MXPA97007074A - Whitening compositions with perf - Google Patents

Abstract

A bleaching composition with perfume is provided which contains: (a) a hydrophobic bleach system selected from (i) a perhydrate in an amount of 0.1% to 60% by weight and combined with a hydrophobic peroxy acid bleach precursor in an amount from 0.1% to 60% by weight, (ii) a preformed hydrophobic peroxyacid in an amount of 0.1% to 60% by weight, and (iii) mixtures of (i) and (ii), wherein a peroxyacid bleach precursor "hydrophobic" is defined as a compound that produces under perhydrolysis a hydrophobic peroxyacid whose carboxylic acid origin has a critical micelle concentration less than 0.5 moles / liter, and wherein a preformed hydrophobic peroxyacid is defined as a compound whose carboxylic acid origin has a lower critical micelle concentration 0.5 mole / liter, and (b) a perfume composition in an amount of 0.05% to 2% by weight comprising one or more flavor chemicals selected from: tertiary alcohols, nitrate the lactones, ketones, acetals, ethers, Schiff bases, esters and mixtures thereof, wherein the total sum of the weight of said flavor chemicals in the perfume is at least 40% by weight of the perfume.

Description

WHITENING COMPOSITIONS WITH PERFUTIBLE FIELD OF THE INVENTION The invention relates to bleaching compositions with perfume. More specifically, it relates to bleaching compositions comprising a hydrophobic bleaching system and a stabilized perfume composition.

BACKGROUND OF THE INVENTION Perfumes are an important and desirable part of detergent compositions. They are used to cover the chemical odors of cleaning ingredients and provide an aesthetic benefit to the washing process, preferably clean fabrics. EP 430315, which describes the use of a laundry detergent composition containing a lipase and a perfume having specific fragrance materials, exemplifies said use. In said patent, the perfume composition counteracts the problem of residual malodor of the laundry treated with lipase. A problem encountered with perfumes is their volatility and many perfume ingredients can be destroyed or damaged in the presence of cleaning ingredients, especially alkali and bleaches. Hydrophobic bleach systems selected from a source of hydrogen peroxide combined with a hydrophobic peroxyacid bleach precursor and a hydrophobic peroxy acid bleach are known in the art as effective dark soil removal agents. The Applicants have discovered that the problem of perfume oxidation may be particularly concerning with the hydrophobic peroxyacid bleach precursors which in the perhydrolysis produce a peroxyacid which is an amino substituted peroxyacid. It has also been discovered that the precursor compounds as well as the peroxyacid compounds by themselves of the substituted amino type, in particular, give rise to the problem. A solution to this problem is the encapsulation of the perfume. This increases the expense and complexity of the formulation and does not always provide sufficient protection. EP 332259 teaches the use of a liquid detergent composition containing peroxyacid bleach and perfume silica particles that protect the oxidation perfume by the bleach. Another solution to this problem is the reduction in the level of the hydrophobic bleaching system. While reducing the level of the hydrophobic bleaching system used in washing, tends to solve these problems, this is accompanied by a marked negative effect on the ability to remove dark stains / dirt. In this way, the detergent formulator meets the challenge of formulating a product that maximizes the removal of stain / dirt, which prevents the degradation of the detergent components, which covers the chemical odors of the cleaning ingredients, that provides an aesthetic benefit and that is also inexpensive. The Applicants have now surprisingly found that the provision of a minimum amount of specific perfume materials allows the use of stabilized perfume compositions in the presence of a hydrophobic bleaching system. The Applicants have also surprisingly discovered that the assortment of the perfume in the fabric improves with the hydrophobic peroxyacid precursor. Without being limited to theory, it is believed that the hydrophobic peroxyacid precursor serves as a carrier material for the perfume composition. Therefore, an object of the present invention is to provide compositions suitable for use in laundry washing methods that produce an excellent fragrance of perfume in the fabrics as well as an excellent perfume stability in the presence of the hydrophobic bleaching system in the liquid of washing and in the product during storage. Another object of the invention is to provide compositions suitable for use in laundry washing methods that produce effective dark dirt removal.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to a perfume whitening composition containing: a- a hydrophobic bleaching system selected from i) - a perhydrate in an amount of 0.1% to 60% by weight and combined with a peroxy acid bleach precursor hydrophobic in an amount of 0.1% to 60% by weight, ii) - a hydrophobic preformed peroxy acid in an amount of 0.1% to 60% by weight, and iii) - mixtures of i) and ii), wherein the hydrophobic peroxy acid bleach precursor is defined as a compound that produces under perhydrolysis a hydrophobic peroxyacid whose origin carboxylic acid has a critical micelle concentration of less than 0.5 moles / liter, and wherein a preformed hydrophobic peroxyacid is defined as a compound whose origin carboxylic acid has a micellar concentration of less than 0.5 moles / liter, and b- a perfume composition in an amount of 0.05% to 2% by weight comprising one or more flavor chemicals selected from: tertiary alcohols, nitriles, lactones, ketones, acetals, ethers, Schiff's bases, esters and mixtures thereof , wherein the total sum of the weight of said flavor chemicals in the perfume is at least 40% by weight of the perfume.

DETAILED DESCRIPTION OF THE INVENTION An essential component of the invention is a hydrophobic bleaching system selected from a perhydrate combined with a hydrophobic peroxyacid bleach precursor, a hydrophobic preformed peroxyacid and any mixture thereof.

Perhydrate bleach The perhydrate is typically an inorganic perhydrate bleach, typically in the form of the sodium salt, as the source of alkaline hydrogen peroxide in the wash liquor. This perhydrate is normally incorporated at a level from 0.1% to 60%, preferably from 3% to 40% by weight, most preferred from 5% to 35% by weight and most preferred from 8% to 30% by weight of the composition. The perhydrate can be any of the inorganic alkali metal salts such as monohydrate or tetrahydrate salts of perborate, percarbonate, perfosphate and persilicate, but is conventionally an alkali metal perborate or percarbonate. Sodium percarbonate, which is the preferred perhydrate, is an addition compound having the formula 2Na2C03.3H2O2 > and it is commercially available as a crystalline solid. Most of the commercially available material includes a low level of heavy metal sequestrant such as EDTfi, 1-hydroxyethylidene 1,1-diphosphonic acid (HEDP) or an aminophosphonate, which is incorporated during the manufacturing process. For the purposes of the detergent composition aspect of the present invention, the percarbonate can be incorporated into the detergent compositions without further protection, but preferred embodiments of such compositions utilize a coated form of the material. A variety of coatings, including borate, boric acid and sodium silicate or citrate can be used in a Si? 2: Na2? Ratio. from 1.6: 1 to 3.4: 1, preferably 2.8: 1, applied as an aqueous solution to give a level of from 2% to 10%, (typically 3% to 5%) of silicate solids by weight of the percarbonate. However, the most preferred coating is a mixture of sodium carbonate and sodium sulfate or chloride. The particle size scale of crystalline percarbonate is from 350 microns to 1500 microns with an average of approximately 500-1000 microns.

Precursor of hydrophobic peroxyacid bleach One form of the component of the essential hydrophobic bleaching system of the invention is a hydrophobic peroxyacid bleach precursor which produces during the hydrophobic perhydrolysis peroxyacid whose origin carboxylic acid has a critical micelle concentration of less than 0.5 mole / liter and wherein said Critical micelle concentration is measured in an aqueous solution at 25 ° C. Preferably, the chain of the peroxyacid base structure contains at least 7 carbon atoms which may be linear or partial and fully branched or cyclic and any mixtures thereof. The peroxyacid bleach precursors are usually incorporated at a level of from 0.1% to 60%, preferably from 3% to 40%, and most preferably from 3% to 25% by weight of the perfume bleaching composition. Preferably, the hydrophobic peroxyacid bleach precursor compounds are selected from bleach precursor compounds comprising at least one acyl group that forms the peroxyacid moiety linked to a leaving group through a -O- or -N- linkage. . The precursors of bleaching p > Suitable hydroxyacid for the purpose of the invention are the substituted amide compounds of the following general formulas: R1N (R5) C (0) R2C (0) L or R1C (0) N (S) R2C (0) L wherein R1 is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R 2 is an alkylene, arylene and alkarylene group with from about 1 to 14 carbon atoms and R 5 is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms and L can be essentially any leaving group. R1 preferably contains from about d to 12 carbon atoms. R2 preferably contains from about 4 to 8 carbon atoms. R1 can be straight or branched chain alkyl, aryl or alkylaryl substituted with branching, substitution or both and can be obtained either from synthetic or natural sources, including, for example, tallow grease. Analogous structural variations for R2 are permissible. R may include alkyl, aryl, wherein said R 2 may also contain halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. Ri and R5 must not contain more than 18 carbon atoms in total. Such substituted amide bleach activator compounds of this type are described in EP-A-0170386. The leaving group, hereinafter group L, must be sufficiently reactive for the perhydrolysis reaction to occur within an optimum time frame (eg, a wash cycle). However, if L is very reactive, this activator will be difficult to stabilize for use in a bleaching composition. The preferred L groups are selected from: and mixtures thereof, wherein Ri is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group. Any of Ri, R3 and R "can be essentially substituted by any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium groups or alkynyl groups. The preferred solubilizing groups are -S? 3 ~ M +, - CO2 -M +, -S0 «-M +, -N + (R3) ?? - and 0 < -N (R3) 3 and most preferably -S03 ~ M + and ~ C02 ~ M + where R3 is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X being a halide, hydroxide, methylsulfate or acetate anion. Another group L suitable for use herein includes a leaving group selected from a leaving group of caprolactam, a leaving group of valerolactane and a mixture thereof. Preferred examples of bleach precursors of the above formulas include substituted amide peroxy acid precursor compounds selected from 6-octanamidocaproyl oxybenzenesulfonate, 6-nonanamidocaproyl oxybenzenesulfonate, 6-decanamido caproyl oxybenzenesulfonate and mixtures thereof, as described in EP-fl-0170386. Also another preferred class of bleach precursor is the class of alkyl percarboxylic acid bleach precursors. Preferred alkyl percarboxylic acid precursors include nonanoyl oxybenzenesulfonate (NOBS described in US 4,412,934) and 3,5,5-tri- ethyl hexanoyl oxybenzenesulfonate (ISONOBS described in EP120,591) and salts thereof. The mixture of any of the peroxyacid bleach precursors described hereinabove can also be used. In addition, conventional peroxyacid bleach precursors such as the tetraacetyl ethylene diamine bleach precursor (TOED) can be added to the bleaching composition of the invention to thereby produce improved soil removal performance.

