IE61343B1 - Detergent/softening compositions containing hectorite clays - Google Patents

Abstract

Detergent compositions are disclosed which comprise, as a fabric softening ingredient, a fabric softening clay. The fabric softening clay is a hectorite of natural origin, having a layer change distribution such that at least 50% is in the range 0. 23-0. 31 The specified clays have excellent deposition and fabric softening properties.

Description

The present invention relates to detergent compositions. More specifically it relates to detergent expositions containing a fabric-softening amount of a hectorite clay, the clay being in tha form of particles having a narrowly-defined layer charge distribution. bi British Patent 1 376 379 teaches the use of synthetic hectorite clays as anti-redeposition agents. However there is no mention of addressing the problem of fabric softening, and the use of natural hectorite clays is discouraged.

European Patent Application 0 225 142 discloses the use of clay materials having certain 5 swellability characteristics. The application deals exclusively with liquid detergent compositions.

European Patent Application 0 011 340 describes the use of a wide range of clays for fabric softening purposes in detergents. The clays described are mainly smectite clays, and, although hectoriie clays are mentioned in passing, there is no disclosure of hectorite clays of natural origin and of the required layer charge characteristics of the present invention,, '5 British Patent 1 400 898 discloses detergent compositors comprising? as a fabric-softening ingredient, a smectite-tvpe clay. Any smectite-type clay having a cation exchange capacity of at least 50 meq/100 g is taught to be suitable. Gelwhite GP* and Volclay BC*, both of which are sodi’UM iBontmorillonite clays? are disclosed to be preferred for reasons of color and cation exchange capacity.

It is now well recognized in the detergent industry that clays of the type disclosed in British Patent 3. 400 898 provide significant fabric softening benefits when used in a laundry detergent. Yet, it is equally well recognized that deposition of these clays onto the fabrics during the laundering process is far from complete; in fact, under typical European laundry conditions, less than half of the available clay is deposited onto the fabrics, the remainder being rinsed away with the laundry liquor during the subsequent rinsing steps. Moreover, the softening effect obtained as a result of the clay deposition is affected by factors that are not well understood.

It is, therefore, an object of the present invention to provide detergent compositions comprising a fabricsoftening clay from which the clay particles are more efficiently desposited onto fabrics during the laundry process- It is another object of the present invention to provide detergent compositions from which clay particles are efficiently deposited, regardless of the builder system used. It is a further object of this invention to select clay materials for use in detergent compositions that provide a signficiantly better fabric-softening performance than th® clay materials used to date in commercial softeness-through-the-wash detergent compositions.

*'. Trade Mark •i The present invention relates to detergent compositions containing & fabric-softening amount of a fabric-softening clay. The amount of clay is froa 1% to 25% by weight of the detergent composition. Said fabric-softening clay is a hectorite clay of natural origin, commonly referred to as trioctahedral smectite. Th® clay is present in the fans of particles. The particles have a narrowly defined layer charge distribution, such that at least 50% of the clay has a layer charge of from 0.23 to 0.31. tWAJ.ie,D-D5SCRimflH Og THE WMEtOW The detergent compositions of the present invention comprise conventional detersive surfactants, conventional detergent builders and, optionally, other conventional detergent ingredients. The compositions further comprise a fabric-s-ofteting amount, i.e. frca 1% to 25% by weight of the detergent composition, of a fabric-softening clay. The clay, which is of the smectite-type, is selected on basis of its layer charge properties. Ihe hecfcorite clays of natural origin, suitable for the detergent compositions of the present invention, have the general formula III [(8¾.^) Si4.y Ktey 0^(0883^))-(^)(25.+ ^)8^+ n wherein y - o; or, if y ψ o, MteAAA is Al, Pe, or Β; is a monovalent (n - 1) or divalent (n «2) metal ion, for example selected from Na, K, Hg, Cs·., Sr. The value of (x + y) is the layer charge of the hecfcorite clay. The hecfcorite clays suitable for th® detergent compositions of the present invention have a layer charge distribution such that at least 50% is in the range of from 0.23 to 0.31.

