CA2166861A1 - Surfactant system - Google Patents

Abstract

According to one aspect of the present invention there is provided an anionic surfactant system containing: (a) alkyl sulfate surfactant derived from natural sources comprising a mixture of alkyl chain lengths wherein the weight distribution of the alkyl chain lengths is such that less than 20 % by weight of the alkyl chain lengths are C12, from 30 % to 80 % by weight of the alkyl chain lengths are C14, from 30 % to 50 % by weight of the alkyl chain lengths are C16 and less than 10 % by weight of the alkyl chain lengths are C18. Said anionic surfactant system preferably also contains alkyl ethoxysulfate surfactant. Said alkyl ethoxysulfate surfactant is preferably a water soluble C12-C18 alkyl ethoxysulfate salt containing an average of from 1 to 7 ethoxy groups per mole derived from the condensation product of a C12-C18 alcohol wherein said C12-C18 alcohol is most preferably derived from a natural source.

Description

~ 21 66~61 ~URFACTANT ~Y~STF.~

This invention relates to a surf~ct~nt system derived from natural sources for incorporation into detelgellt compositions suitable for use in cleaning processes, especially fabric cleaning and more especially to high density granular d~lergent compositions comprising said surf~ct~nt system.

Granular detergelll compositions cont~ining synthetic detergen~, particularly linear allyl benzene sulfonate salts are well known in the art and are in widespread commercial use. Conventionally the linear alkyl benzene sulfonate salt forms part of a surf~c~nt mixture in association with one or more o~er anionic or nonionic surf~ct~ntc.

Current environmental concern has focussed on the undesirability of deriving detefgent coml)o.lents from non-renewable hydrocarbon sources.
Interest has ther~fole increased in the fonn~ tion of well-pelrolnling deterg~t compositions comprising surf~ct~nt systems derived from natural sources.

An example of an anionic surf~ct~nt which is readily biodegradable and which could replace the alkyl benzene sulfonate component either partially or in toto is alkyl sulfate surf~et~nt Detergelll compositions including alkyl sulfate surfactant derived fromnaliurally occuring fats and oils are known in the art. For example, GB-A-1,399,966, in the name of the Procter & Gamble Company, discloses a de~er~,ent composition cont~inin~ alkyl sulfate surfactant derived from tallow oil, or from eoconut oil.

2 ~ ~ 6 8 ~ I PCT/US94/06943 ~

Natural oils and fats provide feedstock material encompassing a range of alkyl chain lengths. The alkyl chains are predomin~ntly linear, in contrast to the branched nature of feedstock obtained from synthetic sources. For example, tallow fat contains a high proportion (typically about 70%) of C1g alkyl chains. Coconut and palm oil on the other hand contain a high proportion of C12 alkyl chains (typically about 55%) and lesser proportions of C14, C16 and C1g alkyl chain lengths.

The deter~,el,cy performance characteristics of surf~ct~ntc having allyl chains are known to depend on the nature and length of the alkyl chain.
In general, surf~t~nt~ having shorter alkyl chains are more hydrophillic, hence more water soluble, and thus tend to pelrorlll better at lower wash temperatures. Those with longer alkyl chains conversely tend to pelro.l.
well at higher wash t~ elal~lres. The form~ tor of a natural surf~et~nt system is hence faced with the problem of how to formulate a surfactant system which provides good detergellcy over a wide range of wash tem~el~lules derived from feedstock material, which as provided by nature, contains a non-opLill.um distribution of alkyl chain lengths for this purpose.

EP-A-342,917 describes a surf~ct~nt system, derived preferably from natural feedstock material, comprising an anionic surf~ct~nt the major ingredient of which is an alkyl sulfate of mixed alkyl chain length such that at least 10% by weight of the alkyl chains present in the alkyl sulfate are C12 chains and at least 20% by weight of the alkyl chains are C1g chains.

The Applicants have found that a surf~ct~nt system cont~ining allyl sulfate surf~ct~nt of mixed allyl chain length such that the level of C12 and C1g alkyl chain lengths is minimi~e~ and wherein the C14 and C16 alkyl chain lengths form the major part, provides good detergency pelÇollnance over a wide range of temperatures.

The Applicants have also found that when form~ te~l with an alkyl ethoxysulfate cosurf~ct~nt, and preferably a nonionic surf~ct~nt, such a surfactant system provides good detergency in the presence of cationic fabric softener compounds even when the total ~evel of anionic surfactant in the composition is at a low level, namely from 5% to 10% by weight of the eomposition.

According to one aspect of the present invention the~e is provided surf~ct~nt system cont~inin~
(a) alkyl sulfate surfactant derived from natural sources comprising a mixture of alkyl chain lengths wherein the weight distribution of the alkyl chain lengths is such that less than 20% by weight of the alkyl chain lengths are C12, from 30æ to 80% by weight of the alkyl chain lengths are C14~ from 30% to 50% by weight of the alkyl chain lengths are C16 and less than 10% by weight of the alkyl chain lengths are Clg.

Said anionic surfactant system prefelably also contains alkyl ethoxysulfate surf~ nt. Said alkyl ethoxysulfate surf~et~nt is pleferably a water soluble C12-Clg alkyl ethoxysulfate salt cont~inin~ an average of from 1 to 7 ethoxy groups per mole derived from the condensation product of a C12-Clg alcohol wherein said C12-Clg alcohol is most preferably derived from a natural source.

To provide good dissolution characteristics for the alkyl sulfate surfactant and provide robust pelrollllallce in the presence of cationic fabric softener components in the wash it is highly ~leferably that where present in said surf~ct~nt system the alkyl ethoxysulfate surf~ct~nt is most preferably in intinn~t~ admi~ture with the alkyl sulfate surf~et~nt The weight ratio of the alkyl sulfate surfactant to the alkyl ethoxysulfate surf~ct~nr is ~lefefably from 2:1 to 19:1.

Most preferably said surfactant system is essentially free of alkyl benzene sulfonate.
.

The total level of alkyl sulfate and alkyl ethoxysulfate surf~ct~nt in the granular detergellt composition is preferably from 5% to 10% by weight of tlhe composition, more preferably from 6% to 9% by weight of the composition and most preferably from 6.5 % to 8 % by weight of the composition. Said granular detel~ent composition provides good 2~86t WO 95/02390 PCT/US94/06943 ~

d~tergellcy performance even when used in wash solutions where cationic fabric softener components are present. Examples of cationic fabric softener components include the well known ~uaternary ammonium compounds. Cationic fabric softeners are disclosed for example in EP-A-0125,122, and co-pending European Application 91-202881.8 which discloses water-soluble quaternary ammonium compounds.

It is an essential aspect of the invention that the alkyl sulfate surfactant is derived from natural sources. By derived from natural sources it is meant herein that the alkyl chain portion of the surf~ct~nt is derived from naturally occuring fats and oil. Allyl chains derived from such natural oils and fats are typically linear and have alkyl chains with even numbers of carbon atoms, most typically C12, C14, C16 and C1g. The alkyl chains may contain a small proportion of lln~tllrated, e.g.: alkenyl, chains which if desired may be hydrogenated, or "hardened" to minimi these in4,ulily levels. Typically the alkyl sulfate surfactant is produced from alcohols obtained by reduction of the natural oils and fats.
Examples of natural oils and fats include those derived from coconut, babassu, palm kernel, beef tallow, kapok, olive, peanut, ses~me and te~ee~l.

