AU630860B2 - Thixotropic aqueous liquid automatic dishwashing detergent composition - Google Patents

Description

QMONWEALT11 Or, MUSTRAT~3 Pcatoant AcI 1952

(ORIQINAL)

App1?1±CaL4n Numbor 1Lodqed~ Cvrpto SPeQ~ffLoatiQ LodgedCCt Accoptedt pub1ished Prioity 30 Qctobor 1987 Aland Art Actu~ll Trnvo'nLoe/E- A I ,3f rv PAIMQLIVECOM4PANY~ 100) p~jr1,Z Avelltw, N(,w Yor NOW York 100 22, United$(I r at Amrnj FahmUJ Ahmed, 28A Nonta~qUe SLL'oot, CQjnlho spe icaxt4on Co bHie inveron o ti tledE: Tht~ot~oIA, oqtW'f)!~IHI~I Q UA tQt MIt L( nIt wut;q "Sqf1XW=QtIn The folowing attmn io a full descriptlonr of tht-i" ±rnventian, Includingj the heut Mthod of~ Vorfrlinq It known to ti PIFrbD OF TIM INVt-NTION The prqsent invention relates to Lt thixotropi ,sueu liquidt a~utt~c ltshwashtng ctorgont wemo)itlon with imrvod wti-fiieiing propeilttefi and mpthod of uiing the dotorgent qornpo~ition to etean diphware, 6,18$wamC C hina, An the U4e, The 01-91w~ishing C0,9410 Qont(1hi 114r vtq,.A, or titanium dip~ido, as thq onti-fMMInTg tigent, Inorganic buidr s~its qlortno bla gh b ht e tobIe dotorqent and A~ hIXcOtrople Nhokener, T dacltqren dcompp41n tion of the orqsont Invention recluCe M~nig on dishweot 9144WWaO, Ohlnw and the Itko* pavtloultiy In hardi ]Q watel', And romidnro WWhl ef~rnst, phaso seporation, Mor'o q iCQftIlY, tho invention 101006s to the tOf a~ldumina OV titarnium di1oxide as atn ttt±iflon ont In -,Xtop1 L(WoU~ II(Wu d '10hwftehlng dotorgont eoe4pesitiolls to vduoe filming.

The dtOr~ont oMpositionn d4o 'no roquie an ad~Qd vlneo Aid, oro o tablo In otorego# do not Oettlo an 've wedII aeipvtl nd are Tho vwont inventioo alsoe voo to thixotropte hoU5 o sa enIn with Im~rovedt phyktodi OtakUity, The Inventiorn volates to thO W ofe lt 4ha-14 fatty aoldsi niotat attlta of ratty (elds and clay as thi~otropio a4vqfts for~ formlng staetI gollitko liqttid 5tjsiolna ,mjttble or i~o tis lquid, tomttio hw~herd~t ont poitIon, heproont, Inventiort spectiflooy relatwi to Iq~u liui auto~I dIshwashiliv dotov~ont corn itiong 1mving thixoti(OI~ proportioei improVet aitti'Ilig 4110 11hysli1a atahillty propoetuio, whloh, aro roadily Iporulblo in the washing medium to provide effective cleaning of dishware, glassware, china and the lilke, PR1IOR ART Commercially available household-m(Achtne dishwasher detergents b provided In pQwdor form have several disadvantnges, eQg. non-Unifor-m composition; costly operations necessary In their manufacture; tendency to cak~e in storage at high humidities, resulting In the formation of Jumps which are difficult to disperseo; duti8nertss, a source of particular 1z'rit"AtIon to users who suiffer al1lergies; and tendency to cak~e in the dishwashv~ machine dispenser, Liquid forms of such compositoa hoer generaly cannot be used in auitomatic dishwashers due to high foam levels, unacceoptably low viscoatieis find exceedingly high Oklalinity.

In addition#, the presently used formulatedl powdeir detel'oots.

frequently require t separate stop of hand toWel wiping and drying of the dtohWaro, &lasware, china and the tlke to avoid loaving unclealriblo traces or talm of precipitated calcium~ and, magnesiuma salts, The use of liquid deter'gent oompooltione present other problems, The btilor 441lts settle In storage ano Ar~e not roadily Teisevd 'ro omposittons also frequently beoofe thick~er In storage arid are not readily poureble Ront rwaroh 4nd developMont actiVity hA4 foousod oil the qe or '"thltroplolf formn of suoh Oompooitions howevetr, atiOh Oompositions hovo 00enOally proen to be nutilnl VISCOUE to O venud "000orvd 1 4% tho dls6ponsor cup of' the 41shwimhor. and, mor~eOor yield tipnty residues on (11thwome afsswaro, ahinna ind the tlko, ldeallys ddffoiropio cleansing compsitionis shoold bo highly vi,9cotus In, a (jQuiCtj e sIt te, 111tilati plastic In 04tu'rdo and have rottively high yield valel, Whon siub)Qcted to shear~ 4tromats howe Ituch as bei09- Shakeni if a cO.titiev or, tqueozed throuigh oii oriloo they should qjuilly Pahito a1(i uponQ1 cessation of the, applied shoar Wtroo, qjuhi(ky N'vert to the high ViseOslty/t1Iinghat plati state, Stabilty is likewise of primary importance, I~e, there should be no significant evidence of phase 9,eporotion or leaking after long standing.

For effective use, It is generally r'eqomfeldod that the di~hwashing detergent,, heroinnftei' also cosignatod ADD, contain sodiumar tipolyphosphato (NuTPP) to soften or tic tap hard-woter Minerals 4i;d to emulsify Andc/or' peptize 0110, sodium silicate to supply thil olkalinity necessary for effective detergency and to pr'ovide protection for fine chino glaze and pattern; sodiumo carbonate, Kenerally conidICeredI to be optionalo to lncenQ whlinity; a chornoaig gnt to aid In the elimination of sol specks Which lead to Water spotting; and clefoamr/surfactont to redctue foam$ thereby onhanoing miachine officionco' Anid supplying' roqisita dotor'gonoy, $00, for example# SP)A DeQtergenta in DePth# "Vormulotions Aspects of machine 18ihWoshings" Thomas Oberlo (1974). Oleansoro oproximating to the ofoa'e-cdesorlbod compositions &1VQ mostly Ilquios- oi powdqrs, 0enerallyo sawh oomposttioflk omit hypocohlozito bloaeh, since It tencls to moci with, other chemically Active Inaroatntso paticularly suractant, thereby deg'vachiig the stwspeniding or thIxotrqep' algent Slid ImpairinK ite fetsees Thus,, V$ Motnt No, 4,0008 Oosorlbos obronlV $0e)Urh,, 010oantersof trel-iko oneistonoy Ooiitalnjng suspo nn aert on te'al 0h Sinecto and ettapul~ito types of ohaoy; (2 oahresive, O#K s$lica sarnd or perlite; 4114 fller OornpHSInq light denstty powdered polymnora, oxpanded porlito and tho like, whioh, ha a 4ouy~aoy- and thuis atahlizng effect on the Oompoolion In addition to servino as a 4ullkng ago"t threby ihaltgln water othorwfoe kivalllo for undesired supernaetant, layer formation due to leaking and phoOn etbleto 4 T'ho foroeInhg arq thi eMsentla Ingrediento. Optional ing(,rodiets include hypaehierito bleach, bleae4h stW410 Ou~rfootant and. buffur, o. g. Iiljotea. eflbonotoo, Awl mnoOPhOsPhateu ilU1ldor, SUCh 44 WIT~, Oan 4a Included o4Cutfo optional, Ingrodlento to aupply Or SUpplement uilWding- function tnot pro)vided by tbh buffer, the amount of q~uch builder not Oceceding 5% of the total comifoflq 4ocording to tho patent, Maintnance or tlwm do4ii-cI (greater than) pH 10 levois 1,4 achievoct by the b fr/~IQ de oponents l~ 1 is $Aid to minimizo Uocompouition if oblor'ine bleach and undesired, Intevacon bcdcon sitrfaqtant and blenoh- Whon, present, NaTPP Is limited to as stated, Vow Mllor 14. not disolosod, to O.K Patent Application CM 2,11,190A arnd (31 2,140,450A, both of whloh are ossned, to Cal Vwate'Imrolve, lic 1 ld ADDl 00omposItIon4 are ciolod whio, hae popertiq4 10,41rably 0 trizng thlxotro'pioQ L0 qql-ypo WttoUMN itnd WhJeh tnolulo, eaoh of the variotus Ingodefltg nosoory for' eoffetivo dotorgenoy with tin autonmati dishwasher.

