CA2069966A1 - Linear viscoelastic aqueous liquid automatic dishwasher detergent composition - Google Patents

Abstract

LINEAR VISCOELASTIC AQUEOUS LIQUID
AUTOMATIC DISHWASHER DETERGENT COMPOSITION
ABSTRACT OF THE DISCLOSURE

Automatic dishwasher detergent composition is formulated as a linear viscoelastic, pseudoplastic, gel-like aqueous product of exceptionally good physical stability, low bottle residue, low cup leakage, and improved cleaning performance, Linear viscoelasticity and pseudoplastic behavior is attributed by incorporation of cross-linked high molecular weight polyacrylic acid type thickener. Potassium to sodium weight ratios of at least 1/1 minimize amount of undissolved solid particles to further contribute to stability and pourability. Control of incorporated air bubbles functions to provide the product with a bulk density of about 1.35 to 1.40 g/cc which roughly corresponds to the density of the liquid phase. Stearic acid or other fatty acid or salt further improve physical stability.

Description

Mf~Y 2~ 3Z ~ P11 C~LI~TE Pf~ l ENl C/EPT . P 1/45 2~69~66 ~P - ~R- 4~81J

l.lN~AR V~SCOEI~ST~C AQUE~OUS
IJIQUID ~UTOMATIC DISHWASH~R
~ET~3RG NT CO~IP :)SITION
Rela~ed Application~

Thi~ appli~tion if2 a Conti~ation~ Par~ of U.~. Serial No. 07~353,71Z filed May 18, 198~.
Fi,çld Q~ II1V~
The pre~ent in~rention relate~ generally to a~ ~utomatic diah~aaher detergen~ compo~i~ion in the Eorm of ~ n aqueou6 linear vi~ccelasti~ liguid.

Liquid automatic diahwa~her deter~ent compo~;i ;ions, bVth aqueou~ and A~onaqueou~ h~ve recerltly received m~A.c.l~ attention~
and the a~ueoll~ product~ have ~chieved con~ercia~ opulari~y.
The ac~e~?tanc~ an~ po~ulari~y of the liquid f 3rmu1ations a~3 compare~ to the more conventiorlal powder produc tc ~t~m~
from the coYlvenience and per~orm~nc~3 of ~he 1i~uicl prod~ct~.
However, ev~n the be3st of th~ rrently availa~ liquid ~ormulation~ sti11 ~uf ~er ~rom two maj or probl~ s, ~rod.uct ~ha~e ir~tability and ~ot~le re~idue, tlncl to ~on~e extell~ c~p lea~caSte f rcm the di~pen~er cup of the a~tomatic d l.~hwa~hing machine .
Rep~e~en~ativ~ o~ the re1~vant pa~ t art i.n thi~ area, m~nt;ion i~ mad~ vf Rek, U.S. Patent a~,5S~5o4i ~3u3h, e~ al., U.S. Patent; 4,~26,736; Ulrich, U.S. Patent 4,43:l.,S59;
Sabatellil U.S. Patent 4,147,650; ~a~lcot, U.S. S~a.cen~
-4,079,015; IJeikh~m, U.S. Patent 4,116,~43; Milol~Gl, U.S. P~tent ~lhY c~ !B J u2~ F~I~I CC~L~HTE PHTEIIT ~:lEPT. p,Z/45 2~69966 4,521,332; Jones, U.5. Pater.Lt 4,597,a8~; Heile, U~S. ~atent 4,512,90a; ~ai~em, ~.5. Patent 4,753,7~8; S~batel-Li, IJ.S, Pa~en~ 3,579,455; ~ynam, U.S. Patent 3,684,722: ot.~er pat~t~
r~lating to thic~ened detergent compooition~ incl~lcl~ U.S.
Patent 3,gP5,668; ~.K. Patent A~plication~ ~ 2,11~ 9A and G~ 240,450A; U.S, Patent 4,511,~87; U.S. Patent 4,'iS2,409 (Drapier, et al.); U.S. ~atent 4,801,395 (Drapi~r, et al.);
U.S. P~ent 4,801,395 ~Drapier, et al.~. Cos~monly a~signed co-pending ~at~r.Lt~ ixLclude, fo~ ex~L~ple, Serial Nb, 204,476 filed June ~, 1988; Serial No. 924,38~, filed o~o:::)er 29, 19B~i S~rial No. 323,138, filed M~Lrch 13, 1989; ',e;sial No.
087,836, filed August 21, 1~87; Serial ~. 328,716, filed Mar~h ~7, 1~8~; Serial No. 323,137, file~ March ~.3, 1~89;
Serial ~o. 323,134, filed ~aLrch 13, 1~89.
The ~resent invention provi~es a solution tc) :he abo~e problems .

Figure3 1-13 ar~ rh~ogxams, plotting ela~tic~ modulec~ G' ~0 and ~iCcou~ modulu~ G" a~ a ~unction o~ a~pl.~ed ~I;rain, ~or the compo~ition~ Oe ~Lmple 1, Form~lations A, ~, D, ~, ~, H, I and ~, E~ample 2, A and ~, ~xam~?le 3, L and M cL:lLd Com~arativ~ ~ample 1, xe~pe~ively.

5Y~
Ac~ording to the pre~ent invention there i~i l?rovided a novel a~ueous liquid autos~L~ic di~hwa~her d~ter~e.~t compo~itiorL. The compo~ition i~ chcaracteriæed by it~ linear Y 29 ~ C~ PM COLG~iTE F'hTEl~T D~F'T . p, 3/45 20B99~

viscoela~tic behavior, Yub~tan~ially in~efinite s~al~ility against ph~ eparation or se~tling of dis olved c,:r ~us~ended particles, low levels of ~ottle re~idue, relativel.y hi~h ~ulk density, and sub~tantial a~ence of unbound or free~ water.
Thi~ unique ,~ombination of pro~ertie~ i9 achieved ~:y vi~tue of the incorpo~atiOn i~to the a~ueous mixture of di~lt,~a~hing de~ergent ~ur~actant, alkali metal de~ergent ~uild~.r 9alt (~) and ~hlorine bleach compound, a ~mall but e~ectivt. amount of high molecular weight cxoss-linke~L polyacrylic acicL type LO thickening agent, a phy~ical stabilizing amoun~ of a long chain fa~ty acid or ~alt thereo~, an~ a ~ource of pota~sium io~ ~o pro~id~ a pota~ium/~odium weight ratio ;.n the range of from ~bout 1:1 to a~o~t 45~ uch that ~ub~tanl,ially all of the detelge~t builder ~alt~ and other normally ~olid deter~en~ additi~es present in the composition ace present di~olved in the a~ueous phase. The compo~ition.~ ~re f~rther characterized by a bulk density o~ at-least about: 1.32 g/cc, ~uch that t'he densit~ o~ the polymeric pha~e and t:he density of the aqueou~ ~continuou~) pha~e are a~proxima~e..y the came.

~.~
~ he compo~ition~ of thi~ inven~iorl are aqueous liquids containing ~arious cleansing active ingr~dients, ,letergent adju~ant~ ruct~ring and ~hickeni~ agent~ ancl 3tabllizing 2S com~onent~, although ~omo ing~edients may serve m~re than one of the~e ~unc~ions.
The a~vantageous characteri~3tic~ o~ the comE~o~ition~3 of this in~ention' inclu~ing physîcal ~tability, lo~l bottl~

