CA2166962A1 - Granular detergent compositions - Google Patents

Abstract

A granular detergent composition is provided containing (a) from 1 % to 30 % by weight of the composition of a surfactant system containing from 30 % to 100 % by weight of the surfactant system of high-sudsing surfactant selected from alkyl sulfate, alkyl ethoxysulfate, polyhydroxy fatty acid amide surfactant, and mixtures thereof; (b) from 0.05 % to 20 % of the composition of a suds-suppressing system comprising in combination (i) a spray-on component, comprising antifoam compound and a carrier fluid wherein said spray-on component is incorporated into said granular detergent composition by being sprayed onto one or more of the granular components of the composition, (ii) a particulate component, comprising in combination an antifoam compound and a water-soluble or water-dispersible carrier material, wherein said granular detergent composition is free from alkyl benzene sulfonate surfactant.

Description

WO 95/0266~;

GRANULAR DETERGENT COMPOSITION COMPRISING ~ SURFACTANT AND
ANTIFOAMING COMPONENT

This invention relates to granular detergent compositions suitable for use in cle~nin~ processes, particularly fabric cle~ning, and more especially t~
granular deter~el,t compositions comprising high-fo~ming surfact~nt and no alkyl benzene sulfonate surfact~nt, wherein suds control is provided by a suds suppression system comprising in combination particulate and spray-on components.

Granular detergent compositions containin~ alkyl benzene sulfonate salts are well known in the art and are in widcs~read commercial use.
Conventionally the alkyl be .~e~e sulfonate salt forms part of a surfactant miJ~ture in association with one or more other anionic or nonionic surfactants.

ILltere~l has recently increased in the use of alternatives to alkyl benzene sul~.~ s as major components of detergent products.

E:camples of primary surf~ct~nts that are readily biodegradable and which could replace the alkyl benzene sulfonate component either partially or in . include alkyl sulfate, alkyl etho~cys~llfate and polyhydro~y fatty acid amide surfact~ntc. The high-slldsin~ nature of these surf~ct~nts is well known. ~n~leed, both alkyl etho~cys~llf~te and polyhydro~y fatty acid amide surf~ct~nts are known in the art, as surf~ct~nts for use in high-slJd~in~ m~nu~l dishw~shin~ compositions as represente~ for e~ample by the composition disclosed in PCT Patent Application No. WO 92/06163.
The high-su~lsin~ characteristic presents a problem when these surf~ct~nts WO 95/02665 PCT/US94/07660 ~
~69~2 ` ` 2 are to be included as major components of the surfactant system of detergent compositions for use in machine washing processes, such as machine laundering processes and machine dishwashing processes, where control of suds is required. The problem is particularly severe where the washing processes are carried out in high temperature and/or soft water conditions.

Suds suppression systems, particularly those utilising silicone antifoam compounds are well-known in the detergent art. The active suds suppressing components of such systems may be incorporated into granular detergent compositions, in a number of ways. ~or example the suds suppressing component may be dissolved or dispersed in an inert carrier liquid and then be sprayed on to the granular components of the detergent composition. Alternatively, the suds suppressing component may be present as a distinct particulate component of the granular composition. It is conventional for the suds ~uppressing component to be added as either a spray-on or as a distinct particulate.

The Applicants have found that where a granular detergent composition contains a high proportion of high-~ sin~ surf~ct~nt in the surfactant system a specific suds suppression system combining both spray-on and particulate components provides highly effective suds control, particularly in stressed high telupcrdture/soft water wash conditions. Where only a spray-on component is employed, ca~in~ of the granular product can be a problem, particularly in view of the high levels of active suds ~up~ressing components which need to be incorporated to combat the high-sudsing nature of the surfact~nts. Where all the suds s~lppression system contains only particulate components flash sll~lsin~, that is high levels of s~ in~
which occur rapidly on dissolution of the detelge~t at the commencement of the wash process, can occur, espccially when the particulate component releases the active suds ~uppressing component slowly into the wash solution.

According to one aspect of the present invention there is provided a granular detergeQt composition cont~inins~

(a) from 1% to 30% by weight of the composition of a surf~c~nt WO 95/02665 ~16 ~ 9 6 2 PCT/US94/07660 system containing from 30~ to 100% by weight of the surfactant system of high-sudsing surfactant selected from alkyl sulfate, alkyl ethoxysulfate, polyhydroxy fatty acid amide surfactant and mixtures thereof;
(b) from 0.05% to 20% of the composition of a suds suppressing system comprising in combination (i) a spray on component, comprising antifoam compound and a carrier fluid wherein said spray-on component is incorporated into said granular detergent composition by being sprayed on to one or more of the granular components of the composition (ii)a particulate component, comprising in combination antifoam compound and a water-soluble or water-dispersible carrier material.

wherein said granular detegent composition is free from alkyl benzene sulfonate surfactant.

The weight ratio of antifoam compound in the spray-on component to antifoam compound in the particulate component is prefeldbly from 5: l to l :5, most preferably from 4:1 to 2: l.

l he granular deterge~t compositions are suitable for use in essentially any wa~hin~, cle~nin~ or l~l)n~lering operation where suds control is required.
~n particular the co~ositions are suitable as machine ~ n~3ering or dishwashin~ co~ osilions.

The first essential component of the granular detergent compositions in accordance with the invention is a surf~c~nt system present at a level of from 1% to 50%, prefe~ably from 3% to 30%, more preferably from 5%
to 15 % by weight of the composition. It is an esse-nti~l aspect of the invention that said surf~c~nt system contains from 30% to 100%
preferably 40% to 95%, most preferably 50% to 90% by weight of the surfac~nt system of high-s~l~lsin~ surfac~ant, selected from alkyl sulfate, alkyl etho~ys~llf~te surfact~nt, polyhydro~cy amide surfact~nt, and mi~ctures thereof.

., ' WO 95/02665 ~ ~ 6 6 9 ~ 4 PCT/US94/07660 ~

By alkyl sulfate surfactant, which is an anionic surfactant, it is meant herein a C6-C20 alkyl sulfate surfactant, particularly a C12-C20 alkyl sulfate salt wherein the alkyl sulfate chain may be linear or branched, and the surfactant may be present as a salt formed with any suitable counter-cation, such as the alkali or ~Ik~line metal or ammonium ions.

The C6-C20 alkyl sulfate salts may be derived from natural or synthetic hydrocarbon sources. Preferred examples of such salts include the subst~nti~lly branched C14-C1s alkyl sulfate salts, that is where the degree of branching of the C14-C1s alkyl chain is greater than about 20%. Such subst~nti~lly branched C14-C1s alkyl sulfate salts are usually derived from synthetic sources. Also preferred are C12-C20 alkyl sulfate salts which are derived from natural sources such as tallow fat coconut oil and marine oils.

By alkyl ethoxysulfate surfactant, which is an anionic surfactant, it is meant herein a water soluble alkyl etho~cysulfate surfactant, particularly a C11-C1g alkyl ethoxysulfate salt cont~inin~ an average of from 1 to 7 etho~y groups per mole.