T

he norm~ally pt-like aqueou omotte, dlohwomhte' clteirgont, ooaipostlon having thxtopto proportio-o Inolodoo, the followiig. ingrodiont~s on A. weight basist 6 to 365% Wa AMOWa triolyphosphatet to 20 nodium .s14lea 0 to 0% AW(at metal Po'bonatot OAt to ohlorifle bloso stoblet Wator d~nperslblo prgiik.

0 to Maron bleaeh Mt13l4 barn dvusantt 01044 ohornoblah OOMP04nd ht n 40 MOUft to- provide About r t4% of AVdlghle ohlorloo; thiXotrople thick11tir Ifl 410 amount suffiietont to provide the 4offioaotton with thixotropv Index, of about 2. to, 101 a I MOdIA161 hyW(der141n ess4,9 to 40just rdbl ADA oonpotlono tio, formulated pro lw-foatrning, are. readily solublo In the ijh~gj~ tg,61ura 4n( otot~tOa d ausha olttet finrniod 01tltiKj pftngo,#s VIz, it 10,5-13.5 ~Tho compositions tire nornia 941 Wsls Itetoy. 1,0, 4 Whlhy via, opaqua JelJly-ttk- t~a bavifig, MAthhAM plahtic 0matoz' and thufl reltively high yield valiuon, ~A044rdlnglyj o dofftito mhomv rovi W~ nmiy to, Initiato or~ Itircos floW, such as would obtain within the agitated dispenser cup of an encrgizod automatic dishwasher or it stream of water. Under such conditions. the composition Is quickly fluidized and easily, dispensed, When the shear force to discontinued, the fluid composition quickly reverts to a high viscosity, l~1ingham plastic state closely appro~dntn -t ro consistecny, U, Patent 40$11,487 dated April 10, 1085 describes a ioW-foaminq detergent paste for dishmashors. The compositton Is based on a mixture of finely 0dI'idd hydrated Sodium, motaailiiato, ain actIVe chlorine compound and a thick~ening agent which Is a foliated silicate of the bectorito typo, 1~O Small amount of nonioolc tenaicioa and alkali metal carbontes and/o hydroxides, may be maecl.

A related copencilrig applcation which Is assigned to the common nGmWgnoe to Serial No, 810,505, filed January 7# 1087 which Is lcr~ae herein In Ito. enttr( t~y by reference thereto, The oopondln ga ppl catin thigotropie aqueous aUtomatic dishWAfshing citrooit composition whic0h Conta~n$ a, long Chanr fatty a_0id asi '9 thixotttplo thicken.-r ,Agent, ADVA NT A GES OVCRt TtL PRIOR ART The thi~otroplo atquoous liquid detergent composition of th osnt 1nVentin OVevcomoe many of the p~rior' art problems associated with powder ZO and liquid detorgonta., ilecuse of the addition of a sauiji oiftotive amount of and iln Or ttaniim dioide ntPf-flmino agent to the om positiona addod rinoo- oid ia not req4ie -n twe wiping and dr~n aent required to Ohtin dr'sprinJcea lhoaj glaSss cups and ea-ting Utensilo. The thtmotropie aquou liquid detergent composition has tho aIdditional tadvantagea of being stablo, hnrwsettllo In otorago and readily rediaeratle1.ho liquid. compositions Of the. 0Oet'ht InVontion. Ore 0a4ilY Pourblot easily moasured. nod easily put, Into thoe dishwushIngt machines, An aditona andunepoeed dvantap, of oddjii the atumina or titanium dioxid akntl ftlmlng agent tO the detergent formulation Is that tho alumina or titaniumi (diwedo Iinibit brown Stain formation In the, dishwashing, machine. The brown stain Is fore byth epu~tton in the dishwashing machine of iron, and/or Managane5o oxides, The brown stainl for~mation Is a particularliy serious problem in Areas havinK hard water,. The alumin4 or titanium dioxide in the formulation act on the Ironl And/or ma flaneloS In the wash Water to prevent theoir deposition In thle djijjwashing machine an Iron, And/or maganese oxides, OflJLCTS OF TIlE1 PRESENT TNVENTION It Is fin object of the present Invention to provide a thigotroplo Aqueous liquid Automatic clikqwse dtrgent qomjposition tthas impt, vod anti-filming properties, It Is another object of the Invention to provide A thixotropic Aqueous liqid dotorgetit composition. which Is Ntable in W1oi'ag, 44,5i1y pourable 41nd readiy Oisporslblq in the dhwashing water, A further object of the Invenltion Is to -provide a mothod or washing cllshware, qlasswaro phina and the IlkO In Anl aUtomati (101WhwARn machine using a thixotropic aq _44sliquid ditorqont composition in which a separate rinso aid Is not added or needed, A still further Object of the Invention io. to provide A method of waahing d~ishwore, RI'AisWAre, Ohlna and the 110 In an aUtOmatIe washi machine Using an aqueoU4s liquid detergent compoition, by Which Method the df~hWarop glasOWares china and the lko are. muohine driled without leavIna, trag0s Or 4 film, tt is a further object of this inventioni to provide stable, aqueous thbot ropic aqueous liqid oompooitionso especially 4utomatic dishwashor detorgent compositions# by Ineorporaiting in the aqueous Suspension at small effectivo Amount or an Alumina or tittanium dioxkide anti-filning agent., Thore to also added a Minot, amount of a tatty acli, Metal satt of' a fAtty 1141d, and/Or, claY tbixotropic thickeneri effective to Inhibit the, aottlino- of the suspended particles and to prevent, phase soparotion, D13TAMt 4 FD DFSCRIPT Ols OV TIME INVElNTION Those. nd4 other' objoQts of the InventioQn which will booomo, moro rea~cily understood from the fotlowing cotallQl (loacVilption of the Inveio~n and proforred embodimuwthoreof tire !s dovecI by in~r~t Ii tin aqiveeus 1(uqtdt dtergent gopoteln a qmonll but offootve ovinf)~ft of tin aTmminua or tittrtim dioxide wlt-fllmlri agent. The physloal Otiblllty Qf tho composition is Improvod by the adition Of a fatty oqjdcI metal salt of Li fatty aoid Anid/or elay thlxqtroplo thloknor# More Pfivtl h1rhyo 0eordlfl to a Prfoer4 Qfld tipQolflo embodiment of the Inventlon# thul'e14 I$Provided ai normally gol11% 414toma~tto dishwasher detergent oompoqItion In which W., Inopoatod from aout 0, to 5$ of tin Aomina or (ttitenm xded inti-fl-rrdng agent, The aluminat or titaltn djovide Ant4ilminq 4geont has; a portiqlo size of abt~ 0,1 to 10, mivron", In A profeiwed embodlment of' the Invontion there, to added1 to the oompooltion 4 a~ufflolgrit amunt~fh of ti eohain fatty eAeld Or metal satlt of 100 lonchon (Atty 0oli or eithoo of thq forogolnR In omttiro with a elny thixotropic (hI(on~r to provtcto 4 thixotropto Index of about 21, to 10 anld to Inhibit aotti~n of tho 4-Wparied pirtlcloso o8Wh U~i ailMetal builder oiatio$ otot In AooQ0Zdallo withi04 diaInpeot# the Prosont Invention povidea 4 nor'mally got-tit 4cjuou& liquid autormatto d ohwishe doterlent Composition hvin thiXotrot Properties- Whleh In t~de4s, onl a Wljoht, t)1,$10 6 to Ut Alall metal t~oyop~e Mb 2. to 40% Nodiutn fillicte" 0.6 to 6$ 4umirna or ttIUM (1ioxid0 ntlf-flmlnI A'gett C)0to 0 t alkL4 metld carbonoei Ot4 to 6W Ohlovr~o tieaoeh 4Wiile, wotor diepor-albk oegt'onto a teZiall MC 0 to 5W Ohlorlno bleach 4t~iblo tom (lopreoftli.