MhY 29 ' 9c' ~ 'J8P~1 CSL~:~HTE PHTEI`IT I~EF'T . p, 4/45 2~69966 re~idue, hi~h cleaning pex~ormance, e.g. low spot~ g and ~ilmi~, dirl: re~idue removal, and 90 on, and ~upexior ae~thetics, are believed to be at~ributed to se~ere~l interrelated factor~ ~uch a~ low ~olid~, i.e. und:~~olved i particulate content, product den~i~y and linear v:i~coela~tic rheology. ~hese factor~ a~e, in turn, depandent oll ~e~eral critical compositional compone~t~ o~ the ~or~lat.ic,n9, namely, (1) the inclu~ion of a thickenin~ effec~ive amount of polymexic thickening agen~ havin~ high w~ter absorption capacit~, exemplified ~y hi~h mol~cular weight c~o;~-linked polyacrylic a~id, (2) inclu~ion of a phyYi.~al ~ta~Llizing ~mount of a lon~ chain fa~ty acid or ~alt thereoi', (3) pota~ium ion to sodium ion weight ratio K/Na in tlle range of from ~bout ~:1 to 4S:l, e~pecially ~rom 1;1 to 3:1, and (4l a product bullc den6ity o a~ lea&t a~out 1.32 g/cc, ~uch that the b-llk derl~ity and liguid pha~e density are ab ~lt the ~ame.
The po~ymeric t~ickening agent~ contribute t:c.l ~he linear vi~coela~tic r~eology o~ the inv~Ntion compo~itioI:!.s. ~ used herein, ~llinear ~i~coela~tic "o~" linear vi~coela~!ticity"
mean~ ~hat the ela~tic (~torage) moduli (G') and.~,he vi~cou~
(lo~s) moduli (G") are both ~ubstantlally independent of ~txain, at least in an applied ~train range of fix()m 0-50~, and preferably over a~ applied ~train range of from 0~80~. More ~peci~lcally, a co~po~ition i~ con~ideLed to ~e l-nea~
vi6coela~t~c for pur~o~ej of ~his invention, if c~er the ~train rang~ o~ 0-50~ the ela~ic modul~ ag a minim~m val~e of 100 dyne~/~q.cm., preferahly at least ~ 0 . _", ~,.. .
dy~efi/s~.cm., and varie~ lea~ ~han about 500 ~yn~ q.cm, Mf:~Y 2~ ' 92 la,~: ~i9PI~1 COL~ TE P~TE~ T ~EPT . p . 5/45 2 ~ 6 preferably le~s than 300 dynes/sq.c~., e~pecially E~referably les~ than loO dyne~/cq.~m. Prefera~ly, the miniml~m valu~ of G~ and maximllm varia~ion of G~ applie~ over the ~t~.~in range of 0 ~o 80'~. Typically; tha varia~ion in lo~ mod~ " will be le~s than that of G~. Ac a furth~r characteri~?:ic o~ the preferred lin~ar ~vi~oela~tic ~ompo~itions the ral~io of G"/G
~tan*~) i9 ~ess than 1, prefer~bly les~ than Q.8, ]:,ut more than 0.05, preferably ~ore than 0.2, at lea~t ov~r the ætrain ran~e of 0 to 50~, and ~referably over the strain :range of 0 to 80~. It ~hould be noted in this ~egard tha~ ~ I;train i~
~hear s~raiu xlO0, By way of ~urther ~xplanation, the ela~tic ~ or~ge) moduluæ G' i8 a meaæure of the energy ~tored a~d ~l~trieved when a Rtraln ic applied to ~he compo~,ition while viscous (103~) modulu~ G~ a ~easure to the amou~t of erler~y dis3ipated as heat when ~tr~in i3 applied. rrherefore, a ~alue of tan , 0.05c tan ~1, prefera~ly ao o.~ c tan c 0.8 means that the compo~ition~ will re~airl ~ufflcienl. energy when a ~tre~s ox str~in ig ap~lied, at least over the lixte~t e~pected to be encou~tered for product~ o~ thiY t',~e, Por exa~ple, w~len poured from or ~hake~ in ~he bottle, or stored ~5 in the di~hwa~hor deteryent di~pen~er cup of an alltomatlc di3hwashing machine, ~o return to it~ previous c:o:ldition when the ~,tre~s or ~train i~ removed. The compo~itior,s with tan va1ues in theBe range , ~herefore, will a1so hav~! a hi~h I~IH~ C~ 'iJPI`I l_OLGHTE PHTEI IT ~EPT . P. 6/45 2~69966 cohesive property, ni~mely, whe~l a shear or strain i.3 applied to a portion of the com~o~ition to cause i~ to flow, the ~urro~n~ing portions will follow. As a recult of t;hi~
cohe~i~e~ess of ~he ~ubject linear viecoela~ic cor:lposition~
S the compo~itions will readily ~low uniformly and h~:lmogeneously from a bottle when ~he bottle is tilted, ~here~y c~:ntributing to the physical (phase) stability o~ ~he ~o~mulation and the low bottle re~idue (low prod~ct 10~8 in ~he bot~ ) which characterizes ~he in~ention compo~itions. The li.nl:ar viscq~laj~ic proper~y al~o contfibutes to improved physical ~tability ac~ain~t pha~e cepa of any undi~cl~ed ~iu;~ended particle~ by providing a resi~ance to movement cf the particle~ c.~le to the ~rain exe~te~ by a particlell~n the ~urrounding ~luid medium.
Al~o cont~ibuting to the phy~ical ~ta~ility ancl l~w ~ottle re~idue of the invention co~posi~ions i~ t:he high potassium to ~odium ion ratios i~ t~e range o~ t~ 45:1, pr~ferably 1:1 to 4;1, e~peçially preferiably from 1~05:1 to 3:1, for exi~mple 1.1;1, 1.2:1, 1.5:1, Z:l, or 2.'i:1. At these ratio~ th~ solubility of ~he ~olid salt componen~ uch a~
de~ergent buildex ~alt~, bleach, alkali metal ~ .cate~, ancl the like, i~ cub~tantially increa~ed ~ince the pr!~ence of the potassium ~+) ion~ require~ water of hyd t:him the sodium (~a+) ions, ~uch that more water ic available to ~ solve these ~alt com~ound~. Ther~fore, all or nearly aLl of the no~m~lly ~oli~ com~onent~ are pre~ent dissolved il~ the a~ueou~
pha~e. Since there i~ none or only ~ very low ~ercentage, i.e. le~ han 5~, pre~orably le~ than 3~ by ~ h~, of I`l~Y 2~ ' ~2 ~ 51~PI`1 C~)L~aflTE P~lTEl`lT DEPT . 2 0 ~ 6 8uspend~d ~oLids presen~ in the formula~ion there i.3 rlo or only reduced ~ende~cy for undi~solved particl~ to ~ettle out o~ the compo~ition~ causin~, or example, for~atic~rl of hard masses of particles, which could reault in hiyh but:tle S residues (i.e. los~ o~ pro~uct). Furthexmore, an~r undi~solved 801id~ tend to be ~xe~ent in extremely ~mall ~art:ic:le ~ize~, usuall~ collold~l or ~ub-col~oidal, ~uch as 1 micron or ~e~, ~h~reby further reducing the tendency for the ~ndi,;l~olved particles t~ settl~.
~ ~till further attribute of t~e invention co:l.lposition~
contributinc~ to the overall product ~tabili~y and ow bottle re~idue i8 t;he high water a~orptio~ capacity of tlle cros~-linked ~olyacrylic acid type thickening agent. P.~ a result of thi3 high wa~er ab~orption capaci~y virtu~lly al:L ~f thQ
~5 a~ueous veh:icl~ componen~ i~ held ti~h~ly bound tCI the ~olymer - matrix. Th~3~ore, there i~ no o~ s~bstantially rlo ~r~e wa~ex pre~ent in ~he invention composition~. This ab~eI!ca of f ree water (a~ well as the cohesivenes~ o~ the compo~:Lt:ion) iæ
manifested ~y ~he o~ervation that when ~he compo~!itio~ i~
poured from a bottle onto a ~locc o~ water ab~or~lnt fllter pa~er vi~tually ~o watex i~ ab~orb~d onto the filler pa~er a~d, furthermo~e, the ~as~ of the linear vi~coela.itic material poured onte the filter pa~er will retain its ~ha~ and ~t~uC~ure ~Intil it i~ a~ain ~u~jected to a ~re~ or ~txain.
2~ A~ a re~ul~ of the ab~énce o~ u~ound or free ~I.t~r, ~here i~
virtually I10 pha~ eeparatin between the aqueou~ l?hase and the polymeri~ mAtrix or di~solved ~olid particle~. T~is . ~, ~ .
cha~acteril3tic i~ manifesced hy the fac~ that when the subject ~ht'l' ~9 ' '~ '.lF'M CUL~fl rE ~TE~`11 rlEPT . p, ~3/45 compo~itions ax~e Yubjected eo centri~u~ation, e.~. at 1000 rp~
for 30 minu~lss, there is no ~hase ~epa and the comEI~sition remains homo~eneou~.
However, it has also been di~covered that linea~
viscoelasticity and K/Na ratio~ in ~he a~ove~menti(:ned range do not, by themselve~, assure long term physical ,s~ability (a~
de~ermi~ed by phase ~epa). In order to maxi~i~e ;p~:,y~ical (phase) sta~ility, ~he density of the compo~itio~ hould be controlled ~uch that ~he bulk ~en~ity of the liqui,l ~hase i~
.0 approx~imatel,y ~he ~ame a~ the bulk dengi~y of the entire composition, including the polyme~ic thickening zl~ent. Thi~
con~rol and equalizatio~ of t.he den~itie~ i~ achie~ed, according to the invention, by providing the coml;~c,~iti~n with a bulk den~:Lty o~ at leas~ 1.32 g/cc, prefer~bly a.c lea~t 1.35 g/cc, up to about 1.42 g/cc, preferably up to abo~l~ 1.40 g/cc.
Furt~ermo~e, to ~chievo the~e relatively high bul~: ~en~itie~, it iB impo~ant to minimize the amoun~ of air incc,rporated into the composition (a den~ity o~ about 1.42 g/cc~ is es.~entially e~ui~alen~ to ze~o air Content).
It ha~ previou~ly been found in connec:tion ~ h other ~ypes of thic~ened agueous liguid, autom~ic di~h~,~a~her ~ter~ent compo~itio~ that incorpo of ~inely di.v:~.ded air ~ubble~ in amount~ up to about a to 10% by ~olume can function effectively to stabilize the com~o~ition a~ain~t,~ha3e ~epa, but that to prev~nt a~lomeration of or eccape o~ the air bu~ble~ it wa~ impor~ant to incorporate cer~ain ~ race active ingrediellt~, ~speclally higher fatty acids and ~;.h3 ~alts th~reof, such as Ctearic acid, behenic acid, pa;lmitic acid, I`IH`~ 2~ 'PM COLGQTE P~iTENT LIEPT. 2 Q

