MXPA02000055A - Bleaching compositions. - Google Patents

Abstract

The present invention relates to a bleaching composition comprising a preformed peroxy carboxylic acid and a metal phthalocyanine colouring agent wherein both the preformed peroxy acid and the colouring agent are storage stable in liquid conditions.

Description

BLEACHING COMPOSITIONS TECHNICAL FIELD The present invention relates to a bleaching composition comprising a preformed peroxycarboxylic acid and a metal phthalocyanine coloring agent which is suitable for use for bleaching fabrics, clothing, carpets and the like.

BACKGROUND OF THE INVENTION Liquid aqueous bleach compositions commonly found suitable for bleaching stains on fabrics and hard surfaces are based on halogen bleaches, especially hypochlorite bleaches. Halogen bleaches are extremely effective bleaching agents, however they also have a number of drawbacks that can sometimes discourage a consumer from choosing the halogen-containing product. For example, halogen bleaches, especially chlorine bleaches, emit a pungent odor during and after use (for example, on the consumer's hands and / or surfaces treated with it) that some consumers find unpleasant.

Furthermore, it is known in the art that compositions containing halogen bleach (typically hypochlorite) are relatively aggressive to fabrics and can cause damage when used in a relatively high concentration and / or repeated use. In particular, the consumer may perceive damage to the fabric itself (for example, loss of tensile strength) or damage to the intensity of the color of the fabric. Although damage to color and fabric can be minimized by using milder oxygen materials such as hydrogen peroxide, the bleach performance characteristics of such peroxygen bleaches are much less desirable than those of halogen bleaching agents. Therefore, aqueous activated peroxygen bleach-containing compositions containing activators, ie, compounds that increase the peroxygen bleaching performance, have been developed. It is an object of the present invention to provide a bleaching composition that not only provides effective bleaching performance, when used in laundry applications, but also security to treated surfaces, for example, fabrics per se and / or fabric colors. It is often preferred, from a consumer acceptability point of view, that the detergent compositions be colored. This is especially true of liquid detergent compositions. However, coloring agents for example pigments and dyes are often not stable or are not stable enough for oxidative bleaching agents.

In addition, the coloring agents may also be susceptible to the chemical environment in which they are formulated, for example, the pH of the composition. This is also very often true when the composition is a liquid form since the components of the composition are free to migrate through the liquid, potentially reacting with each other and consequently resulting in the depletion of some components, for example, agents bleaches and / or coloring agents. Therefore, a further object of the present invention is to provide a liquid bleaching composition further comprising a coloring agent and which is chemically stable, and very particularly chemically stable upon storage. The compositions according to the present invention may be useful in any laundry application, for example, as a laundry detergent or a laundry additive, and when used as a laundry pretreatment agent. A particular advantage of the compositions of the present invention is that they are suitable for bleaching different types of fabrics including natural fabrics (for example, fabrics made of cotton and linen) synthetic fabrics such as those made of polymeric fibers of synthetic origin (for example example, polyamide-elastane) as well as those made of both natural and synthetic fibers. For example, the bleaching compositions of the present invention can be used in synthetic fabrics despite an existing prejudice against the use of bleaching agents in synthetic fabrics, as evidenced by the warnings on clothing labels and bleaching compositions commercially available as compositions containing hypochlorite . Another advantage of the bleaching compositions according to the present invention is that they can be used in a variety of conditions, that is, in hard and soft water as well as when they are used in pure or diluted form. Most particularly, it has been found that the liquid aqueous compositions of the present invention find a preferred application when used in their diluted form in any application and especially in any conventional laundry application. In fact, when diluted (typically at a dilution level of 20 ml / l or more (composition: water) the compositions of the present invention become less acidic, for example, from a pH of about 1.5 to about 6.5 or more. The compositions according to the present invention, while having effective bleaching performance in their pure form surprisingly have an increased increased bleaching performance in their diluted form.In reality, this "pH leap" effect allows to formulate aqueous liquid acidic compositions (ie say, pH less than 7, preferably less than 5) that are physically and chemically stable during prolonged storage periods and that provide outstanding bleaching performance under dilute use conditions.

BRIEF DESCRIPTION OF THE INVENTION In accordance with the present invention, there is provided a liquid bleaching composition comprising a preformed peroxycarboxylic acid and a metal phthalocyanine coloring agent. The present invention further comprises a method of bleaching a surface and the use of said composition.

DETAILED DESCRIPTION OF THE INVENTION The bleaching composition The compositions according to the present invention are liquid compositions as opposed to a solid or a gas. As used herein, the term "liquid" includes suspensions of solid particles in liquid compositions and "pasty" compositions. The liquid compositions herein are preferably aqueous compositions, comprising water at a level preferably of 10% to 99%, most preferably 50% to 98% by weight of the bleaching composition. The liquid compositions according to the present invention have a pH below 7. Preferably, the pH of the compositions according to the present invention is from 0.1 to 6.5, most preferably from 0.5 to 5, most preferably from 2 to 4. The formulation of the compositions according to the present invention in the acid pH range is critical for the chemical stability of the compositions according to the present invention. The pH of the composition is preferably below the pKa of the waste used. The pH of the compositions can be adjusted by any acid or alkaline species known to those skilled in the art. Examples of acid species suitable for use herein are organic acids such as citric acid and inorganic acids such as sulfuric acid, sulfonic acid and / or methanesulfonic acid. Examples of alkaline species are sodium hydroxide, potassium hydroxide and / or sodium carbonate. Other pH adjusting agents include the alkanolamines. It can be advantageous to use alkanolamines, in particular monoethanolamine, since they have an additional effect of regulating the viscosity of the emulsion, without compromising its physical stability. The bleaching performance of the present composition can be evaluated by the following test methods in various types of bleaching spots. An advantage of the compositions of the present invention is that they are physically and chemically stable during prolonged storage periods. The chemical stability of the bleaching agent of the present invention can be evaluated by measuring the concentration of available oxygen in a given storage time after the compositions have been manufactured. By "chemically stable", it is understood that the compositions of the present invention comprise a peracid that does not suffer more than 30% loss of AvO, in 10 days at 35 ° C and preferably at no more than 20%. The available oxygen loss (AvO) of a composition containing peracid over time can be measured by the iodometric titration method in which the peracid is reduced by an excess of potassium iodide and the iodine formed is determined by titration with thiosulfate of sodium. The method is well known in the art and is reported for example in A Bleachers Handbook by Interox and available therefrom. Alternatively, the peracid concentration can also be measured using a chromatography method described in the literature on perishes (F. Di fury et al., Gas-liquid Chromatography Method for Determination of Peracids, Analyst, Vol 113, May 1988, p. -795). The chemical stability of the coloring agent can be evaluated according to a visual scale of color intensity and loss thereof with time compared to a freshly prepared reference (as described below). By "physically stable" it is meant here that phase separation does not occur in compositions according to the present invention for a period of 7 days at 35 ° C which means that there is no phase separation of two liquids and that there is likewise no precipitation nor flocculation of a solid phase of the liquid phase, i.e., a solid particle remains homogeneously distributed throughout the liquid composition.