ohtorittw bls4ah Comipounid In 44 Amfount to provido about, 04 to 4j ot tivallbho 01hioincut thixotropic, thtqkenor In an axmount siuffichint to provide A~ thiotrpph incleXc or aibout 2.5 to o to ss. sodiomr hydr~oxide, An balanco wLator rolatcg1 to thto spoctlo opoot, tho Invention nrov~IO~ 4i rnqth~d for clqnin dishwgtve In on outomatio dlowashing m~lohine with an Aq qou WQih Wt Ontinin anr 00040tYv (imovoft of tho. liquid autornatio dishwoohor (Otorgnt (L.ADD) Qornpoolio as O wtbeci ekovq4 A@coding to thios ospoot of tho inVotionj tho LAPO Oopo~ittion, 4 ot Me~idity poulvod Into the to0 (10dipng0-141 Ou f the OutOMMW1 OisW40hing m4Airo a'nd WiWl within J%.rnt a fqw Noondat ptorptl' hINOW~r to its normanl pleiko or' pasty sttto to r~onndfl 044.uvol within, tho dlponsln eup until, ohoar Noo ArVQ~ apii 4ppliod thqveto. suoh Ao by tho waer spray from, tho c41nhwthln m~ohipa, Tho Invontlon will now b6 o 4ereibo In tritento 4etall by wny of, spoolflo ombodlmonta thclreaf Tho $TADt prodtets O Qf or OOMPlI the prio dlslouro hIn thoa 04)n~ntoo 0fS '.t1U6Q A grid OIn '2,40Q150A ~i~vel~ NWu~iztlon, and geilAtion wolt with1n tho klbeav iategi Oxtgnt withi tho Wtndid dlhiwgbhr fiutehnot. 1n printil toirm", thi 110fia Improvod puriq ond rocott1 liretret AU Well- 40, te08 101kij ill (11q ~etitie d eu~~ comrnpei1 to Vtior liquid or i e ADD1 tMOLt~tI 1 FO r anhold sha root 4orropoadlog to 3 to 30 n rpm Oosittes Olflzota) croeti~dlooiy riouge f~rim Oiiot tU0U0i4 to aio~oo Cp to ihtj, a,000 to O e, ai (00WIIVed at rOOMu t pereutg1( bY Moa ti. a VT hBrko td vinovit r nIOUsto~i usitilr Ei No, 4 61)indtli. A sheiir rato of 7,~4 lse caondasOW to A~ SIndlo rpm~i otsn~ An Xmbo1Ofl 11%46114In Alew V~t J Vducm a wbt as 3 ta 0-fO ueit in tp)I6CO~ity 1 t The eomo~dt~on of 1.he 00Ig 0'e prior Invention tliu4 hbt he~o( nulizationo at lower shear ratos ancl of signiflo~nty gVQ~itr extent In teros of tnoremontal Incrouas in. 8hoor raevso V'I nqromntal docroa~o In viseosity. This property of, the, L~ADD pr 'uots of the prior, invention is s4umm rtzocl In terms of a thixotropie Indiex (TO) which Is the ratlo of the oppo'rpnt visosity At 3 zpm, An at 30 rpm, Tho prior eornpostions havo a Ti of from 2 to 10, The L~APP compo~itlons should exhibit albmtnttl And qloie rtorn to pri1or qiesent state qnsistonoy when tho shoor, foroe to, In termo of Apparent vlaoosltyj it has boon wotodnol, that 00 I001 04 tho visoostty at rcom er vrow (22 0 t 0 C) meatiurd in a, fl~ookfiqld VisoolImotor IIATPj using a number 4 opindlq At 20 rpm, Is less thufl about 2 00 opo, the 00111postton oan be roadily sholme so that 4 thixtr'opla qdmp~4tln O~fl le easi, "ldid "llqvoited" to Allow tho produot, to~ be dispneed th'outh a% oonventloo,4 sqtwezo tube botto or- othetr qOn'Voldqnt, 4sw The prowet iflvoetion, is baso( upon tho puviiU&6 d~iovory that 4ubatant~ly Imrpovod alltl-fllminj proporttgo etwn be obtailng( 4y addituq to the thiXotr6010 aqoLllclueou Uudatorv'ont oootpoliion, 11 6(0411 0 Itihed Amount Of an alunA or titanium oloiedo antil'flminq nownt. Tho, physleivi ntoliY, 4444 r(400 to tnho$O 40arotont sotlloo, co. oan bo- achieved by addintlg to thoe cmpaition a smoll ofrotivo Coouit of A. thintropfc,~l~ne AN1TI-4LMINCI AmiNTrs 2$ Tho alumnritor titn diloxdo nnithnlnt qo~nt maotila that, 0an be us~ed ar't roadily cofimrcially fivailable, Tim alumitna "14torlo that, call wl uamd an ntiming Agent is insolublo in wtwt ond, 11a theo (0or11ul1k A12O~ 03 ultablo matoalh nro availablit Undor tho tradanamoo, Atuid OX to Degu=a i nd Ciapal Do VliaW. A p(rufrru4 atiia reaturial 1 I 9a of oeg4saa, andl catopol P, Vista., Peferr~ed alumina mater als afmed alumna~ And A popitated 41du1ina, The titanium 4dtside maw.$r4 Qhtca eued as an anti-tilMng agn Is~ Insoluble In water and1 has tho cmlo T102i suitable m4 torials are 4V4labl under~ the taden IMs 'toi~n iA x~ %4 V51 4Vaitable tQm Ooqu~s4.

