GB2345065A - Cleaning compositions - Google Patents

Abstract

A detergent composition, which has an excellent cleaning performance and an improved dispensing or dissolution, comprises a particle containing a nonionic alkoxylated fatty acid amide of the formula: <EMI ID=1.1 HE=28 WI=63 LX=345 LY=877 TI=CF> <PC>wherein R<SB>1</SB> is a C<SB>12</SB>-C<SB>18</SB> alkyl or alkenyl group, R<SB>2</SB> is a C<SB>2</SB>-C<SB>4</SB> alkylene group. R<SB>2</SB> is a hydrogen or a C<SB>1</SB>-C<SB>4</SB> alkyl group, R<SB>4</SB> is a C<SB>1</SB>-C<SB>4</SB> alkyl group or hydrogen and n is a number from 3 to 12; and an anionic surfactant, provided that the level of nonionic alkoxylated alcohol surfactant when present, is from 0% to 20% by weight of the particle. The anionic surfactant and the nonionic alkoxylated fatty acid amide can be in an intimate mixture or the nonionic alkoxylated fatty acid amide is sprayed onto a particle core containing the anionic surfactant.

Description

Cleaning Compositions Field of the Invention The present invention relates to solid cleaning compositions which comprise particles containing an anionic surfactant and specific nonionic surfactant which have improved dispensing properties whilst having good cleaning properties.

Background to the Invention Detergent compositions traditionallv employ nonionic surfactants, in particular ethoxylated alcohol surfactants having an ethylene number of from about 2 to 50.

These surfactants are often liquids. When formulating solid detergent compositions. these liquid nonionic surfactants are often sprayed onto the particles of the detergent. thus coaling the particles with the nonionic ethoxylated alcohols.

It has been found that these nonionic ethoxylated alcohols surfactant. gel upon contact with water. In particular. detergent particles comprising these nonionic surfactant on the surface. tend to become trapped in a gel upon contact with water and do not dissolve satisfactorily. This problem occurs in particles in the dispensing drawer or in a dispensing aid, where upon contact with water, a gelling paste of the particles containing a nonionic surfactant coats is formed which does not dispense satisfactorily into the wash water.

Another problem relates to the nonionic etholylated alcohols in the surface of detergent particles. is their tendency to mi-rate or'bleed'from the product. This may not only result in caking of the product upon storage but also the migration of other ingredients. such as for example dyes, brighteners, perfumes or enzymes, which is not desirable. Furthermore, the flowability and the handling of particle or compositions comprising these nonionic surfactants during manufacturing and during use is often poor, due to the viscosity of the nonionic surfactants. their tendency to migrante and cake.

Anionic surfactants can also have a tendency to form gels upon contact with water.

The inventors have found that these gelling problems are even more apparent when the detergent comprises both these nonionic ethoxylaied alcohol surfactants and anionic surfactants. more than one would expect from the oelling of the nonionic surfactant or the anionic surfactant on its ow-n. Therefore. there is also a need to improve the improve the delivery to the washing water of compositions containing anionic surfactants and to reduce the problem related to the incorporation of nonionic a : koxvlated alcohol surfactants The inventors have now found that the incorporation of specific nonionic poiyalkoxylated fatty acid amide surfactants in solid detergent particles containing an anionic surfactant can overcome these problems.

The inventors have found that the amount of nonionic alkoxylated alcohol surfactant can be reduced, even to 0%. when these specific amide surfactants are used. and that this results in reduced gelling of the particles, reduced caking of the particles. reduced'bleeding'of detergent ingredients and an improved handling of the products. improved flowability of the product and at the same time improved dispensing of the product. whilst still excellent cleaning performance is achieved.

! t is believed that the reduced tendency of these specific amide surfactants. to form a gel. is due to its capacitv to dissolve and solubilise other ingredients upon contact with water.

Furthermore, nonionic alkoxylated alcohol surfactants have a tendency to loose performance under hard water conditions. The inventors have surprisingly found that the nonionic polyalkoxylated amide surfactants remain a satisfactory surfactant performance under hard water conditions. This allows simplification of the builder system employed in the detergents or the reduction of the level of builders incorporated in the detergents.

Furthermore. the inventors have found that the specific nonionic potyalkoxy fatty acid amides can easil be combined with an effervescence source. which further improves the dispensing.

Summary of the Invention The present invention provides a detergent composition comprising a particle containing intimately mixed a) of from 0.1 to 50% bN, weight of the particle of a nonionic polyalkoxylated fatty acid amide of the formula :

wherein R, is a C,,-CIS alkyl or alkenyl group, R, is a C2-C4 alkylene group, R3 is a C,-C ; alkvl ; roup or preferably hydrogen R4 is a C,-C, alkvl group or preferably hydrogen and n is a number from 3 to 12 ; and b) an anionic surfactant, provided that the level of nonionic alkoxylated alcohol surfactant when present. is trom 0% to 20% by weight of the particle.

Altematively, the invention provides a detergent composition comprising a particle containing. a) a spray-on component containing of from 0.1% to 50% by weight of the particle of a nonionic alkoxylated fatty acid amide of the formula :

wherein R, is a C12-C18 alkyl or alkenyl group, R2 is a C ;-C\ alkylene group. R, is a C ;-C, alkvl group or preferably hydrogen. R. Is a C,-C, alkyl group or preferably hydrogen and n is a number from 3 to 12 ; and b) a particle core comprising an anionic surfactant, whereby the spray-on component is sprayed onto the particle core: provided that the level of nonionic alkoxylated alcohol surfactant when present. is from 0% to 20% b-, weight of the particle.

Preferably the compositions comprises at least two anionic surfactants.

Preferably the detergent composition comprises an effervescence system. preferably comprised in the particle described herein.

The composition of the invention has a reduced sensitivity water hardness and may thus employ reduced levels of builder. Thus. the detergent compositions herein preferably comprise a builder system up to 60% by weight. more preferably up to 50% or even up to 40% by weight and smaller levels may be preferred, for example up to 35% or even 30% by weight.

Preferably, the detergent composition further comprises one or more enzymes. brighteners. perfumes or dyes or mixtures thereof.

The invention also relates to the use ot a nonionic alkoxs lated fatts acid amide surfactant in detergent particles containing an anionic surfactant for improvement of the dispensing of the detergent composition comprising the particles. preferably a (so comprising an enzyme, dye. brightener. perfume or mixtures thereof.

Detailed Description of the Invention Detergent compositions The solid compositions herein are preferably in the form of granules. pastilles extrudates or tablets. Preferably, the compositions are laundrr or dish washing detergent composition.

The detergent compositions of the invention have an improved dispensing of the detergent composition as a whole. This inclues for the purpose of the invention, that the composition or components thereof have a reduced gelling upon contact with water, in particular upon contact with small amounts of water at the beginning of the wash, such as in the dispensing drawer or in the interior of the washing machine ; have an improved dispensing from the dispensing drawer or from a dispensing device : and/or have an improved dissolution into the wash water.

In one embodiment. the particle of the composition of the invention comprises the alkoxylated fatty acid amide and the anionic anal or additional nonionic surfactant intimately mixed with one another. When used herein.'intimately mixed'means for the purpose of the invention that components of the particle are substantially homogeneously divided in the particle, and'intimate mixture'should be interpreted accordingly-.

The particle or particle core mav have any form and can be made bs ans known method invol-ina the mixing of the surfactants. which can be part of a granulation process, including spray-drying process, spherisaiion process, extrusion process. pastillation processes and in particular agglomeration processes. or be part of a tabletting process or flaking process. as described herein.

The particle or particle core may preferably be made by agglomerating the components with one another. optionally in the presence of an additional liquid or additional powder material. such as inorganic salts. silicates, aluminosilicates. organic acids or salts.

It may also be preferred that the particle or particle core is prepared by a process whereby any sold component are melted and mixed with any liquid component, in Qeneral the alkoxylated fatty acid amides. whereafter any additional powdered components can be dispersed with this liquid/melted mixture. The resulting mixture may optionally be agglomerated to obtain an homogeneouslv mixture. The mixture is then solidifie to form the particle, preferably by solidifying the melt bv reducinz the process temperature.

In one embodiment of the invention, the alkoxylated fatty acid amide is comprised in a spray-on component. which is sprayed onto the particle core comprising an anionic surfactant and/or an additional nonionic surfactant, by anv spray-on method known in the art. The particle core is preferably an agglomerate. a spray-dried particle or an extrudate.

It may be preferred that the particle is substantially anhydrous. When used herein. substantially anhydrous'means that no more than 5% by weight of free moisture is present. preferably no more than 4%. even more preferably no more than 3% and most preferably no more than 2% or even I % by weight. The free moisture content as used herein. can be determined b-placino O orams of the particles in a petri dish and placing this petri dish in a convection oven at 50 C for 2 hours, and subsequently measuring the weight loss. due to water evaporation.

The particle preferably has a weight average particle size of from 150 microns to 2000 microns, or it may be preferred to be from 200 microns to 1600 microns, more preferably from 400 microns to 1400 microns, as measured bv use of Tvler sieves.

The particle preferably has a density of from 400gr/ ! itre to 1500sr'litre. preferably from 4O0gr/litre to 1 700gr/litre or even from 550grilitre to 900ar litre.

The composition. the particle and the particle core preferably comprise additional ingredients. as described hereinafter. The precise nature of these additional ingredients, and levels of incorporation thereof will depend on the application of the particle or the compositions herein and the physical form of the particle and the compositions. When additional components are to be incorporated in the particle, it may be preferred that the nonionic alkoxylated fatty acid amide and the anionic and or nonionic surfactant are premixed prior to admixing any additional ingredients.

Preferably, the particle is present as a separate granule in the composition. However, it may be preferred that the composition is in the form of a tablet or coarse granules, droplets or pastilles which then comprise the particle of the invention intimately mixed with the optional additional ingredients.

The compositions preferably comprise additional particles which do not comprising the alkoxylated fatty acid amide.

The particle is preferably present at a level of from 0. 5% to 80% by weight. more preferably from 1% to 50% by weight, even more preferablv from 5% to 35% by weight of the composition.