It is also an essential aspect of the present invention that the alkyl sulfate surf~ct~nt comprises a mixture of alkyl chain lengths. It is preferred that the level of C12 and C1g alkyl chain lengths is minimi7~ and that the major proportion of the allyl sulfate surfactant comprises C14 and C16 alkyl chain lengths. More particularly the alkyl sulfate surf~ct~nt comprises such surf~ct~nt with a mixture of alkyl chain lengths wherein the weight distribution of the alkyl chain lengths is such that less than 20%, most preferably less than 15% of the alkyl chains are C12, from 30 % to 80 %, ~refel~bly from 35 % to 70 %, most preferably from 40 % to 60% of the alkyl chains are C14, from 30% to 50%, preferably from 30% to 40%, most pl~ferably from 32% to 38% of the alkyl chains are C16, less than 10%, preferably less than 5%, most preferably less than 3 % of the alkyl chains are C18 Alkyl sulfate surf~et~nt of the desired alkyl chain length distribution is obtained from natural feedstock, mP~ning natural oils or fats, or any WO 95/02390 2 ~ 6 6 ~ ~ ~ PCT/US94/06943 .
s mixtures thereof, or the natural alcohols derived therefrom, by any suitable physical process which allows for the separation of such feedstock into different components with the desired alkyl chain length distributions. Suitable physical processes would include, for example, ~i~till~tion processes. The separation of feedstock ;~aterial into different components of desired composition is often referred to in the industry as "cutting" of the feedstock (into desired "cuts"). The dirrelent components (or cuts) may then be used as such, or blended, as a~ropliate to allow for derivation of the alkyl sulfate surf~ct~nt with the desired alkyl chain length distribution in accord with the invention.

In a preferred execution of the invention the surf~ct~nt system also comtains alkyl ethoxysulfate surf~cf~nt prefel~bly C12-Clg alkyl ethoxysulfate surfactant cont~ining an average of from 1 to 7 moles ethylene oxide per mole derived from the condensaion product of a C12-Cl~ alcoho~ wherein said C12-C1g alcohol is most ~reftrably derived from natural sources. Fx~mples of naturally occurring materials from which the alcohols can be derived are coconut oil and palm kernel oil and the corresponding fatty acids. Preferred are C12-C14 alkyl ethoxy-rS~ate salts with an average of from one to five ethoxy groups per mole, and most preferably with an average of from one to three ethoxy groups per mole.

The weight ratio of the alkyl sulfate surf~ct~nt to the alkyl ethoxysulfate surf~ct~nt is ~referably from 2:1 to 19:1 more preferably from 3:1 to 12:1 and most ~leferably from 3.5:1 to 10:1.

It is prefell~d that the alkyl sulfate surfactant and the alkyl ethoxysulfate surfactant are in intim~te admixture. Where incorporated in a particulate composition they should be mixed prior to the formation of any part;culate component of which they may form a part. In the case of a spray dried granule, this mixing can take place in the slurried mixture fed to the spray drying equipment. Where another type of granule is formed an intim~tt? mixlture of the surfactants should be made before agglomeration, milling, fl~king, prilling or any other particulate forming process takes place.

WO 95/02390 PCT/US94/06943 ~

The surf~çt~nt system of the invention may contain as non-essential components other anionic surfactant components including alkane sulfonate and alkyl ester sulfonate surfactants.
.

Use of alkane sulfonate salts as anionic surfactants is well known in the art, being disclosed for example in US Patent 3 929 678. Aliphatic alkane sulfonate salts may be obtained from the reaction of an aliphatic hydrocarbon, which may include the iso-, neo-, meso- and n-paraffins, having 12 to 24 carbon atoms and a sulfonating agent which may for example be SO3, H2SO4 or oleum the reaction being carried out according to known sulfonation methods, including bleaching and hydrolysis. In accord with the present invention the aliphatic C12-C20 alkane sulfonate salts are preferred with the aliphatic C14-C20 alkane sulfonate salts being most preferred. Prefelled as cations are the alkali metal and ammonium cations.

Alkyl ester sulfonate surf~rt~nt~ hereof include linear esters of C12-C20 carboxylic acids (ie. fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society," 52 (1975), pp. 323-329. Suitable starting materials include natural fatty subs~nre~ as derived from tallow, palm oil, etc.

The preferred alkyl ester sulfonate surf~rt~nt~ in accord with the invention comprise methyl ester sulfonate surf~ct~nts of the structural forrnula:
o R3--CH--C oR4 Sl3M
wherein R3 is a C12-C20 alkyl, R4 is methyl and M is a cation which forms a salt with the methyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, pot~sil-m, and lithium, and substituted or unsubstitllte~i ammonium cations, such as monoeth~nt lamine, diethanolamine, and triethanolamine. Most preferably, R3 is C14-C20 alkyl.

~ wo gs/~239~ 2 ~ ~ ~ 8 ~ t PCT/US94/06943 The surfactant system of the invention is desirably incorporated as part of a detergent or cleaning composition for use in, for example, laundry, m~nll~l and automatic dishwashing, and hard-surface cleaner applications.
The level of incorporation of the surf~ct~nt system, and of any further ingredients, will depend upon the nature of the detelgellL or cleaning composition, and in particular its desired application.

The compositions may in addition comprise in general terms those ingredients commonly found in detergent products which may include organic surf~ct~nt~, deler~elll builders, anti-redepo~ition and soil suspension agents, suds suppressors, enzymes, optical brighteners, pholtoactivated bleaches, perfumes, filler salts, anti-corrosion agents and colours.

T.~lln-lry deter~ellt compositions may also comprise fabric softening and ~nti~tatic agents.

The surfact~nt system of the invention may include as a preferred additional component a nonionic surf~ct~nt. Preferably the nonionic surf~ct~nt is incorporated such that the weight ratio of nonionic surfactant to anionic surfactant is from 1:4 to 4:1, ~leferably 1:2 to 2:1.

In one preferred aspect of the invention the surf~rt~nt system of the invention is incorporated within a laundry detergelll composition at a level of from 3% to 50% by weight, preferably from 5% to 30%, mos~
preferably from 7% to 15% by weight of the detergen~ composition.

Machine dishwashing detergellt compostions incorporating the anionic surfactant system of the invention comprise from 0.5% to 10% by weight, preferably from 1% to 10% by weight, most preferably from 1% to 5%
of the surfactant system by weight of the invention. Prefera~ly said machine dishwashing compositions also contain a nonionic surfactant system. Most ~refelled are low-fo~ming nonionic surfactants, especially the water soluble ethoxyleted C6-C16 fatty alcohols and C6-C16 mixed ethoxylated/propoxylated fatty alcohols and mixtures thereof. Preferably, the ethoxylated fatty alcohols are the C10-C16 ethoxylated fatty alcohols WO 95/02390 ~ 6 ~ PCT/US94/06943 ~

with a degree of ethoxylation of from 5 to 50, most preferably these are C12-C16 ethoxylated fatty alcohols with a degree of ethoxylation from 8 to 40. Preferably the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 16 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.

