claim 23 in its undiluted form in an aqueous bath, causing said fabrics to make contact with said aqueous bath containing the liquid composition, and subsequently rinsing or washing and then rinsing said fabrics. 34.- A method for pretreating fabrics comprising the steps of applying a liquid composition according to any of claims 1, 2, 3, 6, 9, 10, 14, 17, 20, 21, 28, 29 in its undiluted form, on said fabrics, preferably on dirty portions thereof, before rinsing said fabrics, or washing them and subsequently rinsing said fabrics. 35.- A process for pretreating fabrics that * comprises the steps of applying a liquid composition according to claim 22 in its undiluted form, on said fabrics, preferably on dirty portions thereof, before rinsing said fabrics, or washing them and then rinsing said fabrics. 36.- A process for pretreating fabrics comprising the steps of applying a liquid composition according to claim 23 in its undiluted form, on said fabrics, preferably on dirty portions thereof, before rinsing said fabrics, or washing them and subsequently rinsing said fabrics. 37.- A method according to claim 31, wherein the fabrics are allowed to soak in said aqueous bath containing the liquid composition for a period ranging from about 1 minute to about 48 hours, preferably about 1 hour to about 24 hours. 38.- A method according to claim 32, wherein the fabrics are allowed to soak in said aqueous bath containing the liquid composition during a period ranging from about 1 minute to about 48 hours, preferably about 1 hour to about 24 hours. 39.- A method according to claim 33, wherein the fabrics are allowed to soak in said aqueous bath containing the liquid composition for a period ranging from about 1 minute to about 48 hours, preferably about 1 hour to about 24 hours. 40.- A method according to claim 31, wherein said aqueous bath is formed by dissolving or dispersing a conventional laundry detergent in water.