The C 1 1-Clg alkyl ethoxysulfate salt comprises a primary alkyl ethoxysulfate which is derived from the con~lene~tion product of a C 11-C1g alcohol con~len~eA with an average of from one to seven ethylene oxide groups, per mole. Prefel~cd are the C12-C1s alkyl etho~cysulfate salts with an average of from one to five etho~cy groups per mole, and most prefe~ably with an average of from one to three etho~cy groups per mole.

The Cl l-C 18 alcohol itself can be obtained from natural of synthetic sources. Thus, C11-C1g alcohols, derived from natural fats, or Ziegler olefin build-up, or OXO synthesic can form suitable sources for the alkyl group. E~camples of synthetically derived materials include Dobanol 25 (RTM) sold by Shell Chemicals (UK)Ltd which is a blend of C12~1s alcohols, Ethyl 25 sold by the Ethyl Corporation, a blend of C12-C1s alcohols in the ratio 67% C13, 33% C1s sold under the trade name T l~ten~ol by BASF gmbH and S~nperonic (RTM) by ICI Ltd., and Lial 125 sold by Liq lichimica It~ n~. E~camples of naturally occuring WO 95/02665 ~ 1 6 6 9 ~ 2 PCT/US94/07660 materials from which the alcohols can be derived are coconut oil and palm kernel oil and the corresponding fatty acids.

The alkyl ethoxysulfate salt is preferably incorporated into the surfactant system of the compositions of the invention of the invention at a level of from 1% to 4{)% by weight of the surfactant system, most preferably in combination with an alkyl sulfate surfactant. The weight ratio of the alkyl sulfate surfactant to the alkyl ethoxysulfate surfactant in the surfactant system is preferably from 2:1 to 19:1 more preferably from 3:1 to 12:1 and most preferably from 3.5:1 to 10:1. The level of alkyl ethoxysulfate surfactant in any particulate component of the granular detergent composition of the invention is preferably from 0.25% to 10% more preferably from 0.5 % to 5 % and most preferably from 1 % to 3 % by weight of the component.

By polyhydroxy fatty acid amide surf~ct~nt, which is a nonionic surfactant, it is meant herein a compound of the structural formula:

Il I .

wherein: RS is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxypropyl, or a mixture thereof, l.re~e~ably Cl or C2 alkyl, most preferably Cl alkyl (ie. methyl); and R6 is a C11-C31 hydrocarbyl, prefe~dbly straight chain C11-C1g alkyl, or aLkanyl most ~refeiably straight chain C1s-C17 alkyl or allcenyl, or mi~ re thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydro~cyls directly conn~octe~ to the chain, or an alkoxylated derivative (preferably ethoxylated or propo~cylated) thereof. Z preferably will be derived from a reducing sugar in a reductive ~min~tion reaction; more ~refeldbly Z is a glycityl.
Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and ~cylose.

As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be lltilis~ as well as the individual sugars listed above. ~hese corn syrups may yield a mix of sugar components for WO 95/02665 PCT/US94/07660 ~
9 ~ 2 6 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-CH2OH, i-CH2-(CHOH)2(CHOR')(CHOH)-CH2OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls 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-hydro~cy ethyl, or N-2-hydro~ypropyl.

R6-CO-N ~ can be, for example, coc~mi~e, stearamide, ole~mide, lauramide, myrist~mi~le, capric~mi~e, p~lmit~mi-le, tallowamide, etc.

Z can be 1-deo~yglucityl, 2-deo~cyfructityl, l~eo~cymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deo~cym~nnityl, 1-deo~ymaltotriotityl, etc.

The most preferred polyhydroxy fatty acid amide has the general formula o ~H3 R6_ C--~--CH2(CHOH)4CH20H
wherein R6 is a Cll-Clg straight-chain alkyl or alkenyl group.

Methods for m~in~ polyhydro1cy fatty acid ~mirles are known in the art.
In eneral, 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 polyhydro~cyamine, a~d then re~cting the N-allcyl polyhdro~cyamine with a fatty aliphatic ester or triglyceride in a con~len~tif n/~mi~l~tion step to form the N-alkyl, N-polyhydro~y fatty acid amide product. Processes for m~l~in~ compositions con~inin~ polyhydro~cy fatty acid ~mi~les are disclosed, for e~cample, in GB Patent Specification 809 060, published February 18, 1959, by Thomas Hedley'~c 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.

~ WO 95/02665 ~ ~ ~ 6 9 ~' ~ PCTIUS94/07660 It is preferable that the alkyl sulfate surfactant or polyhydroxy fatty acid amide surfactant and the alkyl ethoxysulfate surfactant are in intim~te admixture, that is they should be mixed prior to the formation of the granular component. 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 the granule is formed an intim~te mixture of the surfactants should be made before agglomeration, milling, fl~kin~, prilling or any other particulate forming process takes place.

The surf~ct~nt system of the compositions of the invention may also contain surfactants other than the alkyl sulfate, alkyl ethoxysulfate or polyhydroxy fatty acid amide surf~ct~nt at a level of from oæ to 70% by weight of the surfactant system. These surf~ct~nt~ may be anionic, nonionic, cationic, zwitterionic or amphoteric in nature.

Use of ~lk~ne sulfonate salts as anionic surf~ct~nts 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 e~ample be S03, H2S04 or oleum the reaction being carried out according to known sulfonation m~th~, including bleaching and hydrolysis. In accord with the present invention the aliphatic C12-C20 ~Ik~n~ sulfonate salts are prefe~ with the aliphatic C14-C20 alkane sulfonate salts being most prefclred. Preferred as cations are the aL~cali metal and ammonium cations.

Alkyl ester sulfonate surf~ct~nts hereof include linear esters of C12~20 carbo~cylic acids (ie. fatty acids) which are sulfonated with gaseous S03 according to "The Journal of the American Oil Chemists Society," 52 (1975), pp. 323-329. Suitable starting materials include natural fatty subst~nces as derived from tallow, palm oil, etc.
.

The preferred alkyl ester sulfonate surf~ct~nts in accord with the invention comprise methyl ester sulfonate surfactants of the structural formula:

WO 95/02665 '2 166 9 62 ~ PCT/IJ594/07660 ~

R3 CH---C ~R4 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, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanol~mine, diethanol~mine, and triethanol~mine. Most preferably, R3 is C14-C20 alkyl.

The second essential component of the granular detergent compositions of the invention is a suds suppressing system present at a level of from 0.05~ to 20%, preferably from 1% to 10%, most preferably from 2% to 8% by weight of the composition. The suds suppressing system comprises in combination a spray-on component and a particulate component.

The spray-on component of the suds ~u~ressing system is characterized by its fluid nature and by its method of incorporation into the granular detergent composition, namely by a spraying on process.