IA, prr t-Irsan- it fi min~ trOfen TXh4 pLrtiilo1 StZQ of tho Aluina lndc tit~nhImi Oloxtdo4 r ?ud iw ~i I mportont In 401lI0vtfl( tho elo~dI oflt1i4rAlinq~~viQ (vitdg An Con hNVO a JUdzilo 610f 4M O:JO to, 10 1eoZlQs pvrovil4y, 0,60 to a n~ons Ond Mnove prtobvl~y 44ut tU o 6 0 crnn h q 414 n ti(At~UP4iU XW c pi(ItQ C0 or 0114 thNn AsndA 1, the Irnount U4 horolit 4, not A~~jq Tho ftnoly d~d4d, olumin, or tit~nIui d11OXWO motortnl porticWo Ill the 610ilahinq, WOh op to oOQ0r igulo pVQ Ir1~1oE pattiouliti Is fin Iotui tomr In aponsiot to prevqilt thM frorn 40POM1n0 On thO 0104n, q144-4.1 4vi Wthout int tndf to 1iftit~ tho Invontion In Allywiv It in' thovI'oI that the Oltlmlo n- 0n titanluni dIoxido antl-MIng Avowt~ fuiwtlon In IMa following 00 tholr aifci throughi tq SI-Q bon4o' UfualtWe th Y- n Atoms cavry theso Oh~4, tt IH pomihstcI th~tt thwiu negatively 01irod Iona will, W ttract pQ41dlvQ1y 4olxargod pt~oloaul)on thby Will formt~ Oan otI(Il noill 14Yo TWAI, proteotive layor will t mnvpqt th,4, togVIIv food- Ooll and will Incea 014 otio 4ttnopofit poety Of tho, tioI Ihn deosont. Tl.he altimna tmnd tatt~ium (11001d4 portlclou~j ropeottivlV will t,,entite vo~ttively orge~~l partleld WWIIh W1ll bond1 thuniwlve,, to thd v4aswotr' qurfac to forfil tho atiflol soil l~yQi, Which will PoVQun't the nsTho non ofilmn r iati ioil ni. 411tm"gn hl a W~ go~ t ilve th~l dWIve~l til 1ove tnt Int Hm 14111 deond onl the othutw ADIIIn~rdienti, 'Ill iluialnM or tltirnitifl Oloxtdo Anit-tilittt t Agent is partiqtawy orroctivo in hard wash wlltor of,~ for examplot 300 ppm The amount of alUmnu or titonim Olioxido anti-ftil 4gont that 14 Wo o~if W~ tboot 04~ to poororobly 4iou~t I to A1 ori Moro p~eor'tbly tboUt 1,0 to 0% by wol~dit buto on~ thQ weight or tho cntimq oompQositlon 1 Th~e aluminai anc titanlom, dlid.0i 044 oooh tw osoA olono or Wo U$Od MIX togothOr Onldlor (0x With a 911104 ti-fiiMlnit 11 ont- Whom the ant~'fmin ~ofl~ o~ u~i m~oi~,ptho'(ho wolqht porcont amoti M~ntionocO obovo Oro tho totoi for, tho Ingreints In tho mixtumQ Tho tlixotto thigkonurs Or 04pQ11iin U Ont$ thAt oori 40 U1od in aQ4irnq'q. with the prmmt ttivontion to Provicto tho, uquous miTQtmi with thXWtOPlo Pvrt$'40 MOY bo Orguid) fori QxLOMPIC ftty 401i4 Or~ fatty 4Q14 po -Ateft raotal s4dtA-O' IW1410 Collon o id forMino 014y 010004114t ThO tiXotoplo thio)(nos "ho(md4 bo, 8tnblp to high li11 oflnity aq4 gt~ble to Mhoino~ blomh mIo js ch, am vo(11ttil hypociforito TIho profOrrect M0111 saltf lknwi the Ifio 011'1fon[n QIIIy8 or 4mot(I~sw/ fttaptl]6Ate typos Tho A~tfurtjt of ttho thgotopl (1101eIr uck"d will depood 6n thft ptjut~er thiqoInr~ u~uo, but suffieI~nt thiqkotn@p it] v(dod to tho ftVnmuttort to pl'oVt-0 tho 9On~f~101 With ft thixoop Index~ of about to tlott ~i'otntt kfaitty monbortoxyle ,,ds havng frho is.I tu440t; 00604 (10j*~p oitb eot'boxyl goo of thu fa'tty' ij(,d 1 .t Th alptIIte iotca nilky ho ~itvior, un~qktud4 ond may IN jr1ft or brafnchQd. $traight Chain Btura~ta1 N (ttY i(do ao prfro. Mixturvit of tfitty Wda may fft~ N u~odd auoh 44 1;tho~e doiQvod (rootl mautt1d qur'o auolt af tallow ratty 60(1, oneo fatty tid, soyai fatty aqicb otq.. or from '$ynthotic siouroan avallable from Industrial manufoptiuring proop4 Thu$, examples of the fatty aoolIs Which can W, UsP se hotoos ink;udc, for oxtamplo, Ooonnolc ae641 hl4rle 4.66,d~odo.MOnO o lds Pagmti 401 it myristl 4010 si~wj arl 4olodad plconold toan Wqdo tallow fatty ooid, cooo fatty ool1, soya fatty ooid and umt~.ivos of theso 4-tdi Steu ooid and mix~ed fatty neldso oo fatty oold, are proforrod, tho Ometint of the fatty 440d thlqj~qnort ci~ (1Vd VaIU4Of I thixtropy oid physaim tah4y will dopood. on, rn~h faotoig Oc tho n~t'$e of the fatty acd, I genpt active ompolun(, inoroanio saw gpoodmty TtP, Other LADD in) rqdiontss eAi well 44 the antiqipated storage and ohlppln godittooo.