Suitable nonionic surf~ct~nt~ for incorporation as part of a nonionic surfactant system include polyhydroxy fatty acid amide surf~ct~ntc, alcohol ethoxylate surf~ct~nt~ and allyl polyglucoside surf~ct~nt~.

Additionally detergenL compositions in accord with the invention may optionally contain cationic, amphoteric, zwitterionic and semi-polar surf~ct~t~.

The polyhydroxy fatty acid amide surf~ct~ntc in accord with the presentinvention comprise compounds of the structural formula:

wherein: R5 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxypropyl, or a mixture thereof, preferably C1 or C2 alkyl, most preferably C1 alkyl (ie. methyl); and R6 is a C11-C31 hydrocarbyl, ~referably straight chain C 1 1-C 19 alkyl, or alkanyl most preferably straight chain C16-C1g alkyl or alkenyl, or mixture ~ereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connecte~ to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z prefelably will be derived from a reducing sugar in a reductive ~-"i~ ion reaction; more preferably Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, g~ tose, mannose, and xylose.

As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be l)tilise~3 as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for ~ WO 95/0~910 ~ 1 6 ~ PCTAUS94/06943 Z. It should be understood that it is by no means intended to exclude other suitable raw materials. Z preferably will be selected from the group consisting of-CH2-(CHOH)n-CH2OH, -CH(CH2OH)-(CHOH)n l-CH:2OH, i-CH2-(CHOH)2(CHOR')(CHOH)-CH2OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cycl c or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most ~.eferled are gly,cityls wherein n is 4, particularly -CH2-(CHOH)4-CH2OH.

R5 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxypropyl.

R6 CO-N< can be, for example, coc~mi~le, stearamide, oleamide, lauramide, myristamide, capric~mi-le, p~lmh~mide, tallowamide, etc.

Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxy~ ctityl, 1-deoxym~nnityl, 1-deoxymaltotriotityl, etc.

The most preferred polyhydroxy fatty acid amide has the general formula ~, I
R6--C --N CH2 (CHOH)4CH2OH
wherein R6 is a C11-C1g straight-chain alkyl or alkenyl group.

Methods for m~king polyhydroxy fatty acid ~mi~les are known in the art.In general, they can be made by re~ctin~ an alkyl amine with a reducing sugar in a reductive ~min~tion reaction to form a corresponding N-alkyl polyhydroxyamine, and then re~ctin~ the N-alkyl polyhdroxyamine with a fatty aliphatic ester or triglyceride in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product. Processes for m~king compositions cont~inin~ polyhydroxy fatty acid amides are disclosed, for e~ample, in GB Patent Specification 809 060, published FeblUary 18,1959, by Thomas Hedley & Co Ltd, US Patent 2 965 576, issued December 20,1960 to E R Wilson, and US Patent 1 985 424, issued December 25, 1934 to Piggott, each of which is incorporated herein by reference.

W095/0~90 ~ 1 ~ 6 8 6 1 PCT~S94/06943 One class of nonionic surf~ct~nts useful in the present invention comprises condensates of ethylene oxide with a hydrophobic moiety, providing surfactants having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, ~lefeiably from 9.5 to 13.5, more preferably from 10 to 12.5. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of ~e polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of b~l~nre between hydrophilic and hydrophobic elements.

Especially preferred additional nonionic surf~ct~nt~ of this type are the C12-C20 primary alcohol ethoxylates cont~inin~ an average of from 3-11 moles of ethylene oxide per mole of alcohol, particularly the C12-C16 primary alcohol ethoxylates cont~inin~ an average of from 3-7 moles of ethylene oxide per mole of alcohol and most prefer~bly the C12-C16 primary alcohol ethoxylates cont~ining an average of 3 moles of ethylene oxide per mole of alcohol.

Another class of nonionic surfact~nt~ comprises alkyl polyglucoside compounds of general formula RO (cnH2no)tzx wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group ~at contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides. Compounds of ~is type and ~eir use in detergent compositions are disclosed in EP-B 0 070 074 0 070 077,0 075 996 and 0 094 118.

A further class of surf~ct~nt~ are the semi-polar surf~ct~nt~ such as amine oxides. Suitable amine oxides are selected from mono Cg-C20, ~refelably Clo-C14 N-alkyl or alkenyl amine oxides and propylene-1,3-rli~mine dioxides wherein the rem~inin~ N positions are substituted by methyl, hydroxyethyl or hydroxpropyl groups.

~wogs/n1lgO ~66~6~ PCT/US94/06943 Cationic surfactants can also be used in the detergent compositions herein and suitable quaternary ammonium surfactants are selected from mono Cg-C16, preferably C1o-C14 N-alkyl or alkenyl ammonium surfactants wherein rem~ining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Where form~ te~l as a granular composition any particulate components may have any suitable physical form, i.e. it may take the form of flakes, pril~s, marumes, noodles, ~;~bons, or granules which may be spray-dried or non spray-dried agglomerates.

Another highly preferred component deter~,el.L or cleaning compositions in accord with the invention is a detergellt builder system comprising one or more other detergent builders. These can include, but are not restricted to, phosphates, crystalline layered sodium silicates, carbonates borates, alkali metal aluminosilic-~te~, monomeric polycarboxylates, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals seperated from each other by not more than two carbon atoms, carbonates, silicates and Imixtures of any of the foregoing.

The builder system is preferably present in the detergent or cleaning compositions in an amount from 1% to 95 % by weight.

When ~e detergelll composition is a laundry or m~t~hin~ dishwashing deLel~,e.l~ composition the level of builder system is preferably from 1 to 8~% by weight, more preferably 20% to 70% by weight of the compostion.

Suitable silicates are those having an SiO2:Na2O ratio in the range from 1.6 to 3.4, the so-called amorphous silicates of SiO2: Na2O ratios from 2.0 to 2.8 being employed where addition to the mixture of ingredients that are spray dried is required. Where alumiT~osilicates con~tit Ite an ingredient of the mixture to be spray dried, siiicates should not be present in the mixture but can be incorporated in the form of an aqueous solution serving as an agglomerating agent for other solid components, or, where wo 95/02390 ;~ f 6 6 8 6 1 PCT/US94/06943 ~

the silicates are themselves in particulate form, as solids to the other particulate components of the composition. However, for compositions in which the percentage of spray dried components is low i.e. 305~, it is preferred to include the amorphous silicate in the spray-dried components.

Whilst a range of aluminosilic~t~ ion exchange materials can be used, preferred sodium aluminosilicate zeolites have the unit cell formula Naz [(A102 ) z (SiO2 )y ] xH 2 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 S, ~Lefelably from 7.5 to 276, more ~Leferably from 10 to 264. The aluminosilicate materials are in hydrated form and are preferably crystalline, cont~inin~ from 10% to 28%, more preferably from 18 % to 22% water in bound form.

