CA1181652A - Foam enhancing agent for light duty liquid detergent - Google Patents
Foam enhancing agent for light duty liquid detergentInfo
- Publication number
- CA1181652A CA1181652A CA000408825A CA408825A CA1181652A CA 1181652 A CA1181652 A CA 1181652A CA 000408825 A CA000408825 A CA 000408825A CA 408825 A CA408825 A CA 408825A CA 1181652 A CA1181652 A CA 1181652A
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- weight
- liquid detergent
- guar gum
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0094—High foaming compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
Abstract
ABSTRACT
A light duty liquid detergent containing about 0.1 to 0.6 %
of a nonionic hydroxypropyl guar gum derivative as the foam enhancing agent in an aqueous solution containing a maximum of 40%, preferably less than 35% of the ternary surfactant system comprising C8-C18 alkyl ethenoxy ether sulfate, C8-C18 alkyl sulfate and a betaine. The detergent has improved foam stability, cleaning efficiency and consistency with reduced amounts of detergent active ingredients.
A light duty liquid detergent containing about 0.1 to 0.6 %
of a nonionic hydroxypropyl guar gum derivative as the foam enhancing agent in an aqueous solution containing a maximum of 40%, preferably less than 35% of the ternary surfactant system comprising C8-C18 alkyl ethenoxy ether sulfate, C8-C18 alkyl sulfate and a betaine. The detergent has improved foam stability, cleaning efficiency and consistency with reduced amounts of detergent active ingredients.
Description
The present invention relates to novel light duty liquid detergent compositions with enhanced foaming properties, containing small amounts of a nonionic hydroxypropyl guQr gum derivative as the foam stability agent. ~lore specifically, said detergent system comprises a ternary mixture of an alkyl ethenoxy ether sulfate, an alkyl sulfate and a betaine.
Foam boosters commonly used for conventional light duty liquid detergents are either amides or amine oxides. To achieve foam boosting effect, they have to be used at relatively high levels (3 - 6%).
~' ~ 6~;Z
llh9 prlor ~rt is repleto wilth light duty llquid date~
gent compo~itlona conk~ in~ mixt~re~ o~ b~taines and one or more anioni~ dotergent~ s:cemplirl~d by U~ SO Paterlt ~o" 3"849, ¦
548~ where~ i~ dl~¢lo~ed a multidetergent ~ha~poo compo~lklon ~o~k~ g a betalne ~d ~ ulr~te or a lauryl ether slllrat~ (~ample 3 and Table III); 119 So Patent 130. 3995Q9417;
wherein i~ diaclosed a hi gh lathering mult~detergent-containirlg compositis~n compri~ing a bet~ine and a~ anionlc sur~ctant such a~ ~ alkgl ether ~ul~ats or ar:~ slkyl sul~ate and ~ nonlonic surf'~c'Gant 8uch a~ ~ polyo~yeth~lsne sorbit~n raonolaurate; lJ. ~, ;
Pe.tent ~qo. 39996~ 69 ~erein :1R dis~lo~ed an ~oldic ~hampoo for~ tlon compri~ing a cationlG r~in, at l~a~ two ~ionlc deter~;~nts9 ona o~ whloh i~ an alk~l eth~r ~ul~ate~, ~d a b0taino;
~ o Patent 1YOQ 4~009925b whlch D.180 dlaolose~ ~ ~hampoo com- I
po~tior2 oompri~ing a uationlc pol~nor~ a betai~e" and ~n alkyl bther ~ulfatc ~plo YI)3 IJi, ~o Patent NoO 4,11~89762 wh~r~
~8 di~clo~d ~ d~terge~t ~o~osit~o~ ~ompP~ing a betaine and 5-30,g a~io31ic surra~tants suGh a~ alkyl sul~ate, ~lkyl ether ~ulf~te and alkyl ~ryl ether ~ulfate; and U~, $~1~ Patant ]~Oo 43166, !
