CA2095244A1

CA2095244A1 - Fabric treatment composition

Info

Publication number: CA2095244A1
Application number: CA 2095244
Authority: CA
Inventors: Christian August Antoine Marteleur; Andre Christian Convents
Original assignee: Individual
Current assignee: Procter and Gamble Co
Priority date: 1990-10-29
Filing date: 1991-10-25
Publication date: 1992-04-30
Also published as: TR25527A; PT99365A; EP0483411B1; EP0483411A1; DE69019973D1; DE69019973T2; WO1992007927A1; IE913748A1

Abstract

The siloxanes are incorporated at an amount of 0.1 % to 50 % by weight of said softening clay and the flocculating agents are incorporated at an amount of 0.005 % to 20 % by weight of said softening clay. Softening through the wash detergent compositions containing from 1 % to 50 % by weight of said detergent compositions of the fabric treatment compositions are also disclosed.

Description

W092/07927 ~r,r/US~-1/07~
a~ 2~5~

- ~` FABRIC TREATMENT COMPOSITION

Technical Field The present invention relates to fabxic treatment compositions. In particular it relates to fabric treatme~t compositions comprising 50~tening clays and softsning polysiloxanés and floccula~ing agents.
, . . " . ~

Backuround_of the_Inven~ion -- The use of ~oftening clays in ~abric trea~ment compositions is well known in the art and has found wide commercial application. Clays have been us~d in particular because their application and the so~tening they i~par~ on fabrics is different ~rom that of cationic soEteners, Examples and description of clay appli~ation~ can be found in a large number o~ publicati4ns, fQr example U.S.
3,966,629 or U.~. 1,400,89~ describe different ~inds o~
clays and modes of application of ~hem in fabric treatment compositions.

,, W0 92t07927 PCT/IJS91~(379l9 Co~binatioll o~F clay with so:etening am~ne:; ha5 also b2en disc:lo~;ed to provide so~tening enhance~t. Further DE-3 833 648 dess~ proved aggl~meration o~ tergQnts conta~ soft~ing clay. Further a huD~ctant is p:rovicl~l ~n EP-~ 313 146 facilitating impro~red wetalbility o~ t:he slay.

Other agents which have been known for fabric treatment benefit:s are substituted polysiloxanes. They are disclosed for use at law levels for example in E~A-150 867 or EP-~-150 872. Relatively high concentrations of substitu~ polysiloxanes are not uncommon to the textile ~ndustry and have been disc:losed :~or example ir EP-A~58 ~93 or U.S. 4,247,592.

In EP A-354 856 the comb:Lnation of siloxanes and cationi :: quaternary almnonium is disclosed.

EP-A-381 487 disc:loses liquid dete2~ent compositions corltaining a clay component which is pretreated with siloxane to supply phase ar~d viscosi~r stability while not deteriora~:ing the cle~ing performance.

It has now been found that the fabric treatment performance of substikuted polysiloxanes, soft~.ing c:lay and a clay flocculating agent is substantially hi~7her than was to be e:~pected by simple adltlitiYe perfor~mce.
Part~cularly when praviding ~ntimate mixh~es of soft2lling clay ~d substikuted ps:~lysiloxanes in ~e presence o~ clay flocculating agents the so~t~irlg ~rfonnance ris2s beyond the expectable acldlitive softening perfonnance of the com~ounds pro~ided.

., .~W092/07927 P~T/~X~ 7919 2~9 52~-It is an objective of the in~ention to provide fabric treatment co~positions containing substituted polysiloxanes, so~tening clay and a clay floc~ul~ting agent, pr~ferably as an intimate mix*ure. Further it is an objective to provide softening-through~the-wash deterg~nt compositions comprising such fabric treat~ent composition~
preferably granular datergent compositions.

It is another aspec~ of ~he invention to have very good environmen~al compatibility o~ ~he softening composition in all modes of application or use.

Summary__~ the Inventlon The present inven~ion rela~es to fabric treatment compositions cQmprising a sof~ening clay, a clay flocculating agent, and a subs~ituted polysiloxaneO The substituted polysiloxane is present in said composltions at 0.1% to 50% of said softening clay and the clay flocculaking agent is presen~ at 0.005% to 20% of said softening clay.

The fabric treatment composition can be applied in liguid or granular products and used as such in th~ w~sh or in the rin~e cycle of the laundry. In a pre~erred t embodi~ent of the present invention said fa.bric treatmant compositions are co~prised in softening through-the-~ash (STW~ detergent compositions~ According to the in~ention STW detergent ompositions contain at least one surfactant and ~rom 1% to 50~, pre~erably ~rom l-~ to 20%, mor~
preferably ~rom 5~ to 15%, o~ said ~abric tr2atment compositions.

, .

WO 92/07927 PCr/US91/07919 2~5.~Zk,4 ~,,,,,~,;, .-Even more preferred æe particles comprising coaggl~merated ~oftening clay and substituted polysiloxanes.. Together wi~h clay flocculating agents ~hese particles can b~ used in granular softenlng c~mpositions or preferably in granular STW detergent . composi~ions.

Defin~tions Unless stated otherwise, the following definitions will be used hereinafter :
- percentages are ~ _ - softening refers to a range of f~bric treatments o~her ~han cleaning; in particular it includes softening, anti-wrinkling, anti-~tatic and ease o~ ironing treatm~nts.
- clays are softening claYs as described in more detail below siloxanes are subs~ituted polysiloxanes for fabric trea~m~nt as descr~bed in more detail below.

Detailed D2scriptic~ ~' r ention The so_teninq clay one essential component of ~he present compo.sitions consis~s of a clay.

~ ! W092/0792? Pcr/uss 1~07~19 2~9~2~ 1 -- 5 ~ , .

Any clay used in the art or mix~ures thereo~ can be used in ~he present invention.

Included among such clays are various h~at-tre~ed kaolins and various multi-layer s~ecti~es. As kno~ ~ro~
the art, preferred smectite clays exhibit a cation-exchange capacity o~ at least 50 meq per loo grams of clay.

Further pre~erred are clays which have a particle size in the 5-50 micromeker range.