Preferred are hectorite clays of natural origin having a layer charge distribution such that at least 65% is in the range of from 0.23 to 0.31.

Tb.g>, layer charge distribution of the clay material can he detenained using its swelling in the presence of cationic surfactants having specific chain lengths. This method is described in detail by lagaly and Weiss, Zeitschrift fuer Pflamenermehxung und Bodenkunde, 130(1), 1971, pages 9-24.

Recently, a method has been developed for objective assessment of fabric softeners. The method consists of a battery of tests, known in the detergent industry as the KBS-F system of Kawbata- Tbe method is described in S. Kawabata, ''The standardisation and Analysis of Hand Evaluation™, 2nd ScL, Textile Mach. Soc- of Japan,, Osaka. 1380 .

It has been found that one of the parameters, of the KBS-F system, the shear hysteresis parameter 2HG5, is (· particularly useful in the characterization of fabric softening clays. Preferred herein are hectorite clays which, when inccnporated in detergent compositions at 10% by weight, reduce the shear hysteresis of fabrics laundered therein by at least 32%, more preferably by at least 35%. The shear hysteresis parameter 2HG5 is discussed in more detail in Finniraore and Koenig, Kelliand Textilberichte 67 (1986) pages 514-516.

Shear hysteresis is determined on cotton terry towels, with detergent compositions containing 10% (weight) of the clay to toe tested- The test is described xaore fully in the Examples hereinbelow.

The hectorite clays used in the detergent compositions are further characterized by an unusually great propensity for deposition onto fabrics. In a standardized test, deposition onto fabrics of the claimed hectorite clays from a detergent composition is greater than the deposition of conventional smectite-type days or of synthetic hectorites. Examples of suitable hectorite clays include Benton© EW*and Macaloid*from NL Chemicals, MJ., and hectorites from Industrial Mineral Ventures.

O^^r^dgtergent^a^nents Detersive Surfactants - The compositions of this invention will typically contain organic surface-active agents (surfactants) to provide the usual cleaning benefits associated with the use of such materials.

Detersive surfactants useful herein include well-known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants. Typical of these are the alkyl benzene sulfonates, alkyl- and alkylether sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylafced) alcohols and alkyl phenols, amine oxides, alpha-sulfonates of fatty acids and of fattv acid esters, and the like, which are well-known from the detergency art. In general, such detersive surfactants contain an alkyl group in the Cg~C18 range. The anionic detersive surfactants can be used in the form of their sodium, potassium or triethanolammonium salts; the nonionics generally contain from 5 to 17 ethylene oxide groups. U.S. Patent 3 995 559, contains detailed * Trade Mark listings of such typical detersive surfactants.

C^-s-C^ alkyl benzene sulfonates, ci2-c18 paraffinsulfonates and alkyl sulfates, and the. ethoxy lated alcohols and alkyl phenols are especially preferred in the cKaapceitiesns of the present type., Also useful herein as the surfactant are the watersoluble soaps, e.g. the coupon sodium and potassium coconut or tallow soaps well-known In the art» The surfactant component can comprise as little as 1% of the oaopositons herein, but preferably the compositions will contain 5% to 40%, preferably 10% to 30%, of surf,actant. Mixtures of the ethoxylated nonionics with anionics such as the alkyl benzene sulfonates, alkyl sulfates and paraffin sulfonates are preferred for throughthe-wash cleansing of a broad spectrum ot soils and stains from fabrics. Sdwever, excessively high levels of nonionic surfactant negatively affect the deposition of softening clays. Compositions containing 4% or less noniordc surfactant are therefore preferred.