The above aluminosilicate ion exchange materials are further characterised by a particle size ~ m~oter of from 0.1 to 10 micrometers, preferably from 0.2 to 4 micrometers. The term "particle size diameter"
herein represents the average particle size diameter of a given ion exchange rnaterial as determined by conventional analytical techniques such as, for example, microscopic detelmillation lltili7in~ a SC~nning electron microscope or by means of a laser granulometer. The aluminosilicate ion exchange materials are further characterised by their calcium ion exchange capacity, which is at least 200 mg equivalent of CaC03 water hardness/g of alumino~iliç~t~, calculated on an anhydrous basis, and which generally is in the range of from 300 mg eq./g to 352 mg eq./g. The aluminosilicate ion exchange materials herein are still further characterised by their calcium ion exch~nge rate which is at least 130 mg equivalent of CaCO3/litre/mimlte/(g/litre) [2 grains Ca+ +/
gallon/mimlte/gram/gallon)] of aluminosilicate (anhydrous basis), and which generally lies within the range of from 130 mg equivalent of CaCO3/litre/minllte/(gram/litre) [2 grains/gallon/minllte/ (gram/gallon)]
to 390 mg equivalent of CaCO3/litre/mimlte/ (gram/litre) [6 grains/gallon/min~lte/(gram/gallon)], based on calcium ion hardness.

~WO 95/02390 ~ PCT/US94/06943 Optimum aluminosilicates for builder purposes exhibit a calcium ion exchange rate of at least 260 mg equivalent of CaC03/litre/ minnte/
(gram/litre) [4 grains/gallon/minnte/(gram/gallQn)].

Aluminosilicate ion exchange materials useful in the~practice of this invention are commercially available and can be naturally occurring materials, but are preferably synthetically derived. A method for producing aluminosilicate ion exchange materials is ~iiec~esed in US
Pate~t No. 3,985,669. Preferred synthetic cryst~llin~ aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof. In an especially preferred embodiment, the cryst~lline aluminosilicate ion exchange material is Zeolite A and has the formula Na 12 [(A102 ) 12 (SiO2)12 ]- xH2 0 wherein x is from 20 to 30, especially 27. Zeolite X of formula Na86 t(A102)86(SiO2)106]. 276 H20 is also suitable, as well as Zeolite HS of forrnula Na6 [(Alo2)6(sio2)6~ 7-5 H2 )-Suitalble water-soluble monomeric or oligomeric carboxylate builders can be selected from a wide range of compounds but such compounds pleferably have a first carboxyl loga,i~ ic acidity/constant (pKl) of less than 9, I)refe,~bly of between 2 and 8.5, more preferably of between 4 and 7.5.

The l~garithmic acidity constant is defined by ,efere"ce to the equilibrium H+ + A- ~ 'H A
where A- is the fully ionized carboxylate anion of the builder salt.

The equilibrium constant is therefore K1 = (H A) (H+) (A-) and pK1 = lglOK-For the purposes of this specification, acidity conet~nt.e are defined at25C and at zero ionic strength. Literature values are taken where WO 95/02390 ~ 8 ~ 1 PCT/US94/06943 possible (see Stability Constants of Metal-Ion Complexes, Special Publication No. 25, The Chemical Society, London): where doubt arises they are determined by potentiometric titration using a glass electrode.

Preferred carboxylates can also be defined in terms of their calcium ion stability constant (pKCa+ +) defined, analogously to pKl, by the equations PKCa+ + = loglOKCa+ +
where KCa+ + = (Ca+ + A) (Ca+ +) (A) Preferably, the polycarboxylate has a pK Ca+ + in the range from about 2 to about 7 especially from about 3 to about 6. Once again literature values of stability constant are taken where possible. The stability constant is defined at 25C and at zero ionic strength using a glass electrode method of measurement as described in Complexation in Analytical Chemistry by Anders Ringbom (1963).

The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and pelrollnance.

~ wo 9~,02390 ~ 8 ~ 1 PCT/US94/06943 Monomeric and oligomeric builders can be selected from acyclic, alicyclic, heterocyclic and aromatic carboxylates having the general formulae y (a) Z m (b) X C
z (C) yp - O--~- Zq \/

wherein Rl lc~resents H,Cl 30 alkyl or alkenyl optionally substitllte~l by hydroxy, carboxy, sulfo or phosphono groups or ~tt~che~l to a polyethylenoxy moiety cont~ining up to 20 ethyleneoxy groups; R2 represents H,Cl~ alkyl, alkenyl or hydroxy alkyl, or alkaryl, sulfo, or phosphono groups;
X represents a single bond; O; S; SO; SO2; or NR1;
Y represents H; carboxy;hydroxy; carboxymethyloxy; or Cl 30 alkyl or alkenyl optionally substit~lte~ by hydroxy or carboxy groups;
Z represents H; or carboxy;
m is an integer from 1 to 10;
n is an integer from 3 to 6;

8 ~ 1 WO 9~/02390 PCT/US94/06943 p, q are integers from 0 to 6, p + q being from 1 to 6; and wherein, X, Y, and Z each have the same or dirre~ representations when repeated in a given molecular formula, and wherein at least one Y or Z in a molecule contain a carboxyl group.

Suitable carboxylates cont~inin~: one carboxy group include lactic acid, glycolic acid and ether derivatives tnereof as disclosed in Belgian Patent Nos. 831 368, 821 369 and 821 370.

Polycarboxylates cont~inin~ two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, ~llrol~ic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2 446 686, and 2 446 687 and US Patent No.
3 935 257 and the sulfinyl carboxylates described in Belgian Patent No.
840 623. Polycarboxylates cont~inin~ three carboxy groups include, in particular, water-soluble citrates, acGnillates 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. 1 389 732, and arninosuccinates described in Netherlands Application 7 205 873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1 387 447.

Polycarboxylates cont~ininp four carboxy groups include oxydisuccinates disclosed in British Patent No. 1 261 829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates cont~inin~ sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 398 421 and 1 398 422 and in US Patent No.
3 936 448, and the sulfonated pyrolysed citrates described in British Patent No. 1 439 000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates, 2,2,5,5-tetrahydrofuran -tetracarboxylates, 1,2,3,4,5,6-hexane - hexacarboxylates and WO 95/02390 2 ~ I PCT/US94/06943 carboxymethyl derivatives of polyhydric alcohols such as sorbitol, ma~nitol and xylitol. ~romatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1 425 343.

Of the above, the preferred polycarboxylates are hydroxycarboxylates cont~inin~ 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 citrate/citric acid mixtures are also con~ lated as components of builder systems of dete.gent compositions in accordance with the present inve~ntion.

Other suitable water soluble organic salts are the homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl r~iic~l~ separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-l 596 756. Examples of such salts are polyacrylates of MWt 2000-500~ and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20 000 to 100 000, especially from 70 000 to 90 000. These materials are normally used at levels of from 0.5%
to lG % by weight more preferably from 0.75 % to 8 %, most preferably from 1 % to 6 % by weight of the composition.

Organic phosphonates and amino alkylene poly (alkylene phosphonates) inclu,de alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene ~ mine tetra methylene phosphonates and diethylene tri~minç penta methylene phosphonates, although these materials are less preferred where the minimi.c~tion of phosphorus compounds in the compositions is desired.