8453 ~ere~ d~a~losed a ~ligh foamln~; ~nt~d~ndru~f ~hampoo ~o~nprl~ing a bet~e and ~ 3uppl~mental detergent ~hich mny be ~ ~lk~l 9ulfa~eO Fo~ng of a~orssaid composit~on8 are a result o~ the u3e Or ~he con~er~ onal roam boo3ter~ or of the -I
particular combination of deteryents.
However, none of the above mentioned patents disclose a liquid detergent composition containing the ternary mixture of a betaine, an aIkyl sulfate and an alkyl ethen~xy ether sulfate.
IJ. S. Patent No. 4,075,131 to Sterling, discloses a condi-tioning sham~oo comprising an amphoteric surfactant su~h as a betaine, and a zwitterionic polymer, at~ may also contain foam boosters such as the alkanolamide (Ex~nple 1). The ternary mixture of alkyl sulfate, alkyl ether sulfate and betaine is disclosed here in (column 7) as a control concentrate for testing the effectiveness of the conditioning shat~oo containing the zwitterionic polymer con-ditioning agent.
m e prior art also discloses the use of hydroxyalkyl ethers of guar gum (a galactomannan gum) as thickening agents in pr mting pastes, paint dispersions and explosive slurries as shown in U. S. Paten-ts No. 3,748,201 and No. 3,700,612. However, the dis-closed compositions do not include liquid detergent compositions.
me Jaguar catalogue by Stein-Hall and Company, Inc., dis-closes hydroxypropylated guar gum derivatives useful as thickening agents. Guar gum is chemically classified as a galacto~annan, is a high molecular weight car~ohydrate polymer or polysaccharide made up of many mannose and galactose units linked L816S;;: ~
, I
.
koge~her (pag~ 5 o:E c~talogu~ ~a Japa~ Pa~e~t No~, 7~ 20j202 and 20,203 ~197~) by llhita~a dl~o' o~e the preparatio~ Or hydroxypropyl ~ug~r or gluco~ and lt3 u~e as ~ build~r ~or det~rgsnts; arld ths prep~ra tion o~ hydroxyethyl ~taroh or hydrox~propyl a~nylo~e and it3 UBe as a ~oll redap~itiQn irlhlbitor ~or dotergsnt~ 9 ~aid deter- ¦
gent compoa~tion comI)rl~1n~; a f~odium ~alt o:~ cv~onut alcohol sul~ata a~ter~ aodlum oarbonnte arld 30di~ ulr~t~O The parti- ¦
cular e~Qmple cit~d in ths~e pat~n~s înd1cates th~t wlth th~ I
ln~ ohol ~ul~at3 sur~actant, the traditio~l builder, kripo~phosph~Lta can ba replacad by hydro~rpropyl gluco~e and ~ inta~n th~ dokerg~ncy o~ the oomposition. Tho particul~r ¦
build~r sub~tituta3 mentioned her~in are hydrox~ralkyl ~ethyl9 propyl and butyl) ethers o~ mono- and di~saccharlde~O ~aowover, thera i~ no msntion herein Or guar gum or gu~r gum deri~atl~e~
nor Or ~oAm utabili ~tivn~
ll ; ~9~ 1.
It ha~ now b~en found that the ~ddition of ~me.ll amount~ !
Or a nonionio hydrox~propyl gu~r gum dariYat~Y~ ~OoOl~ ) to g.
light duty llquid d~tergenk comprising a tornary mixturo o~ ~ ¦
n~cyl e~h~no~r eth3r ~ul~a~e~ an alkyl ~ul:~t0 and a betaine, .
.
~ 4_ ~
Significantly improves the foam stability, cleaning efficiency and consistency of said liquid detergent.
