AU624577B2

AU624577B2 - Detergent compositions

Info

Publication number: AU624577B2
Application number: AU18585/88A
Authority: AU
Inventors: Andre Baeck; Young Sik Oh
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1987-06-30
Filing date: 1988-06-30
Publication date: 1992-06-18
Anticipated expiration: 2008-06-30
Also published as: JP2595052B2; EP0297673A2; ATE97691T1; CN1025870C; FI92495B; FI92495C; AU1858588A; JPS6465199A; DK171868B1; NZ225217A; IE881972L; KR950013916B1; DK361688A; MX169171B; DE3885801T2; EP0297673A3; DE3885801D1; EP0297673B1; CN1031561A; DK361688D0

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

/jA COMMONWEALTH OF AUSTRALIA 7)f ,-1 PATENTS ACT 1952-69 COMPLETE SPEC IFICAT ION

(ORIGINAL)

Class I t. Class Application Number: Lodg~ed: Complete Specification Lodged: Accepted: 0 Published: 0 riority 0 a0 00 0 o 4, a'me of k;)plicant A'qdress of Applic-ant Actual lnv~ntor:.

Adres o4Srvc THE PROCTER GAM13LE COMPANY One Procter Gamblo Plaza, Cincinnati., Ohio 45202, United States of America.

ANDRE BAECK and YOUNG SIK OH EDWD. WATERS SONS, QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

Complete Specification for the invention entitled; DETERGENT COMPOS ITT ONS edlT~ I 2 I~TfT The following statement is a fuil description of this Invention, including the best method of performing it known to '.US /1 Case 3682R t 44 4 0 4 044 0 44 4 4 4 4 04 4 4.4 4 4 4 4 ~O o 4 4 4 00 4 4 44 4 4 4 44 4 44 4.

DETERGENT COMPOS ITIONS .111111 PE.~ Andrd Baeck Young Sik Oh The present invention relates to detergent .ompositions. Mcze specifically it relateR to detergent compositions containing a fabric-soften,.ng amlount of a hectorite clay, Uhe clay being in the form of particles having a narrowly-defined layer charge distribution.

2 British Patent 1 400 898 discloses detergent compositons comprising, as a fabric-softening ingredient, a smectite-type 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 sodium montmorillonite clays, are disclosed to be preferred for reasons of color and cation exchange capacity.

It is now well recognized in the detergent industry 0 that clays of the type disclosed in British Patent O* 1 400 898 provide significant fabric softeono. benefits when used in a laundry detergent. Yet, it is equally well recognized that deposition of these clays onto the fabrics I during the laundering process is far from complete; in fact, under typical European laundry co:nditions, less than half of the available clay is deposited onto the fabrics, the remainder being rinsed away with the laundry liquor S* 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.

j 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 de|posited onto fabrics during the laundry 7 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 the clay materials used to date in commercial softeness-through-the-wash detergent compostioni.

i1 3 SUMMARY OF THE INVENTION The present invention relates to detergent compositions containing a fabric-softening amount of a fabric-softening clay. Typically, the amount of clay is from 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. The clay is present in the form of particles. The particles have a narrowly defined layer charge distribution, such that at least of the clay has a layer charge of from 0.23 to 0.31.

'.-:TAILED DESCRIPTION OF THE INVENTION t> o The detergent compositions of the present invention oo C comprise conventional detersive surfactants, conventional a detergent builders and, optionally, other conventional detergent ingredients. The compositions further comprise a fabric-softening amount, typically from 1% to 25% by weight of the detergent composition, of a fabric-softening clay.

0 1The clay, which is of the smectite-type, is selected oni a basis of its layer charge properties. The hectorite clays of natural origin, suitable for the detergent compositions of the present invention, have the general formula

III

[(Mg 3 -xLix) Si 4 _y Mey Ol0(OH2zF) (x j )Mn+ n wherein y 0; or, if y 0, Me I I I is Al, Fe, or B; Mn+ is a monovalent (n 1) or divalent (n metal ion, for example selected from Na, K, Mg, Ca, Sr. The value of (x Sy) is the layer charge of the hectorite clay. The hectorite clays suitable for the 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.