0010rodtyj howev'w, iOcouoto of the fatty AMid Wht~troplc 40013t trumt qoar he ttod, Ord In the VATnqo of from, abot 0,03 to 0.0o preferably front ~b~t tQ ai~ ~peea~y refeaby froM o,4oit 0 to povido the dcmdred tenir tcIm 04411ty UnO 4ionoo of phaoo o irtn The pOtl/'/m~it meetal OMW~ of the 4ab0Ov catty 4014,6 00an a1te0 be "Saa In the peotineno a tiltotrapto thteceo r a4ntoi $W1t,410 MOWa salt zo, 903,24 filed $Optolot)O 6 Q ON in the name of OraPIOV ot fil., Whc hIH iing~rortOd hwroin In Ito entfrety by roferotne thorito The pvO(Orrod meutols an the pelyvalent, m~nl ufh mogooltu OololUop, oluminuti and~ 21AC.

Ooorlly 1 tho, metal Iny be praa n the01 OIVa140t to pem-tAVakto satule prtoribly 1 the metill gaitall 4ej U4d IIn their, hi~hor oxidatioll Ntajtoeq turaU~, for %~A~fl cem o ils# a wl enY othur ApplICAtian hr tho Inventioll cloqtt on will or moly OOMe Into cantact with urticleu iwe0d fo h4 hand w trao or, sorviog of food poduoto, or, whiah othorwhio MYco nbto conteot. with or beho naUltd by pooiplo or IQmle h metil 0' 0 th01- toxidity O ot h "s;y t7 1.2a thixotropic, thickeners are disclosed in Ausalian appiciaqton No 7742,7/87 which is incorporated herein in its entirety by rteerence thereto.

The preferred muetaIs ate the polyvalent metals such as magnosaiumi clqiui, aluminum and zinc.

Geqally, the- metals may be pesent in the diva2lnt to pentavlent state, *greferablty the metal salts ace used In their highor oxdation states, Naturally# for LAOD compositions, as well as any other applications where 1O the invention composgtio n will, or may come into contact with articles used for the handlint storaqe oc oorvinq of fod podcts or which otherwise may come Into contact with or be consumed by peopl.o or aniaal$( the metal salt should be seJlecteo by taking into conslder4tion the t$ 6 oxicity o the

S

metal, Vor this purpose, the cLluml (nd Magnesium salts arc espeo-yI ht~hly preorred no jgonor~ly wife lockOd tlvos Many of these alotal salts ar omecal ox~sle Mo 0~ro th aluminuwm salts ar'e ovallable In the trloold form, aluminum stooroto os, aluminum tiarato, A10C 17 COO)a The rmonoaold salts~t' alumhwmm mfoflostoarate, AtO1 2

C

7 and chac44ic salts, alumintun Oimasto~, AI(O!I)C H And~ mixtures of two or thvoq of the monmo-, and, trl-oeit 0al44 can be u~soc for those motala, otgo Al, with V4lenoos of ond mixtures of the mono- and dl-aqid salts oon be used foy those metAlu) Zn with Valences5 of It to Moro profcrrd that the diod of tho +2 valent metal$ andt the trIaas totmoidslh of the, +4 mettals, And the pontooilds 0$00d in proominant oI0ontS o Pe omploo least 60% ospecIaly prqtdoaby from 80 to 1QIM beIn the hif~hoe po)Obt Q0idLItiofl 4teto# sites 41 10rof'Wbyafat ci eiiqe 'lho motal nalts, go Mentioned hbovo, 4v411014. bu~t oan be eaally produced by! for of the +3 vatent meals) the of the V4lont metals be at least 30$t, preferably at of the Itdtal o Sidhould each of the possible valonoe are gefleraly comecilally oxAmP1047 Saponilonctiol' of a fatty fjcid, n nmlft teavrle ncid, ote,, or the oo sopotdl161 fat(y acidesty, 11o~wod by eatmet with on hydrod or Id of the polyvalen tetoll foil emplo In the oase of the alumrium. $alt, With glums plumtna. Oto.

C"aloium ~Jarae ~~ceundsevt~n~e~m sevtI Ma"061UM, 410t0000t, 4113Inui wterate, I'0. Aumlinum tristearmt, and zinc stfiata4 diatoargte, are the profured polyvotent fatty odid galt stab~~zer~M1~ed ty acid metal sattt suowh as the noual eurn 001001Q U-.c00god, Ao well fa mixed fAtty nOida vultin~r from the Commorcigl mnufaetUvi prce~e oae olso aidvontapeously used as anl lnxp1ovt but afttiva 4oroo of the loag chain fatty oold., Tho amount of the fatty ticid salt stabiiers to aohieve the desired Onhnmepe at physical stability will depend on su~eh fCtorS as Lile ontpre of the fatty acid silt, the nature and amount of the thix~otroplc ageatt Cdoterroft fptivo, oomlpo1.fin, inorganio 8,41ts, especially

T

VPPI1 other L~ADD irdieit~,AO welt i the Ant~cipateci storage and ShIppinG, conditions.

Qeanovally, howqver, amountii of the Polyvalont, mettal fatty acid salt stabili~ing agents In the range of eromi 14bQ4t, 0,0 to preforably from about 0,00 to eOipooilly prqferably from tibott OM0 to provid4 the tongf term stability and absenqo or phase sopoa~tion, upon st ici~n or during transport at both low and elevated tomporottreuas tire reqilred for ik oommorcially ikoceptableoduc ThorQ maxy Ono bqea 4In t10 Presenlt invention the eOnVefOfl04 Inor~anio thisotropio clay thiolenoro, The olay th~loknrs may be uised In small amount$ $I Oombl"Ation with thle tatty acid thlel~qoors or in 0ombination with fatty ad polyvi14Qrtt motail stilt thloleriqr. 'Phe alAy thlcfonor, howoV'ev, may be iuoot by themoelvon tas the thihoti'oplo The prefered olay thtekonevis Ompwtso t10 Inoquio 001101d forming e lays of 4moot~toi 400lr tittopuile typoof Smqetito ly nld ete'lo~e (etnt) et~~o ettpti~ith e~te en~nte, nd tho itKef Mootmovillonito qlAysa tit Pr~eferred tOi are ovaible un~der, tvadenumqu nuch os TVh1,xoqe (louivtood, Ttidmtir) No,, I. id COON~t (tRegitorod T edmat) O$III~ Otc., frm Oeovt~ia xaolln comnpanyl And VWOA Um, (otorod Trademovk) O"P it OIL, from, tuthorn Clay pduto* Attaptilgito 0laya Ildc the, mutevialsi comm chily avilabe the tvadnan Attagel (Roglatored Theidetiarik), SAttagol 40* Attagot $0 And Attavel 0 frehi C-oghard, Minoerala andi Ohenilcal Corporation,. Nixtores ot amootitai and att litijj typo nm hiWtotitM MatIOA Of 410 to tt 5 ArOa 4140 U4ful herein, 'lakenif dti 401WOf thd f~orvng typos are woll k~nown, in thep iq, holtw for example, In U.S. Patent No. 3,986,6683 referred, to above. Abrasives or poll.9hing agents should be avoided In the LADD compositions as they may mar the surface of fine dishware, crystal and tile ti~e, When used In combination with the fatty acids or the fatty acid polyvalent MetW saltS, the clay thixotroplo thlckeners are Used in amounts of 0.1 to preferably 0,1 to 2,5% And more proforably In amounts of 0,1 to 2%, When the clay thicotropic thIc~oners are used alone as tj, thixotropto thickener agent they can I~o wsed In~ amounts Qf About to preferably 2' to 5% by weight of the formulation.