Accordingly, the present invention provides a light duty, liquid detergent composition consisting essentially of between about 0.1% -to about 1.0% by weight, preferably between about 0.1% to about 0.6% by weight, of a nonionic hydroxypropyl guar gum derivative in an aqueous vehicle containing a maximum of 40% by weigh-t of a detergent active system comprising a mix-ture of a water-soluble salt of an anionic C8-Cl8 alkyl ethenoxy ether sulfate surfactant containing l to 12 ethenoxy groups in the molecule and a water-soluble salt of a C8-Cl8 alkyl sulfate surfactant, the weight ratio of said alkyl sulfate to said alkyl ethenoxy ether sulfate being from 1:29 to 29:1, and 2% to 5% by weight of a zwitterionic betaine surfactant of the formula:
lR2 Rl - N - COO
wherein Rl is an alkyl group having lO to 20 carbon atoms or the amido radical o H
Il 11 R - C -- N - (CH2) wherein R is an alkyl group having 9 to l9 carbon atoms and a is an integer from l to 4; R2 and R3 are Cl-C3 alkyl; and R4 is an alkylene or hydroxyalkylene group having l to 4 carbon atoms and, optionally, one hydroxyl group; said composition exhibiting enhanced foaming properties as compared with the same composition without said nonionic guar gum.
In another aspect, the present invention provides a method of preparing the liquid detergent as defined above, which comprises the steps of first preparing an aqueous solution of the ternary mixture of surfactants by mixing a-t a temperature up to a maximum of 100C; thereafter slowly adding said guar gum in the foYm cf particles having a slze such that a minimum of 90% passes through a 140 mesh U.S. standard sieve in the presence of agitation; and continuing said agitation until said guar gum is solubilized therein.
The novel liquid detergent composition preferably contains a reduced amount of detergent active ingredients and has improved foaming and cleaning performance.
Preferably the invention attemp-ts -to provide a novel liquid - 5a -,!, ---- . A
detergent with enhanced foaming properties and a viscosity oE at least 100 centipoises, comprising the ternary mixture of an alkyl ether sulfa*e, an alkyl sulfate and a betaine.
The invention will be further set forth in part in the des-cription which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention.
Broadly, the present invention is a novel light duty liquid detergent composition comprising a ternary mixture of the surfactants alkyl ethenoxy ether sulfate, alkyl sulfate and betaine and about 0.01-1%, prefera~ly 0.1 - 0.6% of a nonionic hydroxypropyl guar gum derivative.
Accordingly, the present invention relates to a light duty liquid detergent composition having good foam stability consisting essentially of 0.01 to 1%, preferably 0.025 - .6% and most preferably 0.1 to 0.6% by weight of a nonionic hydroxypropyl guar gum derivative, iJI an aqueous vehicle containing a maximum of 40%, preferably a maximum of 35% by weight of a detergent active system comprising a water soluble ternary mixture of a C8-C18 alkyl ethenoxy ether sulfate, a C8-C18 alkyl sulfate and a betaine. Formulations containing as low as 22%
active ingredients are capable of maintaining foaming and cleaning performance in the presence of small amounts of the hydroxypropyl guar gum derivative.