sodium ctear~te, aluminum ~tearate, and the like. rhe~
s~race acti~e agents a~paren~ly ~nctioned by fo~ ing ~n int;~rfacial ~ilm at the ~bble ~ur~ace while ~190 I'ol~ing hyd~ogen bond~ or co~tributirlg ~o the electro~ta~:Lc attraction with the 6uæ~ended par~icles, ~uch that ~he air bl~.ble~ and attracted pa~ticle~ ~ormed agglomerates o~ ~pprox.i~l:~tely the ~ame density as ~he den~ity of the conti~uou~ u..d phase.
Therefore, in a preferred embodiment of the p:esent invention, .tabiliza~ion of ai~ ~ubble~ which may l)ecom~
incor~oratrecl i~to the composition~ durln~ ~o~mal proce6~ing, ~uch a~ duri.ng ~arious mixing ~te~, iY avoided ~ po~t-addi~g the surface active ingredient~, including fatty acid or fatty acid 3al~ ~t;a~ilizer, to the remainde~ of ~he co~E~ition, under low shear conditions u~ing mixing device~ de:3igned to lS mini~ize cavit~tion and vortex form~tion.
Ac will be de~cri~ed in gre~er d~tail below ~he ~urface acti~e ingredients pre~ent in the co~lposition wiLl incl~de the main detergent ~urface active cleaning agen~, ~nd will alæo ~referably include anti-foaming ayent and hi~her ;I.atty acid or 20 8alt thereof ~ a phy3ical ~tabilizer.
~ emplar~ o~ ~he cro~-linke~ pol~acrylic a.ci.d-ty~
~hick~nin~ age~6 are the products ~old by B.F. ~ odrich under th~ir Car~c~ol trademark, e~pecially Ca~bopol ~41, which i~
the mo~t ion-in~en~iti~e of thi~ cla~6 of pol~m~r3, and 2S Carbopol ~L0 and Carbo~ol ~3~. The Carbopol resi~, al~o known as I~Carbomer~, are hydro~hilic high molecullr weight, croiss-linked ac~yl~c acid polymers having an avh!rilge ~lh~ c~ ' 9c Cl_: '>8PM CC)L~hTE PhTENT L1EPT . 2 0 6 9 9 6 6 P 10/45 eqlivalent wei~ht of 76, and ~he general structur~: illustrated by the ~ollolwing ~ormula;
H H
I I
C C
H C
~O O n.

Carbopol 941 ha~ a molecular wei~ht of abo~t 1,250,~00;
Carbopol 940 a molecular weight o~ approximately 4 000,000 ~nd Car~o~ol 934 a mol~cular weight o~ approximately 3,000,000.
The C~rbopol. r~sin; are cro~-linked with polyalke;~
polye~her, ~.g. ahout 1~ of a polyallyl ether of ~llcro~e lS havin~ an average o about S.8 allyl ~rou~ $or eal~h molecule of ~ucrose. Further detail~d informa~ion on the C',~rbopol re~ina i~ a~ailable from ~.F. Goodrieh, see, for ~ ampl~, the B.F. Goodrich cataloy GC~67, Car~opol~ Wa~r Sol~le ~e6in~.
While mo~t favorable re~ult~ have been achie~ed with ~0 Carbopol ~41 polyacrylic re~in, o~her lightly cro~s-linked polyacrylic acid-type thickeni~g ~g~nt~ can also ~:e used in the compo~itions oE thi~ in~n~io~. As u~ed hex~:ln llpolyacrylic acid-typell r~f~r~ to water-~oluble :h,~mopolymer~
of acrylic a~id or methacrylic acid or water-di~,p~x6ible or wa~er-~oluk~le ~alt~, e~ter~ or amicles ther~of, or water-~oluble coE)olymer~ o~ the~e acid~ o$ their ~alte;, e~ter~ or ameide~ with oach other or with one or more o~er e~lenically unsaturated monomers, ~uch a~, for e~mple, styrelle, malaic acid, maleic anhydride, 2-hydroxyethylac~ylate, a.~rylonitrile, ~inyl acet;~te, e~hylene, propylene, and the lik~.

r I I l lL ~ I L r ~ I Ll ~ I L LI I .
r-20~9~6 The homopol~ner~ or copolymer~ are characterized by their hig~ molecular weight, in the ran~e o from a~ouc 500,000 to 10,400,000, prefera~ly 500,000 to 5,000,000, e~pecially from about 1,000,000 to ~,000,000, and by their water ~olubility, ~enerally at leaæt to an exten~ of up to about 5~ by wei~ht, or more, in water at 25C.
Theee thi~kening agents are uged in their lightly cro~-linked form wherein ~he cro~s-linking may be accomplished by means known in ~he polymer ar~, a~ by irradiation, or, preferably, by the incorporation into the monomer mixture to be pPlymerized of known chemical CrO8~ - linking monomeric agent~, typically polyunsa~ra~ed (e.g. diethylenlcally un~atura~ed~ monomers, such a~, for example, divinylbenzene, divinyle~her of diethylene ~lycol, ~, N'-methylen~-bi~acrylamide, polyalkenylpolyether~ (~uch a~ de~cribed abo~e), and ~he like. Typicall~, amounts of cro~s-linking agent to be incorporated in the final polymer m~y range fro~
about 0.01 to about 1.5 percent, prefera~ly from about 0.05 to abou~ percent, and especially, preerably from a~out 0.1 to about 0.9 percent, by weighc of cro~s-linking agent to ! weight of total polymer. Generally, thoge ~killed in the art will recognize ~hat the degr~e of cro~-linking should be 6ufficient to impax~ some coillng of the otherwi~e ~enerall~
linear polymeric compound while maintaininy the cross-linked polymer at lea~t water di~ersibl~ and hi~hly water-3wella~1e in an i~nic a~ueous medium. I~ is also uIiderstood ~hat the water-swelling of t~e polymer which provide~ the desired thickeni ~ a ~ vi~cou~ propertieg ~enerally depends on one or I Ir~ n I L I r~ I L ~ ~ I L~L.I I . I . L~

~Ofii~g66 .
two mechanism~, nam~ly, conver~ion o~ ~he ~cid group containing polymers to ~he corre~ponding ~alt~, e.g. ~odium, ge~erating negative charge~ along the polymer backbone, thereby ~au~ing the coiled molecules to expand and thicken the S ayueou~ ~olution; or ~y forma~ion of hydrogen bonds, for : oxample, ~etween the ca~oxyl groups of the polymer ~nd hydroxyl donor. The ~or~er mechanism i~ especially important in ~he ~recent invention, and ~herefore, the pre~erred polyacrylic acid-type thickening ayeIltj will co~ain free car~oxylic acid (COOH) groupx along the polymer backbone.
Also~ it will be understood t~t the degree of cross-linking ~hould not be ~o hlgh as to render ~he cross-linked pol~ner completely insoluble or non-digper6ible in water or inhi~it or prevent the ~ncoiling of the polyme~ molecule~ in the presence of the ionic aqueous By~em.
The amount of the high molecular weight, cro~-linked polyacrylic acid or other high molecular weight, hydrophilic cro~s-linked polyacrylic acid-type thickening agent tO impar~
, the de~i~ed rheological proper~y of line~r ~i~coela~ticity will generally be in the range o~ from about 0.1 ~o 2%, preferably from abou~ 0.2 ~o 1.4~, by w~ight, ~d~ed o~ the weight of the compo~ition, althouyh the amou~ will depend on the partlcular croca-linki~g agent, ionic ~rength of the compo~i~ion, hydroxyl donor~ and the like.
The co~po~itions of thi~ inverl~iorl m~l~t include ~ufficient amo~nt of po~a~sium ion~ and ~odium ion~ to provlde a weight ratio of ~/~a of at lea~t 1:1, prefer~ly from 1;1 to 45:1, especially from about 1:1 to 3:1, more preferably from 2~99~6 1.05:1 ~o 3:1, 6uch a6 1.5:1, or 2;1. When r~he K/Na ratio i~
le99 than 1 ~here i~ insuff icient colubility of the normally ~olid i~gredien~s ~herea~ when the K/Na ratio ic~ more than 45, e~pecially when it i~ greater than a~out 3, the product becomes too liquid and phase ~eparation begin~ ~o occur. W.hen ~he K/~a ratio is more t~lan 45, especially whe~l it i~ greater than a~out 3, the product ~ecome~ too liquid and phase separation be~in~ to occur. When the K/Na ratio~ become muc~
larger ~han ~5, ~uch ~8 in all or mostly potassium formulation, the polymer thlckener lo~e~ it~ a~orptior c~pacity and begin6 to ~alt out o~ ~he aqu~ou~ p~a~e.
The potassium arld ~odium ions can be made present in the compo~i~ion~ a~ the ~lkali metal ca~ion o~ the detergent builder ~alt(~), or alkali metal silica~e or alkali metal hydroxide comporlent~ of the compositions. The alkali metal cation ma~ also be present in the compo ition~ aG a componen~
of an ionic de~ergent, bleach or other ionizable salt compound addi~i~e, e.~. alkall m~tal car~onate. In de~er~ining the K/Na weight ratio~ all of these ~ources should be taken into consideration.
Speci~ic ex~mpl~ of ~c~r~en~ huilder 6al~ inclu~e the polypho~pha~e~, ~uch as alkali metal p~oE)hosphar~e, alkaJ.i me~al tripolypho~phate, alkali m~tal metapho~pha~e, and the like, for example, ~odium or potas~ium txipolypho~phate ~ (hydrated or anhydro~ etra~odi~m or tetrapotassium pyropho~phate, ~odium or pota~siu~ hexa-metapho6pha~e, tri~odium or ~ripotassium orthopho~phate ~nd the ~i~e, ~odium or po~a~3ium carbonate, ~odium or po~a~Yium citrate, ~odium ox 2~99~
potassiuM nitrilocriaceta~e, and th~ like. The pho~phate builder~, where no~ pr~cluded d~e to local re~ula~ion~, are pref~rred and mixcure~ of tetrapota4~ium pyropho~phate (TKPP) and sodium ~ripol.ypho~phate (NaTPP) (especially the hexahydrate) are e~pecially p~eferred. Typical ratios of Na~PP to TKPP ~re from a~out 2:1 to i:8, especially from about 1:1.1 to 1:6. The to~al amou~t of ~etergenc builde~ salts i~
prefera~ly ~rom about 5 to 35~ ~y weight, more prefera~ly from abou~ 15 to ~, especially from about 18 to 30~ by w~ight of the compocition.
In connection with the builder 6alts are optionally u~ed a low molecular wei~ht noncros~linked pol~acrylates havlng a ~olecular weigh~ of abouc 1,000 to about 100,000, more preferably about 2,000 ~o about 80,000. A preferred low molecular ~eigh~ polyacrylace i~ Nora~ol LMW45~ man~factured ~y ~orsoshaas and having a molecular wei~ht of abou~ 4,SOO.
These low molecular wei~ht polyacrylate~ are employed at a concentration of about 0.1 to lS ~t.~, more preferably ~.25 to : 10 wt.~.
Other useful low molecular weight noncro~linked polymer~
axe Acusol~640D provided by ~ohm ~ Ha~ c)rasol QR1014 ~rom Norsohaaq having a GeC molec~lar weight of 10,000.
The linear vi~coela~tic compositions of ~is invention ~ay, and preEerably ~ill, contain a ~mall, but stabilizing ~5 effective amount of a long chain fatty acid or monovalent or po].yvalent calt thereof. Although the manner ~y which the fatcy acid o~ ~alt ~oncribute~ to th~ rheolo~y and stabili~y of ~he compo~i~ion ha~ not been fully elucidated it is I Ir~ .J ~.1 1 1 .. ~ .r~ I rl I L.l I I L'~l I . r~