Additionally pre~erred smec~ite clays are hectorite clays of the general foxmula ~(Mg3_xLix) Si4_yMeIIIyOlO(OH2_z~z)] (x Y~X~
n wherein y-o: or, i~ ~$o, MeIII is Al, Fe, or B, is a monovalent (n=l) or divalent (n=2~ metal ion, for example selected fro~ Na, K, Mg, ca, sr. The value o~
(x~y) is the layer charge of the hectorite clay. The hectorite clays suitable ~or the detergent compositions of th~ present invention have a Layer charge distributiDn such that at least 50% i~ in the range of ~rom 0.23 to 0.31.

Pre~erred are hectorite clays o~ natural oriyin having a layer charge distribution such that at least 65% is in the range o~ from 0.23 to 0.31.

, ~ . ...

~

WO 92/07927 ~ItUS~1)7919 eic non-limi~ng examples of fabric so~ten~ng smectite clay mineral~ are: ¦

Sodi~ lt~on~orilloni~e Volclay BC R
Gelwhite GP R
Thixo~Jel R
Ben~A-Gel R

Sodium Hectorite Vee~ F R
Laponite SP R

Sosli~ Sapo~ite -Barasym N~S 100 R

Caic um Montmorillonite Sot Clark R
C~elwhite L ~'s Imvite K ~

Lithlum }le e Barasym hI~ 200 R

~W~ 92/07927 P~/VS~ 7919 J ~

The clay floçcu~ a~LA~ent Clay flo ~ ating agents are not commonly used in fabric treat~e~t compositions~ on the contrary, one is inclined to usz clay dispersants, which aid in removing clay stains fro~ fabrics. Clay flocculating agents are, however, vexy well Xnown in othPr industr.ies like oil well drilling, and for ore flotation in metallurgy. Most of th~se materials ~re fairly long chain polymers and copolymers derived from such monomers as ethylene oxide, acrylamide, acrylic acid, dime~hylam mo e~hyl me~hacrylate, vinyl alcohol, vinyl pyrrolidone, ethylene imine. 5ums, like guar gum, are suitable as well.

Preferred are polymers of ethylene oxida, acryl amide~
or acrylic acid. It has been found that ~hese polymers dramatically enhance the deposition o~ a d ay if their molecular weights (weight average) are in the range of from lOO,OOO^to 10 million. Preferred are -~uch polymers having a (weight average) ~olecular weight of from 150.000 to 5 million, more preferably ~rom 150,000 to 800,000.

The most preferred polymer is poly-(e~hylene-oxide).
Molec~lar wei~ht distributions can be read.ily dPtermln~d usLng gel perm~ation chromat~graphy, ayainst standards of poly-(e~hylene-oxide) o~ narrow molecular weight distrihutions.

m e amount of clay flocculating agent, expr2ss~d as percent of ~he clay, ranges ~rom 0.005~ to 20%. For clay flocculating age~ts having a (w~lght average) molec~llar wPight of less ~han 800~000, the pref2rred amount is ~rom WO 92~07927 l ( . . P'C~/US91~7919 2~244 ~.

2% to 2~% of the clay. For (weight average) molecular weight abov~ 800, 000 the prefPrred amount is f:rom 0. 00596 to 2% of th~ lay.

The amour~t of siloxane ranges from 0.1% to 50% by weigh-t of the clay~ preferably from 0.1% ~o 20%, most pre:Eerably from 1. 0% to 10% .

The siloxanes useful in the present inven~ion can be described as softening, stxaight or branched, organo-functional polydi-C~ alkyl siloxane having the gen~3ral formula:

R'--si--O-- i~ O~ o- i R' wher~in R is Cl_4~alkyl, R~ is R or a polyether of (C2-3~oxides) 1-50~ w ith a capping group c~f H or R;
R" is branched or straight C~ alkyl;
q1 and q2 are integers;
m and ~ql ~ q2) ~r~ integer5 :erom ~ ~o 1700;
n i$ an integer from 0 to 6;
Y is a poly~ther o~ (C2~3-ox.ides) 1~ whe:re :k has an average value ~rom 7 ~o 100, with a capping group of ~I or Cl_4 -alkyl;

W~ 92/~7927 P~r/VS~l/V7919 ~ 2 b g"5'2'~ 4 _ g _ - or y is . -N whereby X and V are selPcted from -EI;
-Cl_3 ~-alkyl, -C-aryl;
C5-6-CYClOa~ Cl_6-M~2;
X V -COR; with the proviso that the nitrogen can be quaterniz~d such as to represerlt:

N ~ W

X V

whereby W can be selected from X and V.

or Y is H ~ C--T whereby T and P axe selected from ~, -COOH, -CO-O-C1_2-alkyl, or H- --C--H epoxy-C~j_6~cycloalkyl P

Pre~erred silox~anes of said general formula arP
charact~rized by ql + q2 being an integer ~rom 50 to 1500 ancl m being an integer from 4 to 1.00~

W0~ 92/0~927 P~r/lJ~;9 I/079l~J
`2~52~ ~
, I . i ~ ~.

The most preferred siloxanes of said gener~l formula are characterized by either of the ~Eollowing - R, R t iS methyJL and Rl' is propyl and (ql ~ q2) is 329 and m is 21 and n is 1 and y i5 a polyether consisting of 12 e thyl oxides ancl an acetic acid capping qroup or - R, R ' is methyl and R" i5 propyl and (ql ~ ~2~ is 485 and m is 15 and n is 1 a~d y i5 a polyether consisting of 12 ethyl oxides and acetic acid capping group or - R, R' is methyl and R'l i5 methyl-2-propyl (~1 ~ q2) is 1470 and m is 30 and n is 1 and y is an - ( ami~o ethyl ) amine Optional,s ~ ina~edients The fabric treatment compositions herein can ::omprise in addition to the ess~ntial compountls other use:eul compounds known in the arlt. These compounds can be present, deperlding on applica~ion and preparation needs or other esires, irl an added amount of up to 85% o:E the fabric treatment compositiorlO

Suiltable ~xamples amons~ thase other sof teniTIg compo~ ds include the followirlg softening amines OI the fsrmula RlR2R3N~ wherein Rl is C6 t~ C;20 hydroca y, R2 is C L ~ C2 0 hydrocar}:3yl ~ and R3 i~ Cl to Clo hydrocarbyl or hydrogerl~ P. pre~e:rred amine of ttl LS
type is ditallowme thylal~ine .