Preformed Peroxycarboxylic Acid The bleaching composition of the present invention comprises a preformed peroxycarboxylic acid (hereinafter called peracid). Any suitable peracid known in the art can be used therein. Preferably, the peracid is in the form of a solid. In a preferred embodiment of the present invention, the peracid has the general formula XRC (O) OOH wherein R is a linear or branched alkyl chain having at least one carbon atom and X is a hydrogen or a substituent group selected of the group consisting of alkyl, especially alkyl chains of 1 to 24 carbon atoms, aryl, halogen, ester, ether, amine, amide, substituted phthalic amide, imide, hydroxide, sulfide, sulfate, sulfonate, carboxylic, heterocyclic, nitrate , aldehyde, phosphonate, phosphonic or mixtures thereof. Most particularly, the R group preferably comprises up to 24 carbon atoms. Alternatively, the R group can be a branched alkyl chain comprising one or more side chains comprising substituent groups selected from the group consisting of aryl, halogen, ester, ether, amine, amide, substituted phthalic amino, amino, imide, hydroxide , sulfur, sulfate, sulfonate, carboxylic, heteocyclic, nitrate, aldehyde, ketone or mixtures thereof.

In a preferred peracid, the group X according to the above general formula is a phthalimido group. Therefore, the particularly preferred perished are those having the general formula: wherein R is C1-20 and wherein A, B, C and D are independently either hydrogen or substituent groups individually selected from the group consisting of alkyl, hydroxyl, nitro, halogen, amine, ammonium, cyanide, carboxylic, sulfate, sulfonate, aldehydes or mixtures thereof. In a preferred aspect of the present invention, R is an alkyl group having from 3 to 12 carbon atoms, most preferably from 5 to 9 carbon atoms. Preferred substituent groups, A, B, C and D are linear or branched alkyl groups having from 1 to 5 atoms, but most preferably hydrogen. The preferred peracids are selected from the group consisting of phthaloylamidoperoxyhexanoic acid, phthaloylamidoperoxyhepatnoic acid, phthaloylamidoperoxyoctanoic acid, phthaloylamidoperoxynanoic acid, phthaloyl amidoperoxydecanoic acid, and mixtures thereof. In a particularly preferred aspect of the present invention, the peracid has the formula such that R C5H10, ie, phthaloylamidoperoxyhexanoic acid or PAP. This permeate is preferably used as a solid substantially insoluble in water or wet cake and is available from Ausimont under the trade name Euroco. The peracid is preferably used at a level of 0.1% to 30%, most preferably 0.5% to 18% and most preferably still 1% to 12% by weight of the composition.

Dye Agent The compositions of the present invention require a metal phthalocyanine coloring agent as an essential characteristic thereof. Applicants have found that as described above, in order to maintain the stability of the peracid, the composition must be formulated in the pH range, however, typically the coloring agents are not stable or are not sufficiently stable in a peracid-containing environment. They are also not stable under acidic conditions. Applicants have identified a group of coloring agents that are suitable not only in the presence of peracid, but also in acidic conditions. This group of coloring agents is metallic phthalocyanines. The metallic agent of the coloring agent is preferably copper, iron, cobalt or nickel. Most preferably still a chlorinated copper phthalocyanine. Coloring agents are classified according to recognized international standards known as color index (very recently published as the 3rd edition of The Society of Dyers and Colourists and the American Association of Textile Chemists and Colourists). Examples of commercially available metal phthalocyanine coloring agents are those available having the color index number Cl 74260 Pigment Green 7 such as those sold under the trade names Pigmasol Green from BASF, Cl 74160 Pigment blue 15 or 15: 1 or 15: 2 such as Cosmenyl Blue from Clariant, Cl 74160 Pigment blue 15: 3 such as luconyl blue from BASF, Pigment blue 76 such as Fastogen blue 76 from Sun Chemicals and mixtures of same. The coloring agents can be used in solid or liquid form. However, it is typical for dyes. They are generally available in liquid form and the pigments are available in solid form. Where a coloring agent of solid form is used, the particle size distribution is preferably less than 200 microns, most preferably in the range of 0.01 to 100 microns and most preferably still from 0.1 to 50 microns. Typically, the coloring agent is present at a level of 0.00001% to 0.1%, most preferably from 0.0001% to 0.001% and most preferably still from 0.002% to 0.005% by weight of the composition.

Optional ingredients The compositions of the present invention may further comprise a variety of other optional ingredients such as surfactants, chelating agents, radical scavengers, antioxidants, stabilizers, builders, soil suspension polymer, polymeric soil release agents, agents of pH control, dye transfer inhibitor, solvents, foam controlling agents, foam enhancers, optical brighteners, perfumes and the like.

