CA2215669A1 - Perfumed bleaching compositions - Google Patents

Abstract

There is provided a perfumed bleaching composition containing: (a) a hydrophobic bleaching system selected from (i) a perhydrate in amount of from 0.1 % to 60 % by weight and combined with a hydrophobic peroxyacid bleach precursor in amount of from 0.1 % to 60 % by weight, (ii) a preformed hydrophobic peroxyacid in amount of from 0.1 % to 60 % by weight, and (iii) mixtures of (i) and (ii), wherein a hydrophobic peroxyacid bleach precursor is defined as a compound which produce under perhydrolysis a hydrophobic peroxyacid whose parent carboxylic acid has a critical micelle concentration less than 0.5 moles/litre, and wherein a hydrophobic preformed peroxyacid is defined as a compound whose parent carboxylic acid has a critical micelle concentration less than 0.5 moles/litre, and (b) a perfume composition in amount from 0.05 % to 2 % by weight which comprises one or more aroma chemicals selected from: tertiary alcohols, nitriles, lactones, ketones, acetals, ethers, schiff bases, esters and mixtures thereof, wherein the total sum of the weight of said aroma chemicals in the perfume is at least 40 % by weight of the perfume.

Description

CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 PERFUMED BLEACHING COMPOSITIONS

Field of the invention The invention relates to perfumed bleaching compositions. More specifically, it relates to bleaching compositions comprising a hydrophobic bleach system and a stabilised perfume composition.

Background of the invention Perfumes are an important and desirable part of detergent compositions. They are used to cover up the chemical odours of the cle~ning ingredients and provide an aesthetic benefit to the wash process and, plefe~ably the cleaned fabrics. EP 430315, which discloses the use of a laundry detergent composition cont~ining a lipase and a perfume having specific fragrance materials, e~cemplifies such use. In said patent, the perfume composition is said to counteract the problem of the residual malodour of lipase treated laundry.

A problem encountered with perfumes is their volatility and many perfume ingredients can be destroyed or ~l~m~ged in presence of cle~ning ingredients, especially alkali and bleaches.

Hydrophobic bleach systems selected from a source of hydrogen pero~cide combined with a hydrophobic pero~cyacid bleach precursor and a hydrophobic pero~yacid bleach are known in the art as effective soil removal agents of dingy stains.

The Applicants have found that the problem of perfume o~idation may be particularly troublesome with hydrophobic pero~cyacid bleach precursors which on perhydrolysis produce a pero~yacid which is an CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 amido substituted pero~cyacid. Precursor compounds as well as pero~cyacid compounds per se of the amido substituted type, in particular, have also been found to give rise to the problem.

One solution to this problem is encapsulation of the perfume. This increases the e~cpense and comple~city of the formulation and does not always provide sufficient protection. EP 332259 teaches the use of a liquid detergent composition cont~inins~ pero~yacid bleach and perfumed silica particles which protect the perfume from o~idation by the bleach.

Another solution to this problem is the reduction in the level of the hydrophobic bleach system. Whilst reducing the level of the hydrophobic bleach system employed in the wash tends to ameliorate these problems, this is accompanied by a marked negative effect on the dingy stains/soil removal ability.

The detergent form~ tor thus faces the challenge of forml-l~tin~ a product which ma~imises soil/stain removal, which avoids degradation of the detergent components, which covers up the chemical odours of the cle~ning ingredients, which provides an aesthetic benefit and which is also ine~cpensive.

The Applicants have now surprisingly found that the provision of a minimllm amount of specific perfume raw materials allows the use of stabilised perfumed compositions in presence of a hydrophobic bleach system.

The Applicants have also suprisingly found, that delivery of the perfume on the fabric is enhanced with hydrophobic pero~cyacid precursor. Not to be bound by theory, it is believed that the hydrophobic pero~cyacid precursor serves as a carrier material for the perfume composition.

It is therefore an object of the present invention to provide compositions suitable for use in laundry washing methods which produces an e~ccellent perfume fragrance on fabrics as well as an CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 e~cellent perfume stability in presence of the hydrophobic bleaching system in the wash liquor and in the product during storage.

It is a further object of the invention to provide compositions suitable ~ for use in laundry w~hin~ methods which produce effective dingy soil removal.

S~-mm~ry of the invention The present invention relates to a perfumed bleaching composition cont~inin a-a hydrophobic bleaching system selected from i)-a perhydrate in amount of from 0.1 % to 60% by weight and combined with a hydrophobic pero~yacid bleach precursor in amount of from 0.1% to 60% by weight, ii)-a hydrophobic preformed pero~yacid in amount of from 0.1 %
to 60% by weight, and iii)-mi~tures of i) and ii), wherein a hydrophobic pero~cyacid bleach precursor is defined as a compound which produces under perhydrolysis a hydrophobic pero~yacid whose parent carbo~ylic acid has a critical micelle concentration less than O.S moles/litre, and wherein a hydrophobic efo,llled pero~cyacid is defined as a compound whose parent carbo~ylic acid has a critical micelle concentration less than 0.5 moles/litre, and b- a perfume composition in amount from 0.05% to 2% by weight which comprises one or more aroma chemicals selected from: tertiary alcohols, nitriles, lactones, ketones, ~-et~l~, ethers, schiff bases, esters and mi~ctures thereof, wherein the total sum of the weight of said aroma 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 bleach system selected from a perhydrate combined with a hydrophobic CA 0221~669 1997-09-16 W O96/29281 PCTÇUS96/02768 pero~cyacid bleach precursor, a preformed hydrophobic pero~cyacid and any mi~ctures thereof.

Perhydrate bleach The perhydrate is typically an inorganic perhydrate bleach, normally in the form of the sodium salt, as the source of ~lk~line hydrogen pero~ide in the wash liquor. This perhydrate is normally incorporated at a level of from 0.1% to 60%, preferably from 3 % to 40% by weight, more preferably from 5% to 35% by weight and most preferably from 8% to 30% by weight of the composition.

The perhydrate may be any of the ~lk~limetal inorganic salts such as perborate monohydrate or tetrahydrate, percarbonate, perphosphate and persilicate salts but is conventionally an alkali metal perborate or percarbonate.

Sodium percarbonate, which is the prefelled perhydrate, is an addition compound having a formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequestrant such as EDTA, l-hydro~cyethylidene 1, l-diphosphonic acid (HEDP) or an amino-phosphonate, that is incorporated during the m~nllf~cturing process. For the purposes of the detergent composition aspect of the present invention, the percarbonate can be incorporated into deter~;ent compositions without additional protection, but ~refelled e~cecutions of such compositions utilise a coated form of the material.
A variety of co~tin~ can be used including borate, boric acid and citrate or sodium silicate of SiO2:Na2O ratio from 1.6:1 to 3.4:1, ,refelably 2.8:1, applied as an aqueous solution to give a level of from

2% to 10%, (normally from 3% to 5%) of silicate solids by weight of the percarbonate. However the most preferled coating is a mi~cture of sodium carbonate and sulphate or sodium chloride.

The particle size range of the crystalline percarbonate is from 350 micrometers to 1500 micrometers with a mean of appro~imately 500-1000 micrometers.

CA 0221~669 1997-09-16 PCTrUS96/02768 W O 96/292~1 Hydrophobic pero~cyacid bleach precursor One form of the essential hydrophobic bleach system component of the invention is a hydrophobic pero~cyacid bleach precursor which produces upon perhydrolysis hydrophobic peroxyacid whose parent carbo~ylic acid has a critical micelle concentration less than 0.5 moles/litre and wherein said critical micelle concentration is measured in aqueous solution at 25~C.

Preferably, the pero~yacid backbone chain contains at least 7 carbons which may be linear or partly or totally branched or cyclic and any mi~ctures thereof.