Rwy i I 0 4 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.

The layer charge distribution of the clay material can be determined 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 Pflanzenernehrung und Bodenkunde, 130(1), 1971, pages 9-24, the disclosures of whicn are incorporated herein by reference.

o 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 0 0 KES-F system of Kawabata. The method is described in S. Kawabata, "The Standardization and Analysis of Hand Evaluation'', 2nd Fd., Textile Mach. Soc. of Japan, Osaka, 1980, the disclosures of which are incorporated herein by reference.

It has been found that one of the parameters, of the KES-F system, the shear hysteresis parameter 2HG5, is particularly useful in the characterization of fabric softening clays. Preferred herein are hectorite clays 6o which, when incoporated in detergent compositions at 10% by :w -o )eight, reduce the shear hysteresis of fabrics laundered therein by at least 32%, more preferably by at least The shear hysteresis parameter 2HG5 is discussed in more detail in Finnimore and Koenig, Melliand Textilberichte 67 (1986) pages 514-516, the disclosures of which are incorporated herein by reference.

7' Shear hystoresis is determined on cotton terry towels, with detergent compositions containing 10% (weight) of the clay to be tested. The test is described more 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. Deposition of hectorite clays of the present invention from a detergent composition onto fabrics is surprisingly greater than the deposition of other naturally occurring clays. Deposition can be measured according to the Relative Deposition procedure described in Examples XI I -XV.

The Relative Deposition of the clays of the present invention is preferably at least about 1 0 2.5 more preferably at least about 2.7, and more preferably at least about 2.9. The Relative Deposition of these clays appears to be proportional to the softness of the treated fabric. Examples of suitable hectorite clays include Bentone EW and Macaloid, both mined in or near Amargosa Valley, Nev. and available from NL Chemicals, N.J.

Naturally occurring hectorite clays within the scope of the present invention also include 1 5 IMV Hectorite, available from Industrial Mineral Ventures, Amargosa Valley, Nev. Also encompassed herein are hectorites mined in Turkey such as, but not limited to, Turkish calcium hectorite clay.

9 94 4 *9 I,9 94 9 4 it, t 5 Shea- I. steoi o ii:- -de n MA- I Id or-e €l with detergent compositions containing 10% (weighc) o the clay to be tested. The test is described more f y in the Examples hereinbelow.

The hectorite clays used in th.e ,dergent compositions are further characterized by a$udually great propensity for deposition onto fabric In a standardized test, deposition onto fabric of the claimed hectorite clays from a detergent compo i ion is greater than the deposition of conventional ectite-type clays or of synthetic hectorits. Examples of suitable hectorite clays include S. Bent e EW and Macaloid from NL Chemicals, NJ., and fI L. 0 Other detergent components Detersive Surfactants The compositions of this invention will typically contain organic su':face-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 ethoxylated) alcohols and alkyl phenols, amine oxides, alpha-sulfonates of fatty acids and of fatty acid esters, and the like, which are well-known from the detergency art.

In general,, such detersive s'ul:actants contain an alkyl group in the C 9

-C

1 8 range. 'he anionic detersive surfactants can be used in the form of their sodium, potassium or triethanolammonium salts; the nonionics generally contain from about 5 to about 17 ethylene oxide groups. U.S. Patent 3 995 669, the disclosures of which are incorporated herein by reference, contains detailed -0W i 6 listings of such typical detersive surfactants.

C

1 1-C 1 6 alkyl benzene sulfonates, C 1 2

-C

18 paraffinsulfonates and alkyl sulfates, and the ethoxylated alcohols and alkyl phenols are especially preferred in the compositions of the present type.

Also useful herein as the surfactant are the watersoluble soaps, e.g. the common sodium and potassium coconut or tallow soaps well-known in the art.