These phosphonate materials are normally present at levels less than 5 %
by weight, more preferably less than 3 % by weight and most preferably less than 1% by weight of the compositions.

WO 95/02390 2 1 6 6 ~ 6 1 PCT/US94/06943 The detergent compositions can also include miscellaneous ingredients preferably in a total amount of from 0% to 45 % by weight, examples of such ingredients being optical brighteners, anti-redeposition agents, photoactivated bleaches (such as tetrasulfonated zinc phthalocyanine) and heavy metal sequestering agents. -When form~ te~l as a granular compostion the particle size of theparticulate components of any dete~ or cleaning composition cont~inin~ the surf~rt~nt system of the invention is conventional and preferably not more than 5 % by weight should be above 1 .4mm, while not more than 10% by weight should be less than 0.15 mm in maximum dimension. Preferably at least 60%, and most plefelably at least 80%, by weight of the powder lies between 0.7 mm and 0.25 mm in size.
Preferred granular delergell~ compositions in accordance with the invention comprise at least one spray dried granular surfactant-cont~inin~: partic~ te component and at least one surf~-t~nt-cont~ining particulate agglomerate component.

For spray dried powders, the bulk density of the particles from the spray drying tower is conventionally in the range from 400 to 450 g/litre and this is then enh~nce~l by further processin~ steps such as size reduction in a high speed cutter/mixer followed by compaction preferably to achieve a final density of greater than 550 g/litre. Alternatively, processes other than spray drying may be used to form a high density particulate directly.

Where the partic~ te components are particulate agglomerates the bulk density of these components will be a function of their mode of preparation. However, the preferred form of such components is a mechanically rnixed agglomerate which may be made by adding the ingredients dry or with an agglomerating agent to a pan agglomerator, Z
blade mixer or more preferably an in-line mixer such as ~ose m~mlf~tured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands and Gebruder Lodige MaschinenbanGmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050 F.R.G. By this means the second component can be given a bulk density in the range from 650 g/litre to 1190 g/litre more preferably from 700 g/litre to 850 g/litre.

~WO 95/0239C~ t PCT/US94/06943 Preferably any particulate agglomerate components include sodium carbonate at a level of from 20 % to 40 % by weight of the component.
PreiFerably, the composition includes from 3% to 18% sodium carbonate by weight of the composition, more preferably from S~ to 15% by weight.

A highly ~refelred ingredient of any particulate agglomerate components is also a hydrated water insoluble aluminosilicate ion exchange material of the synthPti~ zeolite type, described hereinbefore, present at from 10% to SS % by weight of the second component. The amount of water insoluble aluminosilicate material incorporated in this way is from 1% to 15% by weight of the composition, more prefel~bly from 2% to 10% by weight.

In one process for prepa,illg the particulate agglomerate col,~ollent, the surf~ct~nt salt is formed in situ in an inline mixer. The li~uid acid form of the surf~r-t~nt is added to a mixture of particulate anhydrous sodium carbonate and hydrated sodium aluminosilicate in a continuous high speed blender, such as a Lodige KM mixer, and neutralised to form the surfactant salt whilst m~int~ining the particulate nature of the mixture.
The resl~lt~nt agglomerated mixture forms the second component which is then added to other components of the product. In a variant of this process, the surfactant salt is pre-neutralised and added as a viscous paste to the mixture of the other ingredients. In the variant, the mixer serves merely to agglomerate the ingredients to form the second component.

Where there is only one surf~ct~nt-cont~inin~ co",ponent in the composition one or more other ingredients will be added as particulate components and will preferably also be present where more than one surfactant-cont~ininp: particulate components forms part of the composition. Thus one or more of oxygen bleaches, photoactivated bleaches, bleach activators, builder salts, de~ergell~ enzymes, suds suppressors, fabric softening agents, soil suspension and anti-redeposition agents, soil release polymers, and optical brighteners can be added as solids.

Suitable oxygen bleaches include the inorganic perhydrates such as sodium perborate monohydrate and tetrahydrate, sodium percarbonate, sodium perphosphate and sodium persilicate. Sodium percarbonate and the sodium perborate salts are most preferred. These materials are normally added as cryst~llin~o solids and, in the case of sodium percarbonate, may be coated with e.g. silic~te in order to aid stability.
Usage levels range from 3 % to 22 % by weight, more preferably from 8 %
to 18% by weight.

Photoactivated bleaches include the zinc and aluminium salts of tri and tetra sulfonated phthalocyanine which are normally added as dispersions in other materials bec~l)se of their low levels of usage, typically from 0.0005 to 0.01 % by weight of the composition.

Bleach activators or peroxy acid bleach precursors can be selected from a wide range of classes and are preferably those cont~inin~ one or more N-or O- acyl groups.

Suitable classes include anhydrides, esters, imides and acylated derivatives of imi~ oles and oximes, and examples of useful materials within these classes are disclosed in GB-A-1586789. The most preferred classes are esters such as are disclosed in GB-A-836 988, 864 798, 1 147 871 and 2 143 231 and imides such as are disclosed in GB-A-855 735 & 1 246 338. Levels of incol~o,~lion range from 1% to 10% more generally from 2% to 6% by weight of the composition.

Particularly preferred precursor compounds are the N-,N,N1Nl tetra acetylated compounds of formula O O
Il ll CH3 - C . ~ C - CH3 N - (CH2)x - N ~
CH3 C ~ C - CH3 O O

~ WO 95102390 ~ 8 ~ ~ PCT/US94/06943 wherein x can be O or an integer between 1 & 6.

Examples include tetra ace~l methylene ~i~min~ (TAMD) in which x= 1, tetra acetyl ethylene ~ min~ (TAED) in which x=2 and tetraacetyl he~;ylene ~ mine (TAHD) in which x=6. These and analogous compounds are described in GB-A-907 356. The most prefel,ed peroxyacid bleach precursor is TAED.

Solid peroxyacid bleach precursors useful in compositions of the present invention have a Mpt~30C and preferably >40C. Such precursors wil:l normally be in fine powder or cryst~llin~ form in which at least 90%
by weight of the powder has a particle size > 150 micrometers.

This powder is usually agglomerated to form particulate material, at least 85 % of which has a particle size between 400 and 1700 micrometers.
Suilable agglomerating agents include aliphatic mono and polycarboxylic acids,C12-Clg aliphatic alcohols condensed with from 10 to 80 moles of ethylene oxide per mole of alcohol, cellulose derivatives such as methyl, carboxymethyl and hydroxyethyl cellulose, polyethylene glycols of MWt 4,000 - 10,000 and polymeric materials such as polyvinyl pyrrolidone.

The precursors are preferably coated with an organic acid compound such as citric or glycolic acid, as disclosed in the commonly assigned copending British Patent Application No. 9102507.2 filed February 6 1991.

Builder salts that can ~ vantageously be added as solid particulates include silic~t~s and certain polycarboxylate builders such as citrates.