WO 9~/07927 ' ' 2 0 ~.5 2 A ~ P~T/~S~ 7~1~

Preerably, the soften mg amine is present as a complex with a fatty acid of the formula ~COO~, wherein R is a C~
to C20 alkyl or alkenyl. It is desirable that the softening amine/fat~y acid complex be present in the ~o~m of microfine particles, haYi~g a particle size in the ra~ge ~rom 0.1 to 20 micrometers. These softening amine/fatty acid complexes are disclosed more fully in EP-A-133 804.
Preferred are fabric trea~nent compositions that contain from 1% to 10% of the arnine.

Suitable are also complexes of the above described softenLng amine and phosphate esters of the formula O O
Il 11 R80 -p OH and HO ~ I ~ OH

O~g 0~9 wherein R8 2nd Rg ar~ C1-C20 alkyl, or eth~xyla~ed alkyl gr~ups of the general formula alkyl-(OC~2CH2)y, wherein the alkyl substitue~t is Cl-C20, preferably C8-C16, and y is an mteger of 1 to 15, preferably 2-10, most preferably 2-5. Softeniny amine/phosphate es~er complexes of this t:ype are more fully disclosed in EP-A lS8 889 q "
Suitable optional softening inqrediPnts are also the softening am~nes disclose~ in GB 2 173 827, in particular the substi~ted cyclic amines. Suitable arP imidazolines of the gelleral formula -(C12-22 ~ amide-(C~ al}cyl)-2-(C12_22 alkyl i~nidazoline .

: ~ WO 92/~7927 r ~ 1 PC~/~S~It~79 A p.r~ yclic am~ne is ï~tallawa~id~t~yl-2-tallow~idalzol~ne. Pneferred falbric ~reabsle~t c~osi~ions co~itain ~ro~ 1% ~o 109~ ~f t~
s~stitu~d cyclic am~ne.

~ er examE~les of taptional ingredients include the softening ami~aes of the fonnula R~ NC(:)R12~ ~erein Rlo and Rll are ~ndependently select~d f:rom cl-c22 alkyl, alkenyl, hydroxy-alkyl, aryl, and al~yl-aryl yroups~
R12 is hydrogen, or a C1-C22 alkyl or alkenyl~ ~n aryl or alkyl-aryl ~roup. Preferred exa3~1es of these soften ~ g ~ das are ditallow-acetamide and ditallow-benzamide. Good results ~re obtaLn~d when ~he softening amides are present in the c~mposition in the form of a co~posite wi~h a ~a~y acid or wi~h a phosphate est~r, as described hereinbefore for ~he so~teniny amines.
m e soft~nLng a~ides are pre~erably present in ~he fabric treatment softenl~g c~mFosition at 1%-10%.

~ oreover, the fabric trea~ment compositio~s herein can con~ain, in addition to ingredients already men~ioned, various o~her optional i~gredien~s typically used in commercial products to provide aesthetic or additional product performance b~ne~its. Typical ingredien~s include p~ r~gulants, humectants/ which are more fully dis~losed in EP~313 146~ silicones~ perfumes, dyes, hydro~ropes and gel-con~rol agents, freeze-~haw stabiliz ~s, bactericides or pr~serva~ives. Preferred ~abric ~reat~en~ ~omposi~ions contain fr~m 0.05% ~o 30% o~ ~hese in~redients~

W09~/079~7~ P~ S~I/079~1~

. .
Industr al~A.~plicati.ons The fabric treatment compositions of the present invention can be provided in liquid or granular fo~m. Lt can be applied in the rinse cycle or, together with a detergent co~position, in ~he wash. In a preferred embodiment said fabric treatm~nt compvsi~ions are compris~d in soft2ning-through-the-wash (STW) detergent compositions.

Further in a preferred embodimen~ said fabric treatm~nt compositions are particula~e agglomerates, and in a more preferred e~bodiment said agglomera~es are integrated in particulate detergent compositions to form granular STW
detergents.

Liquid and Granular A~plicatiQn .. . . ..
- The fabric treatment compositions of th~ ~resent invention can be provided in liquid form as an agueou~
dispersion. If provided a~ an aqueous dispersion, the fabric treatment composition preferably further compri~es an antisettling agent~ ~ccording to the invention, the aqueous di~persion com~rises clay of thP fabric treatment composition ~ro~ 005~ to 30% of the aqueous di~persion and siloxane and clay ~locculating agent in according amountsO
., A suitable antisettling ag~nt must provide a fully activated suppor~ matrix ~o suspend par~ioles ~ithin ~he liquid compositionsO

WO 92/07927 ~ P~ 7gl9 2 ~ r;

Particles in this sense are granul~s or droplets of suspendable size for the desired properties of the liquid composition. Usually said particle size will be less th~n 200 micr~meters. The individual par~icles can c~mpris2 one or more of the essential or optional c~mpounds o~ the fabric treatment compositions.

Finally, an acceptable antisettling agent must not adversely effect the viscosi~y, elas~icity or aes~hetics of the product~

These antise~tling agents, or mixtures thereo~, are used in the compositions of the present invention at le~els of from 0.25% to 5%.

Organophillic quaternized ammonium-clay compounds for example of the Bentone R family of clays ~nd also f~uned silicas are examples of an~ise~tling agen~s suita~le for use in ~he present invention. Bentone R rheological additi~es axe described as the products of a clay which contains a negative layer-la~ice and an organic compound which con~ains a cation and at least one alkyl group containing at leas~ 10 car~on atoms. Bentones R have ~he propert~ of swelling in certain organic liquids.
Organophillic: quaternized alm~onium-clay cor[~ounds are preferred antisettling agents as described in UOS. pat~nt 4,287,08~.