Surfactants The compositions of the present invention may optionally, but preferably comprise, a surfactant. The surfactants are selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, switerionic surfactants and / or amphoteric surfactants. Suitable anionic surfactants for use in the compositions herein include water-soluble salts or acids of the formula ROSO 3 M wherein R is preferably C 0 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having an alkyl C component; o-C2o, most preferably an alkyl or hydroxyalkyl of C? 2-C? 8, and M is H or a cation, for example, an alkali metal cation (eg, sodium, potassium, lithium), or a cation of ammonium or substituted ammonium (e.g., methyl, dimethyl and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl ammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof and similar). Typically, C 2 -C 16 alkyl chains are preferred for lower wash temperatures (eg, less than about 50 ° C and C 16 -8 alkyl chains are preferred for higher wash temperatures (for example, Other suitable anionic surfactants to be used herein are salts or water-soluble acids of the formula RO (A) mS03M wherein R is an unsubstituted C? or C 24 alkyl or a hydroxyalkyl group which has an alkyl component of C20-C24, preferably C2-C2o alkyl or hydroxyalkyl, most preferably C12-C-is alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, most 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.), an ammonium or substituted ammonium cation, the Ethoxylated alkyl sulfates as well as propoxylated alkyl sulphates are contemplated herein. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium and quaternary ammonium cations, such as tetramethylammonium, dimethylammonium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Illustrative examples are polyethoxylated C12-Ci8 alkyl sulfate (1.0), polyethoxylated C12-Cis alkyl sulfate (2.25), C12-C? 8E (2.25) M), polyethoxylated C12-C.8 alkyl sulfate (3.0), C? 2- C.8E (3.0), polyethoxylated C12-C8 alkyl sulfate (4.0) Ci2-C-? 8E (4.0) M, wherein M is conveniently selected from sodium and potassium. Other anionic surfactants particularly suitable for use herein are alkylsulfonates which include salts or water-soluble acids of the formula RSO3M wherein R is a saturated or unsaturated, straight or branched C6-C22 alkyl group, preferably a C12-C18 alkyl group and most preferably an alkyl group of C 14 -C, 6, and M is H or a cation, for example, an alkali metal cation (eg, sodium, potassium, lithium), or ammonium or substituted ammonium (eg, cations) of methyl, dimethyl and trimethyl ammonium and quaternary ammonium cations, such as tetramethylammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like). Alkylarylsulfonates for use herein include salts or water soluble acids of the formula RSO3M wherein R is an aryl, preferably benzyl, substituted by a saturated or unsaturated, straight or branched C6-C22 alkyl group, preferably a C12 alkyl group. C18 and most preferably a C14-C16 alkyl group, and M is H or a cation, for example, an alkali metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.) or an ammonium cation or substituted ammonium (e.g., 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 ). The alkylsulfonates and alkylarylsulfates for use herein include primary and secondary alkylsulfonates. By "C6-C22 alkylsulfonates or secondary C6-C22 alkylarylsulfonates", it is understood here that in the formula as defined above, the group SO3M or aryl-SO3M is linked to a carbon atom of the alkyl chain located among others two carbon atoms of said alkyl chain (secondary carbon atom). For example, the C 4 -C 16 alkylsulfonate salt is commercially available under the name Hostapur ® SAS and Hoechst and C 8 alkylsulfonate sodium salt is commercially available under the name Witconate ÑAS 8 ® from Witco SA. One example of commercially available alkyl aryl sulfonate is Lauryl aryl sulphonate from Su.Ma. Particularly preferred alkylarylsulfonates are commercially available alkylbenzene sulphonates under the name Nansa® available from Albright & amp;; Wilson. Other anionic surfactants useful for detersive purposes can also be used here. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono, di and triethanolamine salts) of soap, Cs-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed citrate product of alkaline earth metal, for example, as described in the specification of British Patent No. 1, 082,179, C 8 -C 24 alkyl polyglycol ether sulphates (containing up to 10 moles of ethylene oxide); alkylethersulfonates such as Cu-tis methyl ester sulfonates, acyl glycerol sulfonates, fatty oleyl glyceryl sulfates, ethylene oxide ether sulfates of alkylphenol, paraffinsulfonates, alkyl phosphates, isethionates such as acyl and isethionates, N-acyltaurates, alkylsuccinamates and sulfosuccinates, monoesters of sulfosuccinate (especially monster esters of C? 2-C 8 saturated and unsaturated) sulfosuccinate diesters (especially saturated and unsaturated Ce-Cu diesters) alkylpolysaccharide sulfates such as alkyl polyglycoside sulfates (the non-sulphonated nonionic compounds are described below), branched primary alkyl sulphates, alkyl polyethoxycarboxylates such as those of the formula RO (CH2CH2O) kCH2COO-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 colophonic, hydrogenated rosin and resin acids, and hydrogenated resin acids present or derived from wood oil. Additional examples are given in "Surface Active Agents and Detergents" (Vol. I and II of Schwartz, Perry and Berch). A variety of such surfactants are also generally described in U.S. Pat. 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 anionic surfactants particularly suitable for use herein are alkylcarboxylates and alkylalkoxycarboxylates having from 4 to 24 carbon atoms in the alkyl chain, preferably from 8 to 18 and most preferably from 8 to 16, wherein the alkoxy is propoxy and / or ethoxy and preferably is ethoxy at a degree of alkoxylation of 0.5 to 20, preferably 20 to 15. The preferred alkylalkoxycarboxylate to be used herein is sodium laureth 11 carboxylate (i.e., RO (C2H4O)? or -CH2COONa, with R = C12 -C24) commercially available under the name Akyposoft® 100 NV from Kao Chemical Gbmh. Suitable amphoteric surfactants for use herein include amine oxides having the following formula R.R2R3NO wherein each of Ri, R2 and R3 is independently a straight or branched, substituted or unsubstituted hydrocarbon chain, saturated from 1 to 30 carbon atoms. Preferred amine oxide surfactants for use in accordance with the present invention are amine oxides having the following formula R1R2R3NO wherein R1 is a hydrocarbon chain comprising from 1 to 30 carbon atoms, preferably from 6 to 20, most preferably from 8 to 16, most preferably even from 8 to 12, and wherein R 2 and R 3 are independently or unsubstituted linear or branched hydrocarbon chains comprising 1 to 4 carbon atoms, preferably 1 3 carbon atoms and most preferably are methylol groups. R. may be a substituted or unsubstituted, saturated linear or branched hydrocarbon chain. Suitable amine oxides to be used herein are for example C8-C-? Amine or naturally mixed amine oxides as well as C.2-C16 amine oxides commercially available from Hoechst. The surfactant surfactants for use herein contain a cationic hydrophilic group, ie, a quaternary ammonium group, and an anionic hydrophilic group in the same molecule in the same relatively broad pH range. 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 the switerionic surfactants to be used here is: RrN + (R2) (R3) R4X "wherein R1 is a hydrophobic group; R 2 is hydrogen, C 1 -C 6 alkyl, hydroxyalkyl or another substituted C 1 -C 6 alkyl group; R3 is C?-C6 alkyl, hydroxyalkyl or another substituted C -?-C6 alkyl group that can also be attached to R2 to form ring structures with the N, or a Ci-Cß carboxylic acid group or a sulfonate group of Ci-Cß; 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 R-i are substituted or unsubstituted, saturated or unsaturated, aliphatic or aromatic hydrocarbon chains which may contain linker groups such as amido groups, ester groups. R1 more preferred is an alkyl group containing from 24 carbon atoms, preferably from 1 to 18, and most preferably from 10 to 16. These simple alkyl groups are preferred for reasons of cost and stability. However, the hydrophobic R-i group can be an amido radical of the formula Ra-C (O) -NH- (C (R) 2) m > wherein Ra is a substituted or unsubstituted, saturated or unsaturated, aliphatic or aromatic hydrocarbon chain, preferably an alkyl group containing from 8 to 20 carbon atoms, preferably up to 18, most preferably up to 16, Rb is selected from the group it consists of hydrogen and hydroxy groups, and m is from 1 to 4, preferably from 2 to 3, most preferably 3, without more than one hydroxy group in some portion (C (Rb) 2) - R 2 preferred is hydrogen or a C alkyl ? -C3 and most preferably methyl. Preferred R3 is a C1-C4 carboxylic acid group or a C1-C4 sulfonate group, or a C1-C3 alkyl and most preferably methyl. Preferred R 4 is (CH 2) n wherein n is an integer from 1 to 10, preferably 1 to 6, most preferably is 1 to 3. Some common examples of betaine / sulfobetaine are described in the U.S. Patents. Nos. 2,082,275, 2,702,279 and 2,255,082, incorporated herein by reference. Examples of particularly suitable alkyl dimethylbetaines include coco-dimethylbetaine, lauryldimethylbetaine, decyl dimethylbetaine, 2- (N-decyl-N, N-dimethyl-ammonium) acetate, 2- (N-coco N, N-dimethylammonium) acetate, myristyldimethylbetaine, palmityldimethylbetaine. , cetyl dimethylbetaine, stearyldimethylbetaine. For example, cocodimethylbetaine is commercially available from Seppic under the trade name of Amonyl 265®. Lauryl betaine is commercially available from Albright & Wilson under the trade name Empigen BB / L®. Examples of amidobetaines include cocoamidoethylbetaine, cocoamidopropylbetaine or acylamidopropylene (hydropropyl) sulfobetaine C10-C14 fat. For example, acylamidopropylene (hydropropylene) sulfobetaine C10-C14 fat is commercially available from Sherex Company under the tradename "Varion CAS® sulfobetaine". A further example of betaine is Laryl-immine dipropionate commercially available from Rhone-Poulenc under the trade name Mirataine H2C-HA®. Cationic surfactants suitable for use herein include quaternary ammonium, phosphonium, imidazolium and sulfonium derivatives. Preferred cationic surfactants for use herein are quaternary ammonium compounds wherein one or two of the hydrocarbon groups attached to the nitrogen are a linear or branched, saturated alkyl group of 6 to 30 carbon atoms, preferably 10 to 25 carbon atoms. carbon and most preferably from 12 to 20 carbon atoms, and wherein the other hydrocarbon groups (i.e., three when a hydrocarbon group is a long chain hydrocarbon group as mentioned above or two when two hydrocarbon groups are hydrocarbon chain groups long as mentioned above) bonded to the nitrogen are a linear or branched alkyl chain, independently substituted or unsubstituted, of 1 to 4 carbon atoms, preferably of 1 to 3 carbon atoms and most preferably are methyl groups. The preferred quaternary ammonium compounds for use herein are quaternary ammonium compounds that do not contain chloride / do not contain halogen. The counter ion used in said quaternary ammonium compounds are compatible with any peracid and are selected from the methylisulfate group, or methylsulfonate, and the like. Particularly preferred for use in the compositions of the present invention are the trimethylammonium-tertiary compounds such as myristyltrimethylsulfate, cetyltrimethylsulfate and / or tallow trimethylsulfate. Said quaternary trimethylammonium compounds are commercially available from Hoechst, or from Albright & amp;; Wilson under the trade name EMPIGEN CM®. Among the nonionic surfactants, the alkoxylated nonionic surfactants and especially the ethoxylated nonionic surfactants are suitable for use herein. The blocked alkoxylated nonionic surfactants suitable for use herein are according to the formula: R1 (O-CH2-CH2) n- (OR2) mO-R3 wherein Ri is a linear or branched alkyl or alkenyl group of C-C24 , aryl group, alkaryl group, preferably Ri is a C8-C8 alkyl or alkenyl group) most preferably a C10-C15 alkyl or alkenyl group, most preferably still a C10-C15 alkyl group wherein R2 is a group linear or branched alkyl of C1-C10, preferably a linear or branched alkyl group of C2-C? 0; R3 is a C1-C10 alkyl or alkenyl group, preferably a C1-C5 alkyl group, most preferably methyl; and wherein n and m are integers that vary independently in the range 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 Genapol® or from ICI under the trade name of Symperonic®. Preferred blocked nonionic alkoxylated surfactants of the above formula are those commercially available under the tradename Genapol® L2.5 NR from Hoechst and Plurafac® from BASF. Particularly preferred surfactants are those selected from the group consisting of alkylsulfate, alkylsulfonate, alkylethylsulfate, alkylbenzenesulfonate, alkylcarboxylate, alkylethoxycarboxylate, amine oxides and mixtures thereof. Most preferably, the surfactant system comprises an alkyl sulfonate and an amine oxide. Typically, the compositions according to the present invention preferably comprise the surfactant system at a level of 0.1% to 30%, preferably from 0.1% to 15% and most preferably less than 10% and most preferably still less than 0.2% a 5% by weight of the composition.