The spray-on component comprises in combination an antifoam compound and a carrier fluid a~d optionally a dispersant compound. The antifoam compound is dissolved, dispersed, suspended or eml-leifieA in said carrier fluid. The carrier fluid should be inert in nature, that is it should not undergo ~ln~lesirable chemical reaction with the antifoam compound, and also prefeldbly be storage stable under normal atmospheric conditions and in the environment of a granular dete~gent matri~.

The spray-on component is incorporated into the granular detergent compositions of the invention by a spray-on process, that is a process whereby the liquid is sprayed on to some or all of the individual granular components of the composition. Highly preferably the spray~n process will be such as to provide a uniform and sufficient application of the suds WO 95/02665 ~ 1 ~i 6 ~ 6 ~ PCT/US94/07660 suppressing component to any granular components of the composition which comprise a high sudsing surfactant.

A preferred composition for the spray-on component comprises (a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination (i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and (ii)silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound; wherein said silica/silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight of the spray-on component;
(b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78 % and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, preferably 1~ to 10% by weight of the spray-on component; a particularly prefelled silicone glycol rake copolymer of this type is DC0544 (trade name), commercially available from DOW Corning.
(c~ an inert carrier fluid compound, most preferably comprising a C16-C1g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5~ to 80%, preferably 10% to 70%, by weight of the spray-on component;

The sp~ay on component of the suds suppressing system may be incorporatëd as such, or in a preferred e~tec~ltion may be mi~ced with other components such as liquid nonionic surf~ct~nt~, and perfume, and this mi~cture sprayed on as a whole.

Tbe particulate component of the suds suppressing system is characterized by its particulate form and by its incorporation i~to the compositions of the invention in this form.

2 ~ ~ ~ 9 ~ ?~ PCT/US94/07660 ~
- . ,, 10 By particulate form it is meant essentially any of the particulate forms which may be typically adapted by a component of a granular detergent composition. The particulate component can therefore be, for example, in the form of granules, flakes, prills, marumes or noodles. In a preferred execution the particulate is granular in nature. Granules themselves may be agglomerates formed by pan or drum agglomeration or by an in-line mixer, and also may be spray-dried particles produced by atomising 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, eg: by high speed cutter mi~cers and/or compacting mills, to increase density before being reagglomerated.

The particulate component of the suds suppressing system comprises in combination antifoam compound, and a carrier material which is highly preferably water-soluble or water-dispersible in nature.

A suitable particulate antifoam component useful in the compositions herein comprises a mixture of an alkylated siloxane of the type hereinabove disclosed and solid silica.

The solid silica ca~ be a fumed silica, a precipitated silica or a silica, made by the gel formation technique. The silica particles suitable have an average particle size of from 0.1 to 50 micrometers, preferably from 1 to 20 micrometers and a surface area of at least SOm2/g. These silica particles can be rendered hydrophobic by treating them with dialkylsilyl groups and/or trialkylsilyl ~,roll~s either bonded directly onto the silica or by means of a silicone resin. It is preferred to employ a silica the particles of which have been rendered hydrophobic with ~imet:~yl and/or trimethyl silyl groups. A ~refell~ particulate antifoam compound for inclusion in the de~ergent compositions in accordance with the invention suitably contain an amount of silica such that the weight ratio of silica to silicone lies in the range from 1:100 to 3:10, preferably from 1:50 to 1:7.

Another suitable particulate antifoam component is represent~l by a hydrophobic sil~n~te~ (most preferably trimethyl-sil~n~ed) silica having a particle size in the range from 10 nanometers to 20 nanometers and a ~ ~ 6 ~ PCT/US94/07660 WO 95/02665 v ~ V f~

specific surface area above 50m2/g, intim~tely admixed with demethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to sil~n~te~l silica of from about 1:1 to about 1:2.

Suitable particulate antifoam components are disclosed in Bartollota et al.
US Patent 3 ,933 ,672.

A highly preferred particulate antifoam component is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50C to 85C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain cont~inin~ from 12 to 20 carbon atoms. EP-A~210721 discloses other preferred particulate antifoam components wherein the organic carrier material is a fatty acid or alcohol having a carbon chain cont~inin~ from 12 to 20 carbon atoms, or a mixture thereof, with a melting poine of from 45C to 80C.

O ;her highly preferred particulate antifoam components are described in copending European Application 91870007.1 in the name of the Procter and Gamble Company which components comprise silicone antifoam compound, a carrier material, an organic co~ti~ material and glycerol at a weight ratio of glycerol: silicone antifoam compound of 1:2 to 3:1.
Copen~lin~ Europcan Application 91201342.0 also discloses highly preferred partic~ te antifoam components comprising silicone antifoam compound, a carrier material, an organic coating material and cryst~lline or amorphous ~ minQsilicate at a weight ratio of ~ minosilicate silicone antifoam compound of 1:3 to 3:1. The ~referred carrier material in both of the above described highly preferred granular suds controlling agents is starch.

An e~emplary particulate antifoam component for use herein is a particulate agglomerate component, made by an agglomeration process, comprising in combination (i) from 5% to 30%, preferably from 8% to 15% by weight of the component of silicone antifoam compound, preferably comprising in combination poly~imethyl silo~ane and silica;

WO 95/02665 ~ 1 6 6 ~ ~ 2 12 PCT/US94/07660 ~

(ii) from 50% to 90%, preferably from 60% to 80% by weight of the component, of carrier material, preferably starch;
(iii)from 2% to 30%, preferably from 5% to 20% by weight of the component of agglomerate binder compound, where herein such compound can be any compound, or mixtures thereof typically employed as binders for agglomerates, most preferably said agglomerate binder compound comprises a C16-C1g ethoxylated alcohol with a degree of etho~cylation of from 50 to 100; and (iv)from 0% to 15%, preferably from 1% to 10%, by weight of C12-C22 hydrogenated fatty acid.

The incorporation of silicone antifoam compounds as components of seperate particulate components also permits the inclusion therein of C20-C24 fatty acids, microcryst~llin~ waxes and high MWt copolymers of ethylene o~cide and propylene o~cide which would otherwise adversely affect the despersibility of the matri~. Techniques for forming such particulates are disclosed in US Patent No. 3,933,672.

A preferred suds suppressing system in accord with the invention has the weight ratio of antifoam compound comprised in the spray-on component to antifoam compound comprised in the particulate component of from 5:1 to 1:5, mostpreferablyfrom4:1 to2:1.

Antifoam compound is a required element of both the spray on and particulate components of the suds ~upplessing system. By antifoam compound it is meant herein any compound or mi~ctures of compounds which act such as to de~ress the fo~min~ or s~l~isin~ produced by a solution of a det~r~e.lt composition, particularly in the presence of ~git~ion of that solution.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term "silicone" as used herein, and in general throughout the in~h)stty~ encomp~ses a variety of relatively high molecular weight polymers cont~ining silo~cane units and hydrocarbyl group of various types.