Detersive Adjuncts - The comositiom herein can contain other ingredients which aid in their cleaning performance. For example, it is highly preferred that through-the-wash detergent compositions contain a detergent builder and/or metal ion seguestrant. Compounds classifiable and wellknown in the art as, detergent builders include the nitrilotriacetates, polycarboxylates, citrates, carbonates, zeolites, water-soluble phosphates such as tri-polyphosphate and sodium ortho- and pyro-phosphates, silicates, and mixtures thereof. Metal ion sequestrants Include all of the above, plus materials like ethylenediaminetetraacetate, the aminopolyphosphonates (DEQUEST ) and a wide variety of other polv-functional * Trade Mark organic acids and salts too numerttus to mention in detail here. See U.S. Patent 3 579 454 for typical examples of the use of such materials in various cleaning compositions.

In general# the touilder/seguestrant will comprise 0.5% to 45% of the conpositicm. The 1-10 micron size zeolite (e.g. zeolite A) builders disclosed in German patent 2 422 655 are especially preferred for use in lowphosphate cxapositioons.

Particularly suitable phosphate-free builders are ether carboxylate mixtures comprising a) frcm 1% to 99% of a tartrate monosuccinate component of the structure SDCH —— Ca - 0 -- CH - CE2 COOX COOX COOX CQCX vherein X is H or salt-forming cation; and b) from 1% to 99% hy weight of a tartrate disuccinate component of the structure : CH2--- CH - 0 - CH - CH - O --— CH -- (¾ COOX COOX COOX COOX COOX COOX wherein X is H or a salt-forming cation.

Builder systems of this type ar© more fully disclosed in U.S. Patent No. 4 663 071 e, issued May 5, 1987 to Busch et aJL Typical detergent compositions contain from 5% to 35% of tiiis builder.

The laundry compositions herein also preferably contain enzymes to enhance their thrcogh-the-wash cleaning perfomance on a variety of soils and stains. Amylase and protease enzymes suitable for use in detergents are wellknown in the art and in ccemercially available liquid and granular detergents. Commercial detersive enzymes (preferably a mixture of amylase and protease) are typically used at levels of 0.001% to 2%, and higher, in the present expositions. Detergent oellulase enzymes provide both cleaning and softening benefits, particularly to cotton fabrics. These enzymes are highly desirable in the detergent compositions of this invention.

The compositions herein can contain other ingredients which aid in their cleaning performance. For example, the ccasposititans herein can advantageously contain a bleaching agent, especially a peroxyacid bleaching agent. In the context of the present invention, the tens pexoxyacid bleaching agent encompasses both peroxyacids p®r se and systems which are able to yield peroxyacids jn situ.

Peroxyacids per se are meant to include the alkaline and alkaline-earth metal salts thereof. Peroxyacids and diperoxyacids are camraonly used? examples are diperoxydodecanoic acid (DPD&) or peroxyphthalic acid.

Systems, capable of delivering peracids in situ consist of a peroxygen bleaching agent and an activator thereof.

The peroxygen bleaching agents are those capable of yielding hydrogen peroxide in an aqueous solution? these compounds ar© well-known in the art, and include hydrogen peroxide, alkali-metal peroxides, organic peroxide bleaching agents such as urea peroxide, inorganic persalt bleaching agents such as alkali metal perborates, percarbonates, perphosphates and persilicates.

Preferred ar® sodium perborate, commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrsta, sodium pyrophosphate peroxyhydrate and urea peroxyhydxate.

The liberated hydrogen pero30.de reacts with a bleach activator to form the peroxyacid bleach. Glasses of bleach activators include esters, imides, imidazoles, oximes, and carbonates, ϊη these classes, preferred materials include methyl o-acetoxy benzoates; sodium-p-acetoxy benzene sulfonates such as sodium 4-nonanoyloxybenzene sulfonate; sodium-4-cx^fcanoyloxvbenzene sulfonate, and soditan-4-decancyloxybenzenesulfonate ; bisphenol A diacetate; tetra acetyl ethylene diamine? tetra acetyl hexamethylene diamine; tetra. acetyl methylene diamine.