Suspension agent The composition of the present invention may preferably comprise a suspending agent. A suspending agent is an ingredient that is specifically added to the composition of the present invention to suspend an ingredient in solid particles of the composition. With respect to the present invention, a suspending agent is particularly useful for suspending the peracid, wherein the peracid is present as a solid, and the coloring agent, where it is insoluble or substantially insoluble. Suitable suspending agents are those known in the art. Examples of suspending agents include gum-type polymers (e.g., xanthan gum), polyvinyl alcohol and derivatives thereof, cellulose and derivatives thereof, and polycarboxylate polymers. In a particularly preferred embodiment of the present invention, the suspending agent comprises a gum-type polymer or a polycarboxylate polymer. Particularly preferred examples of these suspending agents are xanthan gum and interlaced polycarboxylate polymer respectively. The gum-like polymer can be selected from the group consisting of polysaccharide hydrocolloids, xanthan gum, guar gum, succinoglycan gum, cellulose, derivatives of any of the foregoing and mixtures thereof. In a preferred aspect of the present invention, the gum-type polymer is a xanthan gum or a derivative thereof.

The rubber-like polymer is preferably present at a level of 0.01% to 10%, most preferably 0.1% to 3%. The polycarboxylate polymer can be a homopolymer or copolymer of monomer units selected from acrylic acid, methacrylic acid, meleic acid, malic acid, maleic anhydride. Preferred polycarboxylate polymers are Carbopol from BF Goodrich. Suitable polymers have a molecular weight in the range of 10,000 to 100,000,000, most preferably 1,000,000 to 10,000,000. The interlaced polycarboxylate polymer is preferably present at a level of from 0.01% to 2%, most preferably from 0.01% to 1%. %, very preferably still from 0.1% to 0.8%. In an alternative embodiment, the suspending agent comprises a combination of at least two polymers. In this embodiment, the first polymer is a rubber-like polymer and the second is an interlaced polycarboxylate polymer. The composition may further comprise additional polymers. The polymer ratio of ethoxylated carboxylate polymer gum polymer is from 100: 1 to 1: 100, most preferably from 1: 10 to 10: 1.

Chelating Agents 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, ethylenediamium N, N acids. '-disuccinic or mixtures thereof. The presence of chelating agents contributes to an additional increase in the chemical stability of the compositions. A chelating agent may also be desired in the compositions of the present invention as it allows it to increase the ionic strength of the compositions and hence its performance of stain removal and bleaching on various surfaces. Phosphonate chelating agents suitable for use herein may include ethan-1-hydroxy and alkali metal phosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as aminophosphonate compounds, including amino aminotri (methylene phosphonic acid) (ATMP), nitrile trimetinel phosphonates (NTP), ethylenediaminetetramethylenephosphonates and diethylenetriaminepentamethylenephosphonates (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 for use herein are diethylenetriaminepentamethylenephosphonate (DTPMP) and ethane-1-hydroxy diphosphonate (HEDP). Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®.

Polyfunctionally substituted aromatic chelating agents may also be useful in the compositions herein.

See patent of E.U.A. 3,812,044, issued on May 21, 1974 to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dydroxy-3,5-disulfobenzene. A preferred biodegradable chelating agent to be used herein is ethylene diamine N, N'-disuccinic acid or alkali metal salts, or alkaline earth metal, ammonium or substituted ammonium salts or mixtures thereof. Ethylene diamine N, N'-disuccinic acids, especially the (S, S) isomer, have been described extensively in the U.S. patent. 4,704,233, issued November 3, 1987 to Hartman and Perkins. Ethylene diamine N, N'-disuccinic acids are commercially available, for example, under the tradename ssEDDS® from Palme Research Laboratories. Suitable aminocarboxylates for use in the present include ethylenediaminetetracetats, diethylenetriaminepentaacetates, diethylenetriaminepentaacetate (DTPA), N-hydroxyethylenediaminetriacetates, nitrile acetates, ethylenediaminetetrapropionates, triethylenetetraminohexaacetates, ethanoldiglicine, propylenediaminetetraacetic acid (PDTA) and methyl glycine diacetic acid (MGDA), both in their acid form , or in its alkali metal, ammonium and substituted ammonium salt forms. Particularly preferred aminocarboxylates for use herein are diethylenetriaminepentaacetic acid, propylene diaminetrrethletic acid (PDTA) which is commercially available, for example, from BASF under the tradename Trilon FS® and methyl glycine diacetic acid (MGDA). Additional carboxylate chelating agents for use herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof. Another chelating agent to be used here is of the formula: wherein Ri, R2, R3 and R are independently selected from the group of -H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -NO2, -C (O) R and -SO2R "; R 'is selected from the group of -H, -OH, alkyl, alkoxy, aryl, and aryioxy; R "is selected from the group of alkyl, alkoxy, aryl, and aryloxy and R5, R6, R7 and R8 are independently selected from the group which consists of -H and alkyl. Particularly preferred chelating agents for use herein are amino aminotri (methylene phosphonic acid), diethylenetriaminepentaacetic acid, diethylenetriaminepentamethylenephosphonate, 1-hydroxyethanediphosphonate, ethylene diamine N, 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 0.1% to 1.5% by weight and most preferably from 0.01% to 0.5%.