Hydrophobic peroxy acid compound preformed The component form of the essential hydrophobic bleaching system of the invention is a hydrophobic peroxy acid bleaching agent and salt thereof whose origin carboxylic acid has a critical micelle concentration of less than 0.5 mole / liter and wherein said critical micellar concentration is measured in an aqueous solution at 25 ° C. Preferably, the chain of the peroxyacid base structure contains at least 7 carbon atoms which may be linear or partial and fully branched or cyclic and any mixtures thereof. Preferably, the hydrophobic peroxyacid bleach compounds are selected from peroxyacid bleach compounds comprising at least one acyl group that forms the peroxyacid moiety linked to a leaving group through a ~ 0 ~ or -N- linkage. The preformed hydrophobic peroxyacid compounds will typically be in an amount of 0.1% to 60%, preferably 3% to 20% by weight. Suitable examples of this class of agents include 6-octylamino-6-oxo-caproic acid, 6-nonylamino-6-oxo-caproic acid, 6-decylamino-6-oxo-caproic acid, magnesium monoperoxyphthalate hexahydrate, magnesium of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyrate and diperoxydecanedioic acid. Said bleaching agents are described in the patent of E.U.A. 4,483,781, U.S. Patent. 4,634,551, EP 0,133,354, Patent of E.U.A. 4,412,934 and EP 0,170,386. A preferred hydrophobic preformed peroxy acid bleach compound for the purpose of the invention is monononylamido percarboxylic acid.

Perfume composition The other essential component of the invention is a perfume composition comprising one or more flavor chemicals selected from tertiary alcohols, nitriles, lactones, ketones, acetals, ethers, Schiff's bases, esters and mixtures thereof. The perfume composition is incorporated in the bleaching composition of the invention at a level of from 0.05% to 2% by weight, preferably from 0.01% to 1% by weight of the bleaching composition. The total sum of the weight of said flavor chemicals present in the perfume composition is at least 40%, preferably at least 50% and most preferred at least 60% by weight of the perfume. For the purpose of the invention, aroma chemicals selected from tertiary alcohols, nitriles, lactones, ketones, acetals, ethers and Schiff's bases can be saturated or unsaturated. When in unsaturated form, they comprise a group selected from an aromatic ring and an alkenyl group and mixtures thereof. For the purpose of the invention, the flavor chemicals of the ether class can be saturated or unsaturated. When they are in unsaturated form, they comprise an alkenyl group or are esters of salicylic acid. Non-limiting tertiary alcohols suitable for the purpose of the invention include tetrahydro-linalool, tetrahydro-ircenol, tetrahydro-mug? O and tetrahydro-geraniol compounds and mixtures thereof. When such tertiary alcohol compounds are used they will be at a level of up to 50%, preferably at a level of up to 30% and most preferred up to 20% by weight of the perfume composition. Non-limiting examples of nitriles suitable for the purpose of the invention include lauric nitrile, rniristic nitrile and tridecen-2-nitrile compounds and mixtures thereof. When such nitrile compounds are used they will be at a level of up to 10%, preferably at a level of up to 5% by weight of the perfume composition. Non-limiting examples of lactones suitable for the purpose of the invention include? Ndecalactone, hexadecanolide and cyclopentadecanolide compounds. When such lactones are used they will be at a level of up to 30%, preferably at a level of up to 20% by weight of the perfume composition. Non-limiting examples of ketones suitable for the purpose of the invention include compounds of methyl beta naphthyl ketone, methyl phenyl ethyl ketone and 7-acetyl 1,2,3,4,5,6,7,8 octanhydro 1,2, 6,7 tetra methyl-naphthalene. When such ketones are used they will be at a level of up to 40%, preferably at a level of up to 30% and preferably up to 20% by weight of the perfume composition. Non-limiting examples of suitable acetals for the purpose of the invention include compounds of (indan-alpha-ol, 2-hydroxymethylene) form of ketal, acetaldehyde: phenyl ethyl propyl acetal and 4-phenyl-2,4,6-trimethyl-l- 3-dioxane. When such acétals are used they will be at a level of up to 20%, preferably at a level of up to 10% by weight of the perfume composition. Non-limiting examples of ethers suitable for the purpose of the invention include iso-amyl phenyl ethyl ether compounds, phenyl and methyl ethyl ether, methyl cedril ether and 3,3,5 trimethylcyclohexyl ethyl ether.

When such ethers are used they will be at a level of up to 20%, preferably at a level of up to 10% by weight of the perfume composition. Non-limiting examples of Schiff bases suitable for the purpose of the invention include liral / rnethyl anthranilate, helional / ethyl anthranilate and triplal / methyl anthranilate. When such Schiff bases are used, they will be at a level of up to 15%, preferably at a level of up to 10% and most preferred up to 5% by weight of the perfume composition. Non-limiting examples of esters suitable for the purpose of the invention include compounds of useful cyclohexyl acetate 2-tertiary, butyl cyclohexyl acetate 4-tertiary, hexahydro 4-7-rnetano-inden-5-yl acetate, hexahydro 4-7- methane-inden-6-yl acetate, hexahydro 4-7-rnetano-inden-5-yl propionate, hexahydro 4-7-methano-inden-6-yl propionate, hexyl salicylate and amyl salicylate. When such esters are used they will be at a level of up to 60%, preferably at a level of up to 40% and most preferred up to 30% by weight of the perfume composition. For the purposes of the present invention, a bleaching composition with perfume consists of a bleaching composition and a perfume composition, wherein said perfume is incorporated by any means into a composition selected from: i) - the bleaching composition as a product finished; ii) the bleaching composition during its manufacturing process; or any mixture thereof. For the purposes of the invention, a detergent composition incorporating a bleaching composition with perfume consists of a bleaching composition, a perfume composition, one or more surfactants, one or more builders, and optionally other conventional detergent ingredients, wherein perfume is incorporated by any means into a composition selected from: iii) a detergent composition, as a finished product, and incorporating a bleaching composition, iv) a detergent composition, during its manufacturing process, and incorporating a bleaching composition , v) a bleaching composition as defined above in i) and / or ii) and further incorporated into a detergent composition and any mixture thereof. The methods for incorporating the perfume into the bleaching composition are not critical to the present invention. This can be done by spraying with one or more components of the bleaching composition? another means known to the person skilled in the art. A preferred method, for reasons of cost and practicability, is a sprinkling process. The bleaching composition of the invention may also contain additional components that are not harmful to the perfume composition. Such additional compounds may include fillers such as sodium sulfate. The aspect of the detergent composition of the invention comprises the incorporation of the bleaching composition described hereinbefore together with a surfactant material, a builder, and optionally other conventional components in detergent compositions. Detergent compositions which incorporate the bleaching composition with perfume will normally have from 0.1% to 60% of said bleaching composition with perfume, more often from 2% to 40% and most preferred from 5% to 30%, on a weight basis of the composition. Said detergent compositions will have a surfactant material, a builder and preferably also other conventional components in detergent compositions. In this manner, the preferred detergent compositions will incorporate one or more surfactants, builders together with one or more soil suspending and anti-redeposition agents, foam suppressors, enzymes, fluorescent whitening agents, photoactivated whiteners and colors.