The level of nonionic alkoxylated fatty acid amide surfactant is preferably from 0.5% : o 30% by weight of the composition or particle. preferably from 1.0% to 205 by weight of the particle or composition. or more preferably from 1. 5% to 15% boy weight of the composition or from 3% to 16% by weight of the particle.

The level of the other nonionic surfactant or anionic surfactant or mixtures thereof, is preferably from 1. 0% to 80% by weight of the composition or particle. preferably from 2% to 60% by weight of the particle or from 3% to 505 by weight of the composition. or even from 5% to 35% by weight of the composition or from 10% to 50% by weight of the particle. Herebv, the level of any nonionic alkoxylated alcohol surfactant is from 0% to 20% by weight of the particle and preferably also from 0% to 20% by weight of the composition. more preferably from 0% to 10%, or even 6% by weight of the particle or the composition. It may even be preferred that no nonionic polyaikoxylated alcohol surfactan is present in the particle. or in the composition. This ratio of alkoxylated fatty acid amide to the total of the anionic andl or nonionic surfactant is preferably from 2 : 1 to 1 : 40, preferably from 1 : 1 to 1 : 30. or even from 1 : 5 to 1 : 25.

Nonionic alkoxvlated fatty acid amide The alkoxylated fatty acid amide herein comprises preferably a compound of the formula

wherein R@ is a Cn-C, alkyl or alkenvl group. R ; is a C-C, alkylene group. R ; is a hydrogen or a C,-C alky ! group. R, is a C,-C, alkyl group or hydrogen and n is a number from 3 to 12.

Preferred alkoxylated fatty acid amides have a R1 being a C12-C14 or a C16-C18 alkyl group. R2 being a propylene or more preferably ethylene. n being from 5 to 10 or even 9. more preferablv 5 to 7. most preferably 5. R4 beigne methyl or more preferably hydrogen.Rbeingpreferablyhydrogen, or optionaHyanethy!group.

Anionic surfactant The composition of the invention and the particle thereof comprises an anionic surfactant. Hereby, it may be preferred that the ratio of the nonionic surfactant to the anionic surfactants is from 1 : 10 to l : 1. preferably from 1 : 4 to 5 : 1.

The composition and the particle herein s an anionic surfactant. Essentially any anionic surfactants useful for detersive purposes can be comprised herein. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-and triethanolamine salts) of the anionic sulfate, sulfonate. carboxylate and sarcosinate surfactants. Anionic sulfate and sulfonate surfactants are preferred.

Preferably. the anionic surfactant of the particle comprises at least an anionic sulfate or a sulphonate surfactant. as described herein. It may be preferred that the anionic surfactant in the particle comprises both sulfonate and sulfate surfactants. It may however also be preferred that the aionic surfactant of the particle consist essentially of anionic sulfate surfactant or anionic sulphonate surfactant.

Anionic Sulfate Surfactant Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondarv alkyl sulfates. alkyl ethoxvsulfates. fatty oleoyl glycero ! sulfates. alkyl phenol ethvlene oxide ether sulfates. the C5-C17 acyl-N-(C1-C4-alkyl) and -N-(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkvlpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds beina described herein) and also disulfates of the above.

Alkyi sulfate surfactants are preferably selected from the linear and branched primant C 1 0-C g alkyi suifates. more preferably the C I I-C 15 branched chain alkyl sulfates and the C I-C 1 4 linear chain alkvl sulfates.

Alkvl ethoxvsulfate surfactants are preferably selected from the group consisting of the C I p-C 1g alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxvsulfate surfactant is a C I I-C 18* most preferably C I I-C 15 alkyl sulfate which has been ethoxylated with from 0. 5 to 7. preferably from 1 to 5, moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and/or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.

Anionic Sulfonate Surfactant Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates. in particular &alpha;-methyl ester sulphonates, C6-C22 primary or secondary alkane sulfonates, C6-C4 olefin sulfonates. sulfonated polycarboxylic acids. alkyl glycerol sulfonates, fatty acyl glvcerol sulfonates, fatty oleyl glvcerol sulfonates, and any mixtures thereof.

Anionic Carboxvlate Surfactant Suitable anionic carboxylate surfactants include the alkvl ethoxy carboxylates, the alkN-1 potyethoxy po) ycarboxylate surfactants and the soaps ('alkyl carboxyls'). especially certain secondary soaps as described herein.

Suitable alkyl ethoxy carboxylates include those with the formula RO (CH^CHaO) t CH2C00-M+ wherein R is a C6 to C 18 alkyl group, x ranges from O to 10. and the ethoxylate distribution is such that, on a weight basis. the amount of material x is 0 is less than 20 % and M is a cation. Suitable alkvl polyethoxy potycarboxytate surfactants include those having the formula RO-(CHR1-CHR2-O)-R3 wherein R is a C6 to Clg alkyl group, x is from 1 to 25.R1 and R2 are selected from the group consisting of hydrogen. methyl acid radical, succinic acid radical. hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between ! and 8 carbon atoms. and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants which contain a carboxy ! unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-I-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl- 1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.

Certain soaps may also be included as suds suppressors.

Alkali Metal Sarcosinate Surfactant Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (R 1) CHr COONI, wherein R is a Cs-C 17 linear or branched alkyl or alkenvl group.

R1 is a Cl-C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Other possible anionic surfactants include the isethionates such as the acN-1 isethionates, N-acyl taurates, fatty acid amides of methvl tauride. alkyl succinates and sulfosuccinates. monoesters of sulfosuccinate (especiall saturated and unsaturated C 1 2-C 18 monoesters) diesters of sulfosuccinate (especiall -saturated and unsaturated C6-C 14 diesters). N-acyl sarcosinates. Resin acids and hvdrogenated resin acids are also suitable. such as rosin. hydrogenated rosin, and resin acids and hndrogenated resin acids present in or derived from tallow oil.

Additional ingredients The particle herein and the detergent compositions of the invention preferably comprise additional ingredients. The precise nature of these additional components. and levels of incorporation thereof will depend on the physical form of the composition or particle and the precise nature of the washing operation for which it is to be used.

The compositions of the invention preferablv contain one or more additional detergent components selected from effervescence sources, additional surfactants. bleaches. bleach catalysts, alkalinity svstems. builders, phosphate-containing builders, organic polymeric compounds, enzymes, suds suppressors, lime soap. dispersants, soil suspension and anti-redeposition agents soil releasing agents, perfumes, dyes, dyed speckles. brighteners. photobleaching agents and additional corrosion inhibitors.

Preferablv, the composition comprises one or more brighteners. enzymes. perfume, dye or mixtures thereof. They may be comprised in the particle herein and/or they may be incorporated in the composition comprised in a different particle.

Hereby, it may be preferred that the brightener. perfume and or dye are sprayed onto the particle. In one embodiment of the invention the polvalkoxx lated fatts acid amide may be mixed with the brightener, perfume and. or dye and then sprayed onto the particle core to obtain the particle described herein above.

Effervescence system The compositions and/or the particle herein preferably comprises an effervescence source.

It may be preferred that the effervescence source comprises an alkali source and an acid source. capable of reacting with one another in the presence of water to produce a gas, preferabty carbon dioxide. Therefore. the alkali source is preferaby a carbonate source. Examples of preferred carbonates are the alkaline earth and alkali metal carbonates. including sodium carbonate, bicarbonate and sesqui-carbonate and ans mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No. 2, 21, 1, 001 published on November ! 5. 1973. Aikaii metal percarbonate salts are also suitable sources of carbonate species and are described in more detail in the section'inorganic perhydrate salts'herein.

The acid source may be any suitable organic. mineral or inorganic acid. or a derivative thereof, or a mixture thereof. The acid source may be a mono-. bi-or tri protonic acid. Preferred derivatives include a salt or ester of the acid. The source of acidity is preferably non-hygroscopic, which can improve storage stability. However. a monohydrate acidic source can be useful herein. Organic acids and their derivatives are preferred. The acid is preferably water-soluble. Suitable acids include citric. glutaric, tartaric acid, succinic or adipic acid. monosodium phosphate, sodium hydrogen sulfate. boric acid, or a salt or an ester thereof. Citric acid, maleic acid, malic acid or fumaric acid are especially preferred.

The acid source is preferably present at a level from 1% to 12%. even more preferably from 1% to 7%, most preferably from 2% to 5% by weight of the composition.

The effervescence source mav comprise anhydrous perborate. preferabl stabilised with a coatis. agent or a diluent.

The effervescence source mav preferabln be intimatel mixed with intimate mixture herein. in particular when comprised in a separate particle. prior to addition of the intimate mixture or particle thereof to the composition. Preferred hereby may be that the effervescence source is an intimate mixture of maleic acid or citric acid or fumaric acid. but preferably of malic acid with a carbonate source and preferably also a bicarbonate source.

Preferably. the effervescence source is then comprised in the particle containing the intimate mixture at a level of from 3% to 40% by weight of the particle, more preferably at a level of from 4% to 30% or even from 5% to 25% by weight of the particle.

Dves The dye which may be used herein can be a dye stuff or an aqueous solution of a dye stuff. It ma,, be preferred that the dye is an aqueous solution comprising a dyestuff. at any level to obtain suitable dyeing of the particles, preferably such that levels of dye solution are obtained up to 2% by weight of the speckle particle, or more preferably up to 0.5% by weight. as described above. Optionally. the dye also comprising other ingredients such as organic binder materials.

The dvestuff can be any suitable dyestuff. Specific examples of suitable dyestuffs include E104 - food yellow 13 (quinoline yellow), E 10-food yellow 3 (sunset yellow FCF). E131 - food blue 5 (patent blue \ Ultra Marine blue (trade name).

E133 - food blue 2 (brillant blue FCF), E140 - natural green 3 (chlorophyll and chlorphyllins). E141 and Pigment green 7 (chlorinated Cu phthalocyanine).

Preferred dxestuffs may be Monasirat Blue BV paste (trade name) and or Pigmasol Green (trade name).