The pero~yacid bleach precursors are normally incorporated at a level of from 0.1 % to 60%, preferably from 3 % to 40% and most preferably 3 to 25 % by weight of the perfumed bleaching composition.

Preferably, hydrophobic pero~yacid bleach precursor compounds are selected from bleach precursor compounds which comprise at least one acyl group forming the pero~yacid moiety bonded to a leaving group through an -O- or-N- linkage.

Suitable pero~yacid bleach precursors for the purpose of the invention are the amide subst~ te~l compounds of the following general formulae:

R1N(R5)C(o)R2C(o)L or RlC(o)N(R5)R2C(o)L

wherein Rl is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group cont~inin~ from about 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group cont~inin 1 to 10 carbon atoms and L can be essentially any leaving group. R1 preferably contains from about 6 to 12 carbon atoms. R2 ~ef~rably contains from about 4 to 8 carbon atoms. Rl may be straight chain or branched alkyl, subs~ J~ aryl or alkylaryl cont~inin~ branching, substitution, or both and may be , CA 0221~669 1997-09-16 W O96/29281 PCTrUS96102768 sourced from either synthetic sources or natural sources including for e~ample, tallow fat. Analogous structural variations are permissible for R2. R2 can include alkyl, aryl, wherein said R2 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R1 and R5 should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be dif~lcult to stabilize for use in a bleaching composition.

Preferred L groups are selected from:

--O~, O~Y, and --O~

R3 L=l ' R3 Y

--O--CH--C--CH=CH2 --O--CH=C--CH=CH2 -O C--R1 --N~ NR4 Y ~
O O

--O--C=CHR4 , and I ;--CH--R4 R3 o CA 0221~669 1997-09-16 W O96/29281 PCTrUS96102768 and mi~tures thereof, wherein R1 is an alkyl, aryl, or aL~aryl group cont~inin~ from 1 to 14 carbon atoms, R3 is an alkyl chain con~inin~
from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group. Any of Rl, R3 and R4 may be substituted by essentially any filnctional group including, for e~ample alkyl, hydro~y, alko~y, halogen, amine, nitrosyl, amide and ammonium or alkyl ~mmmonium groups The preferred solubilizing groups are -SO3-M+, -CO2-M+, -SO4-M +, -N+(R3)4X- and O < --N(R3)3 and most preferably -SO3-M+ and -CO2-M+ wherein R3 is an alkyl chain cont~ininE
from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali rnetal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydro~ide, methylsulfate or acetate anion.

Other suitable L group for use herein, include a leaving group selected from a caprolactam leaving group, a valerolactam leaving group and mi~cture thereof.

Preferred e~camples of bleach precursors of the above formulae include amide substit~lte~l pero~cyacid precursor compounds selected from (6-oct~n~mirlo-caproyl)o~cybenzenesulfonate, (6-non~n~mitlocaproyl)o~y benzene sulfonate, (6--lec~n~mi~lo-caproyl)o~cybenzenesulfonate, and mi~ctures thereof as described in EP-A-0170386.

Still another class of bleach precursor is the class of alkyl percarbo~cylic acid bleach precursors. Preferred aL~yl percarbo~cylic acid precursors include nonanoyl o~cy benzene sulphonate (NOBS
described in US 4,412,934) and 3,5,5-tri-methyl he~canoyl o~ybenzene sulfonate (ISONOBS described in EP120,591) and salts thereof.

Mi~ctures of any of the pero~cyacid bleach precursor, herein before described, may also be used.

CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 In addition, conventional pero~yacid bleach precursors such as the tetraacetyl ethylene ~ mine (TAED) bleach precursor may be added to the bleaching composition of the invention so as to produce an enhanced soil removal performance.

Preformed hydrophobic pero~cyacid compound Another form of the essential hydrophobic bleach system component of the invention is a preformed hydrophobic pero~cyacid bleaching agent and salt thereof whose parent carboxylic acid has a critical micelle concentration less than 0.5 moles/litre and wherein said critical micelle concentration is measured in aqueous solution at 25~C.
Preferably, the pero~yacid backbone chain contains at least 7 carbons which may be linear, partly or totally branched, or cyclic and any mi~ctures thereof.

Preferably, hydrophobic pero~yacid bleach compounds are selected from pero~yacid bleach compounds which comprise at least one acyl group forming the pero~yacid moiety bonded to a leaving group through an -O- or-N- linkage.

Preformed hydrophobic pero~cyacid compounds will typically be in amount of from 0.1 % to 60%, preferably from 3 % to 20% by weight.

Suitable e~amples of this class of agents include (6-octylamino)-6-o~co-caproic acid, (6-nonylamino)-6-o~o-caproic acid, (6-decylamino)-6-o~o-caproic acid, m~ne~ium monopero~cyphtl~ te he~cahydrate, the m~nesium salt of metachloro perbenzoic acid, 4-nonylamino~
o~copero~cybutyric acid and dipero~ydo~lec~n~lioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, U.S. Patent 4,634,551, EP 0,133,354, U.S. Patent 4,412,934 and EP 0,170,386.
A preferled hydrophobic preforllled pero~cyacid bleach compound for the purpose of the invention is monononylamido pero~cycarbo~ylic acid.

Perfume composition The other essential component of the invention is a perfume composition comprising one or more aroma chemicals selected from CA 0221~669 1997-09-16 W O 96/29281 PCTrUS96/02768 tertiary alcohols, nitriles, lactones, ketones, acetals, ethers, schiff bases, esters and mi~tures 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 aroma chemicals present in the perfume composition is at least 40%, preferably at least 50% and more preferably 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 schiffs bases can be either saturated or lln~tllrated. When in lm~hlrated form, they comprise a group selected from an aromatic ring and an alkenyl group and mi~ctures thereof.

For the purpose of the invention, aroma chemicals of the ester class can be saturated or lln~ rated. When in lln~lrated form, they either comprise an alkenyl group or are esters of salicylic acid.

Non-limitin~ tertiary alcohols suitable for the purpose of the invention include tetrahydro linalool, tetrahydro myrcenol, tetrahydro muguol and tetrahydro geraniol compounds and mi~ctures thereof.

When used such tertiary alcohol compounds will be at a level of up to 50%, ~referably at a level of up to 30% and more prefelably up to 20% by weight of the perfume composition.

Non-limiting e~camples of nitriles suitable for the purpose of the invention include lauric nitrile, myristic nitrile and tridecene-2-nitrile compounds, and mi~tures thereof.

When used such nitrile compounds will be at a level of up to 10%, preferably at a level of up to S ~ by weight of the perfume composition.

CA 0221~669 1997-09-16 PCTrUS96/02768 Non-limiting examples of lactones suitable for the purpose of the invention include undecalactone, hexadecanolide and cyclopentadecanolide compounds.

When used such lactones 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 e~camples of ketones suitable for the purpose of the invention include methyl beta naphtyl ketone, methyl phenyl ethyl ketone and 7-acetyl 1,2,3,4,5,6,7,8 octanhydro 1,1,6,7 tetra methyl naphtalene compounds.

When used such ketones will be at a level of from up to 40%, preferably at a level of up to 30% and more preferably up to 20% by weight of the perfume composition.

Non-limiting e~camples of ~cet~l~ suitable for the purpose of the invention include (indan-alpha-ole, 2-hydro~cymethylene) formald acetal, ~ret~klehyde phenyl ethyl propyl acetal and 4-phenyl-2,4,6-trimethyl-1-3-dio~ane compounds.

When used such acetals will be at a level of up to 20%, preferably at a level of up to 10% by weight of the perfume composition.

Non-limitin e~camples of ethers suitable for the purpose of the invention include iso-amyl phenyl ethyl ether, phenyl ethyl methyl ether, cedryl methyl ether and 3,3,5 trimethyl cyclohe~cyl ethyl ether compounds.