Surfactant agents Detergent compositions incorporating the perfume bleaching composition of the invention of the present invention will include one or more surfactants. The total amount of surfactants will generally be up to 70%, typically from 1 to 55%, preferably from 1 to 30%, most preferred from 5 to 25% and especially from 10 to 20% by weight of the total composition . Non-limiting examples of surfactants useful herein include the conventional Cu-Cie alkylbenzene sulfonates ("LAS") and the C10-C20 ("AS") alkyl sulphates ("AS") primary, branched chain and random, the alkyl sulphates (2,3) ) secondary Cío-Ciß of the formula CH3 (CH2) x (CH0S03-M +) CH3 and CH3 (CH2) and (CHOSO3- +) CH2CH3 where xy (y + 1) are integers of at least 7, preferably at least about 9, and M is a solubilization cation in water, especially sodium, unsaturated sulfates such as oleyl? lphate, the alkylalkoxy sulfates of Cι-Ciß ("AExS", especially ethoxysulfates EO 1-7), alkylalkyl carboxylates of Cio-Ciß (especially the ethoxycarboxylates EO 1-5), the glycolic ethers of Cio-Ciß, the alkyl polyglycosides of C10-CIT and their corresponding sulphated polyglycosides, and alphasulfonated fatty acid esters of C12-C18. If desired, conventional non-ionic amphoteric surfactants such as C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peak alkyl ethoxylates and the C6-C12 alkyl phenol alcoholates (especially mixed ethoxylates and ethoxy / propoxy), betaines of C12-C18 and sulfobetaines ("s? Ltaínas"), Cío-Ciß amine oxides, and the like, can also be included in the overall compositions. N-C 1 -C 4 alkyl polyhydroxy fatty acid amides may also be used. Typical examples include the C 12 -C 18 N-methylglásamides. See UO 9,206,154. Other surfactants derived from sugar include the N-alkoxy polyhydroxy fatty acid amides, such as N (3-methoxypropyl) C- or C-18 glutamide. N-propyl glucamides via C12-C18 N-hexyl can be It can also be used for a low foam formation.C10-C20 conventional soaps can also be used.If high foaming is desired, Cio-branded chain soaps can be used Other surfactants useful for the purpose of the invention are sarcosinates alkali metal anionic of the formula: R-CONHI) CH2C00M wherein R is a linear or branched C9-C17 alkyl or alkenyl group, R * is an alkyl group of Ci-C and N is an alkali metal ion . Preferred examples are lauroyl, cocoyl (C12-C14), myristyl and oleyl methyl sarcosinates in the form of their sodium salts. Yet another class of surfactant which may be suitable for the purpose of the invention is the cationic surfactant. Suitable cationic surfactants include quaternary ammonium surfactants selected from ammonium surfactants of N-alkyl or alkynyl of Cß-Ci6, preferably Ce-Cyano, wherein the remaining N-positions are substituted by methyl, hydroxyethyl or hydroxypropyl. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.

Detergency builders Builders may optionally be included in the compositions herein to help control the hardness of minerals. Inorganic and organic detergent builders can be used. Builders are typically used in fabric washing compositions to help remove particulate soils. The level of builder can vary widely depending on the final use of the composition and its desired physical form. Granulated formulations typically comprise from 10% to 80%, very typically from 15% to 50% by weight of the builder. Nevertheless, lower or higher detergency builder levels are not excluded. Inorganic or phosphate-containing builders include, but are not limited to, the alkali metal, ammonium and alkanolaronium salts of poly phosphates (illustrated by the vitreous polymeric tripolyphosphites, pyrophosphates and metaphosphates). Non-phosphate builders can also be used. These may include, but are not restricted to, phytic acid, silicates, alkali metal carbonates (including bicarbonates and sesquicarbonates), sulfates, alu inosilicates, monomeric polycarboxylates, homo or copolymeric polycarboxylic acids or their salts in which the polymeric acid consists of at least two radicals separated from each other by no more than two carbon atoms, organic phosphonates and poly (alkylene phosphonates) of aminoalkylene. Importantly, the compositions herein work surprisingly well even in the presence of so-called "weak" detergency builders (as compared to phosphate builders) such as citrates, or in the so-called "lower detergency enhancement" situation that It can occur with zeolite builders or stratified silicate. Examples of silicate builders are the so-called "amorphous" alkali metal silicates, particularly those having a Si 2: Na 2 ratio. in the scale from 1.6: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in US Pat. No. 4,664,839. NaSKS-6 is the trade name for a crystalline layered silicate sold by Hoechst (commonly abbreviated as "SKS-6"). Unlike the zeolite builders, the builder of 1 NaSKS-6 silicate detergency does not contain aluminum. NaSKS-6 has the morphological form of delta-Na2Si0s of stratified silicate. It can be prepared by methods such as those described in German Application DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use herein, but other layered silicates, such as those having the general formula NaMSi ?? 2x +? yH2? wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 may be used herein. Some other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 as the alpha, beta and gamma forms. As indicated above, the delta-Na2Si0e (NaSKS-6) form is most preferred for use herein. Other silicates can also be used such as for example magnesium silicate, which can serve as a tightening agent in granulated formulations, as a stabilizing agent for oxygen bleaches, and as a component of foam control systems. Examples of carbonate builders are the alkali metal and alkali metal carbonates as described in German Patent Application No. 2,321,001 published November 15, 1973. Such carbonate builders act as builders to remove ions. divalent metals such as calcium and also provide alkalinity and help in the removal of dirt.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most of the heavy duty granular detergent compositions currently marketed, and can also be an important detergency builder ingredient in liquid detergent formulations. The aluminosilicate builders include those that have the empirical formula: Naz [(A102) z (Si? 2) y3.xH2? where z and y are integers of at least 6, the molar ratio of z to y is on the scale of 1.0 to 0.5, and x is an integer of 15 to 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally occurring or synthetically derived aluminoeilicates. A method for producing aluminosilicate ion exchange materials is described in US Patent 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the ion exchange material of crystalline aluminosilicate has the formula: N i2 C (A102) l2 (SÍO2) l2 3. H2? wherein x is from 20 to 30, especially from 27. The material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used herein. Preferably, the al-rninosilicate has a particle size of about 0.1-10 microns in diameter. Organic builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylates" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builders can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When used in the salt form, alkali metals such as sodium, potassium and lithium, or alkanolammonium salts are preferred. Included among the polycarboxylate builders are a variety of useful material categories. An important category of polycarboxylate builders include ether polycarboxylates, including oxydisuccinate, as described in the U.S.A. 3,128,287 and in the U.S. Patent. 3,635,830. See also detergency builders of "TMS / TDS" of the U.S. Patent. 4,663,071. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Pat. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful builders include ether hydroxypolycarboxylates, maleic anhydride copolymers with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene, 2,4,6-tris-1-phonic acid, and carboxymethyloxy-succinic acid, various alkali metal salts, ammonium and substituted ammonium of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, poly-aleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof. Citrate builders, for example, citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations because of their availability from renewable resources and its biodegradability. The citrates can also be used in granular compositions, especially in combination with zeolite builders and / or layered silicate. Oxydisuccinates are also especially useful in said compositions and combinations. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1, 6-hexanodiatoe and the related compounds described in the U.S. Pat. 4,566,984. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinato, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are the preferred builders of this group, and are described in EP 0,200,263. Other suitable polycarboxylates are described in the U.S. Patent. 4,144,226 and in the Patent of E.U.A. 3,308,067. See also the patent of E.U.A. 3,723,322. Fatty acids, for example, C12-C18 monocarboxylic acids, may also be incorporated into the compositions by themselves, or in combination with the aforementioned builders, especially citrate and / or succinate builders, to provide Additional detergency improvement activity. Said use of fatty acids will generally result in a decrease in foaming, which would be considered by the formulator. In situations where phosphorus-based detergency builders can be used, and especially in the bar formulations used for hand-washing operations, various alkali metal phosphates such as the well-known sodium tripolyphosphates, pyrophosphate sodium and sodium orthophosphate. Phosphonate builders such as ethane-1-hydroxy-1,1-diphe- phonate and other known phosphonates can also be used (see, for example, U.S. Patents 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137).