Additional surfactant The compositions in accord with the invention or the particles thereof may contain one or more surfactants selected from certain nonionic surfactants. cationic, ampholvtic. amphoteric and zwitterionic surfactants and mixtures thereof.

A typical listing of ampholyic. and zwitterionic classes. and species of these surfactants. is given in U. S. P. 3. 929. 678 issued to Laudhlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Deteraents" (Vol. I and II by Schwartz. Perry and Berch). A list of suitable cationic surfactants is given in U. S. P. 4. 259,217 issued to Murphy on March 31. 1981.

Nonionic Aikvipoivsaccharide Surfactant The particle or detergent may also comprise nonionic alkylpolysaccharide surfactants. such as those disclosed in U. S. Patent 4, 565,647,Llenado, issued January 2 i. ! 986. having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide. e. g., a polyglycoside. hvdrophilic group containing from 1. 3 to 10 saccharide units.

Preferred alkylpolyglycosides have the formula : R20 (CnHonO) t (glycosyI) x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxylalkyl. hydroxyalkylphenyl. and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms: n is 2 or 3 ; t is from 0 to 10. and x is from 1. 3 to 8. The glycosyl is preferably derived from glucose.

Nonionic Alkoxvlated Alcohol Surfactant The particle herein and the compositions herein may comprise alkoxylated alcohol surfactants. preferably only up to 10%, or even 5% or even 2% by weight of the composition or particle. However. it has been found that the level of nonionic alkoxylated alcohol surfactants commonly employed in detergent compositions can be reduced, even to 0%, in the compositions of the invention, containing the pols alkoxylated fatty acid amide surfactants.

When used herein. the nonionic poiyalkoxybted or alkoxxlated alcohol surfactants are selected from the condensation products of aliphatic alcohols with from 1 to 25 moles of alkvlene oxide. particuiarly ethylene oxide andzor propvlene oxide, are suitable for use herein.Thealky) chain of the aliphatic alcohol can either be straight or branched. primant or secondary. and generally contains from 6 to 22 carbon atoms-Typical are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.

Amphoteric Surfactant Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds having the formula R (OR4) XND (R5) 2 wherein R3 is selected from an alkyl. hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof. containing from 8 to 26 carbon atoms ; R4 is an alkylene or hydroxyalkylene group containing from 2 3 carbon atoms, or mixtures thereof ; x is from 0 to 5. preferably from 0 to 3 ; and each R5 is an alkyl or hydroxyalkyl group containing from 1 to 3. or a poln ethylene oxide group containing from I to 3 ethylene oxide groups. Preferred are C} o-C alkyl dimethylamine oxide, and C10-18 acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxe lic acid is Miranol(TM) C2M Conc. manufactured by Miranol. Inc.. Dayon,'J.

Zwitterionic Surfactant Zwinerionic surfactants can also be incorporated into the detergent compositions in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives ofheterocyciic secondary and tertiary amines. or derivatives of quaternar. ammonium. quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemptary zwitterionic surfactants for use herein.

Suitable betaines are those compounds having the formula R (R') 2N-R2COOwherein R is a C6-C i g hydrocarbyl group. each RI is typicallyC-Calky!,andR is a C1-C5 hydrocarbyl group. Preferred betaines are C 12-18 dimethyl-ammonio hexanoate and the C10-18 acylamidopropane (or ethane) dimethy ! (or diethyl) beraines. Complex betaine surfactants are also suitable for use herein.

Cationic Surfactants Suitable cationic surfactants to be used in the detergent herein include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono C6-C 16, preferably C6-CIo N-alkyl or alkenyl ammonium surfactants wherein the remainina N positions are substituted bv methyl. hydroxyethvl or hydroxxpropxl groups. Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.

Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants.

The cationic ester surfactant is a, preferably water dispersible. compound having surfactant properties comprising at least one ester (i. e.-COO-) linkage and at least one cationicallv charged group.

Suitable cationic ester surfactants, including choline ester surfactants. have for example been disclosed in US Patents No. s 4228042. 4239660 and 4260529.

Cationic mono-alkoxvlated amine surfactants Highly preferred herein are cationic mono-alkoxylated amine surfactant preferablv o : the general formula I :

wherein R1 is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms. preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; R2 and R are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R7 and R3 are methyl groups; R4 is selected from hydrogen (preferred), methyl and ethyl; X- is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxy group, especially a ethoxy. propoxv or butoxv group ; and p is from 0 to about 30, preferably 2 to about 15. most preferably 2 to about 8.

Preferably the ApR4 group in formula I has p=l and is a hydroxyalkyi group, having no greater than 6 carbon atoms whereby the-OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred ApR4 groups are -CH2CH2OH, -CH2CH2CH2OH. CH2CH(CH3)OH and -CH(CH3)CH2OH, with -CH2CH2OH being particularly preferred. Preferred RI groups are linear alkyl groups. Linear RI groups having from 8 to 14 carbon atoms are preferred.

Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula

wherein Rl is Clo-CIg hydrocarbyl and mixtures thereof, especially C10-C14 alkyl. preferably C 10 and C 12 alkyl, and X is any convenient anion to provide charge balance. preferably chloride or bromide.

As noted, compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy. isopropoxy [CH (CH3) CH20] and [CH2CH (CH3O] units (i-Pr) or n-propoxv units (Pr). or mixtures of EO and/or Pr and/or i-Pr units.

The levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1% to 20%, more preferably from 0.2% to 7%. most preferably from 0. 3% to 3. 0% by weight of the composition.

Cationic bis-alkoxvlated amine surfactant The cationic bis-alkoxylated amine surfactant preferably has the general formula II :

wherein R1 is an alkyi or alkenyl moiety containing from about 8 to about 18 carbon atoms. preferably 10 to about 16 carbon atoms. most preferably from about 10 to about 14 carbon atoms: R-is an alkyl group containing from one to three carbon atoms. preferably methyl ; R3 and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl. X-is an anion such as chloride. bromide. methylsulfate. sulfate. or the like, sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C l-C4 alkoxy. especiallx ethoxy.

(i. e.,-CHwCHO-). propoxy, butoxy and mixtures thereof : p is from I to about 30. preferably 1 to about 4 and q is from I to about 30. preferably I to about 4. and most preferably both p and q are 1.

Highly preferred cationic bis-alkoxylated amine surfactants for use herein are of the formula

wherein R1 is C10-C18 hydrocarbyl and mixtures thereof, preferably C10,C12,C14 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general cationic bis-alkoxylated amine structure noted above, since in a preferred compound R 1 is derived from (coconut) C 1 r-C 1 4 alkyl fraction fatty acids, R is methyl and ApR3 and A'qR4 are each monoethoxy.

Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:

wherein R I is C 10-C18 hydrocarbyl, preferably C10-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3. R2 is C1-C3 alkyl, preferably methyl. and X is an anion. especially chloride or bromide.

Other compounds of the foregoing tvpe include those wherein the ethoxy (CHrCHnO) units (EO) are replaced bs butoxy (Bu) isopropoxv [CH (cH3) CH2Ol and [CH2CH (CH30] units (i-Pr) or n-propoxy units (Pr). or mixtures of EO and/or Pr and/or i-Pr units.

Perhvdrate Bleaches An preferred additional components of the compositions is a perhydrate bleach. such as metal perborates, metal percarbonates. particularlv the sodium salts. Perborate can be mono or tetra hydrated. Sodium percarbonate has the formula corresponding to 2Na2CO3,3H2O2, and is available commercially as a crystalline solid.

Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.

Organic Peroxvacid Bleaching System A preferred feature of the composition is an organic peroxyacid bleaching system. In one preferred execution the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs b-,-an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inoraanic perhydrate bleaches.

It may be preferred that part of the precursor compound or all of the precursor compound is comprised in the particle described herein. comprising the polyaikoxylated fatty acid amide surfactant In an alternative preferred execution a preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisage.

Peroxvacid Bleach Precursor Peroxvacid bleach precursors are compounds which react with hydrogen peroxide in a perhs drolx sis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as 0 X C L where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is 0 X C OOH Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to ! 5% by weight, most preferably from 1.5% to 10% by weight of the detergent compositions.

Suitable peroxyacid bleach precursor compounds typically contain one or more N-or O-acyl groups, which precursors can be selected from a wide range of classes.

Suitable classes include anhydrides, esters, imides. lactams and acyated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988. 864798.

1147871. 1143'31 Leavms Groups The leaving group, hereinafter L group, must be sufficiently reactive tor the perhvdrolysis reaction to occur within the optimum time frame (e. g.. a wash cvcle).

However. if L is too active. this activator will be difficult to stabilize for use in a bleaching composition.

Preferred L groups are selected from the group consisting of :

and mixtures thereof, wherein R is an alkyl, aryl. or alkaryl group containing from 1 to 14 carbon atoms. R is an a ! kyl chain containing from I to 8 carbon atoms. R is H or R3. and Y is H or a solubilizing group. Any of R1,R3 and R4 may be substituted by essentially any functional group including, for example alkyl. hxdrox. alkox. halogen, amine, nitrosvl, amide and ammonium or alkvl ammmonium groups.

The preferred solubilizing groups are-SO'M,-CO'M-SO'M,-N(R)X' and 0 < --N (R) 3 and most preferably-SO'Mand-CO'M wherein R3 is an alkyl chain containing 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 metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide. hydroxide, methylsulfate or acetate anion.

Alkv ! PercarboxvHc Acid Bleach Precursors Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis.

Preferred aiky) percarboxyiic precursor compounds of the imide type include the . N. N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains from ! to 6 carbon atoms. particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred. The TAED is preferably not present in the agglomerated particle of the present invention, but preferabty present in the detergent composition. comprising the particle.

Other preferred alkyl percarboxvlic acid precursors include sodium 3. 5. 5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS). sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.

Amide Substituted Alkvl Peroxvacid Precursors Particular useful herein, in particular in the particle herein, comprising the polyalokoxylated fatty acid amide surfactant. are amide substituted alkyl peroxyacid precursor compounds. It is believed that the polyalkoxylated fattx acid amide surfactant interacts with the amide precursor in such a manner that the precursor is dissolved or dispensed more sufficiently.