The surfactant component can comprise as little as 1% of the compositons herein, but preferably the compositions will contain 5% to 40%, preferably 10% to 30%, of surfactant. Mixtures of the ethoxylated nonionics with anionics such as the alkyl benzene sulfonates, alkyl S' sulfates and paraffin sulfonates are preferred for throughthe-wash cleansing of a broad spectrum of soils and stains from fabrics. However, excessively high levels of nonionic surfactant negatively affect the deposition of softening clays. Compositions containing 4% or less nonionic surfactant are therefore preferred.

Detersive Adjuncts The composition herein can contain other ingredients which aid in their cleaning performance.

Tool For exarple, it is highly preferred that through-the-wash to detergent compositions contain a detergent builder and/or S metal ion sequestrant. Compounds classifiable and wellknown in the art as detergent buildars 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 poly-functional 1 7organic acids and salts too numerous 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 builder/sequestrant will comprise about to 45% of the composition. The 1-10 micron size zeolite zeolite A) builders disclosed in German patent 2 422 655 are especially preferred for use in lowphosphate compositions.

Particularly suitable phosphate-free builders are ether carboxylate mixtures comprising o° a) from 1% to 99% of a tartrate monosuccinate component So of the structure 0 0 HOCH CH 0 CH CH 2 L4 COOX COOX COOX COOX wherein X is H or salt-forming cation; and b) from 1% to 99% by weight of a tartrate disuccinate Scomponent of the structure CH C 0CHH CH CH CH 2 2 2 COOX COOX COOX COOX COOX COOX wherein X is H or a salt-forming cation.

Builder systems of this type are more fully disclosed in U.S. Patent No. 4 663 071, issued May 5, 1987 to Busch et al, the disclosures of which are incorporated herein by reference.

r 1 8 Typical detergent compositions contain from 5% to of this builder.

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

a 1 The compositions herein can contain other ingredients which aid in their cleaning performance. For example, the compositions herein can advantageously contain a bleaching o, agent, especially a peroxyacid bleaching agent. In the 6 context of the present invention, the term peroxyacid bleaching agent encompasses both peroxyacids per se and systeiz which are able to yield peroxyacids in situ.

p000 Peroxyacids per se are meant to include the alkaline and alkaline-earth metal salts thereof. Peroxyacids and diperoxyacids are commonly used; examples are Se diperoxydodecanoic acid (DPDA) or peroxyphthalic acid.

i 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 are well-known in the art, and include hydrogen peroxide, alkali-metal peroxides, organic peroxide bleaching agents such as urea peroxide, inorganic persalt j- 9 bleaching gents such as alkali metal perborates, percarbonates, perphosphates, persilicates, and the like.

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

The liberated hyd:rogen peroxide reacts with a bleach activator to form the peroxyacid bleach. Classes of bleach activators include esters, imides, imidazoles, oximes, and carbonates. In these classes, preferred materials include methyl o-acetoxy benzoates; sodium-p-acetoxy benzene sulfonates such as sodium 4-nonanoyloxybenzene sulfonate; sodium-4-octanoyloxybenzene sulfonate, and sodium-4-decanoyloxybenzenesulfonate biophenol 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, the disclosures of which are incorporated herein by reference, are alpha-substituted alkyl or alkenyl esters, such as sodium-4-(2-chloroctanoyloxy) benzene sulfonate, sodium 4-(3,5,5-trimethyl hexanoyloxy)benzene S, sulfonate. Suitable peroxyacids are also peroxygen bleach activators such as described in publihed European Patent Application No. 0 116 571, compounds of the general Stype RXAOOH and RXAL, wherein R is a hydroc~rbyl 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 cf the present invention are quaternary ammonium compounds of the formula

R

4

R

5

R

6

R

7 N+X whereir R 4 is alkyl having from 4^ about 8 to 20, preferably from 12-18 carbon atoms, R 5 is j 70 0 0 00 0 4 o 0 0 0 0 0 4 o~ 0 0 00 ,r alkyl having from 1 to 10 carbon atoms, and R 6 and R 7 are each C 1 to C 4 alkyl preferably methyl X- is an anion, e.g. chloride. Examples of such quaternary ammonium compounds include C12-C14 alkyl trimethyl ammonium chloride and cocoalkyl trimethyl ammonium methosulfate.