When used such ethers will be at a level of up to 20%, preferably at a level of up to 10% by weight of the perfume composition.

Non-limitin e~amples of schiffs bases suitable for the purpose of the invention include lyral/methyl anthr~nil~te, helionallmethyl anthr~nil~te and triplal/methyl anthr~nil~te.

CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 When used such schiffs bases will be at a level of up to 15 %, preferably at a level of up to 10% and more preferably up to 5% by weight of the perfume composition.

Non-limiting e~amples of esters suitable for the purpose of the invention include 2-tertiary butyl cyclohe~yl acetate, 4-tertiary butyl cyclohe~yl acetate, he~cahydro 4-7-methano-inden-5-yl acetate, he~cahydro 4-7-methano-inden-6-yl acetate, he~ahydro 4-7-methano-inden-5-yl propionate, he~cahydro 4-7-methano-inden-6-yl propionate, he~yl salicylate and amyl salicylate compounds.

When used such esters will be at a level of up to 60%, preferably at a level of up to 40% and more preferably up to 30% by weight of the perfume composition.

For the purposes of the present invention, a perfumed bleaching composition consists of a bleaching composition and a perfume composition, wherein said perfume is incorporated by any means in a composition selected from:
i)-the bleaching composition as a fini.~he~1 product, ii)-the bleaching composition during its m~kin~ process, or any mi~tures thereof.

For the purposes of the invention, a detergent composition incorporating a perfumed bleaching composition consists of a bleaching composition, a perfume composition, one or more surf~ct~nts, one or more builders and optionally other conventional deteLgent ingredients, wherein said perfume is incorporated by any means in a composition selected from:

iii) a detergent composition, as a fini~he-l product, and incorporating a bleaching composition, iv) a detergent composition, during its m~kin~: process, and incorporating a bleaching composition, CA 0221~669 1997-09-16 W O96/29281 PCTrUS96102768 v) a bleaching composition as defined hereinbefore in i) and/or ii) and further incorporated in a detergent composition and any mi~ctures thereof.

Processes for incorporating the perfume in the bleaching composition are not critical to the present invention. This can be done by spray-on, admi~cture with one or more components of the bleaching composition or other means known to the man skilled in the art. A yrefelled process, for cost and practicability reasons, is a spray-on process.

The bleaching composition of the invention may also contain additional components which are not detrimental to the perfume composition.
Such additional compounds may include fillers such as sodium sulphate.

The detergent composition aspect of the invention comprises the incorporation of the herein before described perfumed bleaching composition together with a surfactant material, a builder, and optionally other components conventional in detergent compositions.

Detergent compositions incorporating the perfumed bleaching composition will normally contain from 0.1% to 60% of said perfumed bleaching composition, more frequently from 2~o to 40% and most preferably from 5% to 30%, on a composition weight basis.

Such detergent compositions will contain a surf~ct~nt material, a builder and preferably will also contain other components conventional in detergellt compositions. Thus, prererled delergent compositions will incorporate one or more surfactants, builders together with one or more soil suspending and anti-redeposition agents, suds suppressors, enzymes, fluorescent whitening agents, photoactivated bleaches and colours.

Surfactants Deterge,lt compositions incorporating the perfumed bleaching composition of the invention of the present invention will include one or more surf~ct~nt~.

CA 0221~669 1997-09-16 W O 96/29281 PCTrUS96/02768 The total amount of surfactants will be generally up to 70%, typically 1 to 55%, preferably 1 to 30%, more preferably 5 to 25% and especially 10 to 205'o by weight of the total composition.
Nonlimiting examples of surfactants useful herein include the conventional C1 1-cl8 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C1o-C20 alkyl sulfates ("AS"), the C1o-C1g secondary (2,3) alkyl sulfates of the formula CH3(CH2)~c(CHOS03-M + ) CH3 and CH3(CH2)y (CHOSO3-M + ) CH2CH3 where ~c and (y + 1) are integers of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, n.c~lrated sulfates such as oleyl sulfate, the C1o-C1g alkyl alko~y sulfates ("AE~S"; especially EO 1-7 etho~y sulfates), C10-cl8 alkyl alko~y carbo~ylates (especially the EO 1-5 etho~cycarbo~ylates), the C10-l8 glycerol ethers, the C10-cl8 alkyl polyglycosides and their corresponding ~-llf~te-l polyglycosides, and C12-C1g alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C12-C1g alkyl etho~ylates ("AE"), including the so-called narrow peaked alkyl etho~ylates and C6-C12 alkyl phenol alko~cylates (especially etho~cylates and mi~ed etho~cy/propo~cy), C12-C1g betaines and sulfobetaines ("slllt~ines"), C1o-C1g amine o~ides, and the like, can also be included in the overall compositions.
The C1o-C1g N-alkyl polyhydro~y fatty acid amides can also be used.
Typical e~amples include the C12-C1g N-methylgl~-c~mi~es. See WO
9,206,154. Other sugar-derived surfact~nts include the N-alko~y polyhydro~cy fatty acid amides, such as C1o-C1g N-(3-metho~cypropyl) gll-c~mitle. The N-propyl through N-he~cyl C12-C1g gll-c~mi-les can be used for low s---l~ing. Clo-C20 conventional soaps may also be used. If high s~ in~ is desired, the branched-chain Clo-C16 soaps may be used.
Other suitable surf~ct~nt~ suitable for the purpose of the invention are the anionic alkali metal sarcosin~tes of formula:
R-CON(Rl )CH2COOM
wherein R is a Cg-C17 linear or branched alkyl or alkenyl group, R
is a C1-C4 alkyl group and M is an alkali metal ion. ~rerelred e~camples are the lauroyl, cocoyl (C12-C14), myristyl and oleyl methyl sarcosinates in the form of their sodium salts.

CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 Still another class of surfactant which may be suitable for the purpose of the invention are the cationic surfactant. Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C6-C16, preferably C6-C1o N-alkyl or alkenyl ammonium surfactants wherein the rem~inin~ N positions are substituted by methyl, hydro~yethyl or hydro~ypropyl groups.

Mi~ctures of anionic and nonionic surfactants are especially useful.
Other conventional useful surfactants are listed in standard te~ts.

Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness.
Inorganic as well as organic builders can be used. Builders are typically used in fabric l~llntlering compositions to assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the composition and its desired physical form. Granular formulations typically comprise from 10% to 80%, more typically from 15% to 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be e~ccluded.

Inorganic or phosphate-cont~inin~ deter~ellt builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (e~emplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates).
Non-phosphate builders may also be used. These can include, but are not restricted to phytic acid, silicates, alkali metal carbonates (including bicarbonates and sesquicarbonates), sulphates, aluminosilicates, monomeric polycarbo~ylates, homo or copolymeric polycarbo~ylic acids or their salts in which the polycarbo~cylic acid comprises at least two carbo~cylic radicals separated from each other by not more than two carbon atoms, organic phosphonates and aminoaL~cylene poly (alkylene phosphonates).
The compositions herein also function in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders.