Suitable amide substituted alkyl peroxvacid precursors herein, including those of the following general formulae: R C N--R2---C L R N C-R2 C L O R5 O or R5 O O wherein RI is an alkyl group with from 1 to 14 carbon atoms. Rn is an alkvlene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.

Hiahly preferred examples of this class of agents include the precursors or the acids such as (6-hexylamino)-6-oxo-caproic acid (6-octylamino)-6-oxo-caproic acid. (6 non-lamino)-6-oxo-caproic acid, (6-decylamino)-6-oxo-caproic acid, magnesium monoperoxvphthalate hexahydrate. the salt of metachloro perbenzoic acid. 4 nonvlamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. or precursors thereof, in particularly having a benzene sulphonate leaving group. Such bleaching agents are disclosed in U. S. 4.483.781. U. S. 4. 634. 551, EP 0,133,354, U. S.

4, 412. 934 and EP 0.170.386 Perbenzoic Acid Precursor Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.

Suitable 0-acylated perbenzoic perbenzoic precursor precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzovlation products of sorbitol, glucose. and all saccharides with benzoylating agents. and those of the imide type including N-BENZOYL SUCCINIMIDE, TETRABENZOYL ethylene diamine and the X-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzol pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Cationic Peroxvacid Precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.

Tvpically, cationic peroxyacid precursors are formed bv substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group. such as an ammonium or alkvl ammmonium group. preferabl an ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.

The peroxyacid precursor compound to be so cationicallv substituted mav be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore. Alternatively. the peroxyacid precursor compound mas be an alky) percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter.

Cationic peroxyacid precursors are described in L'. S. Patents 4.904.406 : 4. 751,015; 4, 988.451 ; 4. 397, 757 ; 5, 269,962; 5, 127,852; 5. 093, 022; 5, 106,528:U. K. 1. 382, 594 : EP 475, 512. 458. 396 and 284. 292: and in JP 87-318. 332.

Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application \os. 08/298903. 08/298650.

08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates. N-acylated caprolactams. and monobenzovltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methyiene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.

Benzoxazin Organic Peroxvacid Precursors Also suitable are precursor compounds of the benzoxazin-type. as disclosed for example in EP-A-332. 294 and EP-A-482. 807. particularly those having the formula

wherein Ri is H. alkyl, alkarvl. aryl. or arylalkyl.

Preformed Organic Peroxvacid The detergent composition may contain. in addition to, or as an alternative to. an organic peroxvacid bleach precursor compound. a preformed organic peroxyacid. typically at a level of from 1% to 15% by weight. more preferably from 1% to 10% by weight of the composition.

A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae : R1-C-N-R2-C-OOH O R5 O or R1 N C R2 C OOH R5 0 0 wherein R1 is an alkyl, aryl or alkaryl group with from I to 14 carbon atoms, R is an alkylene. arylene. and alkarvlene group containing from I to 14 carbon atoms. and R5 is H or an alkyl, aryl. or alkaryl group containing 1 to i 0 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A 0170386.

Other organic peroxyacids include diacyl and tetraacvlperoxides. especially diperoxydodecanedioc acid. diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono-and diperazelaic acid. mono-and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.

Bleach Catalyst The composition can contain a transition metal containing bleach catalyst.

One suitable type are disclosed in U. S. Pat. 4,430. 243.

Other types of bleach catalysts include the manganese-based complexes disclosed in U. S. Pat. 5. 246, 621 and U. S. Pat. 5,244, 594. Others are described in European patent application publication no. 549, 272, U. S. Pat. 4,246,612 and U. S. Pat.

5. 227,084. U. S. Pat. 5. 194,416. U. S. Pat. 5. 114, 606. U. S. Pat. 5. 114. 6 ! 1. in European patent application, publication no. 408. 131 (cobalt complex catalysts).

European patent applications, publication nos. 384, 503. and 306, 089 (metalloporphyrin catalvsts). U. S. 4. 728. 455 (manganese/multidentate ligand catalyst), U. S.

4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst). U. S. 4. 601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U. S. 4,626,373 (manganese/ligand catalyst).

U. S. 4, 119, 557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts), U. S.

A430. 243 (chelants with manganese cations and non-catalvtic metal cations). and U. S. 4. 728, 455 (manganese gluconate catalysts).

Water-Soluble Builder Compound The compositions in accord with the present invention preferably contain a watersoluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 60% by weight, most preferably from 15% to 40% by weight of the composition.

The detergent compositions of the invention preferably comprise phosphatecontaining builder material. Preferably present at a level of from 0. 5% to 60 /ó. more preferably from 5% to 50%, more preferably from 8% to 40.

The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhvdrous sodium tripolyphosphate.

Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates. or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxvlic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.

The carboxylate or polycarboxvlate builder can be momomeric or oligomeric in tvpe although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid. glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid. as well as the ether carboxylates and the sulfinyl carboxylates.

Polvcarboxylates or their acids containing three carboxy groups include. in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.

1. 379, 241. lactoxysuccinates described in British Patent No. !, 389, 732. and aminosuccinates described in Netherlands Application 7205873. and the oxypolycarboxytate materiais such as 2-oxa-I. 1. 3-propane tricarboxylates described in British Patent No. 1, 387, 447. The most preferred polvcarboxylic acid containing three carboxy groups is citric acid. preferably present at a level of from 0.1 % to 15%. more preferablv from 0.5% to 8% by weight of the composition.

Polycarboxylates containing four carboxy groups include oxvdisuccinates disclosed in British Patent No. 1, 261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxyiaies and 1. *-propane tetracarboxylates Polvcarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1, 398. 421 and 1. 398. 422 and in U. S. Patent No. 3. 936. 448, and the sulfonated pyrolyse citrates described in British Patent No. 1,439.000. Preferred polycarboxylates are hydroxycarboxyiates containing up to three carboxy groups per molecule, more particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e. g. citric acid or citratescitric acid mixtures are also contemplated as useful builder components.

Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.

Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates. sodium. potassium and ammonium pyrophosphate. sodium and potassium and ammonium pyrophosphate. sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21. and salts of phytic acid.

Partiallv Soluble or Insoluble Builder Compound The compositions in accord with the present invention may contain a partially soluble or insoluble builder compound. typically present in detergent compositions at a level of from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8% to 40% weight of the composition.

Examples of largely water insoluble builders include the sodium aluminosilicates.

Suitable aluminosilicate zeolites have the unit cell formula Naz [(AIO2) z (SiO2) y]. xHrO wherein z and y are at least 6; the molar ratio of z to y is from 1. 0 to 0.5 and x is at least 5. preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline. containing from 10% to 28%, more preferably from 18% to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably svnthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P. Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula: Na 12 [AIO2) 12 (sio2) 12] xH2O wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(AlO2) 86 (Si02) i06L276H20.

Another preferred builder can be an crystalline layered silicate material, preferably of the formula Na2Si2O5, preferably as sold bv Clariant under the trade name SKS-6, having a a. B, 6 or mixtures thereof.-configuration.

Preferably the crystalline layered silicate material is present at a level of from 0. 1% to 10% more preferably from 0. 25% to 7.5% and most preferably from 0. 5% to 5% by weight of the compositions.

Heavy metal ion sequestrant The compositions preferably contain as an optional component a heavy metal ion sequestrant. which act to sequester (chelate) heay-metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrants are generally present at a level of from 0. 005% to 20%. preferably from 0. 1% to 10%. more preferably from 0. 25% to 7. 5% and most preferably from 0.5% to 5% by weight of the compositions.

Suitable heavy metal ion sequestrants for use herein include organic phosphonates. such as the amino alkylene polv (alkylene phosphonates). alkali metal ethane 1- hydroxy disphosphonates and nitrilo trimethylene phosphonates.

Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1. 1 diphosphonate.

Other suitable heaw metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxvlic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid. ethylenediamine disuccinic acid, ethylenediamine diglutaric acid. 2-hydroxypropylenediamine disuccinic acid or any salts thereof.

Especially preferred is ethylenediamine-N. N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal. ammonium, or substituted ammonium salts thereof, or mixtures thereof.

Other suitable heavy metal ion sequestrants for use herein are described in EP-A317,542, EP-A-399,133,EP-A-516,102 EP-A-509,382,EP-A-476,257, EP-A510,331 adn EP-A-528,859.

Enzvmes The compositions may comprise one or more enzymes.

Preferred additional enzymatic materials include the commercially available enzymes. Said enzymes include enzymes selected from lipases. cellulases. h micellulases. peroxidases. proteases. luco-amvlases. amylases. xvlanases. phospholipases. esterases. cutinases. pectinases. keratanases. reductases. oxidases. phenoloxidases. lipoxygenases, ligninases. pullulanases. ta. nnases. pentosanases. malanases. ss-lucanases. arabinosidases. hn-aluronidase. chondroitinase. laccase or mixtures thereof.

A preferred combination of additional enzymes in a composition according to the present invention comprises a mixture of conventional applicable enzymes such as lipase. protease. amylase. cutinase and or cellulase in conjunction with one or more plant cell R^ail degrading enzymes. Suitable enzymes are exemplified in US Patents 3. 519. 570 and 3. 533. 139.

Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN'). One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12. developed and sold as ESPERASE# by Novo Industries A/S of Denmark. hereinafter"Novo"The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASEt, DURAZYM and SAVIN'ASE from Novo and MAXATASE#, MAXACAL#, PROPERASECR and MAXAPEMO (protein engineered Maxacal) from Gist Brocades. Proteolvtic enzymes also encompass modified bacterial serine proteases. such as those described in European Patent Application Serial ! Number 87 303761. 8. filed April 28, 1987 (particularly pages 17.24 and 98). and which is called herein "Protease B". and in European Patent Application 199. 404. Venegas. published October 29* 1986. which refers to a modified bacterial serine protealytic enzyme which is called"Protease A"herein. Suitable is what is called herein"Protease C". which is a variant of an alkaline serine protease from Bacillus in which IN-sine replaced arginine at position 27. tyrosine rep) aced vaiine at position 104. serine replaced asparagine at position 123. and alanine replaced threonine at position 274.