Conventional detergent ingredients Chelators The chelating agents generally comprise from 0.1% to 10% by weight of the compositions herein. More preferably, if used, the chelating agents will comprise from 0.1% to 3.0% by weight of said compositions. A chelating agent can be selected from amino carboxylate, polyfunctional substituted aromatic compound, nitriloacetic acid and mixtures thereof. Without attempting to be limited by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove transition metal ions such iron and manganese ions from the wash solutions by forming soluble chelates. . The Amino carboxylates useful as optional chelator agents include etilendiamintetraacetatos, etilendiarnindisuccinato, N-hidroxietiletilendiamintriacetatos, 2-hidroxipropilendiamin disuccinate, nitrilotriacetates, etilendiarnintetrapropionatoe, trietilentetraaminhexacetatos, etilentriaminpentaacetato, inpentaacetatos and etanoldigíicinas dietilentria, alkali metal, ammonium and substituted ammonium lae thereof and mixtures the same. Preferred amino carboxylate chelators for use herein are ethylene diamine disuccinate ("EDDS"), especially the ES isomer, SU described in the U.S.A. 4,704,233, ethylene diamine N, N '-diglutarnate (EDDG) and 2-hydroxypropylene diamin-N, N' -disuccinate compounds (HPDDS). A most preferred amino carboxylate chelator is ethylenediamine dieuccinate. Organic phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are allowed in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) available under the trademark DEQUEST from Monsanto, diethylenetriaminpenta ( methylenephosphonate), ethylenediamine (methylenephosphonate), hexamethylenediaminetetra- (methylenephosphonate), α-hydroxy-2-phenyl-ethyl diphosphonate, ethylene-di-phosphonate, hydroxy-1,1-hexylidene, vinylidene 1,1-diphosphonate, 1,2-dihydroxy-ethane-1,1-diphosphonate and hydroxyethylene 1,1 diphosphonate. Preferably, these arninophosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms. Preferred chelators are the diphosphonate derivatives selected from α-hydroxy-2-phenyl ethyl diphosphonate, methylene diphosphonate, 1,1-hexylidene hydroxy, 1,1-diphosphonate vinylidene, 1,2-dihydroxyethane 1,1-diphosphonate and hydroxy-1 ethylene. 1 diphosphonate. Very preferred is hydroxyethylene 1,1 diphosphonate. Polyfunctional substituted aromatic chelating agents are also useful in the compositions herein. See the patent of E.U.A. No. 3,812,044. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as l, 2-dihydroxy-3,5-disulfobenzene.

Enzymes Enzymes can be included in the formulations herein for a wide variety of laundry purposes of fabrics, including removal of protein-based, carbohydrate-based or triglyceride-based spots, for example, and for the prevention of isolated dye transfer, y p > for the restoration of color. Additional enzymes to be incorporated include proteases, amylases, lipases, cellulases and peroxidase, as well as mixtures thereof. Other types of enzymes can also be included. They can be of any suitable origin, such as plant, animal, bacterial, fungal and yeast origin. However, its choice is governed by several factors such as the activity of pH and / or optimum stability, terrnostability, ability to act against active detergents, detergency builders as well as its potential to cause bad odors during use. In this regard, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases and fungal cellulases. Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically from 0.01 mg to 3 mg, of active enzyme per gram of the composition. In other words, co-pollencies herein will typically comprise from 0.001% to 5%, by weight of a commercial enzyme preparation. Suitable examples of proteases are the subtilisins that are obtained from the particular chains of B. subtilis and B. licheni forms. Another suitable protease is obtained from a Bacillus chain, which has a maximum activity through the pH scale of 8-12, developed and sold by Novo Industries A / S under the trademark ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,234,784 of Novo. Suitable proteolytic enzymes to remove stains based on protein that are commercially available include those sold under the brands ALCALASE and SAVINA? E by Novo Industries A / S (Denmark) and MAXATASE by 3.1 International Bio-Synthetics, Inc. (The Netherlands). Other proteases include Protease A (see European Patent Application 130,756) and Protease B (see EP257189). Preferred levels of proteases are from 0.01% to 2.0% by weight of the detergent composition herein. The cellulase that can be used in the present invention includes both bacterial and philic cellulase. Preferably, they should have an optimum pH of between 5 and 9.5. Suitable cel? Laeae are described in the US patent. 4,435,307, which describes fungal cellulase produced by the Humicola insolens and Humicola DSM1800 chain or a 212-fungal cellulase belonging to the genus Aero onas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricular Solander). Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. Especially useful are ENDO A, CAREZYME both from Novo Industries A / S. The preferred levels of cellulases are from 0.01% to 1.0% by weight of the detergent composition herein. Suitable lipase enzymes for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomona stutzeri ATCC 19. 154, as it was prescribed in British Patent 1,372,034.

See also lipases in Japanese Patent Application 53,20487, open for public inspection on February 24, 1987. This lipase is available from Amano Pharmaceutical Co.

Ltd., Nagoya, Dapón, under the trademark Lipasa P "Amano", which is hereinafter referred to as "Amano-P". Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, for example, Chrornobacter viscosum var. lipolyctum NRRLB 3673, commercially available from Toyo 2Jozo Co., Tagata, Japan; and in addition the Chromobacter viscosum lipases from U.S. Biochemical Corp., E.U.A. and Disoynth Co., the Netherlands, and the lipases of ex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lanuginosa and which is commercially available from Novo (see also EPO 341,947) is a preferred lipase for use herein. Preferred levels of lipaeas are from 0.01% to 2.0% by weight of the detergent composition herein. Peroxidase enzymes are used in combination oxygen supplies, for example, percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "bleaching solutions", that is, to avoid transfer of dyes or pigments removed from the substrates during washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoperoxidase such as chloroperoxidase and bromoperoxy asa. Lae detergent compositions containing peroxidase are described, for example, in International Application PCT UO 89/099813, published October 19, 1989, by 0. Kirk. assigned to Novo Industries A / S.

A wide variety of enzyme materials and media p > for its incorporation into synthetic detergent compositions in the U.S. Patent. 3,553,139. Additionally, enzymes are described in the U.S. Patent. 4,101,457 and in the U.S. Patent. 4,507,219. Useful enzyme materials for liquid detergent formulations and their incorporation into such formulations are described in the U.S. Patent. 4,261,868. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and illustrated in the U.S. Patent. 3,600,319 and in European Patent Application Publication No. 0 199 405. Enzyme stabilization systems are also described, for example, in the U.S. Pat. 3,519,570.

Enzyme stabilizers The enzymes employed herein are stabilized by the presence of water soluble sources of calcium and / or magnesium ions in the final compositions that provide said ions to the enzymes. (Calcium ions are generally more effective in some way than magnesium ions and are preferred in the present if only one type of cation is being used). Additional stability can be provided by the presence of several other stabilizers described in the art, especially the borate species: see Severson, U.S. 4,537,706. Typical detergents, especially liquids, will comprise from 1 to 30, preferably from 2 to 20, more preferably from 5 to 15, and most preferred from 8 to 12, calcium ionium oxides per liter of the final composition. This may vary in some way, depending on the amount of enzyme present and its response to calcium and magnesium ions. The level of the calcium or magnesium ions should be selected so that there is always some maximum level available for the enzyme, after allowing the formation of complexes with builders, fatty acids, etc., in the composition. Any water soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium rnalate, calcium maleate, calcium hydroxide, calcium, and calcium acetate, and the corresponding magnesium salts. A small amount of calcium ion, generally 0.05 to 0.4 millimoles per liter, is also often present in the composition due to calcium in the enzyme suspension and water formula. In solid detergent compositions, the formulation may include a sufficient amount of a water soluble calcium ion source to supply said amounts in the wash liquor. In the alternative, the hardness of natural water may be sufficient. It should be understood that the above levels of calcium and / or magnesium ions are sufficient to provide enzyme stability. More calcium and / or magnesium ions can be added to the compositions to provide an additional measure of fat removal performance. Accordingly, as a general proposition, the compositions herein will typically comprise from 0.05% to 2% in p >, that of a water soluble source of calcium or magnesium ions, or both. Of course, the amount may vary with the amount and type of enzyme used in the composition. The compositions herein may also optionally, but preferably, contain several additional stabilizers, especially borate type stabilizers. Typically, said stabilizers will be used at levels in the compositions from 0.25% to 10%, preferably from 0.5% to 5%, more preferably from 0.75% to 3% by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid). Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (for example, ortho-, meta- and sodium pyroborate, and sodium pentaborate) are suitable. Substituted boric acids (eg, phenylboronic acid, butan boronic acid, and p-bromo phenylboronic acid) may also be used in place of boric acid.

Polymeric dispersing agents Polymeric dispersion agents can be advantageously used at levels of 0.5% to 8%, by weight, in the compositions herein, especially in the presence of stratified silicate builders and / or zeolite. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art may be used. It is believed, although not intended to be limited by theory, that polymeric dispersion agents improve the overall performance of the detergency builder, when used in combination with other builders (including low molecular weight polycarboxylates) by inhibition of crystal growth, peptization of particle dirt release and anti-redeposition. The polymeric polycarboxylate materials can be prepared by polymerization or copolymerization of suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citratonic acid and ethylene-aronic acid. The presence in the polymeric polycarboxylates of the present or monomeric segments, which do not contain carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc., is suitable provided that said segments do not constitute more than about 40% by weight. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Said oligomers based on acrylic acid which are useful herein are the water soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from 2,000 to 10,000, most preferably from 4,000 to 7,000 and most preferably even from 4,000 to 5,000. The water-soluble salts of said acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Suitable polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been described, for example, in Diehl, U.S. Pat. No. 3,308,067, issued March 7, 1967. Acrylic / maleic-based copolymers can also be used as a preferred component of the dispersing / anti-redeposition agent. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of said copolymers in the acid form preferably ranges from 2,000 to 100,000, most preferably from 5,000 to 75,000, most preferably even from 7,000 to 65,000. The ratio of acrylate to maleate segments in said copolymers will generally vary from 30: 1 to 1: 1, preferably, from 10: 1 to 2: 1. The water-soluble salts of said acrylic acid / maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / rnaleate copolymers of this type are known materials which are described in European Patent Application No. 66915 published on December 15, 1982, as well as in EP 193,360, published on September 3, 1986, which describe also said polymers consisting of hydroxypropylacrylate. Still other useful agents include the maleic / acrylic / vinyl alcohol terpolymers. Such materials are also described in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic / maleic / vinyl alcohol. Another polymeric material that can be included is polyethylene glycol (PEG). The PEG can exhibit performance of dispersing agent, as well as acting as a remover and anti-deposition of clay dirt. Typical molecular weight scales for these purposes vary from 500 to 100,000, preferably from 1,000 to 50,000, most preferably from 1,500 to 10,000. The dispersing agents of polyaspartate and polyglutamate can also be used, especially together with the zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) Of 10,000.