CA 0221~669 1997-09-16 W O 96/29281 PCTrUS96/02768 E~camples of silicate builders are the so called 'amorphous' alkali metal silicates, particularly those having a SiO2:Na2O ratio in the ~ range 1.6:1 to 3.2:1 and crystalline layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminium. NaSKS-6 has the delta-Na2Si2Os morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-

3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSix02~+ 1 ~yH20 wherein M is sodium or hydrogen, ~c is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and ~mm~ forms. As noted above, the delta-Na2Si2Os (NaSKS-6 form) is most preferred for use herein.
Other silicates may also be useful such as for e~cample magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilising agent for o~cygen bleaches, and as a component of suds control systems.
E~camples of carbonate builders are the ~lk~line earth and alkali metal carbonates as disclosed in German Patent Application No.
2,321,001 published on November lS, 1973. Such carbonate builders act as builders to remove divalent metal ions such as calcium and additionally provides ~lk~linity and aids in soil removal.
Aluminosilicate builders are useful in the present invention.
minosilis~te builders are of great importance in most currently marketed heavy duty granular detergellt compositions, and can also be a significant builder ingredient in liquid detel~;el.t formulations.
~l~lminosilicate builders include those having the empirical formula:
Nazt(Alo2)z(sio2)y] ~cH2o wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to 0.5, and ~c is an integer from 15 to 264.
Useful aluminosilicate ion e~cchange materials are commercially available. These ~ minosilicates can be crystalline or amorphous in structure and can be naturally-occurring ~ minosilicates or CA 0221~669 1997-09-16 W O96129281 PCTrUS96/02768 synthetically derived. A method for producing aluminosilicate ion e~change materials is disclosed in U.S. Patent 3,985,669. Preferred synthetic crystalline aluminosilicate ion e~cchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion e~cchange material has the formula:
Nal2[(A102)12(SiO2)12] ~H20 wherein ~c is from 20 to 30, especially 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein.
Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarbo~ylate compounds. As used herein, "polycarbo~cylate" refers-to compounds having a plurality of carbo~cylate groups, preferably at least 3 carbo~ylates. Polycarbo~ylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralised salt. When l1tili7erl in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are prefel-red.
Included among the polycarbo~ylate builders are a variety of categories of useful materials. One important category of polycarbo~ylate builders encompasses the ether polycarbo~ylates, including o~cydisuccinate, as disclosed in U.S. Patent 3,128,287 and U.S. Patent 3,635,830. See also "TMS/TDS" builders of U.S. Patent

4,663,07L. Suitable ether polycarbo~cylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful deter~;e~cy builders include the ether hydro~cypolycarbo~cylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, or acrylic acid, 1, 3, 5-trihydro~cy benzene-2, 4, 6-trisulphonic acid, and carbo~cymethylo~cysuccinic acid, the various alkali metal, ammonium and substitlltetl ammonium salts of polyacetic acids such as ethylen~i~mine tetraacetic acid and nitrilotriacetic acid, as well as polycarbo~ylates such as mellitic acid, succinic acid, o~ydisuccinic acid, polymaleic acid, benzene 1,3,5-CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 tricarbo~ylic acid, carbo~ymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarbo~ylate builders of particular ~ importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability.
Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders.
O~ydisuccinates are also especially useful in such compositions and combinations.
Also suitable in the compositions cont~inin~ the present invention are the 3,3-dicarbo~y-4-o~ca-1,6-he~anedioates and the related compounds disclosed in U.S. Patent 4,566,984. Useful succinic acid builders include the Cs-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly prefe,ied compound of this type is dodecenylsuccinic acid. Specific e~amples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pent~lecenylsuccinate, and the like.
Laurylsuccinates are the ~refelled builders of this group, and are described in EP 0,200,263.
Other suitable polycarbo~ylates are disclosed in U.S. Patent 4,144,226 and in U.S. Patent 3,308,067. See also U.S. Pat.
3,723,322.
Fatty acids, e.g., C12-C1g monocarbo~ylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a ~iiminlltion of sl~lsin~, which should be taken into account by the formulator.
In situations where phosphorus-based builders can be used, and especially in the formulation of bars used for hand-l~lln~iering operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium ortho-phosphate can be used. Phosphonate builders such as ethane-1-hydro~y-1,1-diphosphonate and other known phosphonates (see, for e~ample, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.

CA 0221~669 1997-09-16 W O96/29281 PCTrUS96102768 Conventional deter~ent in redients Chelants Chelating agents generally comprise from 0.1% to lo~ by weight of the compositions herein. ~ore preferably, if utilized, the chelating agents will comprise from 0.1 % to 3.0% by weight of such compositions.

A chelating agent can be selected from amino carbo~cylate, organic phosphonate, polyfunctionally-substit~lte~l aromatic compound, nitriloacetic acid and mi~cture thereof. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their e~cceptional ability to remove transition metal ions such as iron and m~n~nese ions from washing solutions by formation of soluble chelates.
Amino carbo~ylates useful as optional chelating agents include ethylene~ minetetracetates, ethylene~ mine disuccinate, N-hydro~cyethylethylene~ minetri~cet~tes, 2-hydro~ypropylene Ai~mine disuccinate, nitrilotriacetates, ethylene~ minP telr~roplionates, triethylenetetr~min~.he~acetates, ethylene tri~mine pentaacetate, diethylenetri~minepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substit~lteA ammonium salts therein and mi~ctures therein.
PreÇelled amino carbo~cylates chelants for use herein are ethylen~li~mine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, ethyleneAi~min~-N,N'-diglllt~m~te (EDDG) and 2-hydro~cypropylene-~ mine-N,N'-disuccinate (HPDDS) compounds.
A most ple~elred amino carbo~cylate chelant is ethyleneAi~mint~
disuccinate.
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 permitted in detergent compositions, and include ethyleneAi~mine.tetrakis (methylenephosphonates) available under the trademark DEQUEST from Monsanto, diethylene tri~mine penta (methylene phosphonate), ethylene tli~mine tri (methylene CA 0221~669 1997-09-16 W O96t29281 PCTrUS96/02768 phosphonate), he~amethylene ~ mine tetra (methylene phosphonate), a-hydroxy-2 phenyl ethyl diphosphonate, methylene diphosphonate, hydroxy l,l-he~ylidene, vinylidene 1,1 diphosphonate, 1,2 dihydro~yethane 1,1 diphosphonate and hydro~y-ethane 1,1 diphosphonate.
Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms.
Preferred chelants are the diphosphonate derivatives selected from a-hydro~y-2 phenyl ethyl diphosphonate, methylene diphosphonate, hydro~y l,l-he~ylidene, vinylidene 1,1 diphosphonate, 1,2 dihydro~yethane 1,1 diphosphonate and hydro~cy-ethane 1,1 diphosphonate. A most preferred is hydro~cy-ethane 1,1 diphosphonate.

Polyfunctionally-substitllte-l aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044. Preferred compounds of this type in acid form are dihydro~ydisulfobenzenes such as 1 ,2-dihydro~y-3,5-disulfobenzene.

En7ymes - En_ymes can be included in the formulations herein for a wide variety of fabric l~lln~1ering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for e~cample, and for the prevention of fugitive dye transfer, and for fabric restoration. The en_ymes to be incorporated include proteases, amylases, lipases, cellulases, and pero~cidases, as well as mi~ctures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, ~nim~l~ bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability and stability versus active detergenl~ and builders. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
Enzymes are normally incorporated at levels sufflcient to provide up to 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5% by weight of a commercial enzyme preparation.

CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 Suitable e~amples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. Iicheniforms.
Another suitable protease is obtained from a strain of Bacillus, having ma~cimum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASE and SAVINASE
by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands). Other proteases include Protease A (see EP 130,756) and Protease B (see EP257189).
Preferred levels of proteases are from 0.01% to 4.0% by weight of the detergent composition herein.
Amylases include, for e~cample, a-amylases described in GB
1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries. Fungamyl (Novo) is especially useful.
Preferred levels of amylases are from 0.01 % to 2.0% by weight of the detergent composition herein.
The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, which discloses fungal cellulase pro~ ce-l from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase e~ctracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2.075.028;
GB-A-2.095.275 and DE-OS-2.247.832. ENDO A, CAREZYME both from Novo ~n~ stries A/S are especially useful. P1ererred levels of cellulases are from 0.01 % to 1.0% by weight of the detergellt composition herein.
Suitable lipase enzymes for detergent usage include those produced by microorE~ni~m~ of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034.
See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name CA 0221~669 1997-09-16 W O 96/29281 PCTrUS96/02768 Lipase P "Amano," hereinafter referred to as "Amano-P." Other commercial lipases include Amano-CES, lipases e~ Chromobacter ~ viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB
3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EP 341,947) is a preferred lipase for use herein. Preferred levels of lipases are from 0.01 % to 2.0% by weight of the detergent composition herein.
Pero~idase enzymes are used in combination with o~cygen sources, e.g., percarbonate, perborate, persulfate, hydrogen pero~ide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Pero~idase enzymes are known in the art, and include, for e~cample, horseradish pero~idase, lignin~e, and halopero~cidase such as chloro- and bromo-pero~cidase. Pero~idase-cont~ining detergent compositions are disclosed, for e~ample, in PCT
International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
A wide range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139. Enzymes are further disclosed in U.S.
Patent 4,101,457 and in U.S. Patent 4,507,219. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. Patent 4,261,868. Enzymes for use in detergenls can be stabilized by various techniques. Enzyme stabilisation techniques are disclosed and e~cemplified in U.S. Patent 3,600,319 and EP 0 199 405. Enzyme stabilisation systems are also described, for e~ample, in U.S. Patent 3,519,570.

Fn7~me Stabilisers - The enzymes employed herein are stabilized by the presence of water-soluble sources of calcium and/or m~nesium ions in the fini.~hed compositions which provide such ions to the enzymes. (Calcium ions are generally somewhat more effective than m~gn~sium ions and are prefell~d herein if only one type of CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 cation is being used.) Additional stability can be provided by the presence of various other art-disclosed stabilisers, especially 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 S to 15, and most preferably from 8 to 12, millimoles of calcium ion per litre of finished composition. This can vary somewhat, depending on the amount of enzyme present and its response to the calcium or magnesium ions. The level of calcium or magnesium ions should be selected so that there is always some minimllm level available for the enzyme, after allowing for comple~ation 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 m~l~te, calcium maleate, calcium hydro~ide, calcium formate, and calcium acetate, and the corresponding m~gnesium salts. A small amount of calcium ion, generally from 0.05 to 0.4 millimoles per litre, is often also present in the composition due to calcium in the enzyme slurry and formula water. In solid detergent compositions the formulation may include a sufficient quantity of a water-soluble calcium ion source to provide such amounts in the laundry liquor. In the alternative, natural water hardness may suffice.
It is to be understood that the foregoing levels of calcium and/or m~gnesium ions are sufficient to provide enzyme stability. More calcium and/or m~nesium ions can be added to the compositions to provide an additional measure of grease removal performance.
Accordingly, as a general proposition the compositions herein will typically comprise from 0.05% to 2% by weight of a water-soluble source of calcium or m~gnesium ions, or both. The amount can vary, of course, with the amount and type of enzyme employed in the composition.
The compositions herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers.
Typically, such stabilizers will be used at levels in the compositions from 0.25% to 10%, ~leferably from 0.5% to 5%, more ~rerelably from 0.75 % to 3 5~, by weight of boric acid or other borate compound capable of forming boric acid in the composition (calc~ te~l on the CA 0221~669 1997-09-16 W O96/29281 PCT~US96/02768 basis of boric acid). Boric acid is preferred, although other compounds such as boric o~ide, borax and other alkali metal borates (e.g., sodium ~ ortho-, meta- and pyroborate, and sodium pentaborate) are suitable.
Substituted boric acids (e.g., phenylboronic acid, butane boronic acid, ~ and p-bromo phenylboronic acid) can also be used in place of boric acid.

Polymeric Dispersing Agents - Polymeric dispersing agents can advantageously be lltili~e~i at levels from 0.5% to 8%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarbo~cylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarbo~ylates) by particulate soil release peptization, and anti-redeposition.
Polymeric polycarbo~ylate materials can be prepared by polymerizing or copolymerizing suitable lln~tllrated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarbo~cylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarbo~ylates herein or monomeric segments, cont~inin~ no carbo~ylate radicals such as vinylmethyl ether, styrene, ethylene, etc.
is suitable provided that such segments do not con~ti~lte more than 40% by weight.
Particularly suitable polymeric polycarbo~cylates can be derived from acrylic acid. Such acrylic acid-based polymers 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, more preferably from 4,000 to 7,000 and most pref~lably from 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for e~ample, the alkali metal, ammonium and substi~lte~i ammonium salts. Soluble polymers of this CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S.
Patent 3,308,067, issued march 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form preferably ranges from 2,000 to 100,000, more preferably from 5,000 to 75,000, most preferably from 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from 30:1 to 1:1, more preferably from 10:1 to 2: 1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for e~ample, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydro~cypropylacrylate. Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for e~ample, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
Another polymeric material which can be included is polyethylene glycol (PEG). PEG can e~hibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these purposes range from 500 to 100,000, preferably from 1,000 to 50,000, more ~rerel~ly from 1,500 to 10,000.
Polyaspartate and polyglllt~m~te dispersing agents may also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of 10,000.

Clay Soil Removal/Anti-redeposition Apents - The compositions according to the present invention can also optionally contain water-soluble etho~ylated amines having clay soil removal and antire-deposition properties. Granular detelgent compositions which contain these compounds typically contain from 0.01 % to 10.0% by weight of CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 the water-soluble etho~cylates amines; liquid detergent compositions typically contain 0.01% to 5~o.
~ The most preferred soil release and anti-redeposition agent is etho~ylated tetraethylenepent~mine. E~emplary etho~ylated amines ~ are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in EP
111,965. Other clay soil removal/antiredeposition agents which can be used include the etho~ylated amine polymers disclosed in EP 111,984;
the zwitterionic polymers disclosed in EP 112,592; and the amine oxides disclosed in U.S. Patent 4,548,744. Other clay soil removal and/or anti redeposition agents known in the art can also be l1tili7ed in the compositions herein. Another type of prert;rred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.

Polymeric Soil Release A ent - Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention. Polymeric soil release agents are characterised by having both hydrophilic segments, to hy-drophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic se~m~ont~, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
Soil release agents characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Cl-C6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene o~cide backbones, such as polyethylene o~cide backbones (see EP 0 219 048). Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (VVest Germany).
One type of preferred soil release agent is a copolymer having random blocks of ethylene terephth~l~te and polyet_ylene o~ide (PEO) terephth~l~te. The molecular weight of this polymeric soil release CA 0221~669 1997-09-16 W O 96/29281 PCTrUS96/02768 agent is in the range of from 25,000 to 55,000. See U.S. Patent 3,959,230 to Hays and U.~. Patent 3,893,929.
Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephth~l~te units which contains 10-155'o by weight of ethylene terephth~l~te units together with 90-80% by weight of polyo~cyethylene terephth~l~te units, derived from a polyo~cyethylene glycol of average molecular weight 300-5,000.
E~camples of this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857.
Another preferred polymeric soil release agent is a sulfonated product of a subst~nti~lly linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and o~yalkyleneo~y repeat units and terminal moieties covalently attached to the backbone. These soil release agents are described fully in U.S. Patent 4,968,451. Other suitable polymeric soil release agents include the terephth~l~te polyesters of U.S. Patent 4,711,730, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580 and the block polyester oligomeric compounds of U.S. Patent 4,702,857.
P'leferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, which discloses anionic, especially sulfoarolyl, end-capped terephth~l~te esters.
If lltili7e~1, soil release agents will generally comprise from 0.01 % to 10.0%, by weight, of the compositions herein, typically from 0.1% to 5%, ~refe~ably from 0.2% to 3.0%.
Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, o~cyethyleneo~y and o~y-1,2-propylene units. The repeat units form the backbone of the oligomer and are preferably termin~te~l with modified isethionate end-caps. A particularly l~referled soil release agent of this type comprises one sulfoisophthaloyl unit, 5 terephthaloyl units, o~cyethyleneo~cy and o~cy-1,2-propyleneo~y units in a ratio of from 1.7 to 1.8, and two end-cap units of sodium 2-(2-hydro~cyetho~cy)-eth~nesulfonate. Said soil release agent also comprises from 0.5 % to 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from ~cylene sulfonate, cumene sulfonate, toluene sulfonate, and mi~ctures thereof.