Fumed 5ilicas also provide excellent antisettling characteristics to the compositions of ~he present invention~ Fumed silicas are generally defined as a colloidal fonm of silica made by combustion o:~ silicon tetrachloride in a hydroyen oxygen ~urnace. F~ed silicas are normally used as ~hickener, thixotrop.lc and reinEoxcing W092/07~27 ', ; ~CrlUS91l~7 agents in inks, resins, rubber, paints and cosmetics.
O-SIL~ ~umed silica~ are sui~abl~ antlsettling agent~
for use in th~s invent1on~
.. . . , ~
Other antisettling agents are cellulosic ~uspending agents. For example carboxy-alkyl~celluloses, pre~erably carboxy-methyl-cellulose, are excellent suspending ag~nts.
Furthermore other suspending agents known in the art can be applied.

Mixtures of Bentone R clays, fumed silicas or cellulosic suspending agents are also suitable antisettling agents.

The rheological characteristics o~ the resulting liquld compositions are very importa~t to 2 co~mercially acoeptable product. A liquid which oan be described as stringy ( i . e ., elastie), ~hick or lumpy is undesirable.
The antisettling agents described above avoid these unde~irable rheological properties while maintaining a pourable, homogeneous produc~ with good consumex appeal~ A
viscosity in the range of ~rom about 100 to about 1000 kg/(ms) is desirable.

It is also desirable ~or th liquid oompo~ition to exhibit plastic rheology. Materials th~t exhi~it plastic flow characteristics will flow only ~t~r an ~pplied shearing stress e~ceeds a critical minimum val ue .

Fabric treatment compositions of the present invention can also be provided in granular form as particulate W~92/07927 2 ~ 9 ~ 2 ~ ~ . P~l~U~9~/~79~ l '' ` ~

- 16 - .

-compositions~ ~ccording ~o ~he in~ention p~rticula-~e composition~ co~prise clay of the fabric treatment composition from a~ least 15~, preferably a~ove 50~ 9 of the partic~late compositions and siloxane and clay flocculating agent in according amoun~s.

To provide particulate compositions, th~ compounds o~
said fabric trea~men~ composition are preferably agglomerated. The typical agglomera~e siz~ useful in the present invention is from 0.2 to 1.2 millime~er on average, with in~ividual agglomerates ranging from 0.05 mm ~o 2.5 mm.

According to ~ preferred execution of the inv~ntion the clays, siloxanes and clay flocculating agents ar~
agglomerated together from a slurryO

In a ~urther preferred embodiment the agglomerakes containing clay and siloxane are made separa~ely ~rom the agglomerates containing the clay flocculating agent and both kinds of agglomerates are mixed aocording to the invention.

-Agglomeration methads and equipme~t suitable for use herein include those methods known in ~he art.
Agglomeration methods includP usage o~ agglomeration aids including for example sodium carbona~e, sodi~2m sulfa~e 7 potassium carbona~e, potassium sul~at~, magnesi~m sul~atR, lithium ~ul~ate, lithium carbonat~, sodi~tm citrate~ so~lium sesquicarbonate and water. Non limiting ~xamples of the equipment suitablQ for a~glomeration of clay from smaller W092/07927 2 0 9 ~ 2 ~ ~ PC~/US~/07~

particles include a DravoR pan agglomerator, Loedi~e~
agglomeration XG/Schugi Beldne ~-Granulator~ whirling knife continuous vertical fluidized bed agglomerator.
NiroR Fluidized Bed ag~lomerator, O~rianR
Mixer/~gglomerator, and a Li~tlefordR mixPr (Little~ord 1.
Brothers, Inc., Florence, Kentucky, USA, eg. Model FM130D).

Qther methods and equipment which use larger amounts of water, inclu~ing th~ manufacture o~ agglomerates directly from a slurry, include a spray drying tow~r, and a prilling tower.
On a laboratory scale, food processors which are widely available to the general public can be used ~o agglomerate smaller clay particles into agglomerates in the disclosed size ranges.

Deterqent Compositions .
If applied together with detergent compositions, preferably;as in~egral part o~ S~W-deterg nt compositions the fabric treatment compo~i~ion is present ~rom 1% to 50%~
preferably from 1~ to 20% and most preferably ~rom 5% to 15% of the total composition.

STW detergent co:npositions o:E the pres~nt invention can be provided in liquid or granular ~orm. To provide liquid or granular STW deterg~nt compositions the detergent compounds can be eith~r prepared and then mixed with the aqueous suspension or thQ granular agglolaerates of thP
fabric treatment composition or the detergent compound and the fabric treatment composition compound can be prepared together in an inteyr~l process.

WO 92/!~79~7 2~ 5 2 ~ ~ P~/~ 7~

STW~ekergent compositis:ns a~ pref~rably ~ranular SWT~dete~en~ ~posil;ions o:~ ~e presen~ inYen~ion are characterized l~y camprising ak least one s~Lrfac~t in addition to said :Eabric: treatmen~ ccm~sikions. ~Chey can ~er contain other usual clekerg~t c~pour~3~ in quantities c~mmon ~n the art.

Detersive surfactants particularly use~ul herein mclude well-kno~n synthetic ~nionic, nonionic, amphoteric and æwitterionic surfatants. Typical of th~se are the alkyl benzene sulfonates, alkyl- and alkyle~her sulfates, paraffin sulfona~2s, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, amine oxid~s, alpha sulfonates of ~a~y acid~ ~nd of fatty acid estexs9 and ~he like, which are well-known f~om ~he detergency art. In gene~al, such detersi~e sur~ac~ants contain an alkyl group in the Cg-Cl8 r~nge; the anionic detersive s~rfactants can b~ used ~ the fonm of their sadium, potassium or triethanolammonium salts; the . .
nonionics generally contain from c~ut 5 to about 17 ethylene oxide groups. U.S. patent 3 995 669 cont~ins dekailed listl~gs of such typical detersive surfactantsO
Cll-C16 alkyl benzene sulfonates, C12-Cl~ paraffin sulfonates and alkyl phenols are especially pre~erred in ~he co~positions o~ ~he presen~ ~ype.

Also useful h re m as ~he sur~actant are ~he watar:soluble soaps, e.g. ~he common sodium ~nd potassium c~conu~ or ~allow soaps well~mown in ~he art.