Clay soil removal agents / anti-redeposition The compositions according to the present invention may also optionally contain etholated water-soluble amines having clay dirt removal and anti-redeposition properties. Lae granular compositions containing these compounds typically contain from 0.01% to 10.0% by weight of the water-soluble ethoxylated amines; Liquid compositions typically contain 0.01% to 5%. The most preferred soil release and anti-redeposition agent is tetraethylenepentane ethoxylated. Illustrative ethoxylated amines are further described in the U.S. Patent. No. 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil retardation / anti-redeposition agents are the cationic compounds described in European Patent Application 111,965. Other clay soil removal / anti-redeposition agents that can be used include the ethoxylated amine polymers described in European Patent Application 111,984; the zwitterionic polymers described in European Patent Application 112,592; and the amine oxides described in the U.S. Patent. 4,548,744. Other clay removal and / or anti-redeposition agents known in the art can be used in the compositions herein. Another type of preferred anti-redeposition agent includes carboxymethylcellulose (CMC) materials. These materials are well known in the art.

Polymeric dirt release agent Any polyrnnic soil release agent known to those skilled in the art can optionally be employed in the compositions and methods of this invention. Polymeric dirt-releasing agents are characterized in that they have both polymeric segments, to make the surface of the hydrophobic fibers, such as polyester and nylon, hydrophilic, as hydrophobic segments, to be deposited on the hydrophobic fibers and to remain adhered thereto until the termination of the hydrophobic fibers. washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This allows stains that occur after treatment with the soil release agent to be more easily cleaned in subsequent washing procedures. Dirt release agents characterized by hydrophobic segments of poly (vinyl ester) include graft copolymers of vinyl polyester), for example vinyl ester of C? ~ Cß, preferably poly (vinyl acetate) grafted onto polyalkylene oxide base structures such as polyethylene oxide base structures. (See European Patent Application 0 219 048). Commercially available dirt release agents of this type include SOKALAN * type of material, for example SOKALAN * HP-22, available from BASF (West Germany). One type of preferred 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 25,000 to 55,000. See Patent of E.U.A. No. 3,959,230 to Hays and the U.S. Patent. 3,893,929. Another dirt releasing agent p > Preferred olymeric is a polyester with repeating units of ethylene terephthalate units containing from 10 to 15% by weight of ethylene terephthalate units together with 90 to 80% by weight of p-olioxyethylene terephthalate units, derived from? n polyoxyethylene glycol of average molecular weight 300 to 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. No. 4,702,857. Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeat units and terminal portions covalently attached to the base structure. These soil release agents are fully described in the U.S. Patent. No. 4,968,451.

Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Pat. No. 4,711,730, the anionic outer shell oligomeric esters of the U.S. Patent. No. 4,721,580, and the oligomeric polyester block compounds of the U.S. Patent. No. 4,702,857. Preferred soil release agents also include the soil release agents of U.S. Pat. No. 4,877,896, which describes anionic outer shell terephthalate esters, especially sulfoaryl esters. 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%. Still another preferred soil release agent is an oligomer with repeated units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy units and oxy-1, 2-propylene. The repeated units form the base structure of the oligomer and terminate preferably with extreme covers of modified isethionate. A particularly preferred soiling agent of this type comprises approximately one unit of sulfoieophthaloyl, 5 units of terephthaloyl, units of oxyethyleneoxy and oxy-1,2-propyleneoxy in a ratio of 1.7 to 1.8, and two units of extreme shell of 2- (2-hydroxyethoxy) -etanes? Sodium lonato.

Said soil release agent also comprises from 0.5% to 20% by weight of the oligomer of a reducing-crystalline stabilizer, preferably selected from the group consisting of xylene sulfonate, only eutene fonate, toluene sulfonate and mixtures thereof.

Dye transfer inhibiting agents The compositions of the present invention can also include one or more effective materials to inhibit the transfer of dyes from one fabric to another during the cleaning process. Typically, said dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyarynin 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%. More specifically, the preferred polyamine N-oxide polymers for use herein contain units having the following structural formula: R-A? -P; wherein P is a polymerizable unit to which a group N-0 may be attached or group N-0 may form part of the polymerizable unit or group N-0 may be attached to both units; A is one of the following structures: -NC (0) -, -C (0) 0-, -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 group N-0 can be attached or the group N-0 is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, irnidazole, pyrrolidine, piperidine and derivatives thereof. The group N-0 can be represented by the following general structures: O 0 wherein 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 group N-0 ee can join or form part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, very preferably? Ka < 6. Any polymer base structure can be used as long as the amine oxide polymer formed is soluble in water and has dye transfer inhibiting properties. Examples of suitable polymeric base structures are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and the like of the same. Eetoe p >olimers include random or block copolymers wherein one type of monomer is n-amine N-oxide and the other type of rnonomer is an N-oxide. The amine N-oxide polymers typically have an amine to amine 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 poly (4-vinylpyridine N-oxide) having an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1: Four. Polymer copolymers of N-vinylpyrrolidone and N-vinylimidazole (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 light scattering as described in Barth, and others, Chemical Analysis, Vol. 113. "Modern Methods of Polymer Characterization ") PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1: 1 to 0.2: 1, most preferably from 0.8: 1 to 0.3: 1, most preferably from 0.6: 1 to 0.4 These copolymers can be either linear or branched The compositions of the present invention can also employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of 5,000 to 400,000, preferably 5,000 to 200,000, and most preferably still from 5,000 to 50,000 PVPs are known to those skilled in the detergent field art, see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference, and compositions containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of from 500 to 100,000, preferably from 1,000 to 10,000 Preferably, the ratio of PEG to PVP on a ppm basis in washing solutions is from 2: 1 to 50: 1 , and very preferred 3: 1 to 10: 1. The detergent compositions herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners that also provide a dye transfer inhibiting action. If used, the compositions herein will preferably comprise from 0.01% to 1.2% by weight of said optical brighteners. The hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein Ri is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula, Ri is anilino, R2 is N-2-bis-hydroxyethyl and M ee a cation such as sodium, the brightener is 4,4 'acid, bisC (4-anilino-6- (N-2- bis-hydroxyethyl) -s-triazin-2-yl) amino] -2, 2'-styrylisulfonic acid and disodium salt. This particular brightener species is marketed under the trade name Tinopal-UNPA-GXR by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions of the present invention. When in the above formula R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is such a cation or sodium, the brightener is the disodium salt of 4,4'-bis [4] -anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-i1) ami or 1 -2,2'-stilbenedisulfonic acid. This particular brightener species is commercially marketed under the trade name Tinopal 5BM-GXR by Ciba-Geigy Corporation. When in the above formula R1 is anilino, R2 is oryphine and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bisC (4-anilino-6-morphino-s-triazin- 2-yl) arnino32,2 '-stilbenedisulfonic. This particular kind of brightener is sold commercially under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation. The specific optical brightener species selected for use in the present invention provide performance benefits of dye transfer inhibition especially effective when used in combination with the selected polymeric dye transfer inhibitor agents described above. The combination of said selected polymeric materials (e.g., PVNO and / or PVPVI) with said selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides significant dye transfer inhibition. better in aqueous washing solutions than either of those two components of detergent composition when used alone. Without being limited to the theory, it is believed that such brighteners work in this way because they have high affinity for fabrics in the wash solution and therefore they deposit relatively quickly on these fabrics. The degree to which the brighteners are deposited on the fabrics in the washing solution can be defined by a parameter called "depletion coefficient". The depletion coefficient is in general the ratio of a) the polishing material deposited on the cloth to b) the initial polish concentration in the wash liquor. Brighteners with relatively high depletion coefficients are most suitable for inhibiting dye transfer in the context of the present invention. Of course, it will be appreciated that the other types of conventional optical brightener compounds may optionally be used in the compositions herein to provide conventional "brightness" benefits to the fabrics, rather than a true dye transfer inhibiting effect. Said use is conventional and well known for detergent formulations. Any optical brighteners or brightening or whitening agents known in the art can be incorporated at typically 0.05% to 1.2% by weight, in the detergent compositions herein. Commercial optical brighteners that may be useful in the present invention can be classified into subgroups, including, but not necessarily limited to, stilbene, pyrazoline, c? arina, carboxylic acid, methinocyaninae, 5,5-dibenzothiophene dioxide, azolee, 5 and 6 membered ring heterocyclics, and various other agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents," M. Zahradnik, published by John Uiley & amp;; Sons, New York (1982). Another optical brightener which can also be used in the present invention includes naphthalimide, benzoxazole, benzofuran, benzimidazole and any mixture thereof. Specific examples of optical brighteners that are useful in the present compositions are those identified in the U.S. Patent. 4,790,856. These brightener include the PHORUHITE series of brighteners from Verona. Other brighteners described in this reference include: Tinopal "UNPA, Tinopal CBS and Tinopal 5BM, available from Ciba-Geigy, Artic UhiteR CC and Artic Uhite CUD, available from Hilton-Davis, based in Italy; 2- (4-styryl phenyl) -2H-naphthoCl, 2-d] triazoles; 4, '-bis (1, 2, 3-triazol-2-yl) -stilbenes; 4,4'-bis (styryl) bisphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl-aminocose, 1,2-bis (-benzimidazol-2-yl) ethylene, 1,3-diphenyl-pyrazine, 2,5-bis (benzoxazole-2). -yl) thiophene, 2-styryl-naphthoCl, 2-d] oxazole, and 2- (stilbene-4-yl) -2H-naphtho-Cl, 2-d3-triazole. See also US Patent 3,646,015.