The foam booster utilized in instant invention which also functions as a thickening agent is a nonionic hydroxypropyl guar gum derivative. Aforesaid derivative is prepared by hydroxy-propylating the guar molecule, which is a straight chain mannan branched at quite regular intervals with single membered gal-11~l165~ . ~
actio~ urllt~ on ~ltarn~.};e manrlos~ un:Lta ~5 a~ discloa~d in arore-sald Jaguar catalogue by the Steln-:Hall Comp~ny" Tha hydro~
proyylated guar gum rler:Lvatlva~ utlliæed ln the pregent lnvcIl~iou i ara water ~loluh~ , dr~ partî.culAte~, earbohydrata material~ havlng a part:Lcle ~i.ze su-.h ~:hak a mlnimu:m of 90,~ pa~e~ throu~h a 140 ma~h U~ S,, ~3t;~ndard 9i~9ve amd en MS (molr3a o:~ aubst:ltutlon) value ¦
in the range of V~92 to oO8, prefsxably :rxom 0~3 to 0.~5"
Genelrally,, 1~ aqlleou~ solu~lon~; ther~or hav~ ~ p~ ln the range o:~ 5 to 11 and a vl~co~ tyr of about 3000 to 4000 cps m~asured on ~ Brookrl01d nvF~ v:l~r,omet~r u~ing ~ NoO 3 spindle rotatin~
at 20 RPM at ~ tempa~ature o~ 25G, and the resul~ant ~olution~
aro thixotroplc as v:Lscoslty changes with ~hearlng 3tres3 Suitable hy~droxypropyl guar gum dcrivatives may be obtainod rrom Steln-~all Company under tha name~ Jaguar~R~HP 6û9 Jaguar( ~I~P
f~d ~aguar(~ P 119 wl~lch u~clually co~ta~n 5~13,~" pre~erab~y 8-10,~ Or mo~tura ~ r~c~ived~ j The, hydroxypropyl Kuar gl3m darlYat,iv0~ ~re kno~n ~o ha~re thlckaning prop~r~les in aquoou~ solutionss, ~lowe~rer, a thick~ning agorlt i~ no~t generally known to improve the ~oaming propert~a3 o~
aqueou~ 301ution~ contalning sur~actants, wh~rea~ the hydroxy~ ¦
propyl guar g~n darlvative ds~ined above~ both increase~ tho viacosity of a detargent ~ormulatlon as w~ll ag improve~ it~
foamin~ per~`o~Rnco~ Sinc0 ~o~m volume and fo~n stablllty are o~tcn u~ed to gauga tho cleaning er~-l cisncy~ it is desirable to rormulate a datergent compo~itlon with improved ~o~ming pcr~or~anceO
Another advantage3us ~e~ture o~ instant novcl detergent com- ¦
po~itions contalning ~aid hydro~ypropyl guar gum deri~ativa~ !
i~ that thls roam boo~tor has a thlckenin~ ~unction which allows reduc~lon in the activo ineredlent level Or ~ rormulationr yet m~int0,1~ os~n p~r~ormanee~ thl3r~b~ e~ct:lng ~ ~a~lng ln the co~t o~ m~k~g thls :Light duty liquicl deter~e~t produetO
~111 ~other ~d.v~ntP.~ o '~ ~ ~h~t ~mQller ~mount~ Or thls ~v~m boo~lter (0"01-1% ~18 oppos~d to 3D6~ are n~eded ~omp~red to ~o~
~e3lt~0nal ~o~a boo~ter~9 ~urgher rsdu~ing the ~oat Or ~aid d~t~rgont produat "
It ha~ addlt$onally boen ~ou~d that th0 nonionlc hy-dro~rpropyl guar gum deriY t~.Yo nmcl;iona ~9 a fQ~ ~t,~bllizor ror certain detergent ~y3t,e~ nd ha~ no e~re~t on the ~oam per~ormallca o~ o~her ~y~tems such a~ llnaar alkyl b~nzen,3 ~ul~o~-~t~/sllcyl ~th~r ~ulrake, or lirl~ar alkyl be~ene ~ulronate/~
other oul~te/l~llrlo-~yristio mono~thanol aD~deO Acoordingly, it h~s been round that the p~rtiuular detergent ~y~tem ~heroisl ¦
~oar~ p~rro~mance 1~ ~ignifi~antly impro~0d by the presence o~ ¦
~a~d ~onionl~ guar gu~ dsri~rativ~ i8 a ternary mixture co~pr~n~ I
8~ alk~l ~theno~:y ether sul~ate, a~ alkyl sulf~t ~ and a bet~ine O
Thu~ it ls e~ldant that the ~pec~fi~ deterg~nt ~ystem utll~ed wlth the nonionic hydro~propylated gu~r ~;um derlvati~0 is orltl~al in ordar to obtain a l~ght duty liquid detergent ha~ing ~igni~icantl~ impro~ed ~oam porformulce.