Radical scavengers The compositions of the present invention may comprise a radical scavenger or mixture thereof. Radical scavengers for use herein include well-known substituted mono and dihydroxybenzenes and their analogues, alkyl and aryl carboxylates and mixtures thereof. Preferred radical scavengers for use herein include di-tert-butylhydroxytoluene (BHT), hydroquinone, di-tert-butylhydroquinone, mono-tert-butylhydroquinone, tert-butylhydroxyanisole, benzoic acid, toluic acid, catechol, t-butylcatechol, benzylamine , 1 > 1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-propyl-gallate or mixtures thereof and highly preferred is di-tert-butylhydroxytoluene. Radical scavengers such as N-propylgalate may be commercially available from Ñipa Laboratories, under the trade name Nipanox S1®. Radical scavengers when used, are typically present in amounts of up to 10% by weight of the total composition and preferably from 0.001% to 0.5% by weight. The presence of radical scavengers can contribute to the chemical stability of the bleaching compositions of the present invention as well as to the safety profile of the compositions of the present invention.

Foaming controlling agents The compositions according to the present invention may further comprise a foaming controlling agent such as 2-alkylalcanol, mixtures thereof, as a preferred optional ingredient. Particularly preferred for use in the present invention are the 2-alkylalkanols which have an alkyl chain comprising from 6 to 16 carbon atoms, preferably from 8 to 12 and a terminal hydroxy group, said alkyl chain being substituted at the by an alkyl chain comprising from 1 to 10 carbon atoms, preferably from 2 to 8 and most preferably from 3 to 6. Such suitable compounds are commercially available, for example, in the Isofol® series such as Isofol® 12 (2). -butyloctanol) or Isofol® 16 (2-hexyldecanol). Other foam controlling agents may include alkali metal fatty acids (eg, sodium or potassium), or soaps thereof, containing from about 8 to about 24, preferably from about 10 to about 20, carbon atoms. Fatty acids including those used in making the soaps can be obtained from natural sources such as, for example, glycerides derived from plants or animals (e.g., palm oil, coconut oil, babassus oil, soybean oil, castor oil, tallow, whale oil, fish oil, fat, butter and mixtures thereof Fatty acids can also be prepared synthetically (for example, by oxidation of petroleum materials or by the Fischer-Tropsch process) The alkali metal soaps can be made by direct saponification of fats and oils or by the neutralization of the free fatty acids that are prepared in a separate manufacturing process.Specially useful are the sodium and potassium salts of the fatty acid mixtures. Coconut oil and sebum derivatives, that is, tallow and coconut sodium and potassium soap The term "sebum" is used here in connection with mixtures of fatty acids that They typically have an approximate carbon chain distribution of 2-5% of C14, 29% of C16, 23% of C18, 2% of palmitoleic acid, 41.5% of oleic acid and 3% of linoleic acid (the first three acids listed they are natural). Other mixtures with similar distribution, such as similar fatty acids of various tallow of animal origin and lard, are also included within the term tallow. The tallow can also be hardened (i.e., hydrogenated) to convert part or all of the unsaturated fatty acid portions to saturated fatty acid portions. When the term "coco" is used herein it refers to fatty acid mixtures which typically have an approximate carbon chain length distribution of about 8% C8, 7% C10, 48% C12, 17% C14 , 9% C16, 2% C18, 7% oleic acid and 2% linoleic acid (the first six fatty acids listed being saturated). Other sources having a similar chain length distribution such as palm kernel oil and babassum oil are included with the term coconut oil. Other suitable foam controlling agents are illustrated by silicones, and silica-silicone mixtures. Silicones can be represented generally by alkylated polysiloxane materials whereas silica is normally used in finely divided forms illustrated by silica aerogels and xerogels as well as hydrophobic silicas of various types. These materials can be incorporated as particles in which the foam controlling agent is advantageously releasable, releasably incuborated in a water-soluble or water-dispersible vehicle, substantially impermeable to non-active surface detergent. Alternatively, the foam controlling agent can be dissolved or dispersed in a liquid vehicle and applied by spray to one or more of the other components. A preferred silicone foaming agent is described in Bartollota et al., patent of E.U.A. 3 933 672. Other particularly useful foam controlling agents are self-emulsifying silicone foaming agent controllers, described in the German patent application DTOS 2 646 126 published on April 28, 1977. An example of said compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. Particularly preferred silicone foam controlling agents are described in co-pending European patent application No. 92201649.8. Said compositions may comprise a mixture of silicone / silica in combination with fumed non-porous silica such as Aerosil.RTM. A preferred type of foam controlling agent is an alkyl alcohol alkoxylate. The alkyl chain of the alcohol can be C3-C30, the alkoxylate is preferably ethoxylate preferably comprising from 1 to 30 moles thereof and the blocking group is preferably a linear or branched C1-C6 alkyl group. Especially preferred foaming controlling agents are the foam controlling agent system comprising a mixture of silicone oils and the 2-alkylalkanols. Typically, the compositions herein may comprise up to 4% by weight of the total composition of the foam controlling agent, or mixtures thereof, preferably from 0.1% to 1.5% and most preferably from 0.1% to 0.8%.

Stabilizers The compositions of the present invention may comprise up to 10%, preferably from 2% to 4% by weight of the total composition of an alcohol according to the formula HO-CR'R "-OH, wherein R 'and R" they are independently H or a hydrocarbon chain and / or C2-C10 cycle. The preferred alcohol according to that formula is propanediol. In fact, it has been observed that these alcohols in general and propanediol in particular also improve the chemical stability of the compositions. Other stabilizers such as inorganic stabilizers can be used herein. Examples of inorganic stabilizers include sodium stannate and various metalalkaline phosphates such as the well known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate.