Other highly preferred peroxygen bleach activators, which are disclosed in U.S. Patents 4 483 778 and 4 539 130, axe alpha-substituted. alkyl or alkenyl esters, such as sodium-4-(2-c±doroctanovloxy)benzene sulfonate, sodium 4-(3,5,5-triaethyl hexanoyloxy)benzene sulfonate. Suitable peroxyacids are also peroxygen bleach activators such as described in. published European Patent Application No. 0 116 571, i.e., compounds of the general type RXAOOH and RXAL, wherein R is a hydroxycarbyl group, X is a hetero-atom, A is a carbonyl bridging group and L is a leaving group, especially oxybenzenesulfonate.

Other highly desirable detergent ingredients for use in the detergent compositions of the present invention are quaternary ammonium compounds of the formula R4R5R6R7N‘t'X', wherein R4 is alkyl having from to 20, preferably from 12-18 carbon atoms, R5 is Π alkyl having frcm 1 to 10 carbon atoms, and Κθ and Rare each Cx to C4 alkyl preferably methyl; A is an anion, e.g» chloride. Examples of such quaternary ammonium compounds include Cjg-C^ alkyl trimethyl aimnonium chloride .and cocoalkyl trimethyl ammonium methosulfate.

The quaternary ammonium comswonds can be used at levels from Q.5% to 5%.

Additional Softening Ingredients The detergent expositions ef the present invention may further contain, in addition to the clay material, other softening ingredients. Suitable examples include amines of the formula wherein is (¾ to C,o hydweaxbyl, Kg is c, to Cg0 hydrocarbyl, and R3 is to c1Q hydrocarhyl or hydrogen. A preferred amine of this typ® is ditallowmethylaxaine» Preferably, the softening amine is present as a complex with a fatty acid of the formula SCCOH, wherein K is a Q to Cgg alkyl or alkenyl. It is desirable that the amine/fatty acid complex be present in the for® of microfine particles, having a particle size in the range of from, e.g., 0.1 to 20 micrometers. These amine/fatty acid complexes are disclosed more rally in European Patent Application No. 0 133 804. Preferred are compositions that contain from It to 10% of the amine.

Suitable are also complexes of the above described amine and phosphate esters of the formula Ο ο _ ΟΞ and HO ___ Ρ _ΟΚ \ 0®α 0¾ wherein Sg and Rg are C^-C^q alkyl,, or ethoxy lated alkyl groups of the general formula alkyl-(OCHgC&g) v, wherein the alkyl substituent is c^-c^q, preferably C8~C16, and y is an integer of 1 to IS. preferably 2-10, most preferably 2-3. kmim/phosphate ester complexes ©£ this type are wore fully disclosed in European Patent Application Ho 0 X68 889.

Further examples of optional softening ingredients include the softening amides of the forasxla » wherein R10 and Ri;l are independently selected frcm alkyl, alkenyl, hydroxy alkyl, aryl, and alkyl-aryl groups; is hydrogen, or a C^-C^ alkyl or alkenyl, an aryl or alkyl-aryl group» Preferred eassssples of these amides are. ditallow acetamide and ditallow benzamide. Good results are, obtained when the amides are present in the composition in the form of a composite with a fatty acid or with a phosphate ester, as described, hereinbefore for the softening amines.

The amides are present in the composition at l%-10% by weight.

The amine and amide softening ingredients may be added to the crutcher mix and spray-dried, or may be added as a dxy powder to a detergent granule, or may be sprayed onto the detergent granule or onto a carrier, either in melted or in. dissolved fora. An example of a suitable carrier is perborate monohydrate. χ Suitable softening ingredients are also the amines disclosed in U.K. Patent Application GB 2 173 827, in particular the substituted cyclic amines disclosed therein. Suitable are imidazolines of th® general formula 1-(higher alkyl) amido (lower alkyl)-2-(higher alkyl)imidazoline wherein higher alkyl is alkyl having from 12 to 22 carbon atoms, and lower alkyl is alkyl having from l to 4 carbon atoms. Softener materials of this type are preferably added to the composition as particles or agglomerates as disclosed in European patent application 0 265 187, published on April 27, 1988 (U.S. Patent Application Serial Number 922 912, filed October 24, 1986 by Baker et al).