m~ e~ential oo~ponsllt~ Or thi~ llght du~y llq~aid dat3:rgent e~prlse a water s~luble C8-C18 alkyl etheno~ ether ¦.
sul~ate ~nd an ~mmonium or alk~li metal ~alt o:e a C8 Cl8 alkyl sulrat0, both o~ w}l~ah ~ra ~ioni~ ~Ur~G~nt~; and a beta~e, . ' , . I
prerer~bly ~ fl~ldobatalna, which ~ 3 zwitterloxlic ~urr~lct~nt, dis~olved in 1n aq,ueou8 vehlcl~ " Th~ betai~e ~ompo~nt consti-t;Ut39 about 2~-3,~ and ~ot more th~n 5,9~ by ~rei~ht o~ tha llquld d~tergerlt ~ompo~itlon,9 a~d tho snionlc ~urfactants 50~stituli0 prerer~bly ~bout 20~ 30% by w~ight Or the llquid compo~ltlon ~ith the ratio o~ alkyl ~th~no~r ether ~ulra~s to aL~yl ~ul~a~e b~g noxl~criti¢al,, ~atios o~ 1/29 ~o 29/1 o~ the ~lkyl sulr~te to alkyl eth~no~ her sulrate, and pre~erably 17/13 to 12~J8 r~p~ctl~ , may be utilizad in pre~nt in~ention l~e anionlc 3ur~au~ants ~hich mEIy ba ussd ln the det0rgent co~rposi tion o~ the invention include at lea~t one ~ur~act~t ~lected ~ror~ the group &onsi~t$ng Or water noluble ~lt~, a.gO, the ~odium~ potass~um" ammoniun~ ~nd alkanolR~o ~alt~, Or a CB-C18 ~lkyl sul~t~ and prerer~bly C12- C16 and C12-C15 alkyl sulr~t~s. 9 ~uch a~ the lau~yl ~ulfates" ~rri~tyl 3ul~ate~ Qnd the lîke 9 and at .l~a~t one ~ur~actant ~elocted ~rom the group con~i3ting o~ the water ~oluble alkyl ethenoxy ~ther sulrAte~ ha~r~ng the general ~o:~mula R(C~i2CE~20 ) oso3h , I
whereln R ~ an alkyl radi~al ha~ 18 ~arbon ~tom~, n ~ a~ ¦
integer ha~in~ th3 ~alu~ oî 1-12 and pro~r~bly 1-5,, ~
an alk~ll matal, ar~oniu~ or ~:lkylolammonium" suLch as lauryl trietheno~ th~r 8ul~at3 " tridecyl alcohol tr~ ~theno:~ ether sulf~t0, and the llke~ Other anionio ~urract~ts ~uch as the . ~ , ~odium lauryl ~arco~i.nato~ 9 alkyl ~ul~onake3 3 alkyl bonzeno sulfonate~ and laur~l alcohol ~ul~ate s)r the liko cannot b0 :~ub~3tituted :eor ei th~r o~ the ~bov~ ~wo group~ Or a~ionîc {~ur-r~Otant~ a~ a cornponnnt ~ the terll~ry deterg~nt ~y~tem o~ pre~ont I
. lnventio~ o produce a liqu$d product with impro~ed foam p~r- j ~o~anC~- !
T~19 bet~ine component o~ i~st~t llquid det~rgent cor~positlon ha~ tho gen~ral ~ormuls:
l 1 4 F~3 wharoin R~ lkyl group hsving lO to about 20 carbo~ atoms, pr~rerabl~ 12 to 16 c~rbon atom~ or the ~m~ do radiS~al .