Dirt suspension polymer The compositions according to the present invention may further comprise a soil suspension polymer, for example a polyamine soil suspension polymer or mixtures thereof, as an optional ingredient. Any polyamine slurry polymer known to those skilled in the art can be used. Polyamine polymers particularly suitable for use herein are polyalkoxylated polyamines. Said materials can conveniently be represented as molecules of the empirical structures with repetition units: [. H.H\ . form of amine (alkoxy) and R1 I [N + ß¡. nX- form I quatemized (alkoxy) and wherein R is a hydrocarbyl group, generally 2 to 6 carbon atoms; R1 can be a C1-C20 hydrocarbon. the alkoxy groups are ethoxy, propoxy and the like, and y is 2-30, most preferably 10 to 20; n is an integer of at least 2, preferably from 2 to 20, most preferably from 3 to 5; and X "is an anion such as halide or methylisulfate, resulting in the quaternization reaction.The most highly preferred polyamines to be used herein are the so-called ethoxylated polyethylamines, i.e. the polymerized reaction product of ethylene oxide with ethyleneimine, which has the general formula: (EtO) _ JN. CH2 CH2 N. (EtO) and (EtO) and (EtO) and when y = 2-30. Particularly preferred for use herein is an ethoxylated polyethyleneamine, in particular ethoxylated tetraethylenepentamine, and quatemized ethoxylated hexamethylenediamine. The polyamide polymers of soil suspension contribute to the benefits of the present invention, that is, when added on top of said diacyl peroxide, they improve the stain removal performance of a composition containing them, especially low. laundry pretreatment conditions, as described here. In fact, they allow to improve the performance of stain removal in a variety of spots that include grease stains, enzymatic stains, clay / mud stains as well as in bleach stains. Typically, the compositions comprise up to 10% by weight of the total composition of said polyamine polymer of soil suspension or mixtures thereof, preferably from 0.1% to 5% and most preferably from 0.3% to 2%. The compositions of the present invention may also comprise other polymeric soil release agents known to those skilled in the art. Said polymeric soil release agents are characterized to have both hydrophilic segments, to hydrolyze the surface of the hydrophobic fibers, such as polyester and nylon, as hydrophobic segments, to deposit on the hydrophobic fibers and to remain adhered to them upon completion of the cycles of hydrophobic fibers. washing and rinsing and therefore serve as a means of attachment for the hydrophilic segments. This may allow stains that occur after treatment with the soil release agent to be cleaned more easily in subsequent washing process.

The polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophilic components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of 2 to 10, wherein said hydrophilic segment does not contain any oxypropylene unit unless it is attached to adjacent portions at each end by ether linkages, or (iii) ) a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophilic component has sufficient hydrophilic character to increase the hydrophilic character of the synthetic fiber surfaces of conventional polyester by depositing the soil release agent on said surface, said hydrophilic segments preferably comprising at least about 25% oxyethylene units and most preferably, especially for components having from about 20 to 30 oxypropylene units, so less approximately 50% oxyethylene units or; or (b) one or more hydrophobic components comprising (i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobic components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate: oxyalkylene terephthalate units of C3 is about 2: 1 or less, (I) C-C6 alkylene or C-C6 oxyalkylene segments, or mixtures thereof, (iii) polyvinyl ester segments, preferably polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) C-C alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures thereof, wherein said substituents are present in the form of C 1 -C 4 alkyl ether or C 4 hydroxyalkyl ether cellulose derivatives, or mixtures thereof thereof, and said cellulose derivatives are amphiphilic, so they have a sufficient level of C1-C4 alkyl ether units and / or C4 hydroxyalkyl ether to be deposited on surfaces of cellulose. conventional synthetic polyester fibers and retain a sufficient level of hydroxyls, once adhered to the conventional synthetic fiber surface, to increase the hydrophilic character of the surface of the fibers or a combination of (a) and (b). Typically, the polyoxyethylene segments (a) (i) will have a degree of polymerization of from about 1 to about 200, although higher levels, preferably from 3 to about 150, most preferably from 6 to about 100, may be used. The hydrophobic segments Suitable C4-C6 oxyalkylene include but are not limited to polymeric soil release agent blocking groups such as MO3S (CH2) nOCH2CH2O-, where M is sodium and n is an integer from 4 to 6, as described in US Pat. the US patent 4,721, 580, issued on January 26, 1988 to Gosselilnk. The polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide terephthalate or polypropylene oxide, and the like. Such agents are commercially available and include cellulose hydroxyethers such as METHOCEL (Dow). The cellulosic soil release agents for use herein also include those selected from the group consisting of C 1 -C 4 alkylcellulose and C 4 hydroxyalkyl cellulose; see patent of E.U.A. 4,000,093, issued December 28, 1976 to Nicol, et al. Dirt release agents characterized by hydrophobic polyvinyl ester segments include polyvinyl ester copolymers, for example, C 1 -C 6 vinyl esters, preferably polyvinyl acetate grafted to the polyalkylene oxide base structures, such as oxide base structures of polyethylene. See European patent application 0 219 048, published on April 22, 1987 by Kud, et al. Commercially available dirt release agents of this type include and of SOKALAN material type, for example SOKALAN HP-22, available from BASF (Germany). A preferred type of soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide terephthalate (PEO). The molecular weight of this polymeric soil release agent is in the range of about 25,000 to about 55,000. See patent of E.U.A. 3,959,230 to Hays, issued May 25, 1976 and patent of E.U.A. 3,893,929 to Basadur, issued July 8, 1975. Another polymeric soil release agent is a polyester with repeating units of ethylene terephthalate containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derivative of a polyoxyethylene glycol of average molecular weight of 300-5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also patent of E.U.A. 4, 702,857, issued on October 7, 1987 to Gosselink. Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer composed of an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeat units and end portions covalently bonded to the base structure. These soil release agents are fully described in the US patent. 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents include terephthalate polyesters of U.S. Patent No. 4,711,730, issued December 8, 1987 to Gosselink et al., The oligomeric esters blocked at the anionic ends of the U.S. patent. 4,721, 580, issued on January 26, 1988 to Gosselink, and the oligomeric block polyester compounds of the U.S.A. 4,702,857, issued on October 27, 1987 to Gosselink. Preferred polymeric soil release agents also include the soil release agents of the U.S.A. 4,877,896, issued on October 31, 1989 to Maldonado et al, which describes end-blocked, anionic esters of terephthalate, especially sulfoaroyl. Another preferred soil release agent is an oligomer with repeated units of terephthaloyl units, units of sulfoisoterephtalolyl, oxyethyleneoxy and oxy-1-2-propylene. The repeating units of the base structure of the oligomer are preferably terminated with modified isethionate end blocking groups. A particularly preferred soiling agent of this type comprises about one unit of sulfoisophthaloyl, 5 units of terephthaloyl, oxyethyleneoxy units and oxy-1,2-propyleneoxy in a ratio of about 1.7 to about 1.8, and two units of blocking group of sodium 2- (2-hydroxyethoxy) -ethansulfonate end. Said soil release agent also comprises from about 0.5% to about 20% by weight of the oligomer, of a reducing stabilizer of crystalline material, preferably selected from the group consisting of xylene sulfonate, cumenesulfonate, toluenesulfonate and mixtures thereof. See patent of E.U.A. No. 5,415,807, issued May 16, 1995 to Gosselink et al.

If used, the soil release agents will generally comprise from 0.01% to 10.0% by weight, of the detergent compositions herein, typically from 0.1% to 5%, preferably from 0.2% to 3.0%.