A preferred cyclic amine is l-tallowamidoethyl-2-tallow imidazoline. Preferred compositions contain from 1% to 10% of the substituted cyclic amine.

Moreover, the compositions herein can contain, in addition to ingredients already mentioned, various other optioixal ingredients typically used in commercial products to provide aesthetic or additonal product performance benefits. Typical ingredients include pH regulants, perfumes, dyes, bleach, optical brighteners, soil suspending agents, hydrotrapes and gel-control agents, freeze-thaw stabilizers, bactericides, preservatives, suds control agents and bleach activators.

In a through-the-wash mode, the compositions are typically used at a concentration of at least 500 ppm, preferably 0.10% to 1.5% in an aqueous laundry bath at pH 7-11 to launder fabrics. The laundering can be carried out over the range from 5°C to the boil, with excellent results.

X V IWJSTmALRggXJgmQW The detergent compositions of the present invention are granular.

For incorporation of the clay in a granular detergent 5 several techniques are available.

For exangAa, the clay may be added, as a powder or as a slurry, to a mxtcher mix of taonventional detergent ingredients, wised,, and spray dried to form a detergent granuleOr the clay powder can he agglomerated to a desirable agglomerate size, and then he mixed with granules containing the other detergent ingredients. Clay granules for dry mixing can also bs obtained by selecting a proper sieve fraction of natural agglomerates, by spraying a clay slurry onto a suitable particulate carrier, hy agglomerating clay particles with sodium carbonate. or by spray drying a clay slurry · •ί Ε Ad EXAMPLES I -V y The following granular detergent compositions are prepared : IKSOIEHT CSHFOSinOi (X bv weight) ll III IV .V C alkyl benzene sulfonate (fe) o·· 1¾ Tallow alcohol sulfate (Ha) a -Clefin (t^ ,β;) sulfonate (fe) Tallow alcahel etboxylate (EO^) -j q Fatty alcohol (C^ ^Jethoxylate (i=Q?) liydrogenated Tallow fatty acid Coconut fatty acid Codfecyl triraethyl annKMiun chloride Di stearyl oethyl amir® Oi ta 11 owOetnzarai de Oodecyl diAethyl aananiun M-Oxide Lauryl-SpH-dimethyl amine Sodium tri polyphosphate Zeolite 4a 7.0 1.0 2.5 3.0 .0 2.0 2.0 1.0 1.0 «.0 4.0 2.0 2.0 1.5 1.0 6.0 1.0 S.5 1.0 0.8 1.0 1.0 3.0 0.5 24.0 18 0.5 2.5 32.0 0.4 .0 XMGREDXENir OOWOSZTIOH (* by weight) (COM'D) ϊ n XXX XV y Sodium nitrilotriacetate 5.0 Sodi® sulfate 12.4 11.1 15.0 21.3 12.7 Sodium carbonate - 8.0 - 5.0 - Scdiun silicate s.o 7.0 4.0 5.0 2.0 Sodium perborate(4aq.) 20.0 15.0 18.0 10.0 18.0 Caraoxysetby 1 cel 1 ul os® 0.3 0.3 0.5 0.8 0.4 Polyacrylate - 1.5 - - - Polyacrylate (sw 4000-5000) - - - 3.0 Copolymer ealeic acid/acrylic acid (70/30) 2.0 - 1.5 2.5 - . few 40.000-80.000) Enzymes (protease» amylase, oellulase) 0.6 0.2 0.5 0.5 0.3 Optical brightener 0.2 0.2 0.3 0.3 0.25 Sulphonated zinc phthalocyamine - 25pf» 25ppra EDT& 0.2 0.2 0.3 0.15 0.2 Ethylenedi ami ne tetramethy 1 ene 0.2 0.1 - 0.1 0.1 phosphonic acid letraacetyl ethylenediamine 1.5 - - 1.5 Zso-nonanoyloxy-benzene sulfonate (Ma) - 2.0 - - Si 1 icone/si 1 ica suds suppressor 0.2 0.15 0.15 0.25 0.2 Perfume 0.25 0.25 0.30 0.2 0.25 Hectorite Clay * 10.0 7.0 15.0 5.0 10.0 Hoi store and minors balance to ICO - K * * Bentone a highly purified hectorite from Hector.