Protease C is described in EP 90912958 : 4. corresponding to WO 91 0663" Published May 16, 1991. Genetically modified variants, particularly of Protease C. are also included herein.

. preferred protease referred to as"Protease D"is a carbonyl hvdrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase bv substituting a different amino acid for a pluralits of amino acid residues at a position in said carbonvl hydrolase equivalent to position -76* preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128,-135,-156, +166,-193, +197. +204, +206. +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO95/10591 and in the patent application of C. Ghosh, et al,"Bleaching Compositions Comprising Protease Enzymes"having US Serial No. 08/322, 677, filed October I3. 1994.

Also suitable for the present invention are proteases described in patent applications EP 251 446 and WO 91/06637. protease BLAPS described in W091/02792 and their variants described in WO 95/23221.

See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140AtoNovo.Enzymaticdetergentscomprisingprotease. one or more other enzymes, and a reversible protease inhibitor are described in WO 92 ! 03529 A to Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in V'O 9'07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 by Unilever.

One or a mixture of proteolytic enzymes may be incorporated in the compositions of the present invention. generally at a level of from 0. 0001% to 2%. preferably from 0. 001% to 0. 2%, more preferably from 0.005% to 0. 1% pure enzyme by weight of the composition.

If present in the detergent compositions of the present invention. the lipolytic enzyme component is generally present at levels of from 0. 00005% to 2% of active enzyme by weight of the detergent composition, preferably 0.001% to 1 % boy weight, most preferably from 0.0002% to 0.05% by weight active enzyme in the detergent composition.

Suitable lipolytic enzymes for use in the present invention include those produced by micro-organisms of the Pseudomonas group. such as Pseudomonas stutzeri ATCC 19. 154, as disclosed in British Patent 1, 372, 034. Suitable lipases include those which show a positive immunological cross-section with the antibody of the lipase produced by the microorganism Pseudomonas Hisorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd.. Nagoya, Japan, under the trade name Lipase P"Amano,"hereinafter referred to as"Amano-P."Other suitable commercial lipases include Amano-CES. lipases ex Chromobacter viscosum. e. g. C'hromobacter viscosum var. Iipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U. S. Biochemical Corp..

U. S. A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.

Especially suitable lipases are lipases such as MI LipaseR and LipomaxR (Gist Brocades) and LipolaseR and Lipolase UftraCNovo) which have found to be very effective when used in combination with the compositions of the present invention.

Also suitable are the lipolytic enzymes described in EP 258 068. WO 92 05249 and WO 95. 2261 by Novo Nordisk and in WO 94,'0 3578, WO 95/35381 and WO 96/00292 bv Unilever.

Also suitable are cutinases [EC 3. 1. 1. 501. which can be considered as a special kind of lipase, nameh Iipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.

(Genencor): WO 90/09446 (Plant Genetic Svstem) and WO 94/14963 and WO 94'14964 (Unilever). The LIPOLASE enzyme derived from Humicota ianuginosa and commercially available from Novo (see also EPO 341,947) is a preferred lipase for use in the present invention.

Another preferred lipase for use in the present invention is D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa. Most preferably the Humicola lanuginosa strain DSM 4106 is used.

By D96L lipolytic enzyme variant is meant the lipase variant as described in patent application WO 92/05249 in which the native lipase ex Humicola lanuginosa has the aspartic acid (D) residue at position 96 changed to Leucine (L). Accordina to this nomenclature said substitution of aspartic acid to Leucine in position 96 is shown as D96L. To determine the activity of the enzyme D96L the standard LU assay may be used (Analytical method, internal Novo Nordisk number AF 95/6-GB 1991.02.07). A substrate for D96L was prepared by emulsifying glycerine tributvrate (Merck) usins gum-arabic as emulsifier. Lipase activity is assayed at pH 7 using pH stat. method.

The compositions may also contain one or a mixture of more than one amylase enzyme (&alpha; and/or ss). WO94/02597, Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases. See also W095/I0603. Novo Nordisk A'S. published April 20. 1995. Other amylases known for use in cleaning compositions include both a-and p-amytases.a-AmyIases are known in the art and include those disclosed in US Pat. no. 5. 003. 257 : EP 252. 666 : % k7O, 91 00353 ; FR 2. 676. 456 : EP 285. 123 : EP 525. 610: EP 368,341 : and British Patent specification no. 1. 296. 839 (Novo). Other suitable amylases are stability- enhanced amylases described in W094,'l published August 18, 1994 and W096,'05295. Genencor. published February 22. 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S. disclosed in WO 95/10603, published April 95. Also suitable are amylases described in EP 277 216, WO95/26397 and WO96/23873 (all by Novo Nordisk).

Examples of commercial a-amylases products are Purafect Ox Am# from Genencor and Termamyl Ban. FungamvlC and Duramyl R. all available from Novo Nordisk AS Denmark. W095/26397 describes other suitable amylases : a-amylases characterised by having a specific activitn at least 25% higher than the specific activity of Termamyl# at a temperature range of25 C to 55 C and at a pH value in the range of 8 to 10, measured by the Phadebas a-amylaseactivityassay. Suitable are variants of the above enzymes, described in WO96/23873 (Novo Nordisk). Other preferred amylolytic enzymes with improved properties with respect to the active level and the combination of thennostability and a higher activity level are described in W095/35382.

The amylolytic enzymes if present are generallv incorporated in the compositions at a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%. more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition.

The compositions of the invention may additionally incorporate one or more cellulase enzymes. Suitable cellulases include both bacterial or fungal cellulases.

Preferably, they will have a pH optimum of between 5 and 12 and an activity above 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U. S. Patent 4. 435. 307. Barbesgoard et al. J61078384 and W096/02653 which disclose fungal cellulases produced respectively from Humicola insolens, Trichoderma. Thielavia and Sporotrichum. EP 739 982 describes cellulases isolated from novel Baciilus species. Suitable cellulases are also disclosed in GB-A-'. 075.028; GB-A-2,095.275: DE-OS-2.247. 832 and WO95/26398.

Examples of such cellulases are cellulases produced by a strain of Humicola insoiens (Humicola grisea var. thermoidea). particularly the Humicola strain DSM 1800.

Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about sOItDa~ an isoelectric point of 5.5 and containing 415 amino acids: and a 43kD endoglucanase derived from Humicola insolens, DSM 1800. exhibitina cellulase activitv : a preferred endogiucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91'17243. Also suitable cellulases are the EGIII cellulases from Trichoderma fongibrachiatum described in W094121801, Genencor. published September 29, ! 994. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879. 2. filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A,'S) are especially useful. See also WO91/17244 and WO91/21801. Other suitable cellulases for fabric care and/or cleaning properties are described in WO96/34092, WO96/17994 and W095/'2471.

Peroxidase enzymes may also be incorporated into the compositions herein.

Peroxidasis are used in combination with oxygen sources, e. g. percarbonate. perborate. persulfate, hydrogen peroxide, 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. Peroxidase enzymes are known in the art. and include, for example, horseradish peroxidase. ligninase and haloperoxidase such as chloro-and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed. for example. in PCT International Application WO 89'099813. W089/09813 and in European Patent application EP No.

91202882. 6. filed on November 6. i991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme Preferred enhancers are substituted phenthiazine and phenoxasine 10 Phenothiazinepropionicacid (PPT). 10-ethylphenothiazine-4-carboxylic acid (EPC).

10-phenoxazinepropionic acid (POP) and i0-methylphenoxazine (described in NS'O 94 12621) and substituted syringates (C3-C5 substituted alkyi syringates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.

Said cellulases and/or peroxidases. if present. are normally incorporated in the composition at levels from 0. 0001% ío'0A0 of active enzyme by weight of the detergent composition.

Said additional enzymes. when present. are normally incorporated in the composition at levels from 0. 0001% to 2% of active enzyme by weight of the detergent composition. The additional enzymes can be added as separate single ingredients (prills. Qranulates, stabilized liquids, etc. containing one enzyme) or as mixtures of two or more enzymes (e. g. cogranulates) Additional organic polymeric compound Additional organic polymeric compounds, not present in the photo-bleaching agent or integreted with the photo-bleaching component herein. may be present in the compositions herein. By organic polymeric compound is meant any polymeric organic compound commonly used as dispersants, anti-redeposition or soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.

Such an organic polymeric compound is generally incorporated in the compositions at a level of from 0. 1 % to 30%. preferably from 0.5% to 15%. most preferably from 1 % to 10% by weight of the compositions.

Suitable polymers are disclosed in GB-A-1, D96. 756. Examples of such salts are polyacrylic acid or polvacrylates of MWt 1000-5000 and their copolymers with maleic anhvdride. such copolymers having a molecular weight of from 2000 to 100. 000. especially 40. 000 to 80, 000. Polymaleates or polvmaleic acid polymers and salts thereof are also suitable examples.

Polyamino compounds useful herein include those derived from aspartic acid including polyaspartic acid and such as those disclosed in EP-A-30D'8X. EP-A- 305283 and EP-A-351629.

Terpolymers containing monomer units selected from maleic acid, acrylic acid. aspartic acid and vinyl alcohol or acetate, particularly those having an average molecular weight of from 1, 000 to 30, 000. preferably 3. 000 to 10, 000, are also suitable for incorporation into the compositions of the present invention.

Other organic polymeric compounds suitable for incorporation in the detergent compositions of the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose and hydroxyethylcellulose.

Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000 to 10000, more particularly 2000 to 8000 and most preferably about 4000.

Cationic soil removal/anti-redeposition compounds The composition herein may comprise water-soluble cationic ethoxylated amine compounds with particulate soil clay-soil removal and or anti-redeposition properties. These cationic compounds are described in more detail in EP-B-11196 > .

US 4659802 and L'S 4664848. Particularly preferred of these cationic compounds are ethoxylated cationic monoamines. diamines or triamines.

These compounds where present in the composition. are generallv present in an amount of from 0.01 to 50% by weight, preferably 0.05 to 10% by weight.