Dry mix addition of amorphous sodium silir~tes, particularly those of SiO2:Na2O ratio of from 2.0: 1 to 3.2: 1 is employed where aluminosilicates form part of a spray dried component, in order to avoid the ~ormation of insoluble reaction products. Furthermore the incorporation of cryst~llin~, so called 'layered' silic~tes into detergenl compositions necessitates their addition as solids.

g 6 1 These crystalline layered sodium silicates have the general formula NaMSix02x+ 1.YH20 wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0 164 514 and methods for their preparation are disclosed in DE-A-3 417 649 and DE-A-3 742 043. For the purposes of the present invention, x in the general formula above has a value of 2, 3 or 4 and is prefefably 2. More pleferably M is sodium and y is 0 and preferred examples of this formula comprise the ~ and ~ forms of Na2Si2Os. These materials are available from Hoechst AG FRG as respectively NaSKS-11 and NaSKS-6. The most ple~erled material is ~-Na2Si2Os, (NaSKS-6). Crystalline layered silicates are incorporated either as dry mixed solids, or as solid components of agglomerates with other components.

Anti-redeposition and soil-suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethycellulose, and homo-or co-polymeric polycarboxylic acids or their salts. Polymers of this type include copolymers of maleic anhydride with ethylene, methylvinyl ether or meth~rrylic acid, the maleic anhydride concti1~ltin~ at least 20 mole percent of the copolymer. These materials are normally used at levels of from 0.5% to 10% by weight, more p~efelably from 0.75% to 8%, most ~leferably from 1% to 6% by weight of the composition.

Other useful polymeric materials are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 0.20%
to 5 % more preferably from 0.25 % to 2.5 % by weight. These polymers and the previously mentioned homo- or co-polymeric polycarboxylate salts are valuable for improving whiteness m~intenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.

~WO 95/02390 2 1 6 6 8 6 1 PCT/US94/06943 Preferred optical brighteners are anionic in character, examples of which are disodium 4,41-bis-(2-diethanolamino-4-~nilino -s- triazin-6-yl~rnino)stilbene-2:2 1 disulphonate, disodium 4,4 1-bis-(2-morpholino -4-~nilino-2-triazin-6-ylaminostilbene-2:21-disulphonate,disodium 4, 41-bis-(2,4-~ nilino-s-triazin-6-ylamino)stilbene-2:21 - dislllphonate, monosodium 41,41 1-bis-(2,4-~ nilino-s-triazin-6 yl~mino)stilbene-2-sulphonate, disodium 4,4 1-bis-(2-~nilint -4-(N-methyl-N-2-hydroxyethyl~mino)-2-triazin-6-yl~minQ)stilbene-2,2 1 - disulphonate, disodium 4,41-bis-(4-phenyl-2, 1 ,3-triazol-2-yl)stilbene-2,2 1 disulphonate, disodium 4,41bis(2-anilino~-(1-methyl-2-hydroxyethylamino)-s-triazin-6-yl~mino)stilbene-2,21disulphonate and sodium 2(stilbyl-411-(naphtho-l1,Z.1:4,5)-1,2,3 - triazole-211- sulphonate.

Soil-release agents useful in detergent or cleaning compositions in accord with the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4 116 885 and 4 711 730 and European Published Patent Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-O 272 033 has the formula (cH3(pEG)43)o.7s(poH)o.2s(T-po)2.8(T-pEG)o.4)T(po-H)o 2s((PEG)43cH3)o 75 where PEG is -(OC2H4)0-,PO is (OC3H60) and T is (pCOC6H4CO).

Certain polymeric materials such as polyvinyl pyrrolidones typically of MWt 5000-20000, preferably 10000-15000, also form useful agents in preventing the transfer of labile dyestuffs between fabrics during the washing process.

Another optional detelgent composition ingredient is a suds suppressor, exemplified by silicones, and silica-silicone mixtures. Silicones can be generally represented by alkylated polysiloxane materiats while silica is normally used in finely divided forms, typified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be inco1porated as partic~ tes in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, subst~nti~lly non-surface-active deLeLgellt-imperrneable , 21 ~8~ 1 carrier. Alternatively the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.

As mentioned above, useful silicone suds controlling agents can comprise a mixture of an allylated siloxane, of the type referred to hereinbefore, and solid silica. Such mixtures are plepaled by ~ffixing the silicone to the surface of the solid silica. A preferred silicone suds controlling agent is represented by a hydrophobic ~ n~t~-l (most preferably trimethyl-sil~n~te~l) silica having a particle size in the range from 10 nanometers to 20 nanometers and a specific surface area above 50 m2/g, intim~tely admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to n~tt?~l silica of from about 1: 1 to about 1 :2.

Suitable silicone suds controlling agents are disclosed in US Patent 3 933 672 and DTOS 2 646 126, an example of the latter being DC0544, a self emulsifying siloxane/glycol copolymer commercially available from Dow Corning. A particularly preferred suds suppressor system based on a silica silicone mixture comprises 78% starch, 12% stearyl alcohol binder and 10% of a silica/silicone blend available from Dow Corning under the reference X2/3419. This system is the subject of European Patent No. 0 210 721.

The p~efe,led metho~l.s of incorporation comprise either application of the suds ~uy~lessors in liquid form by spray-on to one or more of the major CO~ lltS of the composition or al~ ati-~ely the formation of the suds ~u~lessors into separate particulates that can then be mixed with the other solid components of the composition. A preferred example of such a particulate is a cryst~llin~ or amorphous alumino~ilic~te zeolite on to which the suds suppressor is absorbed. Suds suppressor particulates of this type are the subject of the commonly assigned copending European Application No. 91201343Ø The incorporation of the suds modifiers as separate particulates also permits the inclusion therein of other suds controlling materials such as C20-C24 fatty acids, microcrystalline waxes and high MWt copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the dispersibility of the matrix.

~WO 95/0239C1 ~ 8 ~ ~ PCT/US94/06943 Techniques for forming such suds modifying particulates are disclosed in the previously mentioned US Patent No. 3 933 672.

An especially preferred suds suppressor system comprises in combination a paLrticulate suds suppressing component and a spray-on suds-suppressing component.

The suds suppressors described above are normally employed at levels of fronn 0.01 % to 5.0% by weight of the composition, preferably from 0.01 % to 1.5% by we~ght, and most ~1efeldbly from 0.1 % to 1.2% by weight.

Another optional ingredient useful in the present invention is one or more enzymes.

Preferred enzymatic materials include ~e commercially available amylases, neutral and ~ lin~ proteases, lipases, esterases and cellulases conventionally incorporated into deLer~elll compositions. Suitable enzymes are discll~se~l in US Palell~ 3 519 570 and 3 533 139.

~ablic softening agents can also be inc~l~ol~Led into del~rg~llt compositions in accordance with the present invention. These agents may be inorganic or organic in type. Inorganic softening agents are exeI:nplified by the smectite clays disclosed in GB-A-1 400 898. Organic fabric softening agents include the water insoluble tertiary amines as discLosed in GB-A-1 514 276 and EP-B-0 011 340.

Their combination with mono C12-C14 quatell~y ammonium salts is discLosed in EP-B-0 026 527 & 0 026 528. Other useful organic &bric softening agents are the dilong chain ~mil1es as disclosed in EP-B-0 242 919. Additional organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0 313 146.