0~ ' R-&-~-(G~2) _ where$n R ~8 Rn alkyl group haYi~g about 9 to 19 carbon atoms and ~ la the integor 1 to ~9 R2 ~nd R3 are e~oh ~lkyl eroup~
havlng 1 3 oarbons snd pro~ersbly 1 Gsrbon; R4 19 an alkylene ~.~ '.' . -10-11~1.65~
or :hydroxyalk~lene group ha~.~g ~rom 1 ~o 4 carbon ato~ and~, optlonally7 orle hydro:~cyl group~, Typical Qlkyld~oth~l betaines in~lude dec~l dlm~ h~l betaln~ or 2~DI decyl-Ia9N-dim~khyl~
~onio~ acet~t~ ~oco dimeth~yl bot~l~s or 2~ 0~0-~911-diDIethyl-ammonlo) ac~teD myrl~tyl dlmothyl beta:~ne9 palmityl d~u~thyl bet~ine; ~auryl d~ thyl bet~ e g ~tyl dlm~thyl bet aine " ~tearyl almeth~l bet~ e~ etG~ The ~m:Ldobotaine~ simllarly lnclude coGoam~doeth~l betaina9 eocoamidopropyl bet~in~,~ and the lik~ao All o~ the afore~aid conapc~n~rata ln thl~ ligh~ duty detorgent are ~r~t~r ~oluble and remal~ wat9r solubl3 dur~g ~tor~ee9 Thi~ partl ~ular cQmbi natlon Or anlo~lc sulrs.te~ ~d bsta~ne provldes a ternary detePgo3lt ~y~tem which ~oa~to with th0 nonionio hydro~propyl g~ar ~5U~ derl Yati~3 to pro~uce ~ ;
li~uid d~tePge~ cvmpo~ltion with de~irabl~ fo~ming~ roam ~t~b~
ity, dster~l~e prop~rtias ~ w81~ a~ d~ir~bl~ co~l~y chaP~t- ¦
er:~tios~, m~ re~ult~nt homog3neous liquld detergent e~hiblts suporior foam p0rrormanGe a~ co~p~red ~o ~he same detergent ~om- !
posltion wlthout th~ no~ionlo guar gwn deriYatiLY~ Rg -~hown ln ~he ~ollowing Table I,, usl~g ~he T~rgoto~etor ~o~m te~, ~8r9i~
soiled pl~hota [1" diamot~r R:~d l/Bn hlg~ ), e~h cont~
on~ gr~m Cri300 SOllg ~r~ ~dded in tlmed in~r0mDnts ~eYe~y . I
minutes), to a 0.1% aqueous test solution of 150 ppm hardness as CaC03 (Ca/~lg = 2/1), and 100 ppm alkalinity as HC03 , at a temperature of 50C, and agitated at 75 rpm for one minute. The foam level is recorded when the agitation is turned off after each addition of planchets, and the -total number of planchets required to kill the foam is recorded.
TABLE I
Number of Planchets Detergent Formulation Washed 1. 17/13/3 AEOS/ALS/Betaine 19
Foam boosters commonly used for conventional light duty liquid detergents are either amides or amine oxides. To achieve foam boosting effect, they have to be used at relatively high levels (3 - 6%).