Suds suppressing svstem It can be preferred that the cleaning composition require low-sudsing. and that thus incorporation of suds suppressant for foam control are desirable. They are preferably present in amounts no greater than 2. 5% and most preferably in amounts no 2relater than 1.5% or even no greater than 0.5% by weight of the composition.

Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including. for example silicone antifoam compounds and 2-alkenyl alcanol antifoam compounds.

By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition. particularly in the presence of agitation of that solution.

Polvmeric dye transfer inhibiting agents The compositions herein may also comprise from 0.01% to 10 %. preferably from 0.05% to 0.5% by weight of additional polymeric compounds, not comprised in the photo-bleaching agnet of the compositions of the invention, which act as dye transfer inhibiting agents.

The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers. copolymers of N-vinylpyrrolidone and N-vinylimidazole. polyvinylpyrrolidone polymers or combinations thereot : whereby these be cross-linked polymers.

Optical brightener The compositions herein may optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.

Hydrophilic optical brighteners usefu ! herein include those having the structural formula :

wherein RI is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl ; R2 is selected from N-2-bis-hydroxyethyl. N-2-hydroxyethvl-N-methylamino, morphilino. chloro and amino; and M is a salt-forming cation such as sodium or When in the above formula, RI is anilino, R2 is N-2-bis-hydroxvethyl and M is a cation such as sodium, the brightener is 4,4',-bis [ (4-anilino-6- (N-2-bis- hydroxyethyl)-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-LAPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula. RI is anilino. R2 is N-2-hydroxsethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4. 4'-bis[(4-anilino-6-(N-2hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2[-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GS by Ciba-Geioy Corporation.

When in the above formula, R1 is anilino, R2 is morphilino and NI 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 tradename Tinopal AMS-GX by Ciba Geigy Corporation.

Polvmeric Soil Release Agent Known polymeric soil release agents. hereinafter"SRA". can optionally be employed in the present compositions. If utilized, SRA's will generally comprise from 0. 01% to 10. 0%, typically from 0.1% to 5%. preferably from 0. /0 to 3. 0 , by weight, of the compositions.

Suitable SRA's include a sulfonated product of a substantiallx linear ester olioomer comprised of an oligomeric or polymeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone. for example as described in U. S. 4. 968.451.

November 6,1990 to J. J. Scheibel and E. P. Gosselink. Other SRA's include the nonionic end-capped 1, 2-propytene/polyoxyethylene terephthalate polyesters of U. S. 4, 711,730, December 8,1987 to Gosselink et al., for example those produced by transesterification/oligomerization of poly (ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly-and fully-anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26,1988 to Gosselink ; the nonionic-capped block polyester oligomeric compounds of U. S.

4, 702, 857, October 27,1987 to Gosselink; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U. S. 4,877,896, October 31, 1989 to Maldonado.

Gosselink et al.

SRA's also include: simple copolymeric blocks ot ethylene terephthalate or propylene terephthalate with potyethyiene oxide or potypropytene oxide terephthalate. see U. S. 3. 959. 230 to Havs, May 25, 1976 and U.S. 3,893, 929 to Basadur, July 8, 1975; cellulosic derivatives such as the hxdroxsether cellulosic potymers available as METHOCEL from Do : the C1-C4 alkyl celluloses and C 4 hydroxyalkyl celluloses. see U. S. 4. 000. 093. December 28. 1976 to Nicol. et al. ; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydrogtucose unit from about 1. 6 to about 2. 3 and a solution viscosits of from about 80 to about ! 20 centipoise measured at 20 C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kaaaku Kogyo KK.

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

Near neutral wash pH detergent formulation While the cleaning compositions are operative within a wide range of wash pHs (e. g. from about 5 to about 12), they are particularly suitable when formulated to provide a near neutral wash pH. i. e. an initial pH of from about 7.0 to about 10. 5 at a concentration of from about 0. 1 to about 2% by weight in water at 20 C.'ear neutral wash pH formulations are better for enzyme stability and for preventing stains from setting. In such formulations, the wash pH is preferably from about 7.0 to about 10.5. more preferably from about 8.0 to about 10.5, most preferably from 8.0 to 9.0.

Preferred near neutral wash pH detergent formulations are disclosed to European Patent Application 83. 200688.6. filed Mav 16.1983, J. H. M. Wertz and P. C. E.

Goffinet.

Highly preferred cleaning compositions of this type also preferably contain from about 2 to about 10% by weight of citric acid and minor amounts (e. less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes. enzymes, enzyme stabilizing agents, polyacids, suds regulants. opacifiers. anti-oxidants, bactericides, dyes, perfumes and brighteners, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein incorporated by reference).

Form of the compositions The compositions in accordance with the invention and the cleaning compositions herein can take a variety of physical forms including solid forms such as granular. tablet. flake. pastille and bar and liquid forms. Liquids may be aqueous or nonaqueous and may be in the form of a gel. however. preferred are solid forms.

The cleaning compositions may be pre-treatment compositions or may be conventional washing detergents. It may be preferred that the cleaning compositions are particularly granular detergent compositions, preferably the so-called concentrated, adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.

Such granular detergent compositions or components thereof in accordance with the present invention can be made via a variety of methods. including spray-drying, drymixing. extrusion. agglomerating and granulation.

The bleaching compositions herein can be added to the other components of the cleaning compositions as a dr-add. mixed with the other component and agglomerated. extruded and, spray-dried.

The bleaching agent and the photo-bleaching agent may be premixed prior to addition to the other ingredients of the cteanins composition or the bleaching composition: the bieaching composition mav also be pre-mixed with one or more of the additional ingredients of the cleaning composition. prior to further addition of the remaining ingredients.

The compositions can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach.

It may be preterred that the mean particle size of the components of granular compositions in accordance with the invention is such that no more than 15% of the particles are greater than 1.8mm in diameter and not more than 15% of the particles are less than 0.25mm in diameter. However. it mas be preferred that the composition comprises particles of mean particle size at least 0.8 mm. more preferably at least 1. 0 mm and most preferably from 1.0. or 1. 5 to 2. 5 mm. Most preferably at least 95% of the particles will have such a mean particle size. Such particles are preferably prepared by an extrusion process.

The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typicallx 5 fractions) on a series of sieves, preferably Tvler 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.

Compacted solid detergents mav be manufactured using any suitable compacting process. such as tabletting, briquetting or extrusion. preferably tabletting.

Laundrv washing method NXlachine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundrs detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from 10g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres. as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods. Dosage is dependent upon the particular conditions such as water hardness and degree of soiling of the soiled iaundrx.

The detergent composition ma, be dispensed for example. from the drawer dispenser of a washing machine or may be sprinkled over the soiled laundry placed in the machine.

In one use aspect a dispensing device is employed in the washing method. Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle. Especiallv preferred dispensing devices for use with the composition of the invention have been described in the following patents; GB-B-. 157. 717. GB-B-2. 157. 718. EP-A 0201376, EP-A-0288345 and EP-A-0288346. An article by J. Bland published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly know as the"granulette"Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. W094/11t62.

Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. Alternatively, the dispensing device may be a Hexible container, such as a bag or pouch. The bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents. such as is disclosed in European published Patent Application No. 0018678. Alternatively it may be termed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501, 0011502. and 0011968. A convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.

*Abbreviations used in Examples In the detergent compositions. the abbreviated component identifications have the following meanings : LAS Sodium linear C l l 13 alkyl benzene sulfonate TAS Sodium tallow alkyl sulfate CxvAS Sodium C I x-C I y alkyl sulfate C46SAS Sodium C 14-C 16 secondary (2,3) alkyl sulfate CxvEzS Sodium C I X-C I \ alkyl sulfate condensed with z moles of ethylene oxide CxyEz C1x-C1 y predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide QAS R2N+(CH3)2(C2H4) with R2 = C12-C14 QAS I Rr. N+ (CH3) 2 (C2H40H) with R) = C8-C 11 SADS Sodium C14-C22 alkyl disulfate of formula 2- (R). C, H-.-1,4-(SO4-)2 where R = C10-C18 SADE2S Sodium C14-C22 alkyl disulfate of formula 2- (R). C, H-.-1. 4-(SO4-)2 where R = C16-C18. condensed with z moles of ethylene oxide MES x-sulpho methylester of C18 fatty acid APA Cg-Clo amido propyl dimethyi amine Soap Sodium linear alky) carboxylate derived from an 80/20 mixture of tallow and coconut fatty acids STS Sodium toluene sulphonate EFAA I C 12-C 14 fatt-,,-acid amide alcohol. condensed with an average of 5 moles ofethy ! ene oxide EFAA 2 C12-C14 fatty acid amide alcohol. condensed with an average of 7 moles of ethylene oxide TPKFA C} 6-C 1 g topped whole cut fatty acids STPP Anhydrous sodium tripolyphosphate TSPP Tetrasodium pyrophosphate Zeolite A Hydrate sodium aluminosilicate of formula Nal (AlO2SiO2) 12.27H2O having a primary particle size in the range from 0. 1 to 10 micrometers (weight expressed on an anhydrous basis) tsaSKS-6 Crystalline layered silicate of formula 5-Na ? S1205 Citric acid Anhydrous citric acid Borate Sodium borate Carbonate Anydrous sodium carbonate with a particle size between 200pm and 900pm Bicarbonate Anhvdrous sodium bicarbonate with a particle size distribution between 400um and 1200um Silicate Amorphous sodium silicate (SiO2 : Na2O ='. 0: 1) Sulfate Anhydrous sodium sulfate Mg sulfate Anhydrous magnesium sulfate Citrate Tri-sodium citrate dihvdrate of activity 86. 4% with a particle size distribution between 4 25 m and 850 m MA AA Copo ! ymer of ! : 4 maleic'acrylic acid. average molecular weight about 70. 000 MAAA (I) Copolymer of 4 : 6 maieic acryiic acid. average molecular weight about 10. 000 AA Sodium polyacrylate polymer of average molecular weight 4. 500 CNIC Sodium carboxymethyt cellulose Cellulose ether Methvl cellulose ether with a degree of polymerization of 650 available from Shin Etsu Chemicals Protease Proteolytic enzyme, having 3.3% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase Protease I Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591, sold bv Genencor Int. Inc.