Levels of sm~ctit~ clay are normally in the range from 5% to 15%, more preferably from 8 % to 12 % by weight, with the material being added as a -WO 95/02390 2 t ~ 6 8 ~ ~ PCT/US94/06943 ~

dry mixed component to the rem~in-ler of the formulation. Organic fabric softening agents such as the water-insoluble tertiary amines or dilong chain amide materials are incorporated at levels of from 0.5% to 5% by weight, normally from 1% to 3 % by weight, whilst the high molecular weight polyethylene oxide materials and the water soluble cationic materials are added at levels of from 0.1 % to 2 %, normally from 0.15 %
to 1.5 % by weight. Where a portion of the composition is spray dried, these materials can be added to the aqueous slurry fed to the spray drying tower, although in some in~nces it may be more convenient to add them as a dry mixed particulate, or spray them as a molten liquid on to other solid components of the composition.

In a particularly ~lefellcd process for m~kin~ deLergellt compositions in accordance with the invention, part of the spray dried product comprising one of the granular components is diverted and subjected to a low level of nonionic surf~rt~nt spray on before being reblended with the rem~in~er.
A second granular compollent is made using the picfel~ed process described above. The first and second components together with perhydrate bleach, bleach precursor partic~ te, other dry mix ingredients such as any carboxylate chelating agent, soil-release polymer, silicate of conventional or cryst~ np layered type, and enzyme are then fed to a conveyor belt, from which they are tral~r~llcd to a horizontally rotating drum in which pelrull'e and silicone suds ~u~lessor are sprayed on tO the product. In highly ~Ic~llcd compositions, a further drum mixing step is employed in which a low (approx. 2 % by weight) level of finely divided cryst~llin~ material is introduced to increase density and improve granular flow characteristics.

The conce~lllated granular compositions of the present invention have abulk density of at least 550g/litre, prefelably at least 650g/litre more usually about 700 g/litre.

Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contellt~ of the funnel to be emptied into an axially ~lign~-l cylindrical cup disposed below the funnel. The funnel is 130 mm and 40 rnrn at its respective upper and WO 95/0239C~ a ~ PCT/US94/06943 lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has an overall height of 90 mnn, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.

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

Subject to the above bulk density limit~tions, the compositions of the invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and gr~n~ tion. A plefel.ed method of m~kin~ the compositions involves a combination of spray drying, agglomeration in a high speed mixer and dry mixing.

Co]npositions in accordance with the present invention comprise a plurality of separate particulate components. The particulates can have any suitable form such as granules, flakes, prills, marumes or noodles but are preferably granular. The granules themselves may be agglomerates formed by pan or drum agglomeration or by an in-line mixer and also may be spray dried particles pro~ re~ by atomi~in~ an aqueous slurry of the ingredients in a hot air stream which removes most of the water. The spray dried granules are then subjected to densification steps, e.g. by high speed cutter mixers and/or compacting mills, to increase density before being reagglomerated.

Preferred compositions in accordance with the invention comprise at least one spray dried granular surfactant-cont~ining component and at ~Past one suri~actant-cont~ining particulate agglomerate coll~ollent.

Where one or more surfactant-cont~ining particulate components are spray dried granules these will preferably comprise in total at least 15 %, more preferably from 25 % to 45 %, by weight of the composition. Where WO 95/02390 ~ PCT/US94/06943--one or more surfactant-cont~inin~ particulate components are particulate agglomerates these will preferably comprise in total from 1% to 50%, more preferably from 10% to 40% by weight of the composition.

Where the surf~ct~nt-cont~inin~ partic~ tes are the only multi ingredient components, the rern~in~ier of the ingredients can be added individually as dry solids, or can be sprayed on to either the particulate components or on to any or all of the solid ingredients.

In preferred concentrated detergent products incorporating an alkali metal percarbonate as the perhydrate salt it has been found n~cess~ry to control several aspects of the product such as its heavy metal ion content and its equilibrium relative hllmi-lity. Sodium percarbonate-cont~inin~
col,lposiLions of this type having enh~nre~l stability are disclosed in the commonly assigned British Application No. 9021761.3 filed October 6 1990 Attorney's Docket No. CM343.

Preferred laundry detelgellt compositions of the invention are form~
to be used with delivery systems that provide transient loc~ e~l high concentrations of product in the drum of an automatic washing machine at the start of the wash cycle. These delivery systems avoid problems associated with loss of product in the pipework or sump of the machine and the high transient concentrations provide fabric cleaning benefits.

High transient concentrations require rapid dissolution/dispersion of the composition but ~is is difficult with surf~ct~nt cont~ining particulate colll~onents in which the alkyl sulfate surf~ct~nt is relatively insoluble and hence make the component hydrophobic in nature. The incorporation of a low level of a water soluble ethoxysulfate surf~ t~nt into the alkyl sulfate surfactant cont~ining particulate has however been found to enable acceptable rate of dissolution characteristics to be achieved whilst ret~ining the deterge.lcy provided by surf~ct~nt Delivery systems for introducing laundry detergell~ compositions in accord with the invention into an automatic washing machine can take a number of forms. Thus a composition can be incorporated in a bag or container from which it is rapidly releasable at the start of the wash cycle ~WO 95/0239C1 ~ 1 6 6 8 6 1 PCT/US94/06943 in response to agitation, a rise in temperature or immersion in the wash walter in the drum. Alternatively the washing machine itself may be adapted to permit direct addition of the composition to the drum e.g. by a dispensing arrangement in the access door.

Products comprising a laundry deLer~elll composition enclosed in a bag or container are usually designed in such a way that container integrity is m~int~inP~l in the dry state to prevent egress of the colllents when dry, but are adapted for release of the container colllellts on exposure to a washing environment, normally on immersion in an aqueous solution.

Usually the container will be flexible, such as a bag or pouch. The bag ma~ be of fibrous construction coated with a water impermeable pro~ective material so as to retain the co-llellts, such as is disclosed in European published Patent Application No. 0 018 678. Allelllali~ely it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or cl~sure lesign~A to ru~lure in aqueous media as disclosed in European published Patent Application Nos.
O 01~ 5~0, 0 011 S01, 0 011 502, and 0 011 968. A convenient form of water frangible closure colll~lises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water hQ~elllleable polymeric film such as polyethylene or polypropylene.
In a variant of the bag or cont~inçr form, l~min~te(l sheet products can be employed in which a central flexible layer is impregnated and/or coated with a composition and then one or more outer layers are applied to produce a fabric-like ~estlletic effect. The layers may be sealed together so as to remain attached during use or may se~arate on contact with water to facilitate the release of the coated or impregnated material.

An altelnalive l~min~te form comprises one layer embossed or deformed to provide a series of pouch-like containers into each of which the detergellt components are deposited in me~c~lred amounts, with a second layer overlying the first layer and sealed thereto in those areas between the pouch-like containers where the two layers are in contact. The components may be deposited in particulate, paste or molten form and the l~min~te layers should prevent egress of the conten~ of the pouch-like cont~iners prior to their addition to water. The layers may separate or may remain attached together on contact with water, the only requirement being that the structure should permit rapid release of the contents of the pouch-like containers into solution. The number of pouch-like containers per unit area of substrate is a matter of choice but will normally vary between 500 and 25,000 per square metre.