hypothe~ized that it ~ay function as a hydrogen bonding ~ 9 or cro~s-linking agent for the polymeric thickener.
The preferred lon~ chain fd~ty ~cid~ are the ~ligher aliph~tic fatty acids having ~rom ~cuc ~ ~o 22 c~rbon atom~, more preerably from a~out 10 to ~0 carbon atomq, and e~pecially preferably from about 12 to 18 carbon atoms, and e~pecially preferably from abou~ 1~ to 18 car~on atoms, inclu~i~e of the carbon atom of the carboxyl group o the fatty acid. The aliphatic radical ~ay ~e ~aturated or un4aturated and m~y be ~raight or branched. Straight chain ~aturated fatty acid~ are p~e~exred. Mi~tures of ~atty acids may be used, such a~ Lho~e derived f~om natu;~al Gources, suc~
a6 ~llow fatty acid, coco fatty acid, ~oya fatty acid, mixtures o these acid~, etc. Stea~ic acid and mixed fatty acids, e.~. stearic acid/palmitic acid, are preferred.
; When the ~ree acid form of the fatty acid i~ u~ed directly it will generally ~s~ociate wi~h ~he pota~ium and sodium ion~ in the aqueou~ phase to fo~1n che co~re~ponding alkali metal fatty acid 90~p. However, the fatt~ acid ~alts may ~e directly added ~o t~l~ comr~o~i~i.on a~ ~odium ~alt or pota~ium salt, or as a ~olyvalent met.al ~1L~ althouyh the ~lkali metal salt~ of the ~a~ty acids are preferre~ fa~ty acid ~alts .
The pre~erred polyvalen~ metals are the di- and tri-valent metals of Grou~ IIA, IlB and III~, such ~s sna~n~sium,calcium, ~luminum and zinc, ~lthou~h other polyv~lent metals, incl~ding those of Groups ~ , rvA~ ~rA, IB, I~rB~ ~7B VIB, and VII~: Qf ~e Periodic ~able oI; che Elernent~3 can alqo be 2~699~;
used. ~pecif1c ex~nple~ of ~uc~l other po~yvalent metal6 include Ti, Zr, v, ~ , Fe, Co, ~i, Cd, Sn, Sb, Bi, etc.
Generally, the metal~ may ~e pre~ent in the divalen~ to pentavalent state. Preferably the metal. ~alt~ ar~ used in t~eir higller oxidacion ~tates. Ndtur~lly, for u e in ~tom~tic di~w~her~, as well a~ any o~her ~pplications where the invention compo~i~ion will or may come in corltact with articles u~ed for the handling, ~orage or se~ving of food product~ or which otherwi~e ma~ c~me into concact with or ~e consumed by people or ani~al~, the metal ~alt ~hould be ~elq~ted by ~aking into con~ideration ~he ~oxici~y of the metal. ~or this purpo~e, the ~lkali metal and calcium and magne~iu~ salt~ axe especially higher preferred a~ generally sae food additives.
The amount of the fa~ty acid or fat~y acid ~alt stabilizer to achieve ~he de6ired enhancemerlt of phy~ical stability will depend on ~uch fac~or a~ ~he na~ure of the atty acid or it~ ~alt, the nature and amount of the thickening a~ent, detergeIIt ac~lve co~po~d, inor~ahic salt~, other ingredients, as well aR the anticipate~ sr.orage an~
~hipping condition~.
Generally, ho~e~er, amount~ of the fat~y acid or fatty acid salt s~abilizing agen~ in the r~nge of from about 0.02 to 2~, preferably 0~04 ~o 1~, more pre~erably from abo~t 0.06 to 0.8~, especially preferably fxom about 0.08 to 0.4~, pro~ide a long term stabili~y and absenc2 of pha~e ~eparation upon standing or d~rin~ transport at bo~h low and elevated _. ~ .

u~ r~ t~l l L l~ . r- . L l / -~_ 2~9~6 temperature~ a~ are ret~ired for a c~nunercially acceptable product.
Depending on ~he amounts, proportion~ and types of fatty acid ph~ical s~abillzers and polyacrylic acid-type thickening at3ents, the addition of the fa~ty acid or salt not only increa6e~ phy~ical ~tabilit~ ~u~ al~o provide~ a simul~aneouq incre~e in apparent vi~coqi~y. ~nount~ of fat~y dcid or salt ~o polymeric thickening a~ent in the range of from abou~ 0.08-~ .4 ~Yeight percent fa~ty a~id ~alt and from a~ou~ O .4-1. 5 weigh~ percent polymeric thickenin~ agent are usually s~f~icient to provide ~he4e ~imultaneous benefit~ antl, therefore, ~he use of the~e irlt~redi~nts in these amount~ is m~t preferred.
In order tO achieve the desired benefit fro~ the fa~ty ~cit~ or fatty acid ~al~ 4tabilizer, ~ithout s~abilization of exce~s incorporated air bubbles and con~equent exces~ive lowerirlg of the product bulk den~ity, the fatty acid or salt ~hould be po~-added to the forrllulaciorl, ~referably together with the other surface active i.n~jr~dient~, includ.ing detergent ao active compound and anri- foamint3 a~erll, when pre~erlt. The~q ~urface active int~redierlts are E~refer~bly addt~d a~ an ~mulsior in wa~r wherein the emul~i~ied oily or f~ety ma~erial~ are finely and homogeneously dispersed ~hroughout the a~ueou~
phase, ~o achieve the de~ired fine emulsification of the 2S fatty acid or fatty acid xalt and o~her surface active ingredien~ u~ally nece6~ary ~o heat th~ emulslon (or preheat the water~ to an elevated eemperature near the ~elting temperatUre o~f the fatty acid or itY ~alt. For example, for r I I ~ l L I r~ I Ll ~ ~ LlL-r I . r . ~

stearic acid having a melting poin~ of 68C-69C, a te~perature in the range of between 50~C and 70C. will be used. For lauric acid (m.p.=47~C) an elevated temperature of about 35dC to 50C
can be ~ed. ~pparently, at the~e elevated temperat~res the fatty acid or salt and other surface active ingredients can he more readily and uniformly dispersed (emulsifled) in the form of fine droplet~ throughout the compo~ition.
In contra~t, as will be shown .in the example~ ~hiCh follow, if the fatty acid is ~impiy poY~-added at ambient temperature, the composition i6 ne~ linear ~i~coelastic as deined above and the stabili~y of rhe co~po~ition i~ cle~rly inf erior .
Foam inhibition ic impor~.ant to increase di~hwa~her machine efficiency a~d minimize de~tahilizing effect~ which might occur due ~o the presence of exce~ foam wi.thin the washer duri~ use. Foam may be red~ce b~ jui~able 6election of the type and/or amount of deter~en~ active ma~erial, the main foam-producing ccmponent. The degree of foam is al~o ~ome~hat dependent on the hardne~s ~f the wa~h water in the machine whereby sui~able a~jus~men~ o ~e ~ro~or~ions of the ~uilder salt~ such as NaTL~e which has a w~ter ~o~tening effect, may aid in providing a degree uf foam inhi~ition.
Ho~ever, it is generally preferred to include a chlorine bleach stable foam depressant or i~hibi~or. Par~icularly effective are the alkyl pho~ph~ri~ aci~ e~ter~ of the formul~

~. ~ .