The quaternary ammonium compounds can be used at levels from 0.5% to Additional Softening Ingredients The detergent compositions of the present invention may further contain, in addition to the clay material, other softening ingredients. Suitable examples include amines of the formula R 1

R

2

R

3 N, wherein R 1 is C 6 to C 20 hydrocarbyl, R 2 is C 1 to C 2 0 hydrocarbyl, and R 3 is

C

1 to CI0 hydrocarbyl or hydrogen. A preferred amine of this type is ditallowmethylamine.

Preferably, the softening amine is present as a complex with a fatty acid of the formula RCOOH, wherein R is a C 9 to C 2 0 alkyl or &lkenyl. It is desirable that the amine/fatty acid complex be present in the form of microfine particles, having a particle size in the range of from, 0.1 to 20 micrometers. These amine/fatty acid complexes are disclosed more fully in European Patent Application No. 0 133 804, the disclosures of which are incorporated herein by reference. Preferred are compositions that contain from 1% to 10% of the amine.

Suitable are also complexes of the above described amine and phosphate esters of the formula ,Pb 11

O

RO O P R OH OR 9 0 and HO P OH

OR

9 O 0 4 4 0 000 04 0 0I 4 4 60 00 I I t wherein R and R 9 are C 1

-C

2 0 alkyl, or ethoxylated alkyl groups of the general formula alkyl-(OCH 2

CH

2 wherein the 10 alkyl substituent is C-C 2 0 preferably C,-C16, and y is an integer of 1 to 15, preferably 2-10, most preferably Amine/phosphate ester complexes of this type are more fully disclosed in European Patent Afpp3~ cabn No.168 889, the disclosures of which are incorporated herein by reference, Further examples of optional softening ingredients include the softening amides of the formula R 1 0

RINCOR

1 wherein Ro and R 1 I are independently selected from C -C 2 2 alkyl, alkenyl, hydroxy alkyl, aryl, and alkyl-aryl groups; 20 R 1 is hydrogen, or a Ci-C 2 2 alkyl or alkenyl, an aryl or alkyl-aryl group, or is 0-R 1 3 wherein R13 is a C -C 22 alkyl or alkenyl, an aryl or alkyl-aryl group. Preferred examples of these amides are ditallow acetamide and ditallow benzamide. Goor 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 1%-10% by weight.

The amine and amide softeni.ng ingredients may be added to the crutcher mix and spray-.dried, or may be added as a dry powder to a detergent granule, or may be sprayed onto the detergent 9ianule or onto a carrier, either in melted or in dissolved form. An example of a suitable carrier is perborate monohydrate.

i 1 12 Suitable softening ingredients are also the amines disclosed in U.K. Patent Application GD 2 173 827, the disclosures of which are incorporated herein by reference, in particular the substituted cyclic amines disclosed therein. Suitable are imidazolines of the general formula l-(higher alkyl) amide (lower alkyl) -2-(higher alkyl)imida- Zoline wherein higher a I is alkyl having from 12 to 22 carbon atoms, and lower alkyl is alkyl havi-j from 1 to 4 carbon atoms. Softener materials of this type are preferably added to the composition as particles or 1 770, agglomerates as disclosed in U.S. Patento I pp i. a:l nu2 lT2 a-f ,^86 by Baker et al, the o disclosures of which are incorporated herein by reference.

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

Moreover, the compositions herein can contain, in addition to ingredients already mentioned, various other optional 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, hydrotropes and gol-control agents, freeze-thaw stabilizArs, bactericides, preservatives, suds control agents, bleaon activators and the like.

i 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.

13 INDUSTRIAL APPLICATION IThe detergent compositions of the present invention can be formulated as granular or as liquid detergents. It has been found that clays having a high swelling capacity, can be easily incoporated in a liquid detergent composition, while maintaining phase stability.

The clay material can be incorporated in a liquid detergent composition by simple mixing, p 2ferably using a high shear mixer.