~; wo ss/0266s ~ l ~ 6 ~ ~ ~ PCT/US94107660 Preferred silicone antifoam compounds are the siloxanes having the general structure:

R R

R- SiO Si R
n R R

where each R independently can be an alkyl or an aryl radical. Examples of such substituents are methyl, ethyl, propyl, isobutyl, and phenyl.
Preferred polydiorganosiloxanes are polydimethylsilo~anes having trimethylsilyl endblocking units and having a viscosity at 25C of from 5 x 10~5m2/s to 0. lm2/s i.e. a value on n in the range 40 to 1500. These are preferred bec~-lse of their ready availability and their relatively low cost.

Other suitable antifoam compounds include the monocarbo~cylic fatty acids and soluble salts thereof. These materials are described in US
Patent 2,954,347, issued Se~telllber 27, 1960 to Wayne St. John. The monocarbo~cylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, prferably 12 to 18 carbon atoms. Suitable salts include the aLkali metal salts such as so~ m, pot~csillm, and lithium salts, and ammonium and nc!l~mmonium salts.

Otlher suitable antifoam compounds include, for e~cample, high molecular weight hydrocarbons such as paraffin, fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C1g-C40 keltones (e.g. stearone) N-alkylated amino tri~7ines such as tri- to he~a-alkylmel~mines or di- to tetra alkylcli~mine chlortri~7ines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine cont~inin~ 1 to 24 carbon atoms, propylene o~cide, and monostearyl di-alkali metal (e.g. sodium, pot~ssillm, lithillm) phosphates and phosphate esters. The hydrocarbons, such as paraffin and W095/02665 ~,i6~6~ PCT/US94/07660 ~;~

haloparaffin, can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40C and about 5C, and a minimum boiling point not less than 110C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100C. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al.
The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or lln~hlrated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin", as used in this suds supressor dicussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.

Copolymers of ethylene oxide and propylene oxide, particularly the mi~ced etho~ylated/propoxylated fatty alcohols with an alkyl chain length of from 10 to 16 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propo~cylation of from 1 to 10, are also suitable antifoam compounds for use herein.

O~tional in~redients The compositions of the invention optionally comprise other ingredientswhich are typically found as components of granular detergent compositions.

A highly ~refe~icd optional ingredient is a builder system comprising one or more inorganic and/or organic builder salts. The builder system will typically comprise from 1% to 80%, preferably S% to 60%, most preferably from 20~ to 60% by weight of the granular detergent compostions.

The inorganic and/or organic builder salts may be water-soluble or water-insoluble and can include, but are not restricted to allcali metal carbonates, cryst~lline layered sodium silicates, bicarbonates, silicates, aluminosilicates, monomeric polycarbo~cylates, homo or copolymeric polycarbo~cylic acids or their salts in which the polycarbo~cylic acid comprises at least two carbo~cylic radicals separated from each other by WO 95/0266!~ i 6 9 g 2 PCTIUS94/07660 not more than two carbon atoms, organic phosphonates and aminoalkylene poly (alkylene phosphonates) and mixtures of any of the foregoing.

The builder salt is preferably present in any individual particulate components of the composition in an amount from 15% to 95 % by weight.

If the particulate component of the composition is a spray dried granule the builder salt component is present more preferably in an amount from 25 % to 85 % by weight of the particulate and if the particulate component is a particulate agglomerate more preferably in an amount from 20~ to 85 % by weight of the particulate.

Preferred builder systems are free of boron compounds and any polymeric organic materials are preferably biodegradable.

Suntable silicates are those having an SiO2:Na2O ratio in the range from 1.6 to 3.4, the so-called amorphous silic~tes of SiO2: Na2O ratios from 2.0 to 2.8 being employed where ~d~lition to the mixture of ingredients that are spray dried is required. Where ~ minosilicates constitute an ingredient of the mi~cture to be spray dried, silicates should not be present in the mi~cture but can be incorporated in the form of an aqueous solution serving as an agglomerating agent for other solid components, or, where the silicates are th~m~elves in particulate form, as solids to the other part~ te components of the composition. However, for compositions in which the perce~ e of spray dried components is low i.e. 30%, it is preferred to include the amorphous silis~te in the spray-dried components.

Whilst a range of ~lllminosilicate ion e~ch~n~e materials can be used, preferred sodium ~l-)minQsilicate zeolites have the unit cell formula Naz t(A102 ) z (SiO2 )y ] ~cH 2 wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and ~ is at least 5, prefe~ably from 7.5 to 276, more preferably from 10 to 264. The ~ minosilicate materials are in hydrated form and are -WO 95/02665 2 ¦ ~ ~ 9 ~ 2 16 PCT/US94/07660 ~

preferably crystalline, cont~ining 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 diameter 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 material as determined by conventional analytical techniques such as, for example, microscopic determination lltili7inp a Sc~nnin~
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 aluminosilicate, 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 exchange rate which is at least 130 mg equivalent of CaC03/litre/minl~te/(g/litre) t2 grains Ca+ +/
gallon/min-~te/gram/gallon)] of ~ll)minosilicate (anhydrous basis), and which generally lies within the range of from 130 mg equivalent of CaC03/litre/minl~te/(gram/litre) [2 grains/gallon/minllte/ (gram/gallon)]
to 390 mg equivalent of CaC03/litre/mim)te/ (gram/litre) [6 grains/gallon/minllte/(gram/gallon)], based on calcium ion hardness.

Optimllm aluminosilicates for builder purposes exhibit a calcium ion e~cchange rate of at least 260 mg equivalent of CaC03/litre/ minl~te/
(gram/litre) [4 grains/gallon/min~lte/(gram/gallon)].

Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available and can be naturally occurring materials, but are yreferably synthetic~lly derived. A method for producing ~ minosilicate ion exch~n,~e materials is discussed in US
Patent No. 3,985,669. Preferred synthetic cryst~lline aluinosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS, Zeolite MAP and mixtures thereof. In an especially preferred embodiment~ the cryst~lline aluminosilicate ion e~cchange material is Zeolite A and has the formula ~ wo 95/02665 ~ ~ ~ 6 9 ~ 2 PCT/US94/07660 Na 12 [(A102 ) 12 (SiO2)12 ]- xH2 0 wherein x is from 20 to 30, especially 27. Zeolite X of formula Na86 [(A12)86(Si2)106~- 276 H2O is also suitable, as well as Zeolite HS of formula Na6 [(Alo2)6(sio2)6] 7-5 H2 )-Suitable water-soluble monomeric or oligomeric carboxylate builders can be selected from a wide range of compounds but such compounds preferably have a first carbo~cyl logarithmic aciditytconstant (pKl) of less than 9, preferably of between 2 and 8.5, more preferably of between 4 and 7.5 The logarithmic acidity constant is defined by refere~ce to the equilibrium H+ + A- ~ ` HA
where A- is the fully ionized carboxylate anion of the builder salt.

The equilibrium constant is therefore K1 = (H A) (H+) (A-) ar d pK1 = lglOK-For the purposes of this specification, acidity conct~nt.e are defined at25C and at zero ionic strength. Literature values are taken where possible (see Stability Conct~nts of Metal-Ion Comple~ces, Special Publication No. 25, The Chemical Society, London): where doubt arises they are determined by potentiometric titration using a glass electrode.