The de~rgent composition can Gomprise a~ little as 1%
surfactan~ composition~ but pref~rab.Ly it will contain S~
to 50%~ more prefe~ably 10% to 30% surf~ctants. Mixture~

WO 92/07927~ 2 0 9 ~2,,~ 4, Pcr/ussl/o7~

of the ethoxylatec3 nonionics with aniDnics such as ~he allyl benzene sulfo~tes, al~yl sul~ates and para:ff~n sulfona~es ar~ preferxed :~or ~hrough-the wash cl~nsing of a broad spectn~ of soils and stains from fabrics.

D~tersiye Ad~unç~;

me dete~ent composition useful in the present invention can contain o~cher ingredients which aid in their cleanin~ performance. For example, it is highly preferred that detergent compositions contain a detergent build2r and/or metal ion sequestrant or chelant. Compou~ds classifiable a~d well~known .Ln ~he art as detergent builders include ~he nitrilokriace~ates, polycarboxylates, citrates, carbona~es, zeolites, water-sol~ble ~hosphat~s such as tri-polyphosphate and sodium ortho- and pyro-phosphates, silicat~s, and mlxt~res thereof. ~etal ion seques~rants include all o~ the ~bove, plus materials like ethylenediaminetetraace~ate, the amino-polyphosphona~s (DE ~ T ~ ~nd a wide variety of G~her poly-fun~tional organic acids and sal~s ~oo numerous to mention in detail here. U.S. pa~enk 3 579 454 discloses typical examples o~ the use of such materials în various cl~aning compo~itions. In general, ~he builder/seguestrant will comprise about 0.~% to 45~ of ~he total c~mposition.
The 1-10 mic~on size zeoli~e (e.g. zeolite A) builders7 disclosed in German paten~ 2 422 ~5j, are especially pre~exred for use in low-phospha~e composi~ions.

Particularly sui~able phosphate-free build2rs are ether carboxylate mixtur~s compris mg WC~ 92/07~27 ~ ; 2 ~ ~ ~ P~r/U~ 7~1 a) from 1% to 99% of the builder o~ a tartrate monosuccinat~ cong?onent o~ the structure HOCE~ o CH --~
,12 coo~ coox cooX ~o~
wherein X is H or salt-forming cation; and b) from 1% to 99% of the builder by weight of a tartrate discussinate component of the structure :

COOX ~OOX COOX COOX CC~OX COO~
wh~rein X .is H or a salt-forming cation.

Builder systems o~ this type are more fully disclosed in U.S. patent 4,663,0710 Typical detergent compositions useful in the present invention contain from 5% to 35~ of this ~uilder syst~mO

m e detergent compositions herein also preferably contain enzymes or enzyme mlxtures to e~hance their cleaning performance on a variety of soils and stains.
Hydrolases and isomerases like amylase, lipase, cell~lase, and protease enzymes suitable for use in de~tergen~s ar~
well-kno~n in ~he art and in 5~mmerr~ially availabl2 li~ui~
2nd granular WO 92/07927 2 1~ 9 ~ 2 ~ 4 ~/U~ 7~

de~ents. Ca~xial ~etersive enzymes (pr~era~ly a mixtu:re of a~ylase, lipase, celllll~;e and protease~ z~e typically used. at levels of 0~ 001% to 5% o:E said dete:rgent cu~positions. I:~ter~ent cellulase enzymes~ w~ich pr~ide ~oth cleaning and softening }~efits, particulæly tQ
~ ton ~abrics, are highly desir~le in the ~positions of thi5 irlvention.

Further said detergent ccmpositions can contain other ingredients which aid in their cleaning performance. For example, the compositions hereln can a*vantageously contain a bleachiny agent, especially a peroxyacid bleaching agent.
In ~he context of the present invention, the term peroxyacid bleaching agent enc~mpasses ~oth peroxyacids per se and systems which are able to yield peroxyaci~s in situO

Peroxyacids per se are meant to include ~he alkaline and alkaline-earth metal salts ~hereof. Peroxyacids and diperoxyacids are commonly used; examples are diperoxydodecanoic acid.(DPDA3 or peroxyph~halic acid~

Systems capable of deliveriny peracids in situ çonsist of a pero~g~n bleaching agent and an activator thereofO

Ihe pero~ygell bleaching agerl~ are those capa;bla of yield~ing h~drogerl ~n an aqueous 501ution; these ~ompounds are well-kna~ in ~e a~, and include ~ydrogen perox:~de, al~l~mel:al peroxides, orgarl~c pero~fida bleaching agents such as urea peroxid~ in~rganic psrsalt bleadling agents such as alkali metal perbora~es, percarborlates, pe~phosph2ltes and persilicates~

W092/07927 2;D ~ 4 ~T/VS~1/07 The libexated hydrogen peroxide reacts with a bleach activator to form the peroxyacid bleach. Class~s of blPach activators include es~ers, imides, imidazoles, oximes, and .carbona~es. In ~hese cla~ses, pre~erred materials includs methyl o-acetoxy benzoates; sodium-p-acetoxy benzene sulfonates such as sodium-4-nonanoxyloxybenez~ne sulfonat~.p and sodium-4-decanoyloxybenzenesulfonate : biophenol A
diacetate; te~ra acetyl ethylene diamine; ~e~ra acetyl hexamethylene diamine; tetra acetyl methylene diamine.

Other highly preferred peroxygen bleach activators which are disclosed in UuS. pa-tents ~ 3.778 and 4.539.130, are alpha-subs~i~uted alkyl or alkenyl esters, such as sodium-4~2-chlorooactanoyloxy)benzene sulfonate, sodium 4-(3,5,5-~rimethyl hexanoyloxy)benzene sulfonateO
Suitable peroxyacids are also peroxygen bleach activators such as described in EP-A--116 571, i.e~, compounds of the general type RX~OO~I and ~X~L, wherein R is a hydroxcarbyl group, X is a hetero-akom, ~ is a carbonyl bri~ging group and L is~a:leaving-group, especially oxybenzenesulfon~te, Also polymeric soil release agents are us~ul in th~
detergent compositions of the present inventionO Thsy include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of sthyle~e ~erp~thalate and polyethylene oxide or p~lypropylene oxide terephthalate, cationic guar gums, and the like.

WO9~/079~7 1~:2,'~ J~ P~T/~5~ 791~
~ ~ .. .