Suitable materials which can be used for the flexible l~min~te layers in this aspect of the invention include, among others, sponges, paper and woven and non-woven fabrics.

However the ~le~.~d means of carl~/in~ out the process of ~e invention is to introduce the composition into the liquid surrolln~ling the fabrics that are in the drum via a reusable dispensing device having walls that are permeable to liquid but impermeable to the solid composition.

Devices of this kind are disclosed in Euro~an Patent Application Publication Nos. 0 343 069 & 0 343 070. The latter Application discloses a device comprising a fle~ible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle of an aul~lllatic process. A
portion of the washing me~ m flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing me~ m The ~uppoll ring is provided with a m~ckin~ arrangement to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which ~e walls have a helical form.

Plefelled dispensing devices are reusable and are designed in such a way that container integrity is m~int~inPr3 in both the dry state and during the wash cycle. Especially ~referled disyensillg devices for use in accord with the invention have been described in the following patents; GB-B-2,157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J. Bland published in ~nllf~cturing Chemist, November 1989, pages 41~6 also describes especially preferred dispensing devices for use wi~ granular laundry produts which are of a type commonly known as the "granulette".

WO 95/02390 2 1 6 ~ 8 ~ 1 PCT/US94/06943 In ~he detergent compositions, the abbreviated component identifications have the following me~ning~:

246AS : Sodium alkyl sulfate surfactant cont~ining a alkyl chain length weight distribution of 15~
C12 alkyl chains, 455~ Cl~ alkyl chains, 35%
C16 alkyl chains, 5% C1g alkyl chains 24AE3S : C12-C14 alkyl ethoxysulfate cont~ining an average of three ethoxy groups per mole TAEn : Tallow alcohol ethoxylated with n moles of ethylene oxide per mole of alcohol 35E7 : A C13 15 primary alcohol condensed with an average of 7 moles of ethylene oxide 25E3 : A C12-C1s primary alcohol condensed with an average of 3 moles of ethylene oxide NaSKS-6 : Cryst~llin~ layered silicate of formula Na2Si2O5 (NaSKS-6) Perborate : Sodiumperborate monohydrate TAED : Tetraacetyl ethylene tli~mine $ilicate : Amorphous Sodium Silicate (SiO2:Na2O ratio normally follows) Carbonate : Anhydrous sodium carbo~Le lBicarbonate : Anhydrous so~ m bicarbonate Zeolite A : Hydrated Sodium Al~ lo.sili~ ~te of formula Nal2(Alo2sio2)l2- 27H20 having a pli,llaly particle size in the range from 1 to 10 micrometers Citrate : Tri-sodium citrate dihydrate MA/AA : Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 80,000.
Enzyme : Mixedproteolytic andamylolytic enzyme sold by Novo Tn~ustries AS.

wo 95l02390 ~ ~ ~ 6 ~ ~ 1 PCT/rJSg4/06943~

Fx~TTple 1 The following low-sudsing granular detergellL composition was prepared in accordance with the invention (percentage, parts by weight).

246AS 8.8 24AE3S 2.2 35E7 4.5 Zeolite A 24.8 Carbonate 15.5 MA/AA 4.6 Sulphate 5.0 Silicate 2.5 Citrate 11.4 Bicarbonate 7.0 Enzyme 1.6 sly~ressor system Particulate anLifo~ll component 2.1 Spray-on antifoam component 2.0 Misc, minors, moisture to b~l~n~e The particlll~te al~lifoalll component was an agglomerate comprising 11%
by weight of the component of polydimethylsiloxane, 14% by weight TAE80, 5% by weight of a mixture of C12-C22 hydrogenated fatty acids and 70 % by weight of starch.

The spray-on all~ifoalll component comprised 30% by weight of the component of silicone/silica antifoam compound comprising 85 % by weight of the antifoam compound of polydimethylsiloxane and 15 % by weight of the antifoalll compound of silica, 3 ~ by weight of silicone glycol rake copolymer (DCO544 from DOW Corning), and 67% by weight of TAE11 carrier fluid.

~wo 9~,02390 ~ 8 ~ 1 PCT/US94/06943 F.x~ le ~

The following laundry detergelll compositions were prepared (parts by weight) in accordance with the invention.
A B ' C D

246AS 7.6 6.5 4.8 6.8 24AlE3S 2.4 - 1.2 1.7 TAE11 1.10 TA]E50 - 0.4 0.4 0.4 35E,7 3.26 35E3 - 5.0 5.0 5.0 Zeolite A 19.5 13.0 13.0 13.0 Citrate 6.5 MA./AA 4.25 4.25 4.25 4.25 NaSKS-6* - 10.01 10.01 10.01 Citric Acid* - 2.73 2.73 2.73 TAlES0* - 0.26 0.26 0.26 Call,o~ e 11.14 9.84 9.84 9.84 Perboldte 16.0 16.0 16.0 16.0 TAlED 5.0 5.0 5.0 5.0 Enzyme 1.4 1.4 1.4 1.4 Silicate (2.0 ratio) 4.38 Waler and mi~cell~neous (Including suds ~uLpressor, sodium sulphate, perfume) to b~l~n~e * Present as components of crystalline layered silic~te particulates.

Claims (10)

1. A surfactant system containing alkyl sulfate surfactant derived from natural sources comprising a mixture of allyl chain lengths wherein the weight distribution of the alkyl chain lengths is such that less than 20% by weight of the alkyl chain lengths are C12, from 30% to 80% by weight of the alkyl chain lengths are C14, from 30% to 50% by weight of the alkyl chain lengths are C16 and less than 10% by weight of the alkyl chain lengths are C18.

2. A surfactant system according to Claim 1 wherein the weight distribution of the alkyl chain lengths is such that less than 15 % by weight of the alkyl chain lengths are C12, from 35% to 70% by weight of the alkyl chain lengths are C14, from 30% to 40% of the alkyl chain lengths are C16, and less than 5% of the alkyl chain lengths are C18.

3. A surfactant system according to either of Claims 1 or 2 containing alkyl ethoxysulfate surfactant wherein the weight ratio of alkyl sulfate surfactant to alkyl ethoxysulfate surfactant is from 2:1 to 19:1.

4. A surfactant system according to any of Claims 1 - 3 additionally containing a nonionic surfactant.

5. A surfactant system according to Claim 4 wherein the weight ratio of nonionic surfactant to anionic surfactant is from 1:4 to 4:1.

6. A surfactant system according to any of Claims 1 - 5 which is essentially free of alkyl benzene sulfonate.

7. A detergent or cleaning composition comprising the surfactant system of any of Claims 1 - 6.

8. A laundry detergent composition according to Claim 7 incorporating the surfactant system at a level of from 3% to 50% by weight.

9. A machine dishwashing detergent composition according to Claim 7 incorporating the surfactant system at a level of from 0.5% to 10% by weight.

10. A detergent composition according to either of Claims 8 or 9 containing a builder system at a level of from 1% to 80% by weight of the composition.