Prefe~ carbo~ylates 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) WO 95/02665 ~ 6 ~ G 2 PCT/US94/07660 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 carbo~ylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarbo~cylates are generally preferred for reasons of cost and performance.

Monomeric and oligomeric builders can be selected from acyclic, alicyclic, heterocyclic and aromatic carboxylates having the general formulae X C ~2 X C

or wherein Rl repr~ssnt~ H,Cl 30 alkyl or allcenyl optionally su~sl;lvt~ by hydro~cy, carbo~cy, sulfo or phosphono groll~s or ~ ch~ to a polyethyleno~cy moiety cont~ining up to 20 ethyleneo~y groul)s; R2 rep~ere"ts H,Cl~ allcyl, alkenyl or hydro~y allcyl, or allcaryl, sulfo, or phosphono groups;
X represents a single bond; O; S; SO; SO2; or NRl;

WO 95/02665 ~ 9~ PCT/US94/07660 Y represents H; carboxy;hydroxy; carboxymethyloxy; or C 1-30 alkyl or alkenyl optionally substituted 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;
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 different 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~ining one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831 368, 821 369 and 821 370.

Polycarboxylates cont~ininP two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) ~i~cetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic 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 carbo~cylates described in Belgian Patent No.
840 623. Polycarboxylates cont~ininp three carbo~cy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carbo~cymethyloxysuccinates described in British Patent No. 1 379 241, lactoxysuccinates described in British Patent No. 1 389 732, and aminosuccinates described in Netherlands Application 7 20S 873, and the o~ypolycarbo~cylate materials such as 2-oxa-1,1,3-pr~aQe tricarboxylates described in British Patent No. 1 387 447.

Polycarboxylates cont~inin~ four carboxy gro,lps include oxydisuccinates disclosed in British Patent No. 1 261 829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarbo~cylates and 1,1,2,3-propane tetracarbo~ylates. Polycarbo~cylates cont~inin~ sulfo sllbstitl~ents 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.

WO 95/02665 ~, PCT/US94/07660 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 carboxymethyl derivatives of polyhydric alcohols such as sorbitol, m~nnitQl and xylitol. Aromatic 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 mi~ctures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as components of builder systems of detergent compositions in accordance with the present invention.

Other suitable water soluble organic salts are the homo- or co-polymeric polycarbo~ylic acids or their salts in which the polycarbo~ylic acid comprises at least two carbo~cyl r~lic~l~ separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1 596 756. E~camples of such salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molec~ r 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 10% 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) include alkali metal ethane l-hydro~y diphosphonates, nitrilo trimethylene phosphonates, ethylene ~i~mine tetra methylene phosphonates and diethylene tri~mine penta methylene phosphonates, although these ~ WO 95/02665 ~ 62 PCT/US94/07660 materials are less preferred where the minimisation 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.

In the concentrated detergent compositions of the present invention it is preferred that water-soluble slllf~te, particularly sodium sulfate, should be present at a level of not more than 5 % and preferably at a level of not more than 2.5% by weight of the composition. Preferably no sodium sulfate is added as a separate ingredient and its incorporation as a by-product e.g. with the sl)lf~tP~ surfactants, should be minimisefl.

The particulate components can also include miscellaneous ingre~lientc preferably in a total amount of from 0% to 45% by weight, e~amples of such ingredients being optical brighte~ers, anti-redeposition agents, photoactivated bleaches (such as tetrasulfonated zinc phthalocyanine) and heavy metal sequestering agents. Where one or more of the particulate components is a spray dried powder it will normally be dried to a moisture content of from 7% to 11% by weight, more preferably from 8~ to 10% by weight of the spray dried powder. Moisture contents of powders produced by other processes such as agglomeration may be lower and can be in the range 1-10% by weight.

The particle size of any partiC~ te components 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 m~simllm ~limPnsiom Preferably at least 60%, and most l)rGfelably at least 80%, by weight of the powder lies between 0.7 mm and 0.25 mm in size.
Preferred detergent compositions in accordance with the invention comprise at least one spray dried granular surfac~nt-cont~inin~ particulate component and at least one surfac~nt-cont~inin~ particulate agglomerate component.

Por 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 WO 95/02665 ~ 62 22 PCT/US94/07660 ~

this is then enhanced by further processing 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 particulate 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 mixed agglomerate which may be made by ~tlin~ the ingredients dry or with an agglomerating agent to a pan agglomerator, Z
blade mixer or more preferably an in-line mi~er such as those m~nllf~ctured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands and Gebruder Lodige l~cchinenbanGmbH, 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.

Preferably any particulate agglomerate components include sodium carbonate at a level of from 20% to 40% by weight of the component.
Preferably, the composition includes from 3% to 18% sodium carbonate by weight of the composition, more yrefe~dbly from 5% to 15% by weight.

A highly prefe~f~ ingredient of any particulate agglomerate components is also a hydrated water insoluble aluminosilicate ion e~cchange material of the s~lLetic zeolite type, described hereinbefore, present at from 10% to 55% 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 preferably &om 2% to 10% by weight.

In one process for preparing the particulate agglomerate component, the surf~ct~nt salt is formed in situ in an inline mi~cer. The liquid acid form of the surfactant is added to a mi~ture of particulate anhydrous sodium carbonate and hydrated sodium ~ minosilicate in a continuous high speed blender, such as a Lodige KM mi~cer, and neutralised to form the sur~ct~nt salt whilst m~int~inin~ the partic~ te nature of the mixture.

wo 95/0266~ 2 PCTIUS94107660 Tlle resultant 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.

Preferred compositions in accordance with the invention comprise one or more multi-ingredient particulate components which may contain one or more additional surfactants which may be water-soluble. These surfactants may be anionic, nonionic, cationic or semipolar in type.

A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in USP 3 929 678 issued to r ~l~ghlin and Heuring on December 30 1975. A list of suitable cationic surfactants is given in USP 4 259 217 issued to Murphy on March 31 1981.

Preferably the granular detergent compositions in accordance with the invention will comprise from 2% to 9% additional nonionic surf~ct~nt by weight of the total detergent composition. Additional nonionic surf~ct~nt is an especially preferred component of the detef~cnt compositions in accord with the invention when the total level of anionic surfactant is from 5% to 15% by weight of the composition.

One class of nonionic surfactant~s useful in the present invention comprises con~lens~tes of ethylene oxide with a hydrophobic moiety, providing surf~ct~nts having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.S to 13.S, more ~rerelably from 10 to 12.5. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyo~cyethylene 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~nce between hydrophilic and hydrophobic elements.