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

o For example, the clay may be added, as a powder or as a slurry, to a crutcher mix of conventional detergent ingredients, mixed, and spray dried to form a deterlgent granule.

Or the clay powder can be agglomerated to a desirable agiolmerate size, and then be mixed with granules containing the other detergent ingredients. Clay granules for dry mixing can also be obtained by selecting a proper sieve fraction of natural agglomerates, by spraying a clay slurry onto a suitable particulate carrier, by agglomerating clay particles with sodium carbonate, by spray drying a clay slurry, etc.

The clay particles may also be incorporated in a substrate, like a pouch or a sheet, optionally with other softening ingredients. Substrates of this kind can be added to the laundry together with a conventional laundry detergent.

I

14 A pref'.:rred substrate is a pouch comprising the clay particles and particles of an alkyl amido alkyl-2-alkylimidazoline of the type described hereinabove.

EXPMP.ES I -V The following granular detergent compositions are prepared: INGREDIENT COMPOSITION b i%,ight) I IIT TI TV V 4 44

C

4 4 C C 4 C CC 4 C C 44 4 44 4$

K

C 1-2alkyl benz--ne sulfonate (Na) Tallcw alcohol sulfate (Na) A -Olef~n (C 1-8) sulfonate (Na) 121 Idl low alcohol ethoxylate CEO ratty alcohol (C 2- 5 )ethoxylate CEO7 Hydrogenated Tallow fatty acid Coconut fatty acid Dodecyl trimethyl amniuin chloride Distearyl methyl mnine, Dital lowbenzamiide Dodecyl dinethyl amiwn N-Oxide Lauryl-N,N-dimethyl mnine Soditin tripe&,ohosphate Zeolite 4A 7.0 5.0 4.0 1.0 2.0 2, 0 0.8 2.5 1.0 q.u 0.5 0.5 0.4 2.5 24.0 18 22 32.0 20.0 4~~j 15 INGREDIENT COPOPSITION (CDN'0) (by weight) I Ii III IV V Sodiumi nitr~1otriacetate Sodiumi sulfate Sodium carbonate Sodium silicate Sodium perborate(4aq.) Carboxymiethylce1 lulose Polyacrylate (umw 1000-20000) Polyacrylate (mw 4000-5000) 12,4 17.1 8,0 6.0 7.0 2- 0 15.0 0.3 0. 3 15,0 21.3 4.0 6.0 18.0 10.0 0.5 0.8 12.7 18.0 0.4 0 ~O 00 n 000 0 p no o 0 C o ~.o o 00 0 0 0 000 0 o 0 0 000000 o 0 0 00 00 0 0'0 0 00 00 0 0 4* o 04 4, 44r Copolymer maleic acid/acrylic acid (70/30) 2.0 (mw1 40.000-80.000) Enzymnes (protease, amylase, cellulase) 0.6 optical brightener 0.2 Sulphonat-ld zinc phthalocyanine 30ppin EDTA 0.2 Ethyl enedi ani ne tetraffthylene 0.2 0.5 0.5 0,3 0,3 25ppm 0.3 0.15 0.1 0.3 0.25 0.2 0.1 phosphonic acid Tetraacetyl ethyl enedi ani ne ~T-nonanoyloxy-benzene sul fonate (Na) silione/s-'lica. suds suppressor Perkm Hecturite Clay* K'oisture and minors 0.2 0.25 10.0 0.15 0.15 0,25 0.30 7, 0 15.0 balance 0.25 0.2 5.0 to 100 0.2 0.25 10.0 Bentone EW, a highly purified hectorite from Hector.

CA. a va ila bIe f r om NL chemicals, NJ. The clay particles have a lath shape, arnd a length :width rat-io of 10:1, or higher (TEM data).