20~66 HV~
OR
and e~pecially the aik~l acid pho~h~e e~ters of the formula HO-P-OR

In the above formulas, one or both R ~roup~ in each type of ester may repre~e~t independently a C~2-C20 alkyl group. The ethoxylated derivative~ of each ty~e of ester, for exa~ple, the conden~a~ion products of one mole of e~er with from 1 to 10 mole~, preerably 2 eo 6 moles, more prefer~bly 3 or 4 mole~, ethylene oxide can al~o be u6ed. Some exa~ples of ~he ~oregoing are commercially av~ilable, ~uch as ~he produc~s SAP
from Hooker and LPK~-158 from Knapsac~. ~ixture~ of ~he ~wo cypes, or an~ other chlorine bleaeh ~table types, or mixt~re~
of mono- a~d di-esters of the same type, may be employed.
Especially pre~erred i~ a mix~ure of mono- and di-C~6-Cl~ alkyl acid pho~phate e~terx ~uch a~ monoYt~aryl./di~te~ryl acid pho~ph~tes 1.2/1, ~nd ~he 3 to 4 mole et;hylene oxide condenaa~es thereof. When ~mployed, proporti.on~ of 0.05 to 1.5 weiyht percent, pre~era~ly 0.1 to 0.5 weight pe~cent, of foam depres~ant in the composition i~ typical, the weight ratio o detergent active component (d) to foam depressant (e) generally ranging from abo~t 10:1 to 1:1 and preferably abou~
5:1 to 1;1. Oth~r defoamer~ which may be u~ed include, for example, ~he known ~ilicone~, such a~ a~a~lable from ~ow Chemical~P ~ a~dition, i~ i~ an advantageo~ feature of ~hi~

~n I ~ L ~rl I L I ~-~ I L I I I ~ Lr I ~

20~9~66 (registered ~rademark) 3~-2 and DOWFAX 2~-1. In addition, ~he surfac~ant 6hould be compa~ible wi~h the other ingredien~ of the compo~ition. Other ~uitable organic anionic, non-~oap s~rfactants include the primary a~kyl~ulphates, alkylsulphonates, alkylaryl~ulphonate~ and sec.-alkylsulphate~. Exampleg in~lude sodi~m Cl0-C,~ alkyl~ulpha~e~
s~ch a~ sodium dodecylsulp~a~e and sodium t~llow alcohol~ulphate; sodium C~O-C~ alkanesulphonate~ such a~ sodiu~
hexadecyl~ ulphonate dnd ~odium Cl2-CI~ -a~k~benzenesulphonate~ ~uch as ~odium dodecylbenzene~ylphonates, ~he corresponding pota~sium salts may also be employed.
~ other ~uitable su~factants or detergen~, the amine oxide surfac~ant~ are typically of the s~ructure R2RINO, in which each R repreeent~ a lower ~l~yl group, for irlstance, methyl, and Rl repxesents a long chain alkyl group having rom 8 to 22 carbon atoms, for in~tance a lauryl, myri~cyl, palmityl or cetyl group. In~tead of an amine oxide, a corre~ponding ~rfactant pho~phine oxide R2R~PO or sulphoxide ~O RRISO can be em~loyed. Betaine ~-lr~.ac~ante are typically ~
the s~ructu~ R2R~NtR"COO-, ln whi~h each i~ repres~nt~ a lower ~lkylene g~oup having from 1 to ~ ca~on a~omY. ~pecific exa~lple~ of theQe surfactant~ incl~1de lauryl-dime~hylamin~
oxide, myristyl-dimethylamine oxide, myri~yl-di~lethyl~mine oxide, t~e corre~ponding ~ho3~hine ox~e~ arld ~ul~hoxide~, and the correeponding betaine~, includin(~ do~ecy]dim~-hylamn~oni-~
aceta~e, tetradecyldiethyl~onium p~ntano~te, hexadecyl~im~4~1a~nonium hex~noa~e and the lL~e. For .

2~

I I r~ L _ I I I _ I ~ L r r 1 I L I ~ I L L I I ~

2G~9966 biodegra~abili~y, ~he alkyl group~ in the~e ~urfac~ant~ should be linear, ~nd ~uch comQc,unds are pre~erred.
Surfactant~ of the foregoing ~ype, all well known in the art, are described, for example, in U.S. Patents 3,985,668 and 5 4,271,030. ~f chloxine bleach 1s not used ~han an~l of the :-well knowrl low-foaming non1onic ~urfactants such as al~oxylated fatty alcohol~r e.s. mixed eShylene oxide-propylene oxide condensa~es of C~-C~2 fatty alcorlols can al~o be used.
The chlorine bleach ~ta~le, ~ater di~Jpe~lble oryanic detergent-active material (suxfac~ant) will noL~ally be presen~ in the composltion 1n minor ~no~nts, ~enerally abou~
1~ hy weight of ~he co~position in ~inor amount~, generally about L~ by weigh~ of the compo4icioII, althou~h smaller or larger a~oun~, such a6 up to about 5~, such as from 0.1 to 5~, preferably fo~m 0.3 or 0.4 to 2~ ~y weight of t~e Composi~ion, may be used.
Alkali ~e~al ~e.g. potas~i~m or ~odium~ si1icace, which provide~ alkalini~y ~nd protectiorl of hard s~rface6, ~uch a~
fine china gl.aze and ~ttern, i~ ~en~rally e~lployed in an amount ranging f~om a~ou~. 5 to 2~ w~i~ht percent, E)refe~ably abouc 5 to 15 weight percen~, more preferably 8 tO 12~ in the composition. The Yodium or po~as~ium Bllicate iY generally add~d in the fox~ of an a~eou~ ~oLu~iorl, p~eferably having Na20:SiO2 or K20:SiO2 ra~io of abo~t 1:1.3 ~o 1:2.8, ~speci~lly preferahly 1:2.0 to 1:2.5. ~ thi~ poin~, it ~hould be mentioned ~hat many of the oth~r componen~s of ~his composit~n,~x~pecially alkali mecal hydroxi~e and bleach, are 2~66 \ -àl~o ofte~ added in ~he ~onm of a preliminaxy prep~red a~ueou~
di~per3ion or solution.
In addition to the de~ergent active surfact~nt, foam inhibitor, alk~li metal silica~e corro6ion inhibitor, and detergent build~r ~alts, whlch all contri.bute to the elean1ng performance, it is also known that t~le efect1ver~e~s of ~he liquid au~omatic di~hwa~her detergenL compositions is related to ~he alkalinity, and par~icularly to moderate to high al~alinity levels. Accordingl~, the compo~i~ion~ of thi~
invention will have p~ value~ of ~t leas~ about 9.5, pref~rably at least about 11 to a~ high as l~, generally up ~o about 13 or mor~, and, when ad~ed ~o ~.he aqueous ~a~h bath a~
a typical concentration level of about 10 gram~ per li~er, will provide a pH in the wa~h bath of a~ lea~t about 9, lS prefera~ly at least about ~C, such as 10.5, ~1, ll.S or 12 or more.
The alkalinity will be achie~ed, in pa~t by the alkali me~al ion~ contributed by the alkali ~etal de~ergen~ b~ilder ~alt~, e.g. sodi~m tripolypho~p~ate, tetrapo~assium pyropho~phate, and alkali metal ~ilic~, however, it i~
u~ually nece~sary to include alkal.i metal hydroxi.de, ~.~. NaOH
or KOH, to achieve ~he deslred high alkalini~y. Amounts of alkali metal hydroxide in the range of (on an active basis) of f~om about 0.5 to 8%, preerably f~om l to ~, mor~ preferably from about 1.2 to 4~, by weight of the composition wil~ be sufficient to achieve ~he de~ired ~H le~el and/o~ to adju~t the X/Na weight racio.