Qenoraulyo LADD effectiveness is directly related to available chlorine lovels; RlWilnity; solubilit odiu Iahn mehn nd(d No inhibition, It Its preferred herein that, th p11 of the L~AIDD composition fi t, 1t4at about 0,5 More preferably ftoM aboult 10,5 to 13,6 and moat 11 pret'orably at loast about 11.5. At th4 rotatively loWQV _Pit vOales, the LADD product to too visdooo, 1.eo oid-Iike, And thus not r'eadily IlGe under the se'-0c levels created Within the disponaoo ouip Under om Machine oper'ating counditions, Achiltllot Of NaOI-t Ns thus often needed to tnereaso the idH to Within the )Above nendto Ine(5 lwbit Prpvoertiois. The presonoe o~f carbonate to Also often needed herein, siriee It oot~ s a buffer helping to tenintalA the de~rod PH' 1001w P ooss carbonate in to be avoided, hOovor, Since It may cuse the formatio-a of 410041dloiiko Cryatald of carbonate, thereby Impairing, the stabilityo thlxotrqpyt and/or detergency of the LAW)O product, as Well as Impairing the, dispensibility of 21.7the product from, for examplo, aquom~ tube bottles. Caustio soda MNOO) srves the further funetin of -noutralking, the Phosphoric oi, phosphonle Acid 084t foam dopres=at When~ present, Abotit 0.5 to 3 WO% ot N4011 and abou 2 e 0w% odu eurhonato in, tho LADD oompo$Ition Are typiCil.

although- It should ho nloted that 4uMOIeOnt tilhalinity may be provided by tho -NATPP and Sodium 411loato.

The NoTPP may be employed in the r 4 ADD compoaition in a ranige of about 8 to 35 wt%, prefoeraly about 20 to 30O wVt, ant should preforably be, free of heavy metal which tends to dcconprsc oe inctvate th' prferred sodium hypochlorIte and other chloino bleach compounds, The NgTPP may jbe anhydrous or hydrated 1 including the stable xithydIrate with a dUreo of hydration of 0 corresponding to about 1M8 by woIqht Qf water or more, Actu4ys in view of' the stability of the hay~ydr'atol the presence of some water of hydration i.9 highly effetive, servig it is thought to form soedls of the atable heahydrxnte which oqxpedts hydration anti solUlztofln of to0 the reMainln NaTPP partlees, If only the hexahydrate 14 used the detergent product may be teo liquiti Convorooly, It only the anhydrous NaWPP is used, the produt may, In some ea see4, be too tia anci, therefore# unoutable, aVpeeilly preferred LADD cmposition are obtained, for xampl, when using o 0,5; tQ 2tl Weight ratio Of Anhydrousto hoxahydrated NaTPP, values of about li being particularly preferredr POaLM Inhibition Is important to Incresee dishWa44he machine effioienoy and minimize destabilizing ofectc which miGht occur clue to the presence of xcod fAm within the washer during use. oa0m. may be sufficiently reduced by suitable selection of tV type and/or amount of detergent active material, the main foom producing component. The derae o foaom Is ao somewhat dependent on the hrdnwes of the wash water' In the machine, Whereby suitable aidjustment of the proportions of NaTPP which has a water: WtOnlng effect may aid In provIding the desired deOrVO of foam lnhibition, flowevor, It Is goneraily preferred to Incltade a chlorine bleach stable foamdepressant or Inhibitor. Particularly effctive are the alkyt phosphonie aid sters of, the formula 0 Ott

II

4v~ialate for excample from BASF-Wyandotto (PCUIK-PAE.). arnd espccially the alky! acoco phosphate ester's of the formula 0 110,-11-011 Ott avnlabloc or o;amvplo, from flwkoor (SAM) and Knapsack In S which one we' both R groups In each type of ostor may represent Iidepenclontly a e%.1 2 alkyl grouip, MNtuLuo f the two typos,, or any other chlIine Weach stable typo or mixtures of WmrIO" and, 4-etors of the samne type, may loe Omployed, 4spotaly preferred Is a miXture, of mono- 441d Cd4~ -In$ allyl Wod phosphate estersi such as to0 mlnt 'l /dillt onryl oeld phspheos 1,2/1 (1 npsaok). Whon employed~ proportioflU of 0,0I. to 5 wtl, preferably Ott to wt%# opodally Abouit 04 to 0.5 wt%# of foamn dprossant In the composition is typical$ tho weight ratio of detergent aetlvo componont to foom dprssnt gqnevally rooging from ab~txt 4Ott to 114 ndPITCeirakly about 4tt to Iti 4 0(hot, defoamers Whkih may be 1tisod tholiudo for ewtnplet tho inown $1100on, Althoug~h any ohlorino bloooh, comPound may We omployed In tho COMPOaltiorw of this, Invqntiono such os dtohloc-1oyanurate, l~oro-dimothyl hydontoinj or ohlwinatod '2$Pt olall Metal, C'.