Dye transfer inhibitor The compositions according to the present invention can also include one or more effective materials to inhibit the transfer of dyes from one surface to another during the cleaning process. Generally, said dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases and mixtures thereof. If used, these agents typically comprise from 0.01% to 10% by weight of the composition, preferably from 0.01% to 5%, and most preferably from 0.05% to 2%. Very specifically, the preferred polyamine N-oxide polymers for use herein contain units having the following structural formula: R-Ax-P; wherein P is a polymerizable unit to which a N-O group can be attached or the N-O group can be part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC (O) -, -C (O) O-, -S-, -O-, -N =; x is 0 or 1; and R is aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrroline, piperidine and derivatives thereof. The N-O group can be represented by the following general structures: (Ri -N? - (Ra) y; = N? - (Rl)? (Root where Ri, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1 and the nitrogen of the NO group can be attached to any of the aforementioned groups.The amine oxide unit of the polyamine N-oxides has a pKa <10, preferably pKa <7, very preferably pKa < 6. Any polymer base structure can be used as long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties Examples of suitable polymeric base structures are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof These polymers include random or block copolymers wherein one type of monomer is an amine N-oxide and the other type of monomer is an N-oxide. of typical amine They have an amine to N-oxide ratio of 10: 1 to 1: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. Polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; very preferred from 1,000 to 500,000; even more preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO". The most preferred polyamine N-oxide useful in the detergent compositions herein is the poly-4-vinylpyridine N-oxide having an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1: 4 Polymer copolymers of N-vinylporrolidone and N-vinylimidazole (also known as "PVPVI") are also preferred for use herein. Preferably, the PVPVI has an average molecular weight in the range of 5,000 to 1,000,000, most preferably 5,000 to 200,000 and most preferably even 10,000 to 20,000. (The average molecular weight scale is determined by the scattering of light as described in Barth, and others, Chemical Analvsis, Vol. 113. "Modern Methods of Polymer Characterization", the descriptions of which are incorporated herein by reference). PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1: 1 to 0.2: 1, preferably from 0.8: 1 to 0.3: 1, most preferably from 0.6: 1 to 0.4: 1. These copolymers can be either linear or branched. The compositions of the present invention may also employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and most preferably still from about 5,000 to about 50,000. . The PVP's are known to those skilled in the field of detergents; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference. The compositions containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a basis of ppm assorted in wash solutions is from about 2: 1 to about 50: 1, and most preferably from about 3: 1 to about 10: 1.

Brightener Any optical brighteners or other brightening agents or whitening agents known in the art can be incorporated into the present compositions when they are designed for fabric treatment or laundry, typically at levels from about 0.05% to 1.2% by weight, of the detergent compositions of the present. Commercial optical brighteners that may be useful in the present invention may be classified into subgroups including, but not necessarily limited to, stilbene, pyrazoline, coumarin, carboxylic acid, methinocyanin, dibenzotifen 5,5-dioxide, azole derivatives, 5 and 6 membered ring heterocycles, and various other agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents," M. Zahradnik, published by John Wiley & Sons, New York (1982). Specific examples of optical brighteners that are useful in the present compositions are those identified in the patent of E.U.A. 4,790,856 issued to Wixon on December 15, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners described in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; Tinopal PLC, Tinopal SOP, Tinopal SWN, Tinopal K. Uvitex AT, all available from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis, based in Italy, '2- (4-styryl-phenyl) -2H-naphthol [1,2-d] triazoles; 4,4'-bis- (1, 2,3-triazol-2-yl) -stilbenes; 4,4'-bis (steryl) bisphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl-aminocoumarin; 1, 2-bis (benzimidazol-2-yl-ethylene; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphthyl- [1,2-s] oxazole; 4-yl) -2H-naphtho- [1,2-d] triazole See also U.S. Patent No. 3,646,015, issued to Hamilton on February 29, 1972. Anionic brighteners are typically preferred herein.

Foam Enhancer If high foaming is desired, it may be incorporated into foam-enhancing compositions such as C.o-C-16 alkanolamides, typically at levels of 1% to 10%. The monoethanolamides and cd-C-0-C14 diethanolamides illustrate a typical class of such foaming enhancers. The use of said foam enhancers with high foaming auxiliary surfactants such as the abovementioned amine oxides, betaines and sultaines are also advantageous. If desired, soluble magnesium salts such as MgCl 2, MgSO 4 and the like can be added at levels of, for example, 0.1% -2% to provide additional foams and to increase the fat removal performance.

Surface treatment methods In the present invention, the surface to be cleaned is treated with a liquid composition of the present invention. By "surface", here is meant any inanimate surface. These inanimate surfaces include, but are not limited to, hard surfaces typically found in homes such as kitchens, bathrooms, or car interiors, for example, tiles, walls, floors, chrome, glass, smooth vinyl, any plastic, laminated wood, or plastic tops. tables, sinks, kitchen tops, dishes, sanitary equipment such as sinks, shower room, shower curtains, sinks, bathrooms and the like, as well as fabrics including clothes, curtains, blinds, bedding, bath linen, clothes of table, sleeping bags, tents, upholstered furniture and the like, as well as carpets. The inanimate surfaces also include household appliances including, but are limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers, etc. By "surface treatment" is meant the bleaching of said surfaces since the compositions of the present invention comprise a bleaching system based on a peracid compound or a mixture thereof and optionally cleaning since said compositions may comprise an agent surfactant or any other conventional cleaning agent. Thus, the present invention also comprises a method of treatment, especially bleaching of a fabric, such as the inanimate surface. In said process, a composition according to the present invention is brought into contact with the fabrics to be treated. This can be done either in a so-called "pretreatment mode" wherein a liquid bleaching composition, as defined herein, is applied in pure form on said fabrics before they are rinsed, or washed and then rinsed, or in a "soaking mode" wherein a liquid whitening composition, as defined herein, is first diluted in an aqueous bath and the fabrics are soaked and soaked in the bath, before they are rinsed, or in a "through" manner. "washing", wherein a liquid bleaching composition, as defined herein, is added on top of a washing solution formed by dissolving or dispersing a typical laundry detergent. It is also essential in both cases, that the fabrics be rinsed after having been contacted with said composition, before said composition has completely dried. The compositions according to the present invention can be used in pure or diluted form. However, the compositions herein are typically used in diluted form in a laundry operation. By "in diluted form" it is meant herein that the compositions for bleaching fabrics according to the present invention can be diluted by the user, preferably with water. Said dilution can occur for example in manual laundry applications as well as any other means such as in a washing machine. Said compositions can be diluted up to 500 times, preferably 5 to 200 times and most preferably 10 to 80 times. Very specifically, the fabric bleaching process according to the present invention comprises the steps of first contacting said fabrics with a bleaching composition in accordance with the present invention, in diluted form, then allowing the fabrics to remain in contact with said fabric. composition, for a period sufficient to whiten the fabrics, typically from 1 to 60 minutes, preferably from 5 to 30 minutes, then rinsing said fabrics with water. If the fabrics are to be washed, that is, with a conventional detergent composition preferably comprising at least one surfactant, said washing can be carried out together with the bleaching of the fabrics by contacting the fabrics at the same time with a bleaching composition according to the present invention, and said detergent composition, or washing can be conducted before or after the fabrics have been bleached. Accordingly, said method according to the present invention allows fabric bleaching and optionally fabric washing with a detergent composition preferably comprising at least one surfactant before the step of contacting the fabrics with the bleaching composition and / or in the step wherein said fabrics are brought into contact with the bleaching composition and / or after the passage wherein said fabrics are brought into contact with the bleaching composition and before the rinsing step and / or after the rinsing step. In another embodiment of the present invention, the fabric bleaching process comprises the step of contacting the fabrics with a liquid bleaching composition in accordance with the present invention, in its pure form and allowing said fabrics to remain in contact with the composition. bleaching for a period sufficient to whiten said fabrics, typically 30 seconds to 30 minutes, preferably 1 minute to 10 minutes and then rinsing said fabrics with water. If the fabrics are to be washed, that is, with a conventional composition comprising at least one surfactant, said washing can be carried out before or after said fabrics have been bleached. Advantageously, the present invention provides liquid bleaching compositions that can be applied in pure form on a bleaching cloth, despite a persistent bias against the use of bleach-containing compositions in pure form on fabrics since the present compositions are safe for colors and the canvases perse. Alternatively, instead of following the method of bleaching in pure form as described hereinabove (pre-processor application) by a rinsing step with water and / or a conventional washing step with a conventional liquid or powder detergent, the operation of Bleach pretreatment can also be followed by the diluted bleaching process as described herein before either in a cuvette (manual operation) or in a washing machine. It is preferred to perform the bleaching procedures herein after the fabrics have been washed with a conventional laundry detergent composition. Instead, it has been observed that bleaching such fabrics with the compositions according to the present invention (typically diluted bleaching methods) after washing them with a detergent composition provides superior whiteness and superior stain removal with less energy and Detergent if these fabrics were bleached first and then washed. In another embodiment, the present invention also comprises a method for treating a hard surface, such as the inanimate surface. In said process, a composition, as defined herein, is contacted with the hard surfaces to be treated. Thus, the present invention also comprises a method for treating a hard surface with a composition, as defined herein, wherein said method comprises the step of applying the composition to said hard surface, preferably only soiled portions thereof, and optionally rinsing the hard surface. In the process of treating hard surfaces according to the present invention, the composition, as defined herein, can be applied to the surface to be treated in net form or in its diluted form typically up to 200 times its weight of water, preferably 80 to 2 times its weight in water, and most preferably 60 to 2 times. When used as hard surface bleach / disinfectant compositions, the compositions of the present invention are easy to rinse and provide good gloss characteristics on the treated surfaces. By "hard surfaces" is meant any hard surfaces as mentioned here above as well as tableware.