rl I ~ L~ ~ r r~ I . r . ~

2~ii9~66 Other alkali me~al qaltY, ~uch ~ alkali me~al ca~bona~e may also be pre~ent in r.h~ compo~ition~ in minor amounts, for example from O to 4%, preferab~y O ~.o ~-, by weight of the composition.
Other conventional lngredlen~ may be included in theie composition~ in ~mall amoun~s, generally le~ than about 3 weight percen~, 3uch as perfume, hydrotropic a~ents such a~
the sodi~m benzene, ~oluene, xy~ e and cume~e sulphonates, preservatives, dyes~uff~ and pigments and ~he like, all of cour~e bein~ table ~o chlorine bleach compound and hi~h alkalinity. E~ecially preferred for coloring are ~he chlorinated phythalocyanine~ and polysuphides of alu~.inosilicate which provide, re~pectlvely, plea~ing green and blue tint~ Tio2 n~y b~ employed for whi~e~ing or neutrali~ing off~hades. Even more preferred coloranc~ u~ed at a Co~Gentration of about 0,01 to 1.0 ~t. ~ are CI Direct Yellow # 28 and Grapthlol Green pigment both made by Sandoz Chemical Corp.
Al~hough for the rea~ons previou~ly fli~cu~ed e~ces6ive ~ir bub~le~ are nv~ often ~esi.r~le in ~he inverl~ion compo~i~ion~, depending on the amoun~s o~ dl.s~o~ved 30lid~ and liquid phaje densltie4, incorporation of cm~ll amounts of finely divided air ~ubbles, generally up to ~bout 1~% by volume, preferably ~p to about ~ by volume, more ~referably up to about 2~ by volume, can be incorporated ~o adjust ~he bulk de~ity to approximate liquid phaYe den~icy. The inco~porated air bubble~ should be finely divided, such a3 up ~o about 1 ~ micron~ i~ diamet~r, prefer~bly from abou~ 20 to : . ~1, ~ _ 2069966 ~

bleac~ compound ~nd remaining detergen~ additive~, includinc3 any previously unuQed alkali metal hydroxide, if any, of;her tha~ the ~urface-active compounds. ~ll o~ the additional ingredient~ can be added ~lmultaneously or 6equentially.
Preferably, the ingre~ient~ are added ~e~uentially, although i~ ic not necesf~ary to complete the addition of one i~gredient before beginning to add the next ingredie~lt. ~urthermore, one or more c7f ~he~e ingredient~ can be divided into portionY and added at different ti~es. These mixing steps should al60 be performed under moderate ~o high ~hear rate~ co ~chieve complete and unifonm mixin~. The~e mi~ing step~ may be carried o~t at xoom temperat.ure, althou~h the polymer thickener neutr~lization (gelation) i9 usually exo~hermic.
The ~ompo~ition may be allowed to age, if necessa~y, ~o cau~e di~c71ved or disper~ed air to di~sipa~e out of the compo~ition.
The remaining surface ~ctive ingredients, including the ~nti-foaming agen~, organic detergent compound, and fatty acid or fatf y acid ~alt stabilizer i~ ~o~t-added ~o ~he pre~iously formed mixture in th~ form of ~n aqlleo~s em~l~ion (u~iny from ~bout 1 to 10%, pre~erably from abo~t 2 ~o ~% of the tocal water added to ~he compo~ition ot~n~r t.han water added as carrier for other inyredlent~ or water of hydra~ion) which i~
pre-hea~ed to a temperature in ~he range cf from a~70u~ Tm+S to ~-20, preferabl.y from abo~t Tm to TM-10, where ~m is the meltiny point temperat~re of the fat~y a.cid or fatty acid salt. For the preferr~d ~tearic acid ~tabilizer the heating te~peratu~.i~ in the range of 50C to 70C. However, if care . 2~

i6 taken to avoid exce~slve air bu~le i.nc~pora~lon ~urls~y the gela~in gtep or during the mixing of ~he det.ergent builder ~ 6 9 9 salt~ and other addi~ive~, for example, by oper~ting unde~
vacu~m, or u~ing low ~hearing condition~, or special mixing ope~atatus, etc., the order of addition of the surface acti~e in~redients ~hould be less impor~ant.
In accordance with an e~peclally preferred embodime~
the ~hickened linear vi~coelastic aqueous automatic di~hwa~er detergent compo~iti~n of ~his invention includes, on a weight basi~;
(a) 10 ~o 35~, preferably 15 to 30~, of at least one alkali metal detergent ~uilder sal~i (b) 0 to lS, preferably ~ to 12~, alkali ntetal 3ilicate;
(c) 1 to 6%, preferably 1.~ ~o 4~, alkali metal hydroxide;
(d) 0 to 3~, pre~erably 0.1 to 2~, chlorine bleac~
s~able, watex-di~persible, low-~oaming organic detergent acti~e material, preferably non-~oap anionic de~ergent;
(e) 0 ~o ~.S~, preferably 0.1 to 0.~, chlorine bleach stable foam depre~sant;
(f) chlorine bleach co~pound in an amoun~ to providç
about 0.2 to 4~, preferably 0.~ to 1.6~, of available chlorine;
(g) high ~olecular wei~ht ~lydrophilic cro~s-linked polyacrylic acid ~hickening agent in an amount to provide a linear ~iscoelas~icity to the for~ulation, pref~rably fro~
a~out 0.1 to 2.0%, more pre~erably from ~bou~ 0.4 to 1.5~;

(h) a long chain fatty acid or a metal salt of ~ long ch~ln fatty acid in an amount efective to increa~e the phycical ~ability of ~he composi~ion~, prefera~ly from o.oa to 2.0~, m~re prefera~ly frcrn 0.04 to 0.5%; and ; (i) balance water, prefera~ly ~rom abont 30 to 75~, more preferably from a~out 35 co ~5~; and ~herein ln (a) ~he alkali metal polypho~pha~e ~ncludes a mixture of from abo~t 5 ~o 30~, preferably from about 12 to 22~ of tetrapota~iu~
pyrophosphate, and fro~ 0 to a~ouc 20~, preferably from abou~
3 ~o 18% of ~odi~m ~ripolypho~phace, and wherein in the entire compo~ition the ratio, by wei~ht, of potaS~iUm ion~ tO sodium ions i~ fro~ about 1.05/1 ~o 3/1, preferably from 1.1/1 to 2.5tl, the composition~ having an amount of air incorporated therein s~ch that the bulk den~ity of the compo~ition i~ fro~
1~ about 1.32 to 1.42 g/cc, preferably from abou~ 1.35 to 1.40 g/cc.
(j) 0.01 eo i.09~ of a chlorine scable dye or chlorine ~table pigment.
The compocitio~ will ~e supplied ~o ~he con~umex in ~0 suitable di6pen~er cont~inerR preferably formed of molded pl~stic, e~pecially polyolefin pla~tic, an~ mo~ preferably polye~hylene, ~or which ~he inverl~ion composition~ appear to have partic~larly fa~orable 91ip chara~teristic~. In addition to ~heir linear vi~coelastic c~arac~er, the compo~itions of t~i9 inven~ion may also ~e characterized as pseudopla~cic gels (non-thixotropic) which are typi.cally near the ~orderline ~ecween liquid and ~olid ~iscoela~cic gel, depending, for example, on the amount of ~he polymeric thickener. The 2069~66 :
invention composition~ can be readily po~red from their containers without a,ny ghaking or 6queezing, ~lthough ~ueezable con~ainer~ are oten convenient and accepted by the con~uner for gel-like product~.
The liquid aqueou~ line~r vi~coela~tic auton~tic dishwa~her compo~itions oi this invention are readily e~ployed in known manner for waghing diahe~, o~her kitchen utensils and the like in an auto;natic dish~a4her, provided with a suitable detergent di~penser, in an aqueous wash bath containing an effectiYe amount of the compo~ition, generally fiufficient ~o fill,or partially fill the automa~ic dispenser cup of the particular machine being u~ed.
Th~ invention also provides a method for cleanin~
diohware i~ an automatic dishwashin~ machine wi~h an aqueou~
waJh ~ath containing an effecti~e amount of the liquid linear vi~coela~tic automa~ic di8hwasher deter~ent compo6i~ion as described ~bove. The com~osi~ion can be readily poured from ~he polyethylene coneainer with little or ~o ~queezing or shaking ~ n~o the di~pensing cllp of the automatic di~hwa6hing machine and will be ~ufficiently vlscous and cohe~ive ~o remain ~ecurely within r.he di~pen~ing cup until ~hear f orcea are again applied ~hereto, su~h as by che water spray from the dishwa~hing ~achine.
~he invention may be put into pr~ctice in ~ario~s way~
and a n~mber of specifi~ em~odiment~ will he de~cribed to illu~trate the in~en~ion with reference to the accompanying exa~ple~.

n I ~ 1 ~1 1 1 ~ ~n I ~ I r~ I Ll I I L ~l I r All the amount~ ~nd proportion~ referred co herein are by weigh~ of the composi cion unle~;~ otherwi~e indicated . -:
E~311;;~
Tl~e following fonnulatlon~ ~-X were prepared a~ deacri~ed below:

, I ~ ~ ~
1~ ~ ~ 1~ ~ 1~1 `'~
~ ~ 1~

, ?