potasum. lithhim,# ma~neSIn and 0ol~ _oiM hyp00ehjii s profeorre4

T

ho gtnpooltion should 00ntain miffleent Chlortilo bloAdh toompound, to providjo aboutt 04' to b wolt',ht of "vollablta ohiorloo, as determIned, for exiai)I, by ilatnoft~iat of tho 0MpdI)O8n101 With Quoss or hydrochloric acid*, A soltiont 00ntttn abot Q.2 to 41 by walght, of sootim~ hypoohlorito 004144 00 oitl~ekij vouvghly tho Sameo proontioo of available ahlicrtlo A 80iUt~on otann abou~t 0, to 1A by weight 40dium hypoohlorito oontain obout, M~ to It,61 by wohght of availablo chleln~andIs sp~Ity pverord., r' xampleo, 44diuim hypoohlorito (NaOQCI) solution of from about 11 to about 1:3% available chlorine In Amounts of about 3 to 20%, preferobly about 7 to 12%, can be adva t~Ou ly used, The sodium silicate, which provides alkalinity and protection of hard sutrfaceS. such as fine china glaze and patten, is employed in an amount ranqjng from about 2,5 to '40 wt%o preferably about 10 to 35 wt%, in the composition, At the hiighor levels specified herein fox, example at levels grouter than about 10 wt% the silicate also provides increas e9d antlopotting actiono The sodium silicate Is generally added in, the form of an aqueous solution, preferably havlng (An N, 2 01$'Q 2 ratio uf about 1:2,2 to 1:2,8, fox-, OXAMPIe# 112,4, Most of tho other components of the composition, especially Na~ll, sodium hypoehiorite and foam depros~sont may also be added In tho form of An aqueous dWspersion or solution, Dee0n active Material useful, herein, must be sab1e In, the preisence of chlorino bleach, especially hypoehiorlte, blooolis and those of the or~'anlc 0anoic amine o~jde, phosphino Woxe, suiphoXido or betalne Water disperolble sufetant typo$ are preferd th nts menoe nlnis beir Most preferred. Thoy 4re Used It! amounts ran&jin from, about 0.4 to proferebly about 003 to 2A0., 1 401tIoarly profeoirod surfaetants heroin Are the lMWa 01' branched alkl~ai metal mnono- and/ori(~ 4 atkyl diphonyl oxide mono ano/or. diasulphatos, Oommeroialy available for "ample as D0WAA (fleltorod TrAdoark-) 30-l2 and 0QW1AX 24, 1n addition# the $ur-faetant should be oompotiblo with the other inj91r0dierits of t14 composition." othorv ostablo suriractonts include the Primary 0.1kylsulphotoo alikyl$Ulphonatos, alylryl-atulphonoton arid $Oaf alltYheUlPhatee, UaMplog InalUdoe sodtqm Cj qlkYhl$1'hat00 SUch 04 sodium daoeylsuphato and sodium tallow aleosiht;sodiuma 4aneaulphoteso auch as sodium e o tsupna and sodium C"1 aiyhozneuphnte uoh as a odium T e~nslpoae.~ he orODPOng, potasium, aat may ao bo employod., As other suitable surfactanto. or dtergnts, the Amno oxido surfactants are typicaty of (he struoture IR NO' in which QOs Rl reopresents a lower aliyl grompo for Inotonco,# motbylt and Itrpresents a, long ch~n a1Iyl ~rop having from 01 to 22 carbon Atoms for Iwn c hiouryl, myrhyt, polliityl or ooy r~ 1 dQ alin OXlO o corresponding !trfi~ctant phosphine oxide a 2P or sulpho~ido R S o be employed, Dotalno sutrfotants Areo typicAlly of the struotur 9 N RI"QOO hI whIgh oal(h IR represenlts 4 10oVe 1(ytWO RQtP huvi(n6 CV04m I to 5 carbofl Atom SpOOMOi uXeMP104 Or 01040e s4fAeznt$ ANo uryl-dimothylomino oxlcde, myrietyidimothylomlno OXddo, t he Oarrospon4Iner phosphino oxides and 4vilphcieoaa Anti the oorme ondinK otaoitlgo# Inotuding dodqoy Idtnw thyloammonium oo(OUQ o aoydhaniruc pemonoate, heocadooyl-dimothylarnmonium hoxanqato and, the like. V blodoevridabUtyl the allqy{ groups In those s~toats should he 1inear, And 4s1.~h oompounds Are preferred, $Ur~aqtants of the toroq~n typo,~ all wel fOWP In~ t tho art, Ave, described# for et xample, In P4dt 3,00$0 and 4,27030, Thew Amount of water oontatnod to thoso, compositions should, o( of e be noither so high os to tp'ocduo unduly low visosity and fluldity! not, sO low As to lroduo uinduly high visoosity and low f~owabWllty#' thxotropia PrOPAWrtlas In either, 04ase WOKn (1aIlnhsho. or- Optod. $uh 4,moUnt Is readily dotfrmlnod by routineo o~poe notaior in any porticuhu' Instancoe, qonmlly rntlnq trm about 2$ to 7$ wt 'Preforably abott $0 to 66 O l The wator should Also bo prororobly dolonized or 'iotonod. Those, 410ounta, Of Water III tho ompositioti ~Inudo thoe water addd as poito ftelqd OlUtionti of' other Ingrodientc, but, do no incliude b un WaW for exAml thagt In NnVTi1l1 jkx~jydjrAtu Other ontvolitional, Inoroventa May, ho Inoludod In the~u comotitions In SMal amounto, 0010ritly lotas than about 3 such an povfume, $0 hydrotrople Agett suoh, iv tho sodiumt botmlae toluonal Xylood wnd ueurin suphontudo. proservotives, 4y4f~ n, pjnnts and tho 1t1~i. oil of ootmve bottng stabto to 0111001111 b'1040 00111POUU 4110 hl~h 411(d1ality (pr~ptwtof til tho ooponotits), BspeciWI1y proM teweQQVnonV the chtlvIludqc4 ph tholocyatines andI poltoulphidoo Of 4Irnnpaliq4tQ which jprovido, roopoQtivQy, pI&looolngr groon oqi'A blu* Onto.~ Tho liquid 00I nimpoaltion o this InnlVolIri LUr reaily tomployca la Xlqown monneo' for~ w~shInR (148hop, q~ss oupat ooinf ut l &ond the 111<0 In Art faltomati Il 4i1hwa<shopo pQvidqcI with Li put:4 44toilt dioponsui In on q14oQu wooh both qontoltjnnr ao offootivo umiAnt ot h hi i p~ifi~r'.iOV. ~dfmtQ(thou invofltin tho fkuqoust4 Ilqtlid MWAi U'rI~yphosphnto AIWIk MOWt~ 04ro-to ('MhYd1V'An) uut Activu Mantria ChI'ovitio njhoh CcOMPOUn4A 0 Eit~y Aold. Vhlxutmpjq Thlo qo 0,3-0, Odluv) llydroido cietarmt Composition~ Odditivs TVho (umi~~o bu prprw with ~ndth~fo~i~t rokiti to a hdsiml partloe mltoi The Invonton may bQ put Into prootiqo in vurfous. woya fncd A numbor' of spocIfo om~lont will bo dsribod to Illoatrat ttho Invontion with roornoco to ttho ompanyting oxaples All amounts uind proport1in rfoorro to tieooh 4re peroont by woqfjht ftho 00p100a401 4"104,4 ottierwi 100it The, pVQunt bIveltion to fartlior iutratod by tho foilqwln oentnpoa Exnmplo I A\ tbiQxpopto oquoous ItqUI ~owok dI4iwIn j~ wpoolonIs foi'mult4 fromn th (011oving ln ~rodlts In dw wnounts quMponQ1nt ohtPot OeIQUIkod Wmqr 309,004 Sodlumi Hiyho d~ (000 2111 $0cUQ1 Cuv phprte (Ihyhdvoqs 4,88 Alwni AO-mn 0aCi 1 0011~0 W 1 tt 11Wa (ofa 3D-2nti Sti4 a4ets htt4 at acki aIl 4rio tiqrn, 4 Uw,1.t3, ~tt~~In whtoh k~ Incorpoad hi In~ jt,- entirety b~y rforence thoreto (Th Igrolotijar a~odto th waterev rol ~I n the ordor 11I'Ied h4 1"wity hOtir4 xu,11it honogenvoUs 0.Itir 41 obtorlne Tho WnllftltlIs tFite(t by kw~hing gbwnwr a( nd ihware t t tf lrtiUto o (Uv~IA~hI atnd the ewan and i(I& difhie are found to hoov iw jpaont Itjn E~xample 2 dioxide Omi-fllminR atprit, formulations wre adding tho al"u o r ci' tI~urn prepared with an without the aoQflt ofl)( 010 compared to o 'TQeo oohdlyioa tirh~e 'fworalul~m to coiptti h,01W~~ 1) Vitteniur Alominlt Dloidoi1 Anti-film Antit"41$,n 12(1Rnpon =Tt A ti~t 1 lajnaic1P( PN-13 VOWe tPhprOini4ut 01001 Soditim C z'kO11tc (Ahrhych~i,a) 4,t8 ,4 too Anti-Aleinjg Agent I C16 Whit It Clay Almnintim Strta Thixopop~ic Th netoir 0,000 Dowfx 31-2SL~facant4,7 0.i~o t'ha In Hpclrteno a' tn' 9170~tii cmw nfrt o ~1tii N,00I~~ ft~1~ t1whe is. I tor t'4ated horvit Ill t~~t~u~In te te~hd by 101n l assitr at In hjatr Wittr (306 Iiipr The throo Rdbove formutiaons (Bl) and WIWO tested andt compaveA With 4 cornmord11y avoiblo powde~r toma1 a 0w~i dtoe'gnt formultiton TVho formulations wereo tosod in a, lKQni$Qi Aiutomatic dishwashor, uini the pria er cdcrlbod i ASTMO 3606"~79, QXQ~c~pt that only fotur coarilri QYQIPS Are Uisi~1, T114 $poQUnL' MAO Mming Oro Oval"tod iOcrcinvr to tho following~ scqale$* Dot n o cpp4roxt, film 21, VIlmtnG slight( booomlng nAppror fl, Notiovahkt rum, Inqmeniduj, 0O inuod~ Incrope of sipnhfloont flm, Mlmin b'~onitn exeive du vor rfet 4lat 'hV0.40 Otainod. Are, POPt~d hI the below Tol 1.