CA, available fro» ML Chemicals, NJ. The clay particles have a lath shape, and a length ; width ratio of 10:1, or higher (TEM data).

Layer Charge Distribution : more than 65% in the range of from 0.23 to 0.31 ** **Trade Mark Th© caBfiffisrci&Uy available material has been treated with a wetting agent. The same material without the wetting agent is equally suitable. Suitable is also Macaloid**. NL Chemicals, NJ), also a hectorite from Hector, CA.

To a detergent composition of example I but without clay and distearyl methyl amine, various smectite clays were added at a level of 10%. A reference did not contain any smectite clay, but 10% Na-sulfate instead.

Each of the compositions was usefl in a laundry test as follows ϊ 3 kg wash load and desired test swatches (cotton terry towels)* ** were laundered in a commercial automatic drum washing machine (ΜΠΧΞ w 726) using one wash cycle at 60'C. The detergent compositions were used at 1,12% «Msoentraticn in 0,303 g CaCQ3/l water hardness. The wash loads were line-dried at 2O'C/65% relative humidity. The test swatches then were instrumentally assessed for softness, using the Kawabata KES-F system (shear hysteresis at 5 degrees 2KG5 as best correlating parameter with softness on KES-F-1 instrument). The sample sise was 29 x 20 as, whereby the area of sample which is actually subjected to shear stress is 20 x 5 cm. From the curves of shear stress against shear angle the shear hysteresis was calculated at 5' (2HG5) in N/m. Each measurement was repeated 8 times to calculate the confidence interval of the mean at 95% confidence level.

Hectorite clays of the present invention gave a shear hysteresis reduction of 40%, on average.

* Supplier : Santens - Belgium (type Lopez, 340 g/m2).

** Trade Mark Fabrics axe laundered with th© above detergent compositions, in usual fashion. The laundered fabrics are evaluated for handle and softness in Kawabata Evaluation System-Fabric (RES-F) with a series of test instruments for measuring parameters that determine softeness" and handle of fabrics. For the purposes of the present invention, shear hysteresis (2HG5) is of particular jtaportance. The test method is described more fully in Ifelliand Textilberichte 67 (1986) pp 514-516.

VI - X The following granular detergent compositions ar® prepared : Trasnroresrr cohpositxqn (% by weight) WfWT·5' Vi 1V«-V»«V* VAX VIII IX X NaC10 linear alkyl benzene sulfonate - - - 17.6 NaC^2 linear alkyl benzene sulfonate 14.3 7.1 6.8 20.X - 10 NaC14_T5 alcohol sulfate NaC-jp alkyl polyethoxylate 3.1 7.1 6.8 20.1 6.5 T 1.0 •3 *| «&· A JU Ια X - - "j'^i - 28.9 27.7 36.9 40.0 Zeolite 4A 16.5 - - 15 Silicate Si ® ίΒ 11.0 10.5 5.7 15.2 Carbonate 7.0 - 16.0 14.5 - Diethylenetriamine pentaacetic acid - 1.2 1.1 - 1., δ Na perborate monohvdrate 4«9 5.0 - 20 Sodium nonanoyloxy benzene sulfonate - 6.8 6.8 - Enzyme (protease) 0.3 - - Hectorite clay * l-tallowamidoethyl-2-tallow- 7.5 6.8 4.7 8.9 9.5 25 imidazoline - - - 5.7 - Water, sulfate & Miscellaneous —.—. balance to 100 - —,— * As, in Examples I-v

Claims (5)

1. A granular detergent composition comprising by weight of said composition at least 1% of a detersive surfactant, from 5% to 35% detergent builders, and from 1% to 25% of a hectorite clay, characterized in that said hectorite clay is of natural origin, and has the general formula: t(«9 3 -A> si 4-y wherein Me 111 is Al, Fe, or B; or y = 0; M n * is a monovalent (n = 1) or divalent (n = 2) metal ion, said clay having a layer charge distribution (x~y) such that at least 50% of the layer charge is in the range of from 0.23 to 0.31.