Suppressors of foams Compounds to reduce or suppress spornae formation can be incorporated into the compositions of the present invention. This suppression of foams can be of particular importance in the so-called "high concentration cleaning procedure" and in front-loading European style washing machines. A wide variety of materials can be used as suds suppressors, and the foam pressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, 3rd Edition, Volume 7, pages 430-447 (John Uiley a Sons, Inc., 1979). A category of foam pressers of particular interest comprises rnonocarbonate fatty acid and soluble salts therein. See Patent of E.U.A. 2,954,347. The monocarboxylic fatty acids and salts thereof used as foam suppressors typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium and lithium salts, as well as ammonium and alkanolammonium salts. Lae detergent compositions herein may also contain non-surfactant suppressants. These include, for example, high molecular weight hydrocarbons such as paraffin, fatty acid esters (eg, fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic ketones of (eg, stearone), etc. Other foam inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiarninochlorothiazines formed as cyanuric chloride products with two or three F? moles of primary or secondary amide containing from 1 to 24 carbon atoms, propylene oxide and rnonostearyl phosphates such as monostearyl alcohol phosphate ester and alkali metal di-metal phosphate mono-ester phosphates (eg, K, Na) , and Li). Hydrocarbons such as paraffin and halogenoparaffin can be used in liquid form. The liquid hydrocarbons will be liquid at room temperature and at atmospheric pressure and will have a pour point on the scale of approximately -40 ° C and approximately 50 ° C and a minimum boiling point not less than approximately 110 ° C (atmospheric pressure). The use of waxy hydrocarbons is also known, preferably having a melting point less than about 100 ° C. Hydrocarbons constitute a preferred category of foam suppressors for detergent compositions. The hydrocarbon foam suppressors are described, for example, in the U.S. Patent. No. 4,265,779. The hydrocarbons, therefore, include aliphatic, alicyclic, aromatic and saturated or unsaturated heterocyclic hydrocarbons having from 12 to 70 carbon atoms. The term "paraffin" as used in this description of eep? Mae supresoree is intended to include mixtures of p > true fines and cyclic hydrocarbons. Another preferred category of non-surfactant foam suppressors comprises silicone foam suppressors. This category includes the use of polyorgano siloxane oils, such as polydimethyl siloxane, oil dispersions or emulsions and the polyorganosiloxane or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is absorbed or fused onto the silica. Silicone foam suppressors are well known in the art and for example are described in the U.S. Patent. 4,265,779 and EP 354016. Other precursors of silicone foams are described in the patent of E.U.A. No. 3,455,839, which relates to compositions and methods for removing foams from aqueous solutions by incorporating in them small amounts of polydi-ethylsiloxane fluids. Mixtures of silicone and silanated silica are described, for example, in the German Patent Application DOS 2, 124,526. Silicone foam scavengers and foam controlling agents in granular detergent compositions are set forth in US Pat. 3,933,672 and in the U.S. Patent. 4,652,392. An illustrative silicone-based foamer eupressor for use herein is a foaming agent suppressing amount of foaming agent consisting essentially of: (i) polydimethisiloxane fluid having a viscosity of 20 cs at 1,500 cs at 25 ° C. (ii) from 5 to 50 parts per 100 parts by weight of (i) siloxane resin composed of units (CH3Í3 SiO? / 2 SiO2 units in a ratio of units of (CH3 3 SÍO1 / 2 to units of SÍO2 of 0.6 : 1 to 1.2: 1; and (iii) from 1 to 20 parts per 100 parts by weight of (i) of a silica gel. In the preferred silicone foam suppressant used herein, the solvent for a continuous phase is formed of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The eupressor of primary silicone foams is branched / interlaced and preferably non-linear. To further illustrate this point, typical liquid laundry detergent compositions with optionally controlled foam will comprise from 0.001 to 1, preferably from 0.01 to 0.7, preferably from 0.05 to 0.5, weight percent of said silicone foam suppressant, which comprises (1) a non-aqueous emulsion of a primary anti-foam agent which is a mixture of (a) a polyorganosiloxane, (b) a resin siloxane or a silicone compound that produces silicone resin, (c) a finely filler material divided, and (d) a catalyst for promoting the reaction of the mixture components (a), (b) and (c), to form silanolates; (2) at least a nonionic silicone surfactant; and (3) polyethylene glycol or polyethylene-polypropylene glycol copolymer having a solubility in water at room temperature of more than 2% by weight; and without polypropylene glycol.

Similar amounts can be used in granular compositions, gels, etc. See also Patents of E.U.A. 4,978,471 and 4,983,316; 5,288,431 and Patents of E.U.A. 4,639,489 and 4,749,740, Aizawa et al. In column 1, line 46 to column 4, line 35. The silicone foam pressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol / polypropylene glycol, which they have an average molecular weight of less than 1,000, preferably between 100 and 800. The polyethylene glycol and polyethylene / polypropylene copolymers herein have a solubility in water at room temperature of more than 2% by weight, preferably more than 5% by weight. % in weigh. The preferred solvent herein is polyethylene glycol having an average molecular weight of less than 1,000, more preferably between 100 and 800, most preferred between 200 and 400, and a copolymer of polyethylene glycol / polypropylene glycol, preferably PPG 200 / PEG 300. Preferred is a ratio in p > that of between 1: 1 and 1:10, most preferred between 1: 3 and 1: 6, of polyethylene glycol: polyethylene-polypropylene glycol copolymer. The preferred silicone foam suppressors used herein do not contain polypropylene glycol, particularly 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101.

Other foam suppressants useful herein include secondary alcohols (eg, 2-alkylene alkanols) and mixtures of said alcohols with silicone oils, such as siliconee described in U.S. 4,798,679, 4,075,118 and EP 150,872. Secondary alcohols include the alkyl alcohols of Cß-Ciß having a chain of Ci-Ciß-A preferred alcohol is octanol of 2-butyl, which is available by Condea under the brand ISOFOL 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 of Enichern. The mixed foam suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1: 5 to 5: 1. For any detergent composition to be used in automatic laundry washing machines, the foams should not be formed to the extent that they protrude from the washing machine. The foam suppressors, when used, are preferably present in a "foam suppression amount". By "foam suppression amount" is meant that the formulator of the composition can select an amount of this foam controlling agent that will sufficiently control to result in a low sputtering laundry detergent for use in automatic laundry washing machines . The compositions herein will generally comprise from 0% to 5% of additional foam suppressors. When used as suds suppressors, the monocarboxylic fatty acids, and salts therein, will typically be present in amounts up to 5%, by weight, of the detergent composition. Preferably, 0.5% to 3% of fatty monocarboxylate foam suppressant is used. Silicone foam suppressors are typically used in amounts up to 2.0%, by weight, of the detergent composition, although larger amounts may be used. This upper limit is practical in nature, mainly due to the interest of keeping costs reduced to the minimum and effectiveness of lower quantities to effectively control foaming. Preferably 0.01% to 1% silicone foam suppressant is used, more preferably 0.25% to 0.5%. As used herein, these weight percent values include any silica that may be used in combination with polyorganosiloxane, as well as any adjunct material that may be used. The rnonostearyl phosphate foam suppressors are generally used in amounts ranging from 0.1% to 2%, by weight, of the composition. Hydrocarbon foam suppressors are typically used in amounts ranging from 0.01% to 5.0%, although higher levels can be used. The alcohol foam suppressors are typically used at 0.2% -3% by weight of the complete compositions.