Aluina. Antt $Udn Agent N(k A tilihi Aqvn& t oil 0 re~'a ll~~q DuorigIt 0aw Tha dodv*i (0 Andtt~i lot no4 on qlwwarod except, sipnfficant flmin~ VImprovements were obtained wlt1b both au~n ad titanium dioxide~.

L-xample 3 A thixotropto ticiocous 11cqtild itomatio dishiwashing doergpnt 'oomfposition W~ forrnu~tted from the followilig ingreints in thq alomQjnts Component Weight" Percent PcqtotnIZa Wowu 321 Xnpu LPKN-I$ VmDpronwitt Q11 $004It,1 044 OQ (ahy4t) A SO(Ijurm T4polyplwsphtAta (ahydous) $toolo Add~ Thin~tvapl ThjhvIorn 0 $Od~ut Itypohlcite (11%) cOraphitol cOrQief 0 .01 100,0 TCho in~ntq iaro o~d tQ hQWitV raly int tho. or~dert Itod (300 ppmn h(INTws~s) fit ttt iutollijtl dishwio8tlog muhwiito Tile clIeana nd Thath~~o(t00 pugott iqu~nidn (Mwainti Imrdilwsfq d tet -7 which aro 6given as ilustrations only, The tnvontiotp is to be Intorprotod In w~ordaunco~ with the below colm1w.

Claims (4)

1. 3. A thixotroplc aquous. liquid automatic dishwasher composition comprising approximately by woIghtt, 5 to 3M% detergent uldier; 2,5 to 40% adlum sMcatos 0,5 to 5$ of art aumiar9 ttranum dioido antif-Alming agent haing a partcle sl of $bv* 0,1 to 10 mioronsi 0 to 9% olkalt motal carbonate; 0.1 to chlorine bleach stable, wate dsporaib e oan q dteret%~l actlve marterI4: 0 to 0 chlozrine bleach stable foam deprO anti chlorine bleach compound In, an amount to provide &ohau 04 to 0% of evailabl. chlorine'; a aUft n flt. amount of a thixotropie, thickener to providO 4 thixot'ropli Indox of *1 0* 2'5 to 0 to of a dluim' hydrom4doi aoanc water,.
2. 4. Who wapositio oft oll 3 wherein tho thixotrople thiokoner compriasd a long chain fatty Acid In an amount of a46%t 0,.03 to 0C,3 r- 28 Th3 composition of claim 3 wherein the thiotropic thickener comprises a polyvalent metal. salt of a long chain fatty acid In an amount of 0.02 to 6, The composition of claim 4 additionally comprising a cay thixotropic thickener in an amount of 0.1 to
3. 7. The Qompboition Of claim 5 additionally omprisin a clay thixo~topc thickener in an amount of 0.4 o
4. 8. The composition Qf claim 3 wherein the alumina or titanium dioxide anti-filming agent has a partiqle size of 0.5 to 8,0 Micron$., 9, A thixott'cpic aqUIOM5 liqu id automatic dishwasher oomposition comprising appcoximotoly by woiqht; S to alkali mtai trpolyphosphatel 2_.5 to 4OW Oodjum silicatole I to 0% an alumina or titanium dioxide anti-filming agent havinq a pa 14elQ size o f 0.5 to, to al~wlil metal cabonatel (g 0.1 to chlorine beeacli rt,,tble, water df,,,perslble oxqganic deta~igen acive Material;:X 0 to 5% ohlorine bleach 5table foam d emarit;. clocine bleaoh compQund in an amut to p Cvid 0,2: to 4 o availablq e Cohoine; a Ouhficoient z!ouint of ai thixo$opcic thiikenor 2 to pcv ide a thixotropiQ idex of 2,.5 to 0to P o~f sodium hydroxiae, and The cQoitiqf of olaint 9 whoeon th e alumina anti-ilmidr agrnt~ has a r ptiae sito of I to 5 microna, $0 11. The omposition of claim Wherein the titanium dixoide atiifilndnq Iqlnt has a particle site o) 1 to 12, The CoMpoition of clatM 9 whe-rein the thixotropic thickener conmprises a loqnc chain fatty acid hoving cl6 to Cuc aron atom,,, in an amount of 0.0$ o Q.2%. v4t4 29 13, The composition of claim 9 wherein the thixotropic thickener comprises a polyvaoent metal salt of a long chain fatty acid having Cl6 to C2. 0 carbon atoms in an amount of 0,06 to 018%, 14, The composition of claim 13 wherein the polyvalent metal is one of aluminum, calcium, zina and magnesium. 1? oThe coQosition of claim 12 ajdditionally comprsisng a clay thixotopic t~hickener in an amount of 0,1 to 16 The composition of claim 13 additionally comprising a clay thixotropic thlckener in an amount of 01 to 17, A method for cleaning soiled glassware and dishware in on autoaaic dishwashing Machine which comprises contacting theo soiled lawsware and dishwe In an automatic 4Ishwahlng maohine in an aqteous washbath I$ haVng dispersed therein an efetcivO Amonunt of the composition of claim 3, A method for cloanifq soi led dishwao in an w mati ihtas~hing machine which crines contactingj the toiled glai~wae and dishwaCQ in an amttotnic dishwashing machine 0 it) an apqeuooa washbath having dispersed therein an effective amoiint ok the c..,ompoQition oif claim 9, D4EnDr this 11thl day of Septpmhe 1991 (OLAT!i1PAtd4MOQf COM4PANY Patent Attorneys for the Appli~ant: Via. RICUI C 'Y L f 'I1_