CA 0221~669 1997-09-16 W 096/29281 PCTrUS96/02768 Dye Transfer Inhibiting A~ents The compositions according to the present invention may also include one or more materials effective for inhibiting the transfer of dyes from ~ one fabric to another during the cle~nin.~ process. Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-o~ide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, m~n~nese phthalocyanine, pero~idases, and mi~ctures thereof. If used, these agents typically comprise from 0.01%
to 10% by weight of the composition, preferably from 0.01% to 5%, and more preferably from 0.05% to 2%.
More specifically, the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-AX-P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form 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=; ~c is 0 or 1; and R is aliphatic, etho~cylated aliphatics, aromatics, 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.
Pre~erled polyamine N-o~cides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
The N-O group can be represented by the following general structures:

N--(R2)y; =N (Rl)x ~R3)Z
wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; ~, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups. The amine o~cide unit of the polyamine N-o~ides has a pKa < 10, ~referably pKa <7, more ~refel~ed pKa <6.
Any polymer backbone can be used as long as the amine o~cide polymer formed is water-soluble and has dye transfer inhibiting properties. E~camples of suitable polymeric backbones are polyvinyls, CA 0221~669 1997-09-16 W O96129281 PCTrUS96/02768 polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mi~tures thereof. These polymers include random or block copolymers where one monomer type is an amine N-o~ide and the other monomer type is an N-o~ide. The amine N-o~ide polymers typically have a ratio of amine to the amine N-o~ide of 10:1 to 1:1,000,000. However, the number of amine o~ide groups present in the polyamine o~ide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-o~idation. The polyamine o~cides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
The most preferred polyamine N-o~ide useful in the compositions herein is poly(4-vinylpyridine-N-o~ide) which as an average molecular weight of 50,000 and an amine to amine N-o~ide ratio of 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimi~1~7ole polymers (refelred to as a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. Cl he average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis, Vol 113. "Modern Methods of Polymer Characterization".) The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more ~referably 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 present invention compositions also may employ a poly-vinylpyrrolidone ("PVP") having an average molecular weight of from

5,000 to 400,000, L,refelably from 5,000 to 200,000, and more prefelably from 5,000 to 50,000. PVP's are known to persons skilled in the deter~ellt field; see, for e~cample, EP-A-262,897 and EP-A-256,696. Compositions cont~ininf~ PVP can also contain polyethylene glycol ("PEG") having an average molecular weight from 500 to 100,000, preferably from 1,000 to 10,000. P~ererably, the ratio of CA 0221~669 1997-09-16 W O96129281 PCTrUS96/02768 PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to 50:1, and more preferably from 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 which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from 0.01% to 1.2%
by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those having the structural formula:
R, R2 ~N I ~ ~ I N(~
R2 SO3M SO3M Rl .
wherein Rl is selected from anilino, N-2-bis-hydro~cyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydro~cyethyl, N-2-hydro~cyethyi-N-methyiamino, morphiiino, chioro and amino, and M is a salt-forming cation such as sodium or pot~csi~lm When in the above formula, R1 is anilino, R2 is N-2-bis-hydro~cyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydro~cyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the pleferred hydrophilic optical brightener useful in the compositions herein.
When in the above formula, R1 is ~nilino, R2 is N-2-hydro~yethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydro~yethyl-N-methylamino)-s-triazine-2-yl)amino~2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the - tradename Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is ~nilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tr~1en~m~ Tinopal AMS-GX by Ciba Geigy Corporation.

CA 0221~669 1997-09-16 Other specific optical brightener species which may be used in the present invention provide especially effective dye transfer inhibition performance bene~lts when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described. The combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal SBM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone.
Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics. The e~ctent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "e~haustion coefficient". The e~haustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high e~haustion coefficients are the most suitable for inhibiting dye transfer in the conte~ct of the present invention.
Of course, it will be appreciated that other conventional optical brightener types of compounds can optionally be used in the present compositions to provide conventional fabric "bri~htness" benefits, rather than a true dye transfer inhibiting effect. Such usage is conventional and well-known to deterge-lt formulations.

Conventional optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from 0.005% to 5%, prefelably from 0.01% to 1.2% and most preferably from 0.05% to 1.2%, by weight, into the deter~ e.lt compositions herein. Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limiterl to, derivatives of stilbene, pyrazoline, coumarin, carbo~cylic acid, methinecyanines, dibenzothiophene-5,5-dio~cide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. E~camples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John CA 0221~669 1997-09-16 W O 96/29281 PCTrUS96/02768 Wiley & Sons, New York (1982). Further optical brightener which may also be used in the present invention include naphth~limicle, benzoxazole, benzofuran, benzimidazole and any mi~tures thereof.
Specific e~camples of optical brighteners which are useful in the ~ present compositions are those identified in U.S. Patent 4,790,856.
These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal SBM; available from Ciba-Geigy;
Artic White CC and Artic White CWD; the 2-(4-styryl-phenyl)-2H-naptho[l,2-d]triazoles; 4,4'-bis(1,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins. Specific e~camples of these brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-ben7imicl~7:01-2-yl)ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis(benzo~azol-2-yl)thiophene; 2-styryl-naptho-[1,2-d]o~cazole; and 2-(stilbene-4-yl)-2H-naphtho[1,2-d]triazole. See also U.S. Patent 3,646,015.

Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cle~nin~ process" and in front-loading European-style w~hin~ machines.
A wide variety of materials may be used as suds suppressors, and suds ~u~-essors are well known to those skilled in the art. See, for e~cample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds ~u~ressor of particular interest encompasses monocarbo~cylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347. The monocarbo~cylic fatty acids and salts thereof used as suds ~uppressor 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 lithillm salts, and ammonium and ~lk~nol~mml)niurn salts.
The detergent compositions herein may also contain non-surf~t~nt suds ~ressors. These include, for e~cample: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, CA 0221~669 1997-09-16 W O96/29281 PCT~US96/02768 aliphatic C1g-C40 ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino triazines such as tri- to he~ca-alkylmel~mines or di- to tetra-alkyltli~mine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine cont~inin~ l to 24 carbon atoms, propylene o~ide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin and haloparaffin can be l~t~ ed in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of -40~C and 50~C, and a minimum boiling point not less than 110~C (atmospheric pressure). It is also known to utilize wa~cy hydrocarbons, preferably having a melting point below 100~C.
The hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for e~ample, in U.S. Patent 4,265,779. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or lln~lrated hydrocarbons having from 12 to 70 carbon atoms. The term "paraffin," as used in this suds suppressor discussion, is intended to include mi~ctures of true paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds suppressors comprises silicone suds suppressors. This category includes the use of polyorganosilo~ane oils, such as polydimethylsilo~cane, dispersions or emulsions of polyorganosilo~ane oils or resins, and combinations of polyorganosilo~cane with silica particles wherein the polyorganosilo~cane is chemisorbed or fused onto the silica. Silicone suds su~ressors are well known in the art and are, for e~ample, disclosed in U.S. Patent 4,265,779 and EP 354016.
Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which relates to compositions and processes for defo~min~
aqueous solutions by incorporating therein small amounts of poly-limet~ylsilo~cane fluids.
Mi~tures of silicone and ~ n~tefl silica are described, for in~t~nce, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672 and in U.S.
Patent 4,652,392.

CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 An e~cemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
(i) polydimethylsilo~ane fluid having a viscosity of from 20 cs.
tol,SOOcs.at25~C;
(ii) from S to 50 parts per 100 parts by weight of (i) of silo~cane resin composed of (CH3)3SiO1/2 units of SiO2 units in a ratio of from (CH3)3 SiOl/2 units and to SiO2 units of from 0.6: 1 to 1.2: 1; and (iii) from 1 to 20 parts per 100 parts by weight of (i) of a solid silica gel.
In the preferred silicone suds suppressor used herein, the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mi~ctures thereof (preferred), or polypropylene glycol. The primary silicone suds suppressor is branched/crosslinked and prefelably not linear.
To illustrate this point further, typical liquid laundry detergent compositions with controlled suds will optionally comprise from 0.001 to 1, preferably from 0.01 to 0.7, most preferably from 0.05 to 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mi~ture of (a) a polyorganosilo~cane, (b) a resinous silo~ane or a silicone resin-producing silicone compound, ~c) a finely divided filler material, and (d) a catalyst to promote the reaction of mi~cture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than 2 weight %; and without polypropylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also U.S.
Patents 4,978,471 and 4,983,316; 5,288,431 and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35.
The silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than 1,000, preferably between 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 solubility in water at room temperature of more than 2 weight %, preferably more than 5 weight %.
The preferred solvent herein is polyethylene glycol having an average molecular weight of less than 1,000, more preferably between 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG
300. Preferred is a weight ratio of between 1: 1 and 1: 10, most preferably between 1 :3 and 1 :6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol.
The preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight.
They also preferably do not contain block copolymers of ethylene o~ide and propylene o~cide, like PLURONIC L101.
Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mi~tures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the C6-C16 alkyl alcohols having a C1-C16 chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12. Mi~ctures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mi~ed suds suppressors typically comprise mi~ctures of alcohol + silicone at a weight ratio of 1:5 to 5:1.
For any detergent compositions to be used in automatic laundry washing machines, suds should not form to the e~ctent that they overflow ~he washing machine. Suds suppressors, when ~ltili7e~l~ are prefeLably present in a "suds suppressing amount. By "suds suppressing amount" is meant that the formlll~tor of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detel~ el.t for use in automatic laundry washing machines.
The compositions herein will generally comprise from 0% to 5%
of suds suppressor. When lltili7~1 as suds ~uppressors, monocarbo~cylic fatty acids, and salts therein, will be present typically in amounts up to 5 %, by weight, of the detergent composition.
Preferably, from 0.5 % to 3 % of fatty monocarbo~cylate suds ~u~l~ressor is lltili7efl. Silicone suds suppressors are typically lltili7e-1 CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 in amounts up to 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimi7e~1 and effectiveness of lower amounts for effectively controlling sudsing.
Preferably from 0.01% to 1% of silicone suds suppressor is used, more preferably from 0.25% to 0.5~. As used herein, these weight percentage values include any silica that may be lltili7erl in combination with polyorganosilo~cane, as well as any adjunct materials that may be ~ltili7e~1. Monostearyl phosphate suds suppressors are generally lltili7e~ in amounts r~n~in~ from 0.1% to 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically lltili7erl in amounts r~n~in~ from 0.01% to 5.0%, although higher levels can be used. The alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.

Fabric Softeners - Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10%, preferably from 0.5% to 2%
by weight in the present compositions to provide fabric softener benefits concurrently with fabric cle~nin~. Clay softeners can be used in combination with amine and cationic softeners as disclosed, for e~ample, in U.S. Patent 4,375,416 and U.S. Patent 4,291,071.

Other In~redients - A wide variety of other functional ingredients useful in deter~ t compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, proces~in~ aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions. If high s~ ing is desired, suds boosters such as the Clo-C16 alkanol~mi~les can be incorporated into the compositions, typically at 1%-10% levels. The C1o-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing adjunct surfactants such as the amine o~ides, betaines and s~lt~ines noted above is also advantageous. If desired, soluble magnesium salts such as MgCl2, MgSO4, and the like, can be added at levels of, typically, CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 0.1%-25~, to provide additional suds and to enhance grease removal performance.
Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is admi~ed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admi~ced with a proteolytic enzyme solution cont~inin.~: 3%-5~ of C13 15 etho;~ylated alcohol (EO 7) nonionic surfactant. Typically, the enzyme/surfactant solution is 2.5 X the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matri~. 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 deter~ ents.

The detergellt compositions herein will l~lefelably be formulated such that, during use in aqueous cle~nin~ operations, the wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5. T.~lln~lry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

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

Form of the com~ositions CA 0221~669 1997-09-16 W O 96/29281 PCTrUS96/02768 The detergent compositions of the invention can be form~ ted in any desirable form such as powders, granulates, pastes, liquids, and gels.

Liquid compositions The detergent compositions of the present invention may be form~ ted 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, e.g., water, preferably a mi~ture of water and organic solvent.

~el compositions The detergent compositions of the present invention may also be in the form of gels. Such compositions are typically form~ te~ with polyakenyl polyether having a molecular weight of from about 750,000 to about 4,000,000.

Solid compositions The detergent compositions of the invention may also be in the form of solids, such as powders and granules.

The mean particle size of the components of granular compositions in accordance with the invention should pre~rably be such that no more that 5 % of particles are greater than 1 .4mm in diameter and not more than 5 % of particles are less than 0.15mm in diameter.

The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.

The bulk density of granular deter~;ellt compositions in accordance with the present invention are particularly useful in concentlated granular detergent compositions that are characterised by a relatively high density in comparison with conventional laundry deter~ent CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 compositions. Such high density compositions typically have a bulk density of at least 600 g/litre, more preferably from 650 g/litre to 1200 g/litre, most preferably from 800g/litre to lOOOg/litre.

Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower e~ctremity to allow the contents of the funnel to be emptied into an a~cially aligned cylindrical cup disposed below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower e~ctremities. It is mounted so that the lower e~tremity is 140 mm above the upper surface of the base. The cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.

To carry out a measurement, the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup. The filled cup is removed from the frame and e~cess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge. The filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.

Making processes - granular compositions In general, granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mi~ing, spray drying, agglomeration and gr~n~ tion.

The invention is illustrated in the following non limitin~ e~camples, in which all percentages are on a weight basis unless otherwise stated.

In the bleaching compositions of the invention and detergent compositions incorporating the bleaching compositions of the invention, the abbreviated component identifications have the following me~ning~;

CA 0221~669 1997-09-16 W O96/29281 PCT~US96/02768 CXYAS : Sodium C 14-C 15 predomin~n~ly linear alkyl sulphate TAE 50 : Tallow alcohol etho~ylated with 50 moles of ethylene oxide per mole of alcohol - C25E3S : Sodium C12-C1s branched alkyl sulphate condensed with three moles of ethylene o~cide C24 E5 : A C12 14 branched primary alcohol condensed with an average of 5 moles of ethylene o~ide NaSKS-6 : Crystalline layered silicate of formula ~ -Na2Si205 Carbonate : Anhydrous sodium carbonate with a particle size between 200~Lm and 900~1m Zeolite A : Hydrated Sodium Aluminosilicate of formula Nal2(Alo2sio2)l2- 27H20 having a primary particle size in the range from 0.1 to 10 micrometers MA/AA : Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 70,000.
Percarbonate : Sodium Percarbonate of nominal formula 2Na2C03.3H202 TAED : Tetraacetyl ethylene ~ mine (86% active) agglomerated with MA/AA
Hydrophobic : (6-non~n~midocaproyl) o~cybenzene sulfonate pero~cyacid (72% active) agglomerated with citric acid and precursor TAE 50 Brightener : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2'-disulphonate.