Alcalase Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO Industries A/S Cellulase Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme Amylase Amylolytic enzyme, having 1. 6% by weight of active enzyme, sold by \OVO Industries A/S under the tradename Termamvl 120T Amylase 11 Amylolvtic enzyme. as disclosed in PCT/US9703635 Lipase Lipotytic enzyme, having 2. 0% bv weight of active enzyme. sold by \OVO Industries A'S under the tradename Lipolase Lipase (1) Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase L'ltra Endolase Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries AS PB4 Sodium perborate leirahydrateof nominal formula NaBO. HO HO PB I Anhydrous sodium perborate bleach of nominal formula \aBO. H2O2 Percarbonate Sodium percarbonate of nominal formula 2Na2CO3.3H2O2 DOBS Decanovl oxvbenzene sulfonate in the form of the sodium salt NOBS Xonanoyloxybenzene sutfonate in the form of the sodium salt NACA-OBS (6-nonamidocaproyl) oxybenzene sulfonate TAED Tetraacetvlethylenediamine DTPA Diethylene triamine pentaacetic acid DTPMP Diethylene triamine penta (methylene phosphonate). marketed by Monsanto under the Tradename Dequest 2060 EDDS Ethylenediamine-N. N'-disuccinic acid, (S. S) isomer in the form of its sodium salt.

Photoactivated Sulfonated zinc phthlocn-anine encapsulated in bleach (1) dextrin soluble polymer Photoactivated Suifonated aiumino phthiocyanine encapsutated in bleach (2) dextrin soluble polvmer Brithtener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1,3,5 triazin-2-yl)amino) stilbene-2:2'-disulfonate HEDP 1. 1-hydroxyethane diphosphonic acid PEGx Po)yethytenegiycot.wilh a molecular weight of x (ypically 4. 000) PEO Polvethylene oxide, with an average molecular weight of 50. 000 TEPAE Tetraethylenepentaamine ethoxylate PVI Potyviny ! imidosote. with an average molecular weight of 20. 000 PVP Polyvinylpyrolidone polymer, with an average molecular weight of 60. 000 PVNO Polvvinylpyridine N-oxide polymer. with an average molecular weight of 50. 000 PVPVI Copolymer of polyvinylpyrolidone and vinvlimidazole. with an average molecular weight of 20. 000 QEA bis ((C2H5O)(C2H4O) n) (CH3)-N±C6H12-N+ (CH3) bis ((C2H5O)-(C2H4O))n. wherein n = from 20 to 30 SRP 1 Anionically end capped poly esters SRP 2 Diethoxylated poly (1. 2 propylene terephtalate) short block polymer PEI Polvethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen Silicone antifoam Polydimethylsiloxane foam controller with siloxane oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10 : 1 to 100: 1 Opacifier Water based monostyrene latex mixture. sold by BASF Aktiengesellschaft under the tradename Lytron 621 Wax Paraffin wax Particle 1 agglomerate containing. by weight 20% EFAA 1, 20% C,, 5AS, 30% zeolite A, 20% sodium carbonate and 10% citric acid (anhydrous) Particle 2 agglomerate containing, by weight 20% EFAA 2, 40% LAS, 40% SKS-6 Example 1

A B C D E F Agglomerate EFAA 1 or 2 5.0 2.0 10.0 - - 7.0 LAS 7.0 5.0 10. 0 14.0 2.0 @ C245AS 3.0 2. 0 2. 0 2.0 2.5 2.5 C45AE3S 1. 0 1. 0 1. 0 - - 0.5 C28AS 2.0 1.0 2.0 1.0 0.5 3.5 Silicate 0. 2 - 1.0 - 0.3 0.8 Sodium carbonate 5. 0 5. 0 6-0 2. 0 10. 0 MBAS - 2.0 - - 5.0 8.0 SKS-6 0.7 4.0 - 0.5 1.0 2.0 HEDPEDDS0.2 0.4 - - 0.2 0.7 Zeolite. ! 10. 0 6. 0 6.0 12.0 9.0 10.0 @ CMC 0.5 0. 8 0. l Agglomerate , ! TAED 5.0 3.0 - 2.0 4.0 3.0 MA AA 1.0 0.5 - 0.5 - 1.0 CMC - 0.5 - 0.5 - Agglomerate Zeolite A 2.0 1.0 - 1.0 - 2.0 Sud suppressor 0.5 0.5 0.3 0.2 0.1 0.2 MA/AA 0. 5 - - 0.2 - 0.2 Aglomerate QAS 1.0 0.5 1.0 - 1.0 EFAA 1 - - - - 3.0 Zeolite 2.0 1.0 - - 2.0

Carbonate 0. 5 1.0 MA/AA - 0.1 - - - Drv add .

Partricle 1 - - - 10 10.0 5.0 QEA 1. 0 0. 5 - - 1.0 HEDP/DTPA/EDDS 0. 3 0.5 - 0.5 0.5 0. 5 MA/AA 1.0 2.0 3.0 - 2.0 2.0 Mg sulphate 0. 1 0.2 - - - 0.3 Brightener 0.1 - 0.2 0.2 - 0.2 Zeolite 1.0 2.0 3.0 4.0 5.0 2.0 SKS-6/silicate 10.0 6.- 5.0 10.0 10.0 12.0 i Enzymes 0.5 0.8 0.3 1.2 1.2 1. 0 CM 0.2 - 0.3 - 0. 5 0.5 . I Soap0.5--0.51.0 NACA OBS - 3.0 - - - 3.0 Photobleach 0. 1 0.1 - - 0.2 0.2 I Speckles 0.5 0.2 0.7 - 0.3 Carbonate 6.0 5.0 2.0 - 8. 7. 0 I Sodium chloride 0. 2 - 0.5 - 0.5 i Sodium sulphate 2.0 3. 0-'8. 0-3. 0 Percarbonate 18.0 10.0 - 22.0 20.0 10.0 Citric acid 1.0 0.5 2.0 3.0 2.0 i Spray on EFAA - 2.0 - - 1.0 AE5 - - - - 0.5 Perfume 0.2 0.1 0.5 0.2 0.2 0.2 Brightener 0.1 0.2 0.1 0.1 0.1 0.1 Example 2

G l K L Spray dried powder Base: LAS 7.0 6.0 3.0 - 4.0 MBAS - - - 5.0 - Tallowalkyl sulphate 1.0 - 1.0 1.0 - 1.0 C245AS - - 0.5 - - 1.0 Sodiumsulphate 3.0 5.0 3.0 2.0 - 3.0 C24AE35 - 0.5 - 0.5 - 0.7 : EFAA 1 or 2 5.0 7.0 - - - AdditivesAdditives: Sodiumcarbonate 3.0 6.0 1.0 3.0 5.0 3.0 Sodium sulphate-2. 0 ZeoliteA 16.0 10.0 5.0 10.0 6.0 MA/AA 1.0 - 1.0 0.5 1.0 Via sulphate I0. 1I0. 1I0. 1 Brightener 0.2 0.1 - - 0.3 0.5 I,, Chelant 0.5 0.5 - 0.3 0.2 0.4 i 1 Water 0.2 0.1 0.1 0.050. 050. 3 i Agglomerate EFAA 1 5.0 7.0 - - - LAS - 3.0 5.0 2.0 - 5.0 C45AS - 2.0 3.0 2.0 - Carbonate - 5.0 7.0 5.0 - Sulphate - 3.0 - 2.0 - 3.0 ZeoliteA - 4.0 8.0 3.0 - 9.0 Dry add 1. 0. 0 1. 0

Sudsuppressor 0. 5 0. 5 0.51. 0 0. 2 0. 3 Percarbonate/perborate 20. 0 14. 0-22. 0 18.0 10.0 TAED 4. 0 3.0 - - 2.0 3.5 NACA OBS - 3.0 - 4.2 2.5 Zeolite A 6. 0 3.0 5.0 - 7.0 12. 0 SKS-6/silicate 8.0 12. 0 5. 0 9. 0-8.0 Citric acidlcitrate 2. 0 1.0 3.0 - - 2.0 Speckle (carbonate) 0.3 0.5 0.4 - - 0.5 Sodium carbonate 5.0 - 8.0 10.0 - 6.0 ..

Sodium sulphate 10.0 5.0 - 3.0 - 14.0 CMC 0.5 0.5 0.2 - - 0.3 Soap 0.5 0.5 - - 0.5 Enzymes1.0 1.5 1.0 1.0 1.0 1.0 SRP 0.1 0.2 0.3 - 0.3 HEDP ! EDDS, DTPA 0. 5 0. 5 0 3 Spray-on EFAA - - 1.5 2.0 4.0 2.5 Perfume 0.3 0.3 0.2 0.5 0.2 0.3 Example 3

m N O P Q R Blownpowder LAS 23. 0 8 0 7.0 9.0 7.0 7.0 TAS----1. 0- C45AS 6.0 6.0 5. 0 8.0 - EFAA 2.0 - 5.0 - - 3. 0 C45AE35 - 1.0 1.0 1.0 - 2. 0 . |,.

1 i i C45E35 - - - - 2.0 4.0 ZeoliteA 10.0 18.0 14.0 12.0 10.0 14.0 MA/AA - 0.5 - - - 2.0 MA/AA (1) 7.0 - - - - AA - 3.0 3.0 2.0 3.0 3. 0 Sulfate 5.06.3 6.3 14. 3 11. 0 15. 0 19. 3 Silicate 10.0 1.0 1.0 1.0 1.0 1.0 Carbonate 15.0 20.0 10.0 20.7 8. 0 6. 0 PEG 4000 0.4 1.5 1.5 1.0 1.0 1.0 :....

DTPA-0. 9 0. 5 0.