The cellulosic derivatives that ar~ functional as soil release agents are commercially available ~nd includa hydroxyethers of cellulose ~uch as MethocelR (Dow~ and c~tionic cellulose ether derivative~ such as Poly~er JR-124R, JR-400R, and JR-30MR (Union Carbide).

Othar e~fective ~oil rel~ase agen-ts ar~ cationic guar gums ~uch as Jaguar PlauR (Stein Hall) and Gendrive 458R (General Mills~.

Pxeferred cellulo~ic soil release agents for use herein have a viscosity in aqueous solution at 20~C of 15 to 75,000 kg/(ms) and are selected ~rDm the group consisting of methyl cellulose; hydroxypropyl methylcellulos~, hydroxybutyl methylcallulose, or mixtures thereof.

A more prsferred soil release agent is a copolymer having random blocks o~ ethylene terphthalate and polyethylene oxide ~PEO) ~erephthala~2. Mor~ speci~ica~ ly9 these pol~ers are ccmprised o~ repeating units of ethylene terephthalte and PEO tereph~halate in a mol2 ratio of ethylene ~erephthalate unit5 0~ ~rom about 25:75 to about 35 65~ said PEO ter~phthalate units containing polyethylene oxide having molecular weights o~ ~rom 300 to 2000. Tha molecular weight o~ this polymeric soil release agen~ .is in the range of from 25,000 ~o ~59000. U.S. paten*s 3,9~230 and 3,893,929 disclose similar copolymers in a large variety~ It has been ~ound previously that these polymeric soil release agent~ provide a more uniform distribution over a range o~ fabrics and can there~ore yiield :improved ~abric care ~ualities.

W092/07927 2` Q 9 ~ ~ 4 ~ P~r/vs~ 79 ,~

Another preferred poly~eric soil releasQ agent is a crystallizable polyes~er wi~h repeat units of et~ylenQ
terephthalate units containing about 10-15% by weight of ethylene terep~thalate uni~s togeth~r with about ~0% to about 90% by weight of polyo~yethylene terephthal~te units, derived from a polyoxyethylene glycol of average molscular weight 300-5,000, and the mole ratlo of ethylene terephthalate units to polyoxyethylene terephthalate units in the crystallizable polymeric compound is between ~:1 and 6:1. Examples of this ~ype o~ polymer include the commercially available material ZelconR 5126 (from Dupont) and MileaseR T ~from ICI~.

Preferred soil release polymers and methods for their preparation are described in EP-A-1~5,417.

If utilized, these soil release agents will generally comprise from 0.05~ to 5% of the ~etergent compositions~

. ~ . . ,. ~

` wo 92~07927 2 ~ `~ 5 2 4 4 PCT/US91/07919 ~,, .1~,. , EXAMPLES

The following examples illustrate preferred ex~cutions of this inv2ntion, an~ facilitate i~s under~tanding.
Abbreviations for individual ingredien~s in the examples have the ~ollowing meaning :

LA5 : Sodium salt o~ linear dodecyl benzene sulfonate TAS : Sodium sal~ of tallow alcohol sul~ate AOS ~ Sodium salt o~ alpha-olefin (C12-18 sulfonate TAE 11 : Tallow alcohol ethoxylate~ with about 11 moles of et~ylene oxide FA25E7 : Fatty alcohol (C12-15) ethoxylated with 7 moles o~ ethylene oxide DTMA : Ditallow methyl amine ~FA : Coconut fatty acid .
HFA . Hrdrogenated C16-~2 ~atty acid Zeolite A :-- Sodium salt of fully hydrated zeollte 4A
(average p rticle size be-tw~en 2-~ microns~
NTA : Sodium salt of nitrilotriacetate Copolymer O AA30/M~7~ = copolymer o~ acryli acid 30 mole~% and malsic acid 70 mole-~-50-70 ~mole weight CMC : Sodium ~alt o~ carbox~methylcellulose EDTA o SOdium salt of ethylen~ diamine tetra-ace.tate W092/07~27 2 ~ 9~-2~ PCT/~S91/~7 Example I

For compositions A,B,A',B' the following was preparPd 500g of ~mectite clay having a cation exchange capacity of '.
70-80meg/lOOg was mixed with 50g polysiloxane (10% of clay). The polysiloxane was of th~ general ~ormula with R
being methyl, R' being a strait propyl, q being 329, m being 21, n being 1 and y being a polyether of 12 ethyl oxides capped with acetic acid. Both compounds were intimately mixed and agglomerated by using a BraunR
multipractic-electronic-de-luxe mixer. The agylom~ration aid was water and ~h2 agglomerates were sie~ed to a particle size from 0.15 ~o 0.85 mm. A reference without the siloxane was also prepaxed in the same manner.

Composition A was prepared by dry mixing of the clayJsiloxane granules with the deterg~nt granules of composition I, according to Table I, such that the resulting softening through~the wash detergent contained 1005~ of-the s~ectite clay. ~s a reference compDsition B
wa~ prepared by dry mixing the clay granules wi~h the same detergent granules of composition I, Table I, such that the resulting STW detergen~ also contained 10.5% of th~
sm~ctite clay. Further composikions A',B' were prepared in the same way as compositions ~,B respectively bu~ uslng detergent-compo~ition II of Table I which contain~ clay flocculating agent.

To facilitate a softness comparison of A,~,A',B1 the following test procedure was used :

3.5 kg of clean fabric laundry loads ar~ wa~hed in an automatic drum washing machine ~ieleR ~23 at 60~C for 1.

: W~92/07927 . PCT~VS91/~7~19 2 ~3 9 S ~
27 - .

hoursn The hardness of the water was 3~0 mmol o~ Ca2t and Mg2~ per liter and -the composition concPntration was 1% in the wash liguid. For softness evaluation swa~ches of terry towel softness ~racers were added. The o~-tness tracers were line dried prior to assessment of sc~tness.
~omparative softness a~ e~sment was done by expert judg~s using a scale of O to 4 panel-score-units (PSU). In this scale 0 is given for no difference and 4 is given for maximum difference. Softness was assessed after one and after four wash cycles.