2. A granular detergent composition according to claim 1, wherein said hectorite clay has a distribution off layer charge (se+yji such that at least 65% off the layer charge is in the range off from 0.23 to 0.31.

3. A granular detergent composition containing from 1% to 25% of a hectorite clay, characterized in that said hectorite clay is of natural origin, said hectorite clay being further characterized in that cotton terry towels laundered, with a detergent composition containing 10% (weight) of the clay show reduction of the shear hysteresis, 2HG5, of at least 32%.

4. A granular detergent composition according to claim 3, characterized in that the clay gives a reduction off said shear hysteresis parameter off at least 35%. 5. A granular detergent composition, according to any one of thepreceding claims further comprising, as an additional softening ingredient, from 1% to 10% off an amine off the formula Kj, wherein is C A to C? o hydrocarbyl, is Cj to C ?o hydrocarbyl, or 9· ί te 1 hydrogen, and R 3 is C-, to C 2Q hydrocarby1 or hydrogen. 6. A granular detergent composition according to claim 5 wherein R-3 and Rg are each alkyl having from 12 to 18 carbon 5 atcas, and is methyl. 7. A granular detergent composition according to claim 6 wherein the amine is present in the form of a ccnplex with a fatty acid of the formula R OXH, wherein S is a Co to C, o alkyl or alkenyl. 10 S.A granular detergent composition according to claim 7 wherein the amine is present in the fora of a. complex with a phosphate ester of the foraula 0 0 R^O ____ P_ OH and HO _ ? ______OH I \ ORg ORg wherein R g and R^ are C^~C 20 alkyl, or ethoxylated 15 alkyl groups of the general formula alkyl-(0CH 9 C2i 9 ) v , wherein the alkyl substituent is and y is an integer of X to 15. 9. A granular detergent composition according to any one of the preceding· claims further comprising from 1% to 10% of an 20 amide of the formula wherein θ and R^ 1 are independently selected from alkyl, alkenyl hydroxy alkyl, aryl, and alkyl-aryl groups; hydrogen, or a C l C 22’ alkyl or alkenyl, aryl or alkyl-aryl group, oris O-R 13 , wherein R 13 is a C^~C, 2 alkyl or alkenyl, an aryl or alkyl-aryl group. 5 10. A granular detergent composition according to claim 9 wherein the amide is present in the form of a composite vith the fatty acid of claim 7. 11.. A granular detergent composition according to any one of the preceding claims, further cmprising from It to 10% of a 10 l-(hi^ser alkyl) amido (lower alkyl)-2-(higher alkyl) isisazeline, wherein higher alkyl is alkyl having froB 12 to 22 cartoon atoms, and lover alkyl is alkyl having from i to 4 carbon atoms» 12» A granular detergent composition according to any one of the 15 preceding claims, further coa^rising from 5% to 35% of a builder system, said builder system comprising a) free l% to 991 by weight of a tartrate monosuccinate component of the structure : HOCd - GH - 0 - G& - «i 2 ccox coax coox coox 20 wherein X is H or salt-forming cation; and to) from 1% to 99% by weight of a tartrate disuccinate component of the structure : ch 2 — CH- 0-CH-CH — o — ca — ch 2 I I coox coox coox ccox coox ccox wherein X is H or a salt-forming cation. 13. A granular detergent composition according to claim 1, substantially as hereinbefore described and exemplified. 14. A granular detergent composition according to claim

5. 3, substantially as hereinbefore described and exemplified.