2~99~6 r ~ ~ ~

L r ~ -- .c _ r u~ F~
~' r~ r~ O O ~r~ ~ V

I 1 ~ a ~
~ ll ~ o ~ ~x~a~

_ r _ _ _ :~
~ . I o ~ .~ aJ a ~ ~ ~ o o o~

_ __ _ O O ~I) O ~
_ o o .~
~D r~ O rd~ O ''~5 :

_ r ~ A A A ~1 0 ~

~ ---- N ~: v-~,.a O
~ .~ o O ,u v ~ ~ ~
_ r~ _- O ~ ho rd al ~ o o j (d _ _ _ _ ~ ~ ~

_ r~ t:) O o h ~ ~ ~ V
_ ~rt r~ o o ~ ,rd SV ~a~ ~
_ r l l ~ , U ~ O r~l U a) h o~
~ r ~ ~ I ~ ~ ~o~ 0~
~ ~; h cn ~ ~ D ~ ~ r~
lil ~ D :~ ~ ~ La o ~ k tn ~ u~
_ _ _ ~

r Form~lation~ A, B, C, ~, E, G, J, and K are prepared by fi~t forming a ~niform dlYper~ion of the Carbopol 941 or 940 thickener in abo~t 9~ of the water (balance). The Carbopol i~ 810wly added to deionized water ~L room temperature using a mixer equipped with a premier blade, wi~h agitation ~et at a medium ~hear rate, ac recon~e~ded by ~he manufact~rer. The disper~ion is then neutralized by addition, u~dex mixi~g, of the ca~stic s~da (50~ ~aOH or ~OH) component to form a thickened product of gel-like consi~tency.
To the res~lting gelled di~persion the ~ilicate, tetrapota~ium pyropho6pha~e (TKPP), ~odium tripolyphosphate TP(TPP, Na) and bleach, axe added ~quentlally, in the ~rder stated, ~ith the mixing continued at medium ghear.
Separacely, an emul~ion o~ the phoephate anci-foaming ~:
agent (LPKN), ~tearic acid/palmi~ic acid mix~ure and detergent (Dowfax 3B2~ i6 prepared by adflin~ thecl~ lngredient~ to the remaining 3~ o water (balance) and hea~ing the res~lting mixture to a ~emperature in the range of 50C to 70C.
Thi~ ~eated emulBion i~ ~hen ~dded ~o the previou~ly prepared gelled di~persion under low ~hear conditions, such that a vortex i8 not formed.
The remaining ~ormulations E~, H and I are prepaLed in e~entially the ~ame manner a6 de~cribed above ~xcept that ~he heated emulsion of LY~N, ~teari~ acid and Dowfax 3B2 i8 dixectly added ~o the neut~ali~ed Carbopol di~pe~ion prior to the addition of ~e remaini~4 ingre~ien~s. A~ a re~ult, formulation~ F, H and I, have hi~her level~ of incorporated air and ~c~ie~ below 1.30 ~/cc.

r~ r~ I L~ ~r I

The rheogrdm~ for the formulations ~, C, D, G and J are shown in figure~ 1-5, re~pectively, and rheogra~ for formulaLions H, I and K are ~hown in figure~ 6, 7 an~ 8 respectlvely.
The~e rheogram~ are o~tained with the Syr~tem 4 Rheometer from Rheometrics equipped wit~ a ~luid Se~o with a 100 gra~s-c~ntime~er ~orque tran3ducer and a 50 millimet~r pa.rallel pla~e geo~etr~ having an 0.8 millimeter gap ~etween plates.
~11 mea~urem~nts are m~de at room tem~era~ure ~25~C~1C) in a humidlty chamber after a 5 m~nute or 10 minute holding period o~ the sample in the gap. The measuremen~ are made by applying a frequency o~ 10 radians per ~econd.
~11 o ~he compogition fonmulation6 A, B, C, ~, G and J
according to the preferred embodiment of the invencion which include Carbopol 941 and ~earic ~cid exhi~it linear viscoela~ticity a~ ~een ~rom the ~heogram4 of figure 1~5.
Formulacion E whlch includes Carbopol 941 but no~ ~teari~ acid showed no p~ase separation at eic~er room ten~perature or 100F
after 3 week~, but exhibi~ed lO'~ phase~ paratlon af~er 8 week~ at room tempera~rc anfl aft~ only ~; w~ks a~ 100P.
Form~l~tion ~, conta1ni.ng C~opol '~0 in plac~ o~
Carbopol 941, a~ ~een from ~he rheo~ram i~\ figure 8, exhibi~
~ub~tantial linearity over ~he ~train range of rom 2~ to 50%
(G' at 1~ ~rain-G' at 50~ s~rain 500 dynes/~q,cm.) ~l~ho~gh 2S tan 1 at a ~r~in above 50~.

J ~
~99~6 This example demonstrates the i~portance o~ the order of ~dition of the surface active eonlponent premix to the rem~inder of the composition on prod~c~ den~i~y and stabili~y.
The following formula~ion~ are prepared by methods A and B:
Inq~di~nt~ ::
Water, deionized Balance Car~opol ~41 0.5 I.
~aOH (50~) 2.4 Na ~ilicate (47.5~) 21 TPP, Na 13 ~Bleach (1~) 7.S
~PKN 0.16 Stea~ic Acid 0.1 Dowfax 3B2 MQ5h~9 ~he Carbopol 341 i~ disperged, under medium ~hear ra~e, ~sing a premier blade mixer, in deiorlized water at ambient ~emp~ra~ure. The NaOH i~ ~dded, ~nder mixing, to neutralize and gel the Carbopol 94~ di~per~ion. To the thickened mixture the following ingredien~ aLe add~d ~equen~ially while the 8tirring is concinu~d: ~odium ~ ate, TKPP, TPP, and bleach.
Separately, an emul~ion i~ prepared by adding the Dow~ax 3B2, stearic aci~ and LeKN ~o wa~er while mlxing at ~oderate ~hear and heating the mixture ~o about 654(' tO ~inely di~per~e the emul~ified ~urf~ce active ingLedien~s in the Wdter pha~e.
Thie emulsion pre~ix is then ~lowly added to ~he Carbopol diiper~ion while mixing under lo~ ~hear ~onditiorls without forming a vortex. Th~ resul~ are ~howrl below.

r I I ' .` 1_`~1~ 1 ~ I n I ~ 'L_r`

2~6996~
et~p~ B~
~ thod ~ i~ repeated except ~hât the heated emulsion premix i9 added to the neu~ra~ized ~arbopc,l ~41 dispersion befoxe the ~odium stearate, TKPP, TPP, and ~leach~ The S resul~s are al~o ~hown below.

Me~hod A Method B
Density (g/cc) ~.38 1.30 Stability (RT-8 week~) 0.00% 7.00~
Rheogram Fig~ 9 Fig.10 From ~he rheograms ~f fiyure~ 9 and 10 lt i~ ~een ~hat both products are linear vi~coela~tic although the elastic and ~i~c~u~ moduli G' and G~ are ~ligher for Method A than for ~ethod B.
From the r~ults it i~ seen ~hat ea.rly addition of the surface active i~gre~ie~ o che Carbopol gel significanrly increases the deyree of aeration and lowers the bulk density of the final product. Since the bulk den~ity i~ lower than the density of the continuou~ liquid pha~e, the liquid phase under~oes i~er~e separation (a ciear li~uid pha~e forms on ~he bot~om of the composicion). T~is proces~ o inver~e ceparation appears to be kine~icall.y ~onr.rolled and will occur a~ter a~ ~he den~ity of the pro~uc~ become~ ~ower.

E~3m~1Y
~hi~ exa~ple ~hows ~e :im~or~.~n~ of the tempera~ure a~
which r,he premixed ~ur~ac~ant ~mu`L~ion 19 prepared.
~wo form~lation~, L and M, ha~ing che sa~e compo~i~ion as in Example 2 e~cept that the amo~m~ of ~tearic aci~ was increase~,r~ 0.1~ to 0.2~ are prepared as ~hown in rqethod A

I lr1 ~ ~r~ I ~ ~ r1 1 1_1 ~ I L~L r I . r~

2~iig96~
for formulation L and by the ~ollo~ g M~thod C ~or form~llation ~.
Met~d_C
The procedure of Me~hod A is repe~ted in all detail~
5 excep~ that emul~i~n premix o~ the surf~c~ acti~e ingredient~
is prepared at room temperat~re a~d i~ not heated beore being po~t-added to the thickened Car~opol dl~persion co~ltai.ning ~ilicate, builders and bleach. ~he fheogram~ for for~ulation~
L and M are jhown in figure~ 11 arld 12, re~pecti~ely. From these rheograms it i~ ~een that formulation L is linear ~i~c~ela3tic i~ bo~h ~' and G" whereas fornlulation M is non-linear vi~coela~tic pa~icularl~ fox elastic modulus G' (G~ at 1~ ~train-G' at 30~ .Qtrain ~ 500 dynes/cmA) and also for G" (G~
at 1~ ~train-G" at 30~ str~in 300 dynes/cm').
Fonmula~ion ~ remai~ cable ate~ storag~ at RT and 100~F
for at le~t 6 weeks whereax formuld~ion M undergoe~ phaRe separa~ion .
m~ C.~0~
The following or~1ation i8 prepared without any pota6~ium salts:
Wei~ht Wa~er ~alance Carbopol 941 0.2 NaOH (50~) 2.~
2S TPP, ~a (50~) 21.0 Na Silicate (47.5~) 17.24 ~ledch (1~) 7,13 Ste~ric Ac~d 0.1.
LPKN (5~) 3.2 Dow~ax 3B2 0.~
Soda Ash 5.0 Acr~ol LMW 45-~ 2.O

~9~

The proced-?re used i~ analogou~ to Method ~ of Example 2 wit~ the oda ash an~ Acrysol L~W 45-N (low molecular weight polyacrylate polymer) bein~ added before and after, re~pecti~ely, the silicate, TPP and ~le~ch, to the thickened Car~opol 941 di~persion, followed by addition to the heated surface active emulsion p~emix. The rheogram is shown in flgure 13 and is non-linear with G~/G' (tan ) ~ 1 over the range of ~rain of from about 5~ to 80~.