HEDP : Hydro~cy-ethane 1,1 diphosphonate CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 DTPMP : Diethylene tri~mine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest 2060 Silicone antifoam: Polydimethylsilo~ane foam controller with Silo~ane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.
Photoactivated: Sulphonated Zinc Phthalocyanine encapsulated in bleach de~ctrin soluble polymer Savinase : proteolytic enzyme of standard activity 10T/g Cellulase : cellulytic enzyme of activity 1000 CEVU/g Termamyl : Amylolytic enzyme of activity 60KNU~g Lipolase : Lipolytic enzyme of activity 100kLU/g Endolase : Endoghlc~n~e A of activity 2T/g all sold by NOVO Industries A/S

PVNO : Polyvinylpyridine N-o~cide PVPVI : Copolymer of polyvinylpyrolidone and vinylimitl~7.ole CMC : Sodium carbo~cymethyl cellulose ~ SRA : Sulfobenzoyl end capped esters with o~yethylene (Soil Release : o~cy and terephthaloyl backbone Agents) F~ample 1 The following perfume formulation was prepared:

Aroma chemicals %

He~yl Salicylate 20 Tetrahydromuguol 10 Tetrahydrogeraniol 6 Phenyl ethyl alcohol 8 CA 0221~669 1997-09-16 W O96/29281 PCTrUS96102768 Cyclopentadecanolide 10 4-tertiary butyl cyclohe~yl acetate 10 7-acetyl 1,2,3,4,5,6,7,8 9 octanhydro 1,1,6,7 tetra methyl naphthalene He~cahydro 4-7-methano-inden-5-yl 5 acetate Methyl phenyl ethyl ketone 4 Acetaldehyde:Phenyl ethyl propyl 7 acetal Iso-amyl phenyl ethyl ether 5 2-tertiary butyl cyclohe~yl acetate 4 Phenyl ethyl methyl ether 0.5 Lauric nitrile 0.5 Cis-3-He~enyl Acetate 0.5 Dynascone 10% 0.5 E~ample 2 The following detergent compositions according to the invention were prepared, where the perfume is as defined in E~cample 1.

Components A B
AgglomerateC25 AS/C45 AS 6.44 6.44 C25 E3S 1.61 1.61 ZeoliteA 4.61 4.61 Carbonate 2.10 2.10 MA/AA 2.51 3.44 CMC 0.28 0.28 PVNO/PVPVI 0.02 0.02 TAED 1.75 Hydrophobic 3.70 4.79 pero~cyacid bleach DTPMP 0.38 0.38 MgSO4 0.38 0.38 Dry additiveZeolite A 6.90 7.14 CA 0221~669 1997-09-16 W O96/29281 PCTrUS96/02768 SKS-6/citric 8.50 8.50 Carbonate 8.25 8.25 MA/AA 0.65 0.93 SRA 0.20 0.20 Savinase 0.60 0.60 Lipolase 0.14 0.14 Cellulase 0.19 0. 19 Termamyl 0.40 0.40 Endolase 0.15 0.15 Percarbonate 13.25 13.25 HEDP 0.40 0.40 Brightener 0.21 0.21 Photoactivated 0.002 0.002 bleach Silicone 2.00 2.00 antifoam Spray on C24 E5 3.10 3.10 C16-C18 1.33 1.33 polyhydro~cy fatty acid amide Perfume 0.44 0.44 Minors and miscellaneous to balance The compositions in accordance with the invention were all seen having an enhanced perfume stability as well as producing an effective soil removal performance.

Claims (11)

What is claimed is:

1. A perfumed bleaching composition containing:
a. a hydrophobic bleaching system selected from i) a perhydrate in amount of from 0.1 % to 60% by weight and combined with a hydrophobic peroxyacid bleach precursor in amount of from 0.1 % to 60% by weight, ii) a preformed hydrophobic peroxyacid in amount of from 0.1 % to 60 % by weight, and iii) mixtures of i) and ii) wherein a hydrophobic peroxyacid bleach precursor is defined as a compound which produces under perhydrolysis a hydrophobic peroxyacid whose parent carboxylic acid has a critical micelle concentration less than 0.5 moles/litre, and wherein a hydrophobic preformed peroxyacid is defined as a compound whose parent carboxylic acid has a critical micelle concentration less than 0.5 moles/litre, and b. a perfume composition in amount from 0.05% to 2% by weight which comprises one or more aroma chemicals selected from: tertiary alcohols, nitriles, lactones, ketones, acetals, ethers, schiff bases, esters and mixtures thereof, wherein the total sum of the weight of said aroma chemicals in the perfume is at least 40%
by weight of the perfume.

2. A composition according to Claim 1, wherein the backbone chain of the peroxyacid bleach precursor and/or the peroxyacid bleach contains more than 7 carbons.

3. A composition according to Claim 1, wherein said hydrophobic bleach precursor is selected from bleach precursor compounds which comprise at least one acyl group forming the peroxyacid moiety bonded to a leaving group through an -O- or-N- linkage.

4. A composition according to any one of Claim 1-3, wherein said bleach precursor is selected from 3,5,5-tri-methyl hexanoyl oxybenzene sulfonate, nonanoyl oxybenzene sulfonate, an amide substituted peroxyacid precursor compound and any mixtures thereof.

5. A composition according to any one of Claim 1-4, wherein said bleach precursor is an amide substituted peroxyacid precursor compound selected from (6-octanamido-caproyl)oxybenzene sulfonate, (6-nonanamidocaproyl) oxybenzene sulfonate, (6-decanamido-caproyl)oxybenzene sulfonate, and mixtures thereof.

6. A composition according to any one of Claim 1-5, wherein said preformed hydrophobic peroxyacid is an amide substituted peroxyacid compound.

7. A composition according to Claim 6, wherein said preformed hydrophobic peroxyacid bleach is monononylamido peroxycarboxylic acid.

8. A composition according to any one of Claim 1-7, wherein a. said tertiary alcohols are selected from tetrahydro linalool, tetrahydro myrcenol, tetrahydro muguol and tetrahydro geraniol compounds, b. said nitriles are selected from lauric nitrile, myristic nitrile and tridecene-2-nitrile compounds, c. said lactones are selected from undecalactone, hexadecanolide and cyclopentadecanolide compounds, d. said ketones are selected from methyl beta naphtyl ketone, methyl phenyl ethyl ketone and 7-acetyl 1,2,3,4,5,6,7,8 octanhydro 1,1,6,7 tetra methyl naphtalene compounds, e. said acetals are selected from (indan-alpha-ole, 2-hydroxymethylene) formald acetal, acetaldehyde: phenyl ethylpropyl acetal and 4-phenyl-2,4,6-trimethyl-1-3-dioxane compounds, f. said ethers are selected from iso-amyl phenyl ethyl ether, phenyl ethyl methyl ether, cedryl methyl ether and 3,3,5 trimethyl cyclohexyl ethyl ether compounds, g. said schiff bases are selected from lyral/methyl anthranilate, helional/methyl anthranilate and triplal/methyl anthranilate, and h. said esters are selected from 2-tertiary butyl cyclohexyl acetate, 4-tertiary butyl cyclohexyl acetate, 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 amylsalicylate compounds.

9. A composition according to any one of Claims 1-8, wherein the total sum of the weight of said aroma chemicals in the perfume is at least 50% by weight of the perfume.

10. A composition according to any one of Claims 1-9, wherein the total sum of the weight of said aroma chemicals in the perfume is at least 60% by weight of the perfume.

11. A detergent composition comprising a surfactant material, a builder and a perfumed bleaching composition as claimed in any one of Claims 1-10.