Layer Charge Distribution imre than 65 in the range of fromn 0.23 to 0.31 T- j The commercially avai l'"e 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 duitearyl methyl amine, various smectite clays were added at a level of 10%. A reference did not contain S any smectite clay, but 10% Na-sulfate instead.

o &a Each of the compositions was used in a laurdry test as follows 3 kg wash load and desired test switches (cotton o. terry towels) were laundered in a comm~rii al automatic «.oo drum washing machine (MIELE W 726) using one wash cycle at Th. detergent compositions were used at 1,12% concentration in 0,308 g CaCO3/1 water hardness. The wash °oO' loads were line-dried at 20°C/65% relative humidity. The test swatches then were instrumentally assessed for softness, using the Kawabata KES-F system (shear hysteresis 0 o0 at 5 degrees 2HG5 as best correlating parameter with softness on KES-F-1 instrument). The sample size was x 20 cm, whereby the area of sample which is actually °t.ob subjected to shear stress is 20 x 5 cm. From the curves of oo' 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/m 2 17 Fabrics are Laundered with the above detlergent. compositions, in usual fashion. The laundered fabrics are evaluated for handle and softness in Kawabata Evaluation System-Fabric (KES-F a series of test instrumrents for measuring parameters that determine "'softeness" and "handle'! of fabrics). For the purposes of the present invention, shear hysteresis (2HG5) is of particular importance. The test method is described more fully in Melliard Teytilbel'ichte.67 (1986) pp 509-516.

EXAMPLE VI The following liquid detergent composition. is prepared.

INGREDIENT

*4*4 1*

I.

4 4

C

1 1 1 2 alkyl benzene sulfonic acid Fatty alcohol (C 12 1 5 ethoxylate (E0 7 Ccconut fatty acid Triethanoa.irjine PolIyacrylate (1000-20000) Enzyme (protease) Ethanol Polydimcthylsiloxane Hectorite clay 11 2 propylene glycol water i,,inors

COMPOSITION

(by weight) 12.0 10.0 6.8 0.8 0.1 balance to 100 As in Examples I-V .1 18 EXAMPLES VII XI The following granular detergent compositions are prepared

INGREDIEIPT

COMPOSITION

by weight) VIII IX X 44 4 9 499 9 49 9 9 9 99 99 99 9 4 O 90 9 9 o t.o 994-794 o 9 9 99 4 9 94 4 99 09 I $4 4 NaC 1 2 linear alkyl be~izene sul fonate NaC 13 linear alkyl benzene sul fonate NaC1-15alcohol sulfate NaC 1 2 alkyl. polyethoxylate 6.5 T

STPP

Zeolite 4A silicate Carbonate Diethylenetrianine pentaacetic acid Na perborate monohydrate sodiu nonanoyl benzene sul fonate Enzyme (protease) Hectorite clay l-tallowamidoethyi-2 -tallowimidazoline Water, sulfate Miscellaneous 17.6 14.3 3.1 1.0 16.5 6.8 7.0 7.1 6.8 20.1 7.1 6.8 20.1 1.1 28.9 1.1 27.7 36.9 5.7 14.5 11.0 10.5 16.0 1.2 1.1 4.9 6.8 6.8 40.0 15.2 1.6 0.3 7.5 8.9 5.7 balance to 100--- As in Examples I-V 18a EXAMPLES XII-XV Relative Deposition Measurement A. Washing procedure: Prewash: Cotton Polyester terry cloths (Style 4025, Dundee Mills, Griffin, Ga.) that are 1' X 11 square inches (27.9 X 27.9 square cm) and weigh about 50 g each are used for the Relative Deposition test. The c' ths are washed two times with a conveniontal non-clay containing detergent formulation (shown below) in 0 grain/gallon water at 1250 F. (520 for 12 minutes each, then washed two times in 0 grain/gallon water at 1250 F. (520C.) without detergent and dried in a Whirlpool 3 Cycle Portable Dryer (Model #LE4905XM, Whirlpool Corp., Benton Harbor, Mich.) Prewash Detergent Composition Ingredient (Wt.) C12 Linear Alkyl Benzene Sulfonate (Na Salt) 4.1 S, Tallow Alcohol Sulfate (Na Salt) Neodol 23-6.5 (Alkyl Ethoxylate) Tallow Soap 1.9 Sodium Tripolyphosphate 32.0 i Silicate Water and Miscellaneous balance to 100 Test Wash: A miniwasher with five pots (such as those manufactured by t Yorktown Tool Die Corp., Yorktown, Ind.) is used. 9.12 g of detergent product S' (Testwash Detergent Composition, as shown below) and 0.58 g of a clay of the present S invention (77 ppm in the wash) are added to two gallons of 5 grain/gallon water at 950 F. (350 in each mini-washer pot and agitated for two minutes. A load of fabrics weighing about 341 g and including test fabrics of four of the prewashed terry cloths, six polyester/cotton 11 X 1 square inch (27.9 X 27.9) square cm) swatches (product #7435, Test Fabrics, Middlesex, weighing a total of about 37 g. three 11 X 11 Inchi nylon swatches (product #322, Test Fabrics) weighing a otal of about 18 g, three 11 X 11 inch polyester swatches (product #720-H, Test Fabrics) weighing a total of about 44 g, and one polyacrylic sock (Burlington Socks, Balfour Inc., Asheboro, tN o v Ii 18b weighing about 42 g are added to the wash water. The fabrics are washed for 12 min., spin dried for two minutes, rinsed with two gallons of 6 grain/gallon water at 700 F. (210 for two minutes, spin dried for two minutes, and dried in a Whirlpool 3 Cycle Portable (Model No. LE4905XM, Whirlpool Corp., Benton Harbor, Mich.) This test wash procedure is repreated for a second cycle, and the Relative Deposition is measured as described below.