Especially preferred additional nonionic surfactants of this type are the C12-C20 primary alcohol etho~ylates cont~inin~ an average of from 3-11 moles of ethylene o~ide per mole of alcohol, particularly the C12-C1s WO 95/02665 ~ ~ ~à 6 ~ ~ 2 PCT/US94/07660 ~

primary alcohol ethoxylates Con~inin~ an average of from 3-7 moles of ethylene oxide per mole of alcohol and most preferably the C12-C1s primary alcohol ethoxylates cont~inin.~ an average of 3 moles of ethylene oxide per mole of alcohol.

Another class of nonionic surfact~nts comprises alkyl polyglucoside compounds of general formula RO (cnH2no)tz~c wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that 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 &tty alcohol and less than 50% short chain alkyl polyglucosides. Compounds of this type and their 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 surfactants are the semi-polar surf~ct~nts such as amine oxides. Suitable amine oxides are selected from mono Cg-C20, preferably Cl~C14 N-alkyl or alkenyl amine o~ides and propylene-1,3-~i~mine dioxides wherein the rem~ininE N positions are substi~uteA by methyl, hydro~cyethyl or hydro~cpropyl groups.

Cationic surf~c~nts can also be used in the detergent compositions herein and suitable quaternary ammonium surf~ct~nt~ are selected from mono Cg-C16, preferably Cl~C14 N-alkyl or alkenyl ammonium surfactants wherein rem~inin~ N positions are substitllte~ by methyl, hydro~cyethyl or hydro~cypropyl groups.

The particulate components may have any suitable physical form, i.e. itmay take the form of flakes, prills, marumes, noodles, ribbons, or granules which may be spray-dried or non spray~ried agglomerates.

Although any further component could in theory comprise a water-soluble surf~ct~nt on its own, in practice at least one organic or inorganic salt is included to facilitate processin~. This provides a degree of WO 95/0266~ i 6~ ~ 2 PCT/US94/07660 crystallinity, and hence acceptable flow characteristics, to the particulate and may be any one or more of the organic or inorganic salts present in the first component.

Where there is only one surfactant-cont~inin~ component 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~ining particulate components forms part of the composition. Thus one or more of oxygen bleaches, photoactivated bleaches, bleach activators, builder salts, detergent enzymes, suds suppressors, fabric softening agents, soil suspension and anti-redeposition agents, soil release polymers, and optical brighteners can be added as solids to one or more surf~ct~nt-cont~inin~ particulate components.

Suitable oxygen bleaches include the inorganic perhydrates such as sodLium perborate monohydrate and tetrahydrate, sodium percarbonate, sodlium perphosphate and sodium persilicate. Sodium percarbonate and the sodium perborate salts are most preferred. These materials are normally added as cryst~lline solids and, in the case of sodium percarbonate, may be coated with e.g. silicate in order to aid stability.
Us~ge levels range from 3% to 40% by weight, more preferably from 5%
to 30% by weight.

Photoactivated bleaches include the zinc and ~ minium salts of tri and tetra sulfonated phthalocyanine which are normally added as dispersions in other materials bec~llce of their low levels of usage, typically from 0.~005 to 0.01% by weight of the composition.

Bleach activators or pero~y acid bleach precursors can be selected from a wide range of classes and are preferably those cont~inin~ one or more N-or 0- acyl groups.

Suitable classes include anhydrides, esters, imi~es and acylated derivatives of imi~7oles and o~imes, and e~camples of useful materials within these classes are disclosed in GB-A-1586789. The most preferred classes are esters such as are disclosed in WO 9~/02665 . PCT/US91/07660 ~ & 9 ~ 2 26 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 incorporation range from 1 % to 10% more generally from 2% to 6% by weight of the composition.

Particularly preferred precursor compounds are the N-,N,NlN1 tetra acetylated compounds of formula Q O
Il 11 = N - (cH2)x- N
CH3 11 \ C - CH3 O O
wherein x can be O or an integer between 1 ~ 6.

Examples include tetra acetyl methylene ~ mine (~AMD) in which x= 1, tetra acetyl ethylene rli~mine (rAED) in which x=2 and tetraacetyl he~cylene ~ mine (TAHD) in which x=6. These and analogous compounds are described in GB-A-907 356. The most preferred peroxyacid bleach precursor is TAED.

Solid peroxyacid bleach precursors useful in compositions of the present invention have a Mpt ~ 30C and prefeidbly > 40C. Such precursors will normally be in fine powder or crys~lline form in which at least 90 by weight of the powder has a particle size ~ 150 micrometers.

This powder is usually agglomerated to form partic~ te material, at least 85% of which has a particle size between 400 and 1700 micrometers.
Suitable agglomerating agents include aliphatic mono and polycarbo~cylic acids,C12-Clg aliphatic alcohols con~e~e~ with from 10 to 80 moles of ethylene oxide per mole of alcohol, c~llulose derivatives such as methyl, carbo~cymethyl and hydroxyethyl cellulose, polyethylene glycols of MWt 4,000 - 10,000 and polymeric materials such as polyvinyl pyrrolidone.

~1 ~6~

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

Builder salts that can advantageously be added as solid particulates include silicates and certain polycarboxylate builders such as citrates.

Dry mix addition of amorphous sodium silicates, particularly those of SiO2:Na2O ratio of from 1.0:1 to 3.2:1 is employed where alurninosilicates form part of a spray dried component, in order to avoid the formation of insoluble reaction products. Furthermore the incorporation of crystalline, so called 'layered' silicates into detergent compositions necessitates their addition as solids.
.

These crystalline layered sodium silicates have the general formula NaMSix02x+1 YH2 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 types are disclosed in EP-A-0 164 514 and methods fortheir 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 preferably 2. More preferably 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 preferred material is ~-Na~Si2Os, (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 methacrylic acid, the maleic S~JBSTl~U~E SHEET ~RULE 2~) -WO 95/02665 2 ~. ~ 6 9 6 2 2 8 PCTIUS94/07660 ~

anhydride constituting at least 20 mole percent of the copolymer. These materials are normally used at levels of from 0.5% to 10% by weight, more preferably from 0.75% to 8%, most preferably 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~int~n~nce, fabric ash deposition, and cle~nin~ performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.

Preferred optical brighteners are anionic in character, e~camples of which are disodium 4~4l-bis-(2-diethanol~mino~nilino -s- triazin-~ylamino)stilbene-2:2 1 disulphonate, disodium 4,41-bis-(2-morpholino -4-anilino-2-triazin-~yl~ minostilbene-2 :2 4isulphonate,disodium 4, 4 1 -bis-(2,4~ nilino-s-triazin-~ylamino)stilbene-2:21 - disulphonate, monosodium 41,411-bis-(2,4~i~nilino-s-triazin-6 yl~mino)stilbene-2-sulphonate, disodium 4,41-bis-(2-~nilin~(N-methyl-N-2-hydro~cyethyl~mino)-2-triazin-~yl~mino)stilbene-2,21 - disulphonate, disodium 4,41-bis-(4-phenyl-2,1,3-triazol-2-yl)stilbene-2,21 disulphonate, disodium 4,41bis(2-~nilino~(1-methyl-2-hydro~ hyl~rnino)-s-triazin-~yl~mino)stilbene-2,21disulphonate and sodium 2(stilbyl41 1-(naphtho-11,21:4,5)-1,2,3 - triazole-211- sulphonate.