Packaging form of the liquid compositions: Depending on the end use contemplated, the compositions herein may be packaged in a variety of containers including conventional bottles, bottles equipped with pivotable ball, sponge, brush or sprinklers.

In one embodiment of the present invention, the composition is packaged in a two compartment container, wherein the bleaching composition as described herein is packaged in a compartment and a second composition is packaged in the second compartment. In a particularly preferred aspect, the second composition is a conventional heavy duty liquid detergent composition, preferably comprising ingredients, particularly bleach sensitive ingredients such as surfactants, enzymes and perfumes.

EXAMPLES The invention is further illustrated by the following examples which are not intended to be limiting. All levels are described in percent by weight of the total composition.

The coloring agent 1 is Pigmosol Green 7 The coloring agent 2 is Cosmenyl Blue A2R The coloring agent 3 is Luconyl Blue 7080 PAP is phthaloilamidoperoxyhexanoic acid Carbopol ETD 2691 is a polysaccharide polymer available from BF Goodrich Tinopal SOP is a brightener Norasol LMW 45N is a polyacrylate polymer.

EXAMPLE 2 The storage stability of the color of the compositions I, II and III of Example 1 were evaluated against comparison compositions. Comparison compositions comprised identical components at identical levels of compositions I, II and III but with different coloring agents that were not metal phthalocyanines, ie Ultramarine Blue (ultramarine blue) and Violet 16 (violet 16). The comparison composition A comprises Ultramarine Blue (ultramarine blue) and the comparison composition B comprises Violet 16 (violet 16). The color intensity was visually graded against a freshly made sample that did not contain peracid after 7 days at 23 ° C and 7 days at 35 ° C. The results of the color stability tests show that only metallic phthalocyanine coloring agents are in fact stable to peracid. The scale was from 0 to 4 where: 0 means that there is no visible change in color intensity; 1 means that it is thought that there is a small change in the intensity of the color; 2 means that you can see a small change in the intensity of the color; 3 means that you can see a big change in the intensity of the color; 4 means that you can see a very large change in the intensity of the color.

EXAMPLE 3 Example 2 was repeated but comparing the compositions IV, V and VI against comparison compositions C and D. The comparison composition C comprises Ultramarine Blue (ultramarine blue) and the comparison composition D comprises Violet 16 (violet 16).

Claims (15)

NOVELTY OF THE INVENTION CLAIMS

1. - A liquid bleaching composition characterized in that it comprises a preformed peroxycarboxylic acid, and a metal phthalocyanine coloring agent.

2. A bleaching composition according to the preceding claim, further characterized in that the composition has a pH less than 7.

3. A bleaching composition according to any of the preceding claims, further characterized in that the peroxycarboxylic acid has the formula general: XRC (O) OOH wherein R is a linear or branched alkyl chain having at least one carbon atom and X is a hydrogen or a substituent group selected from the group consisting of alkyl, especially alkyl chains of 1 to 24 carbon atoms, aryl, halogen, ester, ether, amine, amide, substituted phthalic amino, metric, hydroxide, sulfide, sulfate, sulfonate, carboxylic, heterocyclic, nitrate, aldehyde, phosphonate, phosphonic or mixtures thereof.

4. A bleaching composition according to any of the preceding claims, further characterized in that the R group of the peroxycarboxylic acid is an alkyl chain comprising up to 24 carbon atoms.

5. A bleaching composition according to any of the preceding claims, further characterized in that the R group of the peroxycarboxylic acid is a branched alkyl chain comprising one or more side chains comprising substituent groups selected from the group consisting of aryl, halogen , ester, ether, amine, amide, substituted aminophthalic, amino, imide, hydroxide, sulfide, sulfate, sulfonate, carboxylic, heterocyclic, nitrate, aldehyde, ketone or mixtures thereof.

6. A bleaching composition according to any of the preceding claims, further characterized in that the group X of the peroxycarboxylic acid is a phthalimido group.

7. A bleaching composition according to any of the preceding claims, further characterized in that the peroxycarboxylic acid is phylolamidoperoxyhexanoic acid.

8. A bleaching composition according to any of the preceding claims, further characterized in that the preformed peroxycarboxylic acid is present at a level of 1% to 12% by weight of the composition.

9. A bleaching composition according to any of the preceding claims, further characterized in that the preformed peroxycarboxylic acid is in the form of a solid.

10. - A bleaching composition according to any of the preceding claims, further characterized in that the metal phthalocyanine is selected from phthalocyanine copper, iron, cobalt or nickel.

11. A bleaching composition according to any of the preceding claims, further characterized in that the metal phthalocyanine is selected from the group consisting of compounds having a color index number Cl 74260 Pigment Green 7, Cl 74160 Pigment blue 15 or 15 : 1 or 15: 2 or 15: 3 or 76 mixtures thereof.

12. A bleaching composition according to any of the preceding claims, further characterized in that the metal phthalocyanine is Fastogen blue 76.

13. A bleaching composition according to any of the preceding claims, further characterized in that the metal phthalocyanine is a particle solid substantially insoluble.

14. A process for cleaning a fabric by applying a bleaching composition to said fabric as claimed in the preceding claims and optionally rinsing.

15. The use of a bleaching composition comprising peroxycarboxylic acid and a metallic phthalocyanine coloring agent for fabric bleaching.