Example 4 ,~ormula~ions ~, B, C, P and ~C ~ccording to ~his invention and comparati~e formulations F and a commercial li~uid automatic di~hwa~her detergent product as shown i~ Table l above were subjected to a bo~tle residue test using a standard polyethylene 28 ounce bottle a~ ~e~ for current commercial liquid dighwasher detergent bottle~ :
Six bottles aro filled with th~ re~peetive samplas and the prod~ct is dispensed, with a minimum of force, in 80 gram do~ages, with a ~ minute re~t period between do~ages, until flow stops. At thi~ poi~t, the bottle wa~3 ~i~orou~ly ~haken ~o ~ry ~o expel additional product.
The amount of produc:t -remair~ g in ~.he ~oLt].e. is meafiured a~ a percentage of ~he total product originally f.illed in ~he bottle. The result~ are ~hown below.

~` ~ .
3~

20699~i6 Bottle Re~ldue Formu~i~ a Commercial Product 20 ~T~e jam~le ~eparates upon aging ~xampl e S
The following forrnula, A-I were p-~pared accordin~ to the proc~dure of ~xample 1.

., __ _ __~ _ c~ ~ _ _ ___ __ I
t` O ~ N r~ 0 o u~ o o . . . . ~ . r~ C~ . . U) ~
~ o ~ ~ ~ o o ~\J ~ ~` r~ ~ o o _ _ _ _ _ _ _ _ . . ~_ _ _ _ ~ _ ~ o U~ O ~ (~ r~ 0 O O O 117 U~ O O
td o _ _ _ o o .. ~ __ r o _ _ _ _ _ _ _~ _ _ _ __ o U~ o o o o Lrl o r ~ ~ ~ r~ ~ . . . L~ . o t~ O rl ~i ~ r~l r1 N t~ ~f ) O r1 _ _ _ ~ ~ _ _ ___ ___ ~ _ ~ ~ ' C~ O ~ ' U~ O O O U~ Ll~ ) r u~ ~ ~ ~ a~ ~ u`~ N Ll') r` O ~
1~ O O ~ (~ O O N r1 ~ r~ (' ) O rl _ ___ ~ ~ _ _ __ .____ ,~ _ . __ _ _ ~1) Ln O C~ U~ t'~ C~ ~
r~ O ~ N r~ O r; O In ~n Yr ~ u~
li~ O ~ ~1 ~Y) t~ r~ ~ ~I t-- r_ /'~ r1 ~ ~:
_ _ _ _ _ ~ O --~---- N--~ -- ~D O

t" O ~ ~r~l ~ r;c; O L~J I~ ~ rl O ~ ~I ~) ~ O ~<~I r., t~ ~1) r I ~1 _ _ _ _ ~ , ---- 1 -------- - --~ O ~ ~ rAI a~ O Cl O I~ O r C~
t.) C l rl ~ ~ o O ~ _ ~ ~ ~--1 t~ ~ r~J r~
_ _ _ _ _ _ O O _._.._. _ U~ _ .__ O O ~3 t" Ll~ ~( ~ I_~ ) r; Il~ ~ Ll~ 1~ ~) N L) ~1 O O ~ N O O ~ rl '-I t'` 1' r~ r~
_ . _ ~ _ __ __ ___ L~'l ,~ __ _ O
n ~ ~ r~ a~ o o c, u~ ~ c~ rl :i I¢ C; O ~ O O r U~ r1 r r __ _ _ rl I r _ ` ~
A

O

2~99B6 _ _ _ __ _ _ _ _ _ _~t _ __j . ~;t ~t _ ~ r _ _ _ __ _ ~t L L ~0 O _ _ _ _ _ _ _ _ _ _ __ __ _ ¦ ~
~0 w .p~ , e~ ~ ~ ~r 1- t tl t~ ~ It~
hO Ll'~ ~ O a~ O ~ ~ r ~ ~s) ll C~ C~ r ~ ¦ ~ t O_ r-i _ __ O _~ _ u~ u~ rl t` _ O rt _ ¦ 11~
:) r~) ~ r1 t~ c~ 1~ ~t ~t_ rt _ N O O N O _ rt ~ O O (li ~1 _ _ _ _ _ _ ~ ~ g ~O C~

~ Ll~ a I Irl I ~ L_'~I I I L I 1-1 I L 1 1 1 ~ 1 1 . r -t~ --~_ 20~9966 WXAT IS C.L~IMEP IS;
1. A lin~a~ visGoela~tic aqueous liquid automatic dlshw~cher de~ergen~ composition ~ompri~ing approximately by weight:
(a~ lO ~o 35~ of at lea~t one alkali metal de~ergent builder ~alt, ~aid alkali metal detergent builder : Qalt belng selected from tha group c~onsi~ing essen~ially of al~ali ~ne~al tripolypho~phate, alkali metal pyropho~phate, alkali metal mecapho~ph~te, alkal.i me~al carbonate, al~ali metal citrate and alkali met~l ni~ri.lo~riace~ate an~ mixt~re~
ther~of;
(b) 5 to 15~ alkali me~al silicate;
(c) 1 to 6~ alkali ~etal hydroxide;
~d) 0 to 3.0~ chlorine ~leach sta~l~, ~ater-di~per~ible, organic detergen~ active material;
(e) 0 to 1.5~ chlorir~e bleach stable foam depre~ant;
(f) chlorine ble~ch cornpound in an ~nount to provide 0.2 ~o 4~ o~ a~ailable chlorine;
(g) 0.1 to 2.0~ of a cro~-lixlked pnlya~rylic acid shickening agent having a Molecular weigh~ of from about 1,000,000 to 4,000,000i (h) 0.02 to 2~ of a long chain fat~y aci~ or a metal sal~ o~ a atty aci~;
(i) 0.01 to ~.0 wL. % of ~ ~igment. and/or dye;
(j) water, wherein ~id ~olyacrylic acid thickening agent being ~elected from che ~rou~ c~n~i~tin~ e~entially of acrylic a~ d ~r ~ethacrylic aci~, water-diYper~ible or wa~er-~;~

soluble ~a~.~s, e~ter~, or amldes ~he~o~, and watex-soluble copolymers of these acitls or their s~lt~, e~ter, or amide~
~ith each other or with one or mo~e other ethylenically ~nsaturated monomerj, wherein cha a~ueou~ ph~e include~ both ~odium and pota~6i~n ion~ a~ a K/Na weight xatio of from ~bou~
lJl to abo~t 45/1, wherein subs~arl~ially all of the normally solid component~ of the compo~ition are pre~ent dissolved in ~he aqueou~ pha~e, and sub~tanti.ally all of the wa~er in the compo~ition i~ tightly bound to rhe c-ro3~-linked polyacrylic acid thickening agent, ~aid compo~i~ion having a bulk density of rom 1.32 g/cm3 to 1.~2 tJ/Cm3 an~ ~aid composi~l.o~ doe~ not exhibit phase ~eparation and re~mains homo~enous, when said compo3ition i~ cerltrifugetl at 1000 rpm ~or 30 minu~e~.
2. ~he co~poYi~ion of Clalm 1, wherein ~aid alkali metal builder ~alt i~ a mixture of sodium tripolypho~pha~è and potas~ium tripolypho~phate.
3. The compo~:ition of Claim 1, whercin caid ~lkali metal builder ~alt is a mixLu~e oL ~ot~iu~n ~.rlpol.yphosp~a~e and po~a~sium pyropho4phat~.

4~ T~e compo~it ion of Cl~i.m 1 whereirl Gdid alk~l.i m~tal.
builder ~alt i~ a mixture o~ ~o~lium t~i.poJyE)hosE~hdct~, potassium ~ripolyph~phate, and ~ota~iurn pyropho~phate and mixture thereof.

5. The compo~ition of C'laim 1, wherein the long chain ~a~ty a~id o~ sal~ ~hereo~ iB pre~e~ in a~ ount of from about 0.06 ~o 0.B~ by weiyht.

Claims

6. The composition of Claim 1 which further comprises up to about 2% by volume, based on the total volume of the composition, of air in the form of finely dispersed bubbles.
7. The composition of Claim 1 wherein the cross-linked polyacrylic acid thickening is present in an amount of from about 0.4 co 1.5% by weight of the composition.
9. The composition of Claim 1 wherein the K/Na ratio is from about 1/1 to about 3/1.
9. The composition of Claim 1 which the chlorine bleach compound is sodium hypochlorite.
10. The composition of Claim 1 further including a fragrance.