~' ~ 6~;Z
llh9 prlor ~rt is repleto wilth light duty llquid date~
gent compo~itlona conk~ in~ mixt~re~ o~ b~taines and one or more anioni~ dotergent~ s:cemplirl~d by U~ SO Paterlt ~o" 3"849, ¦
548~ where~ i~ dl~¢lo~ed a multidetergent ~ha~poo compo~lklon ~o~k~ g a betalne ~d ~ ulr~te or a lauryl ether slllrat~ (~ample 3 and Table III); 119 So Patent 130. 3995Q9417;
wherein i~ diaclosed a hi gh lathering mult~detergent-containirlg compositis~n compri~ing a bet~ine and a~ anionlc sur~ctant such a~ ~ alkgl ether ~ul~ats or ar:~ slkyl sul~ate and ~ nonlonic surf'~c'Gant 8uch a~ ~ polyo~yeth~lsne sorbit~n raonolaurate; lJ. ~, ;
Pe.tent ~qo. 39996~ 69 ~erein :1R dis~lo~ed an ~oldic ~hampoo for~ tlon compri~ing a cationlG r~in, at l~a~ two ~ionlc deter~;~nts9 ona o~ whloh i~ an alk~l eth~r ~ul~ate~, ~d a b0taino;
~ o Patent 1YOQ 4~009925b whlch D.180 dlaolose~ ~ ~hampoo com- I
po~tior2 oompri~ing a uationlc pol~nor~ a betai~e" and ~n alkyl bther ~ulfatc ~plo YI)3 IJi, ~o Patent NoO 4,11~89762 wh~r~
~8 di~clo~d ~ d~terge~t ~o~osit~o~ ~ompP~ing a betaine and 5-30,g a~io31ic surra~tants suGh a~ alkyl sul~ate, ~lkyl ether ~ulf~te and alkyl ~ryl ether ~ulfate; and U~, $~1~ Patant ]~Oo 43166, !
8453 ~ere~ d~a~losed a ~ligh foamln~; ~nt~d~ndru~f ~hampoo ~o~nprl~ing a bet~e and ~ 3uppl~mental detergent ~hich mny be ~ ~lk~l 9ulfa~eO Fo~ng of a~orssaid composit~on8 are a result o~ the u3e Or ~he con~er~ onal roam boo3ter~ or of the -I
particular combination of deteryents.
However, none of the above mentioned patents disclose a liquid detergent composition containing the ternary mixture of a betaine, an aIkyl sulfate and an alkyl ethen~xy ether sulfate.
IJ. S. Patent No. 4,075,131 to Sterling, discloses a condi-tioning sham~oo comprising an amphoteric surfactant su~h as a betaine, and a zwitterionic polymer, at~ may also contain foam boosters such as the alkanolamide (Ex~nple 1). The ternary mixture of alkyl sulfate, alkyl ether sulfate and betaine is disclosed here in (column 7) as a control concentrate for testing the effectiveness of the conditioning shat~oo containing the zwitterionic polymer con-ditioning agent.
m e prior art also discloses the use of hydroxyalkyl ethers of guar gum (a galactomannan gum) as thickening agents in pr mting pastes, paint dispersions and explosive slurries as shown in U. S. Paten-ts No. 3,748,201 and No. 3,700,612. However, the dis-closed compositions do not include liquid detergent compositions.
me Jaguar catalogue by Stein-Hall and Company, Inc., dis-closes hydroxypropylated guar gum derivatives useful as thickening agents. Guar gum is chemically classified as a galacto~annan, is a high molecular weight car~ohydrate polymer or polysaccharide made up of many mannose and galactose units linked L816S;;: ~
, I
.
koge~her (pag~ 5 o:E c~talogu~ ~a Japa~ Pa~e~t No~, 7~ 20j202 and 20,203 ~197~) by llhita~a dl~o' o~e the preparatio~ Or hydroxypropyl ~ug~r or gluco~ and lt3 u~e as ~ build~r ~or det~rgsnts; arld ths prep~ra tion o~ hydroxyethyl ~taroh or hydrox~propyl a~nylo~e and it3 UBe as a ~oll redap~itiQn irlhlbitor ~or dotergsnt~ 9 ~aid deter- ¦
gent compoa~tion comI)rl~1n~; a f~odium ~alt o:~ cv~onut alcohol sul~ata a~ter~ aodlum oarbonnte arld 30di~ ulr~t~O The parti- ¦
cular e~Qmple cit~d in ths~e pat~n~s înd1cates th~t wlth th~ I
ln~ ohol ~ul~at3 sur~actant, the traditio~l builder, kripo~phosph~Lta can ba replacad by hydro~rpropyl gluco~e and ~ inta~n th~ dokerg~ncy o~ the