Softness evaluation results of composi~ions A,B,A',B7 Result comparison of one wash cycle four wash cycl s composition 1.A to B- 0.1 PSU O . O PSU

2 u- A~ ~to B ' o . 6 3?SU O . 9 PSU

Taking result 1 there is no additive so~tening ef ~ect realized by adding siloxane to a clay-containing STW
detergent. ~he effect of the invention is demons~rated in result 2 where the combinatiorl of clay, flocclalatirlg agent and siloxane shows surprislngly clear softening super:Lority over prior art co~aposi1:ion c:ontainirlg clay and fl3cculatlng agent .

_xample II

~ he same compositions a,b,~',b' respectively as in example I were prepared except ~or using 5g o~
polysiloxane, i.e. l~ of the we.ight of the clay. The W~g2/079~7 ~r/-US~ 7919 2~9~

polysiloxane used in this example II was Silwet L720 ~rom Union Carbide~

Result comparison of one wash cycle four wash cycles composition 3. a to b - 0.2 O.l 4. a' to b' 0.3 0.6 Examples III - XII

Accordins to the inven~ion other detergent compositions can be used together with the clay siloxane agglomerates and flocculating agent. Alternative granular detergent compositions are listed in Table IIo Similar compositions in which the clay/siloxane granules are initially dry mixed with granules containing the flocculating agent have be~n found to be equally effective when a~ded to granular detergent compositions.

Exam~le_XIII

Exe~plifying u~age of the fabric treatment composition as aqueous dispersion ~he following composi~ion showe~
excellent 50ftening per~ormanc~ when ad~ed in an appropriate amount to the last rinse of th~ wash o 80g o~ sm~ctite clay are dispersed in l kg of water. 8g of siloxane as described in example I or II are added under strong agitation. The flocculating agent and thi~ mixture are added together to the last rinse of the wash.

~ W092/07~27. 2 ~ 9 5 ~ ~ ~ PCT/US~I/07~

Exam~le XV

A stabilized aqueous dispersion o~ the ~abric treat~entcomposition is prepared by using a propeller mixer at rotation of 100 to ~OOD per second and combininy liquid carrier, sof~ening clay, siloxane and an an~isettling agent in said propeller mixer ~or abou~ 30 minutes. The resulting mixture is the~ passed 4 to lO ~imes through a colloid mill (e.g~ model SD-40, distribut~d by Tekmo ~
Corporation) providing a shear of 10 40x103 per second at a temperature o~ 20-40~C. Then the flocculating agent is added slowly using said propeller mixer for an ad~itional 5 minutes.

The resulting mixture is stable, iOe. shows ~OW phase separation or set~ling of the clay, for several wePks at amblent conditions~

, . .

WC~ 92/07927 % ~ 9 5 2 4 4 ! p~r/us~3/o7~19 ''' ~

Table I

Composition of ~ranular detergents. All values in wei~ht percent. - ¦

. Composltion I II

C12-C14 Dimsthyl(hydrDxyethyl)ammonium chloride 2 2 Zeolite A 23 23 Copoly~er 5 5 Diethylene tri-amine penta (me~hylene phosphonic acid) 0.5 0.5 Sodium perborate (1 aq.) 12 12 Tetra~cetylethylene diamine 4 ~n phtalocyanine sulphonate 20ppm 20ppm Perfume O.4 0.4 En2yme (protPase) 2 2 Montmorrillonite clay ll 11 Glycerol 0 5 0.5 Polyethylene oxide (MW 300.000) - O.25 Sodium carbonate 11 ll Sodium silicate 5 5 Silicone/silica suds suppressor CMC 0.4 0.4 Optical brightener 0.2 0.2 moisture and minor balance t~ 100 ~ ` ` Wl) 92/07927. 2 0 9 5 2 ~! 4 P~V~g 1/D7~ 19 INGREDIE~ a~OSI~12~S
(% by w~i~;ht III IV V VI VII VIII~ ~ IX X XI X:[I

IAS 7.0 5.0 4.01.0 6.520.16.77.0 8.0 'rAS ~ 2.0 - - 1.0 - - - 2.02.0 C14 15alkyl sulfate ~Na) - 6.7 AOS - - 2.0 - - - - - - -Tallow~a~no Cl 4-alkyl - - - 8.0 gl~Y:ose amide TAE-ll 1.0 2.0 2.0 - 0.8 - - 1.0 FA25E7 - - - 6.0 - - 1.0 - 1.01.0 HFA 2.5 1.0 - 1.0 1.0 - - 2.5 CFA - - 1.5 ~12'C14 D~ethYl thydroxy 1.5 - 1.5 - 2.0 2.0 ethyl) Anium cloride Sodium tripolyphosphate 24.018.022.0 32.0 - 36.9 26.3 24 Zeoli~e.A - - - - 20.0 - - - .23.0 23.0 Polye~ylene oxide 5~ le wt0.05 - - - 0.05 0.10.1 Polyethylene oxide 0.3M~ mole wc - - - 0.2 - - - 0.2 0.25 Polyacrylate - O.2 Polyacrylamide - - 1.5 ~A - - - - 5.0 Sodium sulfate 12.6.17.715.0 21.312.728.3 13.012.4 Sodium ca~bonate - 8.0 - 5.0 - - 15.05.0 11.011.0 ~WQ\ 92/07~327 ~2 ~ J591/l~l79l~
i; ,.;:

Table II - Cont-inued a~POS,~EI, O S
- !
(9~ by wei~ht) III IV V VI VII VIII IX X XI XII
~ ..
Sodium silicate 6.0 7.0 4.0 6.0 2.0 5.75.6 6.0 5.0 5.0 Sodium pexborate t4aq.) 20.015.0 18.010.0 18.0 - 5.0 15.0 Sodium perbora~e ~laq.) - - - - - - - - 12.0 12.0 ~IC 0.3 0.3 0.5 0.8 0.4 - - 0.3 0.4 0.4 Polyacrylate (~1000 20000) - 1.S - - - - O.80 Polyac~ylate (MW4000-5000) - - - - 3.0 Copolymer 2.0 - 1.5 2.5 - - - 2.0 4.0 5.0 Enymes (protease, amylase, lipase, cellul3se) 0.6 0.2 0.5 0.5 0.3 - 0.6 0.6 2.0 2.0 Optical brightener 0.2 0.2 0.3 0.30.25 - 0.8 0.2 0.4 0.4 Zn phthalocyarune sulphonate 30ppm - -25ppm 25ppm - - 30ppm 20ppm 20ppm D~ 0.2 0.2 0.3 0.15 0.2 - 0.1 0.2 Ethylenediarnine te cra~ethylene phosphonic acid 0.2 0.1 - 0.1 0.1 - - 0.2 Diëthylenetriamine penta - - - - - - - - 0.2 0.5 (~ethylene phosponic acid) Tetrsace~yl et~ylenediamine1.5 - - - 1.5 - - 2.0 4.0 4.O
Iso-non~sloyloxy-benzene sulfonate (Na) - 2.0 - 2.0 Silicone/silica suds suppressor0.2 0.150.15 0.250.2 - 0.30 0.2 1.0 1.0 Per~ume 0.25 0.250.30 0.20.25 0.20.250.25 0.4 0.4 Mont morillonite clay10.0 7.015.0 5.010.0 - 5.6 9.5 11.011.0 Hectorite clay - - - - - 8.9 Moisture ar~d minors bal~nce to 100_ _ ' ,:

Claims

1. A fabric treatment composition comprising a softening clay and - 0.005%-20% by weight of said softening clay of a clay flocculating agent and - 0.1%-50% by weight of said softening clay of straight or branched, substituted polysiloxane of the general formula wherein R is C1-4-alkyl;
R' is R or a polyether of (C2-3-oxides)1-50, with a capping group of H or R;
R" is branched or straight C1-4-alkyl;
q1 and q2 are integers;
m and (q1 + q2) are integers from 4 to 1700;
n is an integer from 0 to 6;
Y is a polyether of (C2-3-oxides)k, where k has an average value from 7 to 100, with a capping group of H or C1-4-alkyl;

or Y is :

whereby X and V are selected from -H;
-C1-30-alkyl, -C-aryl;
-C5-6-cycloalkyl; -C1-6-NH2;
-COR; with the proviso that the nitrogen can be quaternized such as to represent :

whereby W can be selected from X and V.

or Y is whereby T and P are selected from -H, -COOH, -CO-O-C1-2-alkyl, or epoxy-C5-6-cycloalkyl

2. A fabric treatment composition according to claim 1 characterized in that said softening clay is a smectite clay with a cation exchange capacity of at least 50 meg/100 gr.

3. A fabric treatment composition according to claims 1 or 2 characterized in that said clay flocculating agent has a weight average molecular weight from 800,000 to 5,000,000 and is present from 0.005% to 2% of said softening clay amount.

4. A fabric treatment composition according to claims 1 or 2 characterized in that said clay flocculating agent has a weight average molecular weight from 150,000 to 800,000 and is present from 2% to 20% of said softening clay amount.

5. A fabric treatment composition according to claim 1 characterized in that the substituted polysiloxane amount ranges from 0.1% to 20% of said softening clay amount.

6. A fabric treatment composition according to claim 5 characterized in that the substituted polysiloxane amount ranges from 1% to 10% of said softening clay amount.

7. A fabric treatment composition according to claim 1 characterized in that the substituted polysiloxane of the general formula of claim 1 has said integers (q1 + q2 from 50 to 1500 and said integer m from 4 to 100.

8. A fabric treatment composition according to claim 7 characterized in that the substituted polysiloxane of the general formula of claim 1 is selected from either - R, R' is methyl and R" is propyl and (q1 + q2) is 329 and m is 21 and n is 1 and y is a polyether consisting of 12 ethyl oxides and an acetic acid capping group or - R, R' is methyl and R" is propyl and (q1 + q2) is 485 and m is 15 and n is 1 and y is a polyether consisting of 12 ethyl oxides and acetic acid capping group or - R, R' is methyl and R" is methyl-2-propyl (q1 + q2) is 1470 and m is 30 and n is 1 and y is an -(amino ethyl)amine

9. A fabric treatment composition according to claim 1 characterized in that it further contains softening amines in an amount from 1% to 10% by weight of said fabric treatment composition.

10. A fabric treatment composition according to claim 1 characterized in that it further contains humectant in an amount from 1% to 10% by weight of said fabric treatment composition.

11. A fabric treatment composition according to claim 1 characterized in that it further contains silicone in an amount from 1% to 30% by weight of said fabric treatment composition.

12. A fabric treatment composition according to claim 1 characterized in that it is in the form of an aqueous dispersion and containing said softening clay in an amount from 0.5% to 30%
by weight of said aqueous dispersion.

13. An aqueous dispersion according to claim 12 characterized in that it also contains an antisettling agent at an amount from 0.25% to 5% by weight of said aqueous dispersion.

14. A fabric treatment composition according to claim 1 characterized in that it is in the form of granular agglomerates having an average size range of 0.5mm to 1.2mm with individual agglomerates having a size range from 0.05mm to 2.5mm and comprising said softening clay in an amount of at least 15% by weight of said fabric treatment composition.

15. A fabric treatment composition according to claim 14 characterized in that it comprises said softening clay in an amount of more than 50% by weight of said fabric treatment compositions.

16. A laundry detergent composition comprising at least one surface active agent characterized in that it also contains from 1% to 50% by weight of said laundry detergent composition of the fabric treatment composition according to claim 1.

17. A laundry detergent composition according to claim 16 characterized in that said fabric treatment composition is present in an amount from 1% to 20%, preferably 5% to 15%, by weight of said laundry detergent composition.

18. A laundry detergent composition according to claim 16 characterized in that it further comprises a detergent builder in an amount from 0.5% to 45% by weight of said laundry detergent composition.

19. A laundry detergent composition according to claim 16 characterized in that it further comprises amylase, lipase, cellulase or protease enzymes or mixtures thereof in an amount from 0.001% to 5% by weight of said laundry detergent composition

20. A laundry detergent composition according to claim 16 characterized in that it further comprises a bleaching agent or soil release agent.

21. A laundry detergent composition according to claim 16 characterized in that said laundry detergent composition is liquid.

22. A laundry detergent composition according to claim 16 characterized in that said laundry detergent composition is granular.