Soil-release agents useful in compositions of the prcs~nt invention are conventionally copolymers or terpolymers of terephth~lie acid with ethylene glycol and/or propylene glycol units in ~arious arrangements.
Examples of such polymers are disclosed in the commonly ~s~i~n~ 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~ 272 033 has the formula (CH3(PEG)43)0.75(PoH)o.25(T-po)2.8(T-pEG)o 4)T(po-H)o 2s((PEG)43cH3)0 75 where PEG is ~OC2H4)0-,PO is (OC3H60) and T is (pCOC6H4CO).

WO 95102665 ~1 6 6 9 ~ 2 PCT/US94/07660 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 ingredient useful in the present inventioD is one or more enzymes.

Preferred enzymatic materials include the commercially available arnylases, neutral and ~ lin~ proteases, lipases, esterases and cellulases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3 519 570 and 3 533 139.

Fabric softening agents can also be incorporated into detergent - compositions in accordance with the present invention. These agents may be inorganic or organic in type. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898. Organic fabric softening agents include the water insoluble tertiary ~mines as disclosed in GB-A-1 514 276 and EP-B-0 011 340.

Their combination with mono C12-C14 quaternary ammonium salts is disclosed in EP-B~ 026 527 ~ 0 026 528. Other useful organic fabric softening agents are the dilong chain ~mi~es as disclosed in EP-B~ 242 919. Additional organic ingredie~ts of fabric softening systems include high mo~ r weight polyethylene oxide materials as disclosed in EP-A-0299S75andO313 146.

Levels of sm~octite 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 dry mi~ed component to the rem~in~er of the formulation. Organic fabric softening agents such as the water-insoluble tertiary ~mines 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 o~ide 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, WO 95/02665 ~ PCT/IJS94/07660 these materials can be added to the aqueous slurry fed to the spray drying tower, although in some instances 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.
The granular compositions of the present invention preferably have a bulk density of at least 5~0g/litre, preferably 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 contents of the funnel to be emptied into an axially ~ ne~ cylindrical cup disposed below the funnel. The funnel is 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 14t) mm above the upper surface of the base. The cup has an overall height of 90 mm, an internal height of 87 mm and an internal ~ meter of 84 ~n. Its nominal volume is 500 ml.

To carry out a measurement, the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup.
The filled cup is removed from the frame and e~ccess powder removed from the cup by p~csin~ 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 m,o~urements 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 mi~cing, spray drying, agglomeration and gr~mJI~tion. A preferred method of m~king the compositions involves a combination of spray drying, agglomeration in a high speed mi~cer and dry mi~cing.

The granular compositions in accordance with the present i~vention preferably comprise a plurality of separate particulate components. The partic~ tes can have any suitable form such as granules, flakes, prills, marumes or noodles but are preferdbly granular. The granules themselves may be agglomerates formed by pan or drum agglomeration WO 95/02665 ~,3L ~; ~ g 6 2 PCT/US94/07660 or by an in-line mixer and also may be spray dried particles produced by atomising 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 derlsification 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~ininP component and at least one surfactant-cont~ining particulate agglomerate component.

Where one or more surfactant-cont~inin~ 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 one or more surf~ct~nt-cont~ining 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~ininP particulates are the only multi ingredient components, the rem~in~ler 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 a particularly l,refelred process for m~kinp dcter~;e~t compositions in accordance with the invention, part of the spray dried product colnprising one of the granular components is diverted and subjected to a low level of nonionic surf~ct~nt spray on before being reblen~ieA with the rem~in~ier.
A second granular component is made using the prefe~l~ process described above. The first and second components together with perhydrate bleach, bleach precursor particulate, other dry mi~c ingreAient~
such as any carbo~cylate chelating agent, soil-release polymer, silic~te of conventional or cryst~llin~ layered type, and enzyme are then fed to a conveyor belt, from which they are transferred to a horizontally rotating drum in which perfume and silicone suds ~.lp~ressor are sprayed on to the product. In highly preferred compositions, a further drum mi~in5~ step is employed in which a low (appro~c. 2% by weight) level of finely divided cryst~lline material is introduced to increase density and improve granular flow characteristics.

W0 95/02665 2~ 3 2 PCT/US94/07660 ~

In preferred concentrated detergent products incorporating an alkali metal percarbonate as the perhydrate salt it has been found necessary to control several aspects of the product such as its heavy metal ion content and its equilibrium relative humidity.

The detergent compositions of the invention may 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 cle~nin~ benefits.

High transient concentrations require rapid dissolution/dispersion of the composition but this is difficult with surf~c~nt cont~ininE particulate components in which the one or more primary anionic or nonionic surfactants are relatively insoluble and hence make the component hydrophobic in nature. The incorporation of a low level of a water soluble Cl1-C1g alkyl ethoxysulfate material into the primary anionic or nonionic surfactant-cont~inin~ particulate has however been found to enable acceptable rate of dissolution characteristics to be achieved whilst ret~inin~ the detergellcy provided by the primary aniorlic or nonionic surfactants.

Delivery systems for introducing the compositions of the invention into an automatic w~shin~ m~chine 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 in response to agitation, a rise in te~elature or immersion in the wash water in the drum.
Alternatively the w~chin.~ machine itself may be adapted to permit direct addition of the composition to the drum e.g. by a dispencin~ arrangement in the access door.

Products comprising a detergent composition enclosed in a bag or container are usually designed in such a way that container integrity is m~int~ine~ in the dry state to prevent egress of the contents when dry, but WO 95/02665 ~ 9 ~ 2 PCTIUS94/0766 are adapted for release of the container contents 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 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. 0 018 678. Alternatively it may be formed 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.
O ~11 500, 0 011 501, 0 011 502, and 0 011 968. A convenient form of water frangible closure comprises a water soluble adhesive disposed along and se~ling one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.
In a variant of the bag or container form, l~min~te~l sheet products can be employed in which a central fle~cible layer is impre~n~te~ and/or coated with a composition and then one or more outer layers are applied to produce a fabric-like ~esthetic effect. The layers may be sealed together so as to remain attached during use or may separate on contact with water to facilitate the release of the coated or imprePn~te~ material.

An alternative l~min~te form comprises one layer embossed or deformed to provide a series of pouch-like conhiners into each of which the detergent components are deposited in m~c~red 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 co~nents may be deposited in particulate, paste or molten form and the l~min~te layers should prevent egress of the contents of the pouch-like containers prior to their addition to water. The layers may set)aYate 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.