*1 14 oC *r C Cri Test Wash Detergent Composition Ingredient (Wt.)

C

13 Linear Alkyl Benzene Sulfonate

C

14 1 5 Alkyl Sulfate Neodol 23-6.5T (Alkyl ethoxylate) (Mgf. by Shell Chem. Co.) Sodium Tripolyphosphate 38.4 Silicate 14.6 Sodium Carbonate 21.3 Water and Miscellaneous balance to 100 B. Relative Deposition Measurement The deposition of the clay containing compositions is calculated based on the deposition of silicon (Si) of terry cloth swatches washed with the test wash detergent composition relative to terry cloth swatches that were prewashed but not subjected to the test wash procedure (blank swatches). Silicon deposition is determined by measurement of the X-ray fluorescence of the silicon. Each Silicon fluorescence is measured in the following manner: An EDAX 9500 X-ray fluorescence unit with a rhodium anode X-ray source (Philips Electronics, Inc., Cincinnati, Ohio) is used. Each terry cloth swatch is analyzed for 100 live seconds. Count rate of SI (on a per second basis) for each sample is measured and recorded.

Relative Deposition 'f clay is calculated by the following equation: STF SBF Relative Deposition SW X 1000

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18c wherein, STF is the Si count rate of clay-treated terry cloth fabric, SFB is the Si count of blank terry cloth fabric and SW is the Si count rate of a clay sample wafer (pressed clay particles of same area of terry cloth fabric). Count rates of Si for the clay sample wafer and clay deposition on fabric are measured as follows: Si count rate for clay sample wafer: The X-ray generator is set at kV/500 microamps. About 2 g of clay powder is pressed at about 20,000 psi into a pellet with a 30 ton hydraulic press (Angstrom, Inc., Chicago, III.). The sample is rotated during the count rate analysis in a vacuum atmosphere (less than 300 millitorr).

Si count rate for the terry cloth treated with clay: The X-ray generator parameter is set at 15 kV/500 microamps. A disk with a 3 cm diameter is cut from a terry cloth swatch. The disk is compressed at about 20,000 psi to form a flat smooth disk using a 30 ton hydraulic press, then rotated during the count rate analysis in a vacuum atmosphere Typical Relative Depositions of clays of the Present Invention added during o, the wash stage as described in the preceding procedure are shown below: Natural Hectorite Clay Relative Deposition Example XII 3.1 Bentone EW (available from NL Industries) Example XIII 3.1 Macaloid (available from NL Industries) Example XIV 3.9 Turkish Ca Hectorite (mined in Turkey) I Example XV 2.9 jIMV Hectorite (mined by Industrial Mineral Ventures, "l Amargoss Valley, Nevada)