Brightener2 0. 3 0.2 0.3 - 0.1 0.3 Sprayon EFAA 1 or 2 3.0 2.0 1.0 - - C23E9 - - 1.5 - - Perfume'0. 3 0. 3 0. 3 2. 0 0. 30. 3 Agglomerates C45AS - 5.0 5.0 2.0 - 5.0 LAS - 2.0 2.0 - - 2.0 ZeoliteA - 7.5 7.5 8.0 - 7.5

Carbonate-4. 0 4.0 5. 0-4.0 PEG 4000 0. 5 0.0.5 Misc(water etc) - 2.0 2.0 2.0 - 2.0 Particle I or 2 - 5.0 - 10.0 5.0 Dry additives QAS(I) - - - - 1.0 Citricacid - - - - 2.0 PB4 - - - - 12.0 1.0 PB1 - 4.0 3.0 - - Percarbonate 4.0 - - 2.0 - 10.0 I. I Carbonate-4. 0 4. 0 NOBS 4. 0 6. 0 0. 6 Methyl cellulose SKS-6 8.0 - - - - STS-1. 0- i Cumene sulfonic acid-1. 0-2. 0 , I Lipase0.2 - 0.2 - 0.2 0.4 Cellulase 0.2 0.2 0.2 0.3 0.2 0.2 Amylase 0. 2-0. 1 0. 2- Protease 0.5 0.5 0.5 0.3 0.5 0.5 PVPVI - - - - 0.5 0.1 PVP - - - - 0.5 PVNO - - 0.5 0.3 - QEA - - - - 1.0 i SRP1 0.2 0.5 0.3 - 0.2 Silicone antifoam 0.2 0.4 0.2 0.4 0.1 Mg sulfate - - 0.2 - 0.2 Silica 0.2 0. 2 0.2 - 0.2 Misc/minors to 100% Example 4 The following nil bleach-containing detergent formulations of particular use in the washing of coloured clothing, according to the present invention were prepared:

S T U BlownPowder Zeolite A 15.0 15.0 Sulfate 0.0 5.0 I LAS 3.0 3.0 DTPMP 0.4 0.5 CMC 0.4 0.4 MA/AA4.04.0 Agglomerates C45AS - - 11 LAS 6.0 5.0 TAS 3.0 2.0 2. 0 EFAX A 1 5.0 EFAA 1 5.0 - Silicate 4.0 4.0 Zeolite A 10.0 15.0 13.0 CMC - - 0.5 MA/AA - - 2.0 I Carbonate 9. 0 7. 0 7. 0 Spray On Perfume 0.3 0.3 0.5 EFAA 2 4.0 3.0 C25E3 2.0 2.0 2.0 Dry additives Particle I or 2 10. 0

MA/AA - - 3.0 NaKS-6 - - 12.0 Citrate 10. 0-8. 0 Bicarbonate 7.0 3.0 5.0 Carbonate 8.0 5.0 7.0 PVPVI/PVNO 0.5 0.5 0.5 Alcalase 0.5 0.3 0.9 Lipase 0. 4 0. 4 I Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0. 6 ! Silicone antifoam 5.0 5.0 5.0 Dry additives Sulfate 0.0 9.0 0.0 Misc/minors to 100% 100.0 100. 0 100. 0 Density (g/litre) 700 700 700 Example5 The following detergent compositions. according to the present invention were prepared :

V W X Blown Powder Zeolite A 15.0 15.0 15.0 Sulfate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 QAS - 1.5 1.5 DTPMP 0.4 0.2 0.4 EDDS - 0.4 0.2 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray On Perfume 0.3 0.3 0.3 EFAA 1 1.0 3.0 2.0 Dry additives Particle 1 or 2 5.0 - Citrate 5.0 - 2.0 Bicarbonate - 3.0 Carboante 8.0 15.0 10.0

TAED 6. 0 2. 0 5. 0 PBI 14. 0 7. 0 10. 0 PEO - - 0.2 Bentonite cla-10. 0 Protease 1. 0 1. 0 1. 0 Lipase 0. 4 0. 4 0. 4 Amylase 0. 6 0. 6 0. 6 Cellulase 0. 6 0. 6 0. 6 Siliconeantifoam 5.0 5.0 5.0 , Dry additives Sodium sulfate 0.0 3.0 0.0 Misc/minors to 100% 100.0 100.0 100.0 Density (g/litre) 850 850 850 Example 6 The following formulations are examples of compositions in accordance with the invention. which may be in the form of granules or in the form of a tablet.

Y Z AA BB CC C45AS/TAS 8.0 5.0 3.0 3.0 3.0 LAS 8.0 - 8.0 - 7.0 C25AE3S 0.5 2.0 1.0 - EFAA 1 5.0 10.0 4.0 - 2. 0 C25AE5/AE3 - - - 2.0 2.0 QAS 1. 1.0 Zeolite A 20. 0 10.0 10.0 - SKS-6 (drv add)--2. 0 MA,, A/AA 2.0 2.0 2.0 particle 1 or 2 - - - 15 - - - - 4. 0 ~ 1.

Citrate - 2.0 - - Citric acid 2.0 - 1.5 2.0 DT DTP.A 0.2 0.2 - - EDDS - - 0.5 0.1 HEDP - - 0.2 0.1 PBI 3.0 5.0 10.0 - 4. 0 Percarbonate - - - 18.0 NOBS 3.0 4.0 - - 4.0 NACAOBS - - 2.0 - TAED--2. 0 5. 0 Caronate 15.0 18.0 8.0 15.0 15.0 Sulphate 5.0 12.0 2.0 17.0 3.0

Silicate 1. 0 8. 0 Enzyme 0.3 0.3 1. 0 1. 0 0. 2 Minors (Brightener/SRP1/ 0.5 0.5 0.5 0.5 0.5 CMC/Photobleah/ MgSO4/ PVPVI/Suds suppressor/ PEG) Perfume 0.20.3 0.5 0.2 0.1 Example 7 The following laundrx bar detergent compositions were prepared in accord with the invention (levels are given in parts per weight).

DD EE FF GG HH II JJ KK LAS - - 19.0 15.0 21.0 6.75 8.8 C28AS 30. 5 - - - 15.75 11.2 l Sodium laurate 2.5 9.0 - - - - - Zeolite A 2.0 1.25 - - - 1.25 1.25 1.25 Carbonate'0 0, 3. 0 13. 0 8. 0 10. 0 15.0 15.0 10.0 Calcium 27.5 39.0 35.0 - - 40.0 - 40.0 carbonate Sulfate 5.0 5.0 3.0 5.0 3.0 - - 5.0 STPP 5.0 15.0 10.0 - - 7.0 5.0 10.0 Bentonite clay - 10.0 - - 5.0 - - DTPMP 0. 7 0. 6-0. 6 0. 7 0.7 0.7 C\tC 1. 0 1. 0 1.0 1.0 - - 1.0 Talc 10. 0 15. 0 10. 0 4 Silicate - - 4.0 5.0 3.0 - - PVNO 0.02 0.02 - 0.01 - 0.02 - MA/AA 0.4 1.0 - - 0.2 .4 0.5 0.4 SRP1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Protease-0. 12 - 0.08 0.08 - - 0.1 Lipase - 0.1 - 0.1 - - - Amylase - - 0.8 - - - 0.1 Cellulase - 0.15 - - 0.15 0.1 - PEO - 0.2 - 0.2 0.3 - - 0.3 Perfume 1.0 0.5 0.3 0.5 0.4 - - 0.4

Mg sulfate 3. 0. 3 Brightener 0.15 0.10 0. 15 - - - - 0.1 Photoactivated - 15.0 15.0 15.0 15.0 - - 15.0 bleach(ppm) EFAA 1. 0 3. 0 0 0 1 0 8. 0 2.0 10.0 3.0

Claims (10)

1. Claims 1.. A detergent composition comprising a particle containing a) of from 0.1 to 50% by weight of the particle of a nonionic alkoxylated fatty acid amide of the formula :

   wherein R, is a C12-C18 alkyl or alkenyl group. R is a C2-C4 alkylene group.

   R ; is a hydrogen or a C,-C, alkyl group. R, is a C1-C4 alkyl group or hydrogen and n is a number from 3 to 12 : and b) an anionic surfactant. whereby a) and b) are intimately mixed, provided that the level of nonionic alkoxylated alcohol surfactant is from 0% to 20% by weight of the particle. preferably 0% by weight.
2. 2. A detergent composition comprising a particle containing a) a spray-on component containing a nonionic alkoxylated fattv acid amide at a level of 0. 1 zo to 50% by weight of the particle. being of the formula :

   wherein R, is a C,,-C, S alkyl or alkenyl group. R, is a C,-C, alkylene group, Roi ils a hydrogen or a C,-C4 alkyl group. R4 is a C,-C, alkyl group or hydrogen and n is a number from
3. 3 to 12; b) a particle core comprising an anionic surfactait. whereby the spray-on component is sprayed onto the particle core. provided that the level of nonionic alkoxylated alcohol surfactant when present. is from 0% to 20% by weight of the particle. preferably 0% by weight.

   A detergent composition according to claim I or 2, whereby the particle comprises an anionic surfactant at a leve ! of from 3% to 50% by weight of the particle.
4. 4 detergent composition according to any preceding claim, wherein the particle comprises an effervescence source, preferably comprising an acid and an alkali source, capable of producing a gas upon contact with water. preferably an organic carboxylic acid and a carbonate source.
5. 5. A detergent composition according to any preceding claim being substantially free of nonionic polvalkoxylated alcohol surfactants.
6. 6. A detergent composition according to any preceding claim wherein the alkoxylated amide surfactant is a polyethoxyalted C12-C18 fatty acid amide with an average ethoxylation degree of 5 to 9. preferably 5.
7. 7. A detergent composition according to any preceding claims, comprising a dye. brightener, enzyme or perfume of mixture thereof.
8. S. A detergent composition according to any preceding claim wherein the particle is present at a level of from 1% to 50% by weight, preferably from -5% to 35% by weight of the composition.
9. 9. A composition according to anv preceding claim in the form of granules, pastilles, extrudates or tablets.
10. 10. L'se of a nonionic alkoxylated fatty acid amide surfactant in detergent particles comprising an anionic surfactant for improvement of the dispensing of a detergent composition comprising the particles.