WO 95/02665 p ~ 2 ; PCT/US94/07660 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 preferred means of carrying out the process of the invention is to introduce the composition into the liquid surro~lnAin~ 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 European Patent Application Publication Nos. 0 343 069 & 0 343 070. The latter Application discloses a device comprising a flexible sheath in the form of a bag e~ctending from a support ring defining an orifice, the orifice being adapted to admit to the - bag sufficient product for one washing cycle of an automatic process. A
portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium. The support ring is provided with a ma~lring arrangement to prevent egress of wetted, ~ln~iicsolved, product, this arrangement typically comprising radially e~ten~lin~ walls e~te~AinP
from a central boss in a spoked wheel configuration, or a simil~- structure in which the walls have a helical form.

Preferred dispencing devices are reusable and are designed in such a way that container inte~ ity is ~ ntainefl in both the dry state and during the wash cycle. Especially yrefel~ed dispencin~ 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~201376, EP-A~288345 and EP-A-0288346. An article by J. Bland published in Man~f~c~-ring Chemist, November 1989, pages 4146 also describes especially ~referled dispensing devices for use with granular laundry produts which are of a type commonly known as the "gr~n--lette".

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

1~ WO 95/02665 ~ 2 PCT/US94/07660 In ~he detergent compositions, the abbreviated component identifications have the following meanings:
.

45AS : Sodium C14-Cls alkyl sulfate 25AE3S : C12-C1s alkyl ethoxysulfate cont~inin~ 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 Silicate : Amorphous Sodium Silicate (SiO2:Na2O ratio normally follows) Carbonate : Anhydrous sodium carbonate Bicarbonate : Anhydrous sodiumbicarbonate Zeolite A : Hydrated Sodium Aluminosilicate of formula Nal2(Alo2sio2)l2- 27H20 having a primary 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 : Mi~ced proteolytic and amylolytic enzyme sold by Novo Tn~lJstries AS.

WO 95/02665 PCT/US94/07660 _ Example l The following low-sudsing granular detergent composition was prepared in accordance with the invention (percentage, parts by weight).

45AS 8.8 25AE3S 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 Suds su~pressor system Particulate antifoam component 2.1 Spray-on antifoam component 2.0 Misc, minors, moisture to b~l~nce The partic~ te antifoam component was an agglomerate comprising 11%
by weight of the component of poly~limtothylsilo~cane, 14% by weight TAE80, 5% by weight of a mi~ture of C12-C22 hydrogenated fatty acids and 70% by weight of starch.

The spray-on antifoam component comprised 30% by weight of the component of silicone/silica antifoam compound comprising 85 % by weight of the antifoam compound of poly~imethylsilo~cane and 15% by weight of the antifoam compound of silica, 3 % by weight of silicone glycol rake copolymer (DCO544 from DOW Corning), and 67% by weight of TAEl 1 carrier fluid.

Claims (10)

1. A granular detergent composition containing (a) from 1% to 50% by weight of the composition of a surfactant system containing from 30% to 100% by weight of the surfactant system of high-sudsing surfactant selected from alkyl sulfate, alkyl ethoxysulfate, polyhydroxy fatty acid amide surfactant, and mixtures thereof;
(b) from 0.05% to 20% of the composition of a suds suppressing system comprising in combination (i) a spray on component, comprising antifoam compound and a carrier fluid wherein said spray-on component is incorporated into said granular detergent composition by being sprayed on to one or more of the granular components of the composition (ii)a particulate component, comprising in combination an antifoam compound and a water-soluble or water-dispersible carrier material.

wherein said granular detegent composition is free from alkyl benzene sulfonate surfactant

2. A granular detergent composition according to Claim 1 wherein the weight ratio of anifoam compound in the spray-on component to antifoam compound in the particulate component is from 5:1 to 1:5.

3. A granular detergent composition according to either of Claim 1 or 2 wherein said spray-on component comprises (a) silicone antifoam compound, comprising in combination (i) polydimethyl siloxane, at a level of from 50% to 99%, by weight of the silicone antifoam compound; and (ii)silica, at a level of from 1% to 50%, by weight of the silicone antifoam compound; wherein said silicone antifoam compound is incorporated at a level of from 5% to 50%, by weight of the spray-on component;
(b) dispersant compound comprising silicone glycol rake copolymer with a polyoxyalkylene content of 72-78 % and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, by weight of the spray-on component;
(c) carrier fluid comprising a C16-C18 ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, at a level of from 5 % to 80%, by weight of the spray-on component;

4. A granular detergent composition according to any of Claims 1 -3 wherein said spray-on component comprises silicone antifoam compound, comprising in combination (i) polydimethyl siloxane, at a level of from 75% to 95%
by weight of the silicone antifoam compound; and (ii) silica, at a level of from 5 % to 25%, by weight of the silicone antifoam compound; wherein said silicone antifoam compound is incorporated at a level of from 10% to 40%, by weight of the spray-on component;
(b) dispersant compound comprising silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, by weight of the spray-on component;
(c) carrier fluid comprising a C16-C18 ethoxylated alcohol with a degree of ethoxylation of from 8 to 15, at a level of from 10% to 70%, by weight of the spray-on component;

5. A granular detergent composition according to any of Claims 1 - 4 wherein said particulate component is a particulate agglomerate comprising in combination (i) from 5% to 30% by weight of the component of silicone antifoam compound comprising in combination polydimethyl siloxane and silica;
(ii) from 50% to 90% by weight of the component of carrier material;
(iii) from 2% to 30% by weight of the component of agglomerate binder compound;
(iv) from 0% to 15% by weight of the component of C12-C22 hydrogenated fatty acid.

6. A granular detergent composition according to any of Claims 1 - 5 wherein said particulate component is a particulate agglomerate comprising in combination (i) from 8 % to 15% by weight of the component of silicone antifoam compound comprising in combination polydimethyl siloxane and silica;
(ii) from 60% to 80% by weight of the component of starch carrier material;
(iii) from 5 % to 20% by weight of the component of agglomerate binder compound comprising a C16-C18 ethoxylated alcohol with a degree of ethoxylation of from 50 to 100; and (iv) from 1% to 10% by weight of the component of C12-C22 hydrogenated fatty acid.

7. A granular detergent composition according to any of Claims 1 - 6 wherein said surfactant system is present at a level of from 3 % to 30% by weight of the composition, and wherein the surfactant system contains from 40% to 95% by weight of the surfactant system of said high-sudsing surfactant.

8. A granular detergent composition according to any of Claims 1 - 7 wherein said alkyl sulfate surfactant is a C12 - C20 alkyl sulfate surfactant, said alkyl ethoxysulfate surfactant is a C11 - C18 alkyl ethoxysulfate containing an average of from 1 to 7 ethoxy groups per mole and said polyhydroxy fatty acid amide surfactant has the general formula (CHOH)4CH2OH

wherein R6 is a C11-C19 straight-chain alkyl or alkenyl group.

9. A granular detergent compositon according to Claim 8 containing both alkyl sulfate surfactant and alkyl ethoxysulfate surfactant wherein the weight ratio of the alkyl sulfate surfactant to the alkyl ethoxysulfate surfactant is from 2:1 to 19: 1.

10. A granular detergent composition according to any of Claims 1 - 9 comprising a builder system at a level of from 1% to 80% by weight of the composition.