Claims

1. A detergent composition comprising at least 1% of a detersive surfactant, from 5% to 35% detergent builders, and from 1% to 25% of a hectorite clay of natural origin, said hectorite clay having the general formula (Mg-xLi Si 4 -y Me Ol 0 (OH 2 -zFz) (x _)Mn+ n S, wherein Me III is Al, Fe, or B; or y O; Mn+ is a monovalent (n 1) or divalent (n metal ion, said clay having a layer charge distribution such that at least o *50% of the layer charge is in the range of from 0.23 to S0.31.

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

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

4. A detergent composition according to claim 3, characterized in that the clay gives a reduction of the shear hysteresis parameter of at least A detergent composition according to any one of the preceding claims further comprising, as an additional softening ingredient, from 1% to 10% of an amine of the formula R 1 R 2 R 3 N, wherein R 1 is C 6 to C 2 0 hydrocarbyl, R 2 is C 1 to C 2 0 hydrocarbyl, or CIV ydrg, and R 3 is C 1 to C 2 0 hydrocarbyl or hydrogen.

6. A detergent composition according to claim 5 wherein R 1 and R 2 are each alkyl having from 12 to 18 carbon atoms, and R 3 is methyl.

7. A detergent composition according to claim 6 wherein the amine is present in the form of a complex with a fatty o* .acid of the formula R COOH, wherein R is a C 9 to C 2 0 S- alkyl or alkenyl.

8. A detergent composition according to claim 7 wherein the vmine is present in the form of a complex with a phosphate ester of the formula 0'0 0 0 0 a II II Ro OH and HO P OH ORg OR9 wherein R 8 and R9 are Ci-C 2 0 alkyl, or ethoxylated alkyl groups of the general formula alkyl-(OCHCH)y, wherein thd alkyl substituent is Ci-C 2 0 and y is an integer of 1 to

9. A detetgent composition according to any one of the preceding claims further comprising from 1% to 10% of an amide of the formula R 1 oRIlNC0R 1 2 wherein R 1 0 and RI1 are C 1 independently selected from C 1 -C 2 2 alkyl, alkenyl t *41 21 01-022 hydroxy alkyl, 06-022 aryl, and C7-CPR alkyl-aryl groups; R 12 Is hydrogan, or a C 1 -C 22 alkyl or alkenyl, aryi or alkyl-aryl group, or i; O43 I wherein R, 3 is a 01-022 alkyl or alkenyl, an aryl or alkyl-aryl group. 1 0. A detergent composition according to claim 9 wherein the amnide is present in the form of a composite with the fatty acid of claim 7.

11. A detergent composition according to any vie of the preceding claims, further comprising from 1% to 100% of a 1-(hlgher alkyl)amldo (lower alkyI)-2-([~jfgher alkyl)lmidazoline. wherein higher alkyl Is alkyl having from 12 to 22 carbon atoms, and lower alkyl Is alkyt' having from 1 to 4 carbon atoms. 1 2, A detergent. composition according to any one of the preceding i wherein said builder system comprises a) from 1% to 99% by weight of .9 ta tiale monosuccInate component of the structure, HOCH OH 0 O H 2 CLa 10OX OaX COOX wherein X Is H or salt-forming cation; and b) from 1% to 99% by weight of a tartrate disuccinate component of the structure: *0 00 o*4 09p 4 a 44" .22 coOX roo cooUA x K~o wherein X is H or a salt-forming cati.. S V z. 44 *4 4 ~V 94 9 .54 54 4 4. 4 4 o V~9 4 9444~0 4 4 l)A'[1E) TI-Il S 29Lth day of June, 1988 '111E PSO/CTER CAMBI. COMPANY EDWD. WATERS SONS, PATENT ATTORNEYS, 50 QUEEN STREET, MELBOURNE. VIC. 3000. o 4 44 4 o 44 o 5244 44 9 4 5~4 49 4t 4 44~4 9 4 449' 4* 44 -5 4 4 54