Fabric softeners Varioe fabric softeners that soften during washing, especially the impalpable smectite clays of U.S. Pat. 4,062,647, as well as other softening clays known in the art, can optionally be used typically at levels of 0.5% to 10% by weight in the present compositions to provide softening benefits concurrently with fabric cleaning. Clay-based softeners can be used in combination with amine and cationic softeners as described, for example, in US Pat. 4,375,416 and the U.S. Patent. 4,291,071.

Other ingredients A wide variety of other ingredients useful in detergent compositions can also be included in the compositions herein, including other active ingredients, vehicles, hydrothogens, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions , etc. If high foaming is desired, foamed impellers such as Cio-Ciß alkanolamides can be incorporated into the compositions, typically at a level of 1% -10%. Cio-CIA ethanol and diethanol amides illustrate a typical class of such foam impellers. It is also advantageous to use said foam impellers with adjuvanted high-spraying surfactants such as the amine oxides, betaines and sultaines indicated above. If desired, the soluble magnesium salts such as MgCl2, MgSO *, and the like may be added at a level of, typically, 0.1% -2%, to provide additional oil and to improve the performance of fat removal. Various detersive ingredients employed in the present compositions can be further stabilized by absorbing said ingredients on a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is mixed with a surfactant before being absorbed into the porous substrate. During use, the detersive ingredient is released from the substrate in the aqueous wash liquor, where it performs its intended detersive function. To illustrate this technique in more detail, a porous hydrophobic silica (trade name SIPERNAT DIO, Degussa) is mixed with a proteolytic enzyme solution containing 3% -5% nonionic ethoxylated alcohol surfactant of C13-IS (EO 7 ). Typically, the enzyme / surfactant solution is 2.5X the weight of the silica. The resulting powder is dispersed with agitation in silicone oil (various viscosities of silicone oil can be used in the range of 500-12,500). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents. The detergent compositions herein will preferably be formulated such that during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5. The formulations of automatic dishwashing products preferably have? N p > H between 6.8 and 9.0. Laundry products typically have a pH of 9 to 11. Techniques for controlling pH at recommended usage levels include the use of pH, alkali, acid regulators, etc., and are well known to those skilled in the art.

Other optional ingredients Other suitable ingredients for inclusion in the compositions of the invention include perfumes, colors and filler salts, with sodium sulfate being a preferred filler salt.

Form of the compositions The detergent compositions of the invention can be formulated in any desirable form such as powders, granules, pastes, liquids and gels.

Compositions líq? Idae The detergent compositions of the present invention can be formulated as liquid detergent compositions. Such liquid detergent compositions typically comprise from 94% to 35% by weight; preferably from 90% to 40% by weight, most preferably from 80% to 50% by weight of a liquid carrier, for example, water, preferably a mixture of water and an organic solvent.

Compounds in gel The detergent compositions of the present invention may also be in the form of gels. Such compositions are typically formulated with polyalkenyl polyether having a molecular weight of from about 750,000 to 4,000,000.

Solid compositions The detergent compositions of the present invention may also be in the form of solids, such as powders and granules. The average particle size of the components of the granulated compositions according to the invention should preferably be such that no more than 5% of the particles are larger than 1.44 mm in diameter and no more than 5% of the particles are less than 0.15. m in diameter. The term "average particle size" as used in the preend, is calculated by sifting a sample of the composition in a number of fractions (typically 5 fractions) in a series of Tyler sieves. The fractions of weight thus obtained are compared against the opening size of the sieves. The average particle size is considered as the size of the aperture through which 50% by weight of the model would be paired. The overall de? Ciency of the granular detergent compositions according to the present invention is also useful in concentrated granular detergent compositions which are characterized by relatively high de? Ciency compared to conventional laundry detergent compositions. Such high density compositions typically have an overall density of at least 600 g / liter, preferably from 650 g / liter to 1200 g / liter, most preferably from 650 g / liter to 1200 g / liter and more preferably 800 g / liter. liter at 1000 g / liter. The overall density is measured by means of a simple funnel and container device consisting of a conical funnel rigidly molded on a base and provided with a flap valve at its lower end to allow the contents of the funnel to be emptied into a cylindrical container axially aligned below the funnel. The funnel is 130 m high and has internal diameters of 130 mrn and 40 mrn in its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mrn on the upper surface of the base. The vessel has a total height of 90 mm, an internal height of 87 mm and an internal diameter of 84 nm. Its nominal volume is 500 ml. To carry out a measurement, the funnel is filled with a powder by manually emptying, the flap valve is opened and the powder is allowed to overflow from the container. The full container is removed from the frame and the excess powder is removed from the container by passing an implement with straight edges, for example, a knife through its upper edge. The filled container is then weighed and the value obtained for the weight of the powder is doubled to provide a global density in g / liter. Similar measurements are made as required.

Manufacturing procedures - granulated compositions In general, the granular detergent compositions according to the present invention can be manufactured by a variety of methods including dry blending, spray drying, agglomeration or granulation. The invention is illustrated in the following non-limiting examples, in which all percentages are on a weight basis, unless indicated otherwise. In the bleaching compositions of the present invention, the abbreviated component identifications have the following meanings: CXYAS To the predominantly linear sodium salt of C14-C15 TAE 50 Ethoxylated tallow alcohol with 50 moles of ethylene oxide per mole of alcohol C25E3S C12- C15 branched alkyl alkyl sulfate condensed with three moles of ethylene oxide C24 E5 A branched primary alcohol of Ci2-? 'Condensed with an average of 5 moles of ethylene oxide NaSKS-6 Crystalline layered silicate of the formula 6-Na2 Si2 O5 Carbonate Anhydrous sodium carbonate with a particle size between 200um and 900μm Zeolite A Hydrated sodium aluminosilicate of the formula Nai2 (IO2 SÍO2) i2 27H20 which has a size of p >Primary material in the range of 0.1 to 10 micrometers MA / AA Coppermer of maleic acid / acrylic 1: 4, average molecular weight of approximately 70,000 Percarbonate Sodium percarbonate of the nominal formula 2Na2C? 3.3H2? 2 TAED Tet aacetylethylenediamine (86% active) agglomerated with MA / AA Peroxyacid 6-nonanamidoca? Roil oxibencens? L fonate (72% active Hydrophobic) agglomerated with citric acid and precursor TAE 50 Brightener 4,4'-bis (4-anili o-6-morpholino-l, 3,5-triazin-2-yl) amino) stilbene-2: 2'-disulfonate of disodium HEDP 1,1-dihydrogenphosphonate ethylene DTPMP Diethylene tria in penta methylene phosphonate manufactured by Monsanto under the trademark Dequest 2060 Antispray Silicone polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1 Photoactivated sulfonated zinc phthalocyanine encapsulated in bleach - Savinase Normal activity proteolytic enzyme 13KNPU / g Carezyrne Activity cellulite enzyme 1000 CEVU / g Termamyl Activity amylolytic enzyme d 60KNU / g Lipolase Lipolytic activity enzyme lOOkLU / g Endolase Endogl? Nasa All sold by NOVO Industries A / S PVNO N-oxide of polyvinylpyridine PVPVI Copolymer of polyvinylpyrrolidone and vinylirnidazole CMC Carboxymethylcellulose sodium SRA Esters blocked at the ends of sulfobenzoil with oxyethylene (Agents structure of base of oxy and terephthaloyl Dirt Releases) EXAMPLE 1 The following perfume formulation was prepared: EXAMPLE 2 The following detergent compositions were prepared according to the invention, wherein the perfume is as defined in example 1.

It was observed that all the compositions according to the invention had an improved perfume stability as well as produced an effective soil removal operation.

Claims (17)

NOVELTY OF THE INVENTION CLAIMS

1. A bleaching composition with perfume containing: a hydrophobic bleaching system selected from the group consisting of i) a perhydrate in an amount of from about 0.1% to about 60% by weight and combined with a bleach precursor of hydrophobic peroxyacid in an amount of from about 0.1% to about 60% by weight, ii) a hydrophobic peroxyacid preformed in an amount of from about 0.1% to about 60% by weight, and ii) mixtures of i) and ii) wherein A hydrophobic peroxyacid bleach precursor is defined as a compound that produces under perhydrolysis a hydrophobic peroxyacid whose origin carboxylic acid has a critical micelle concentration of less than about 0.5 moles / liter, and wherein a preformed hydrophobic peroxyacid is defined as a compound whose preformed carboxylic acid has a critical micelle concentration of less than about 0.5 moles / liter, and b- a composition of pe rfume in an amount of about 0.05% to about 2% by weight comprising at least one flavor chemical selected from the group consisting of: tertiary alcohols, nitriles, lactones, ketones, acetals, ethers, Schiff's basee, esters and mixtures of any of the foregoing, wherein the total weight of said flavor chemicals in the perfume is at least about 40% by weight of the perfume.

2. A composition according to claim 1, further characterized in that the base structure chain of the peroxyacid bleach precursor and / or the peroxyacid bleach contains more than about 7 carbon atoms.

3. A composition according to one of claims 1 or 2, further characterized in that said hydrophobic bleach precursor is selected from the group consisting of bleach precursor compounds comprising at least one acyl group forming the portion of peroxyacid linked to a leaving group through a ligation -0- or -N-.

4. A composition according to claim 3, further characterized in that said bleach precursor is selected from the group consisting of 3,5,5-tri-methyl hexanoyl oxybenzene sulfonate, nanoyl oxybenzenesulfonate, a peroxyacid precursor compound substituted amide and mixtures of any of the foregoing.

5. A composition according to claim 4, further characterized in that said bleach precursor is a precursor compound of substituted peroxyacid amide selected from the group consisting of 6-octanamido-caproyloxy encensulfonate, 6-nonan-amidocaproyl oxybenzenesulfonate, 6-decanamido-capropil oxybenzenesulfonate, and mixtures thereof.

6. A composition according to claim 2, further characterized in that said preformed hydrophobic peroxyacid is a substituted peroxyacid amide compound.

7. A composition according to claim 6, further characterized in that said preformed hydrophobic peroxyacid bleach is percarboxylic rnonononylamido acid.

8. A composition according to one of claims 5 or 7, further characterized in that said tertiary alcohols are selected from the group consisting of compounds of tetrahydro-linalool, tetrahydro-ircenol, tetrahydro-muguol and tetrahydro-geraniol, and mixtures thereof. the same, b- said nitriles are selected from the group consisting of compounds of lauric nitrile, nitrile myristic and tridecen-2-nitrile, and mixtures thereof, c-dichae lactones are selected from the group that connects co undecactone, hexadecanolide and cyclopentadecanolide pueetoe, and mixtures thereof, d- said ketones are selected from the group consisting of methyl beta naphthyl ketone, rethyl phenyl ethyl ketone and 7-acetyl 1,2,3,4 compounds, 5,6,7,7-octanhydro-1,1,6,7-tetra-rnethyl-naphthalene, and mixtures thereof, said acetals are selected from the group consisting of indan-alpha-ol, 2-hydroxymethylene formaldacetal, acetaldehyde: phenyl ethyl propyl acetal and 4-phenyl-2,4,6-trirnethyl-1- 3-dioxane, and mixtures thereof, f- said ethers are selected from the group consisting of iso-aryl phenyl ethyl ether compounds, phenyl ethyl methyl ether, methyl cedril ether and 3,3,5 trimethyl ethyl cyclohexyl ether , and mixtures thereof, said Schiff bases are selected from the group consisting of lyral / methyl anthranilate, helional / methyl anthranilate and triplal / methyl anthranilate, and mixtures thereof, h- said esters are selected from p >Composite of the group consisting of butyl cyclohexyl acetate 2-tertiary, butyl cyclohexyl acetate 4-tertiary, hexahydro 4-7-methano-inden-5-yl acetate, hexahydro 4-7-methano-inden-6-yl acetate , hexahydro 4-7-methano-inden-5-yl propionate, hexahydro 4-7-methano-inden-6-yl propionate, hexyl salicylate and amyl salicylate and mixtures thereof.

9. A composition according to claim 8, further characterized in that the total weight of said flavor chemicals in the perfume is at least about 50% by weight of the perfume.

10. A composition according to claim 9, further characterized in that the total weight of said flavor chemicals in the perfume is at least about 60% by weight of the perfume.

11. A detergent composition comprising a surfactant material, a detergency builder and a perfume whitening composition containing: a- a hydrophobic bleach system selected from the group consisting of i) a perhydrate in an amount of about from 0.1% to about 60% by weight and combined with a hydrophobic peroxyacid bleach precursor in an amount of from about 0.1% to about 60% by weight, ii) a preformed hydrophobic peroxyacid in an amount of about 0.1% to about 60% by weight, and ii) mixtures of i) and ii) wherein a hydrophobic peroxyacid bleach precursor is defined as a compound that produces low hydrophobic peroxyacid peroxyacid whose carboxylic acid origin has a critical nitric concentration less than about 0.5. moles / liter, and wherein a preformed hydrophobic peroxyacid is defined as a compound whose preformed carboxylic acid has a critical micelle concentration of less than about 0.5 moles / liter, and b- a perfume composition in an amount of about 0.05% to about 2% by weight comprising at least one flavor chemical selected from the group consisting of of: tertiary alcohols, nitriles, lactones, ketones, acetals, ethers, Schiff's bases, esters and mixtures of any of the foregoing, wherein the total weight of said flavor chemicals in the perfume is at least about 40% by weight. weight of the perfume.

12. A composition according to claim 11, further characterized in that the base structure chain of the peroxyacid bleach precursor and / or the peroxyacid bleach contains more than oximately 7 carbon atoms.

13. A composition according to one of claims 11 or 12, further characterized in that said hydrophobic bleach precursor is selected from the group consisting of bleach precursor compounds comprising at least one acyl group forming the portion of peroxyacid linked to a leaving group through a ligation -0- or -N-.

14. A composition according to one of claim 12, further characterized in that said tertiary alcohols are selected from the group consisting of compounds of tetrahydro-linalool, tetrahydro-ircenol, tetrahydro-muguol and tetrahydro-geraniol, and mixtures thereof. , b- said nitriles are selected from the group consisting of lauric nitrile, myristic nitrile and tridecen-2-nitrile compounds, and mixtures thereof, c-dichae lactonae ee selected from the connecting group of undecalactone compounds , hexadecanolide and cyclopentadecanolide, and mixtures thereof, d- said ketones are selected from the group consisting of methyl beta naphthyl ketone, methyl phenyl ethyl ketone and 7-acetyl 1,2,3,4,5,6 compounds. , 7,7-octanhydro-1,1,6,7-tetra-methyl-naphthalene, and mixtures thereof, said acetals are selected from the group consisting of indan-alpha-ol, 2-hydroxymethylene formal acetal, acetaldehyde compounds : phenyl ethyl propyl acetal and 4-phenyl-2,4,6-trimethyl-l-3-dioxane, and mixtures thereof, f- said ethers are selected from the group consisting of iso-amyl phenyl ether compounds ethyl, phen.ethyl ethyl methyl ether, methyl cedril ether and 3,3,5 trimethyl cyclohexyl ethyl ether, and mixtures thereof, said Schiff bases are selected from the group consisting of liral / ethyl anthranilate, helional / methyl anthranilate and triplal / rnetyl anthranilate, and mixtures of the miemoe, h- said esters are selected from the group consisting of butyl cyclohexyl acetate 2-tertiary, butyl cyclohexyl acetate 4-tertiary, hexahydro 4-7-methano- inden-5-yl acetate, hexahydro 4-7-methano-inden-6-yl acetate, hexahydro 4-7-methano-inden-5-yl propionate, hexahydro 4-7-methano-inden-6-yl propionate, hexyl salicylate and arnil salicylate and mixtures thereof.

15. A composition according to one of claim 13, further characterized in that said tertiary alcohols are selected from the group consisting of compounds of tetrahydro linalool, tetrahydro mircenol, tetrahydro muguol and tetrahydro geraniol, and mixtures thereof , said nitriles are selected from the group consisting of lauric nitrile, myristic nitrile and tridecen-2-nitrile compounds, and mixtures of the is or, c-said lactones are selected from the group consisting of compounds of undecalactone, hexadecanolide and cyclopentadecanolide, and mixtures thereof, d- said ketones are selected from the group consisting of methyl beta naphthyl ketone, methyl phenyl ethyl ketone and 7-acetyl 1,2,3,4,5 compounds , 6,7,7-octanhydro-1,1,6,7-tetra-rnethyl-naphthalene, and mixtures of the same, said acetals are selected from the group consisting of indan-alpha-ol, 2-hydroxymethylene formaldacetal compounds, acetaldeh Ido: phenyl ethyl propyl acetal and 4-phenyl-2,4,6-trimethyl-l-3-dioxane, and mixtures thereof, f- said ethers are selected from the group consisting of iso-amyl ether compounds ethyl phenyl, phenyl ethyl methyl ether, methyl cedril ether and 3,3,5 trimethyl cyclohexyl ethyl ether, and mixtures thereof, said schiff bases are selected from the group consisting of liral / methyl anthranilate, helional / ethyl anthranilate and triplal / methyl anthranilate, and mixtures of the same, said esters are selected from the group consisting of butyl cyclohexyl acetate 2-tertiary, butyl cyclohexyl acetate 4-tertiary, hexahydro 4-7-methano- inden-5-yl acetate, hexahydro 4-7-rnetano-inden-6-yl acetate, hexahydro 4-7-methano-inden-5-yl propionate, hexahydro 4-7-methano-inden-6-yl propionate, hexyl salicylate and amyl salicylate and mixtures thereof.

16. A composition according to claim 14, further characterized in that the total sum of the weight of said flavor chemicals in the perfume is at least about 50% by weight of the perfume.

17. - A composition according to claim 15, further characterized in that the total sum of the weight of said flavor chemicals in the perfume is at least about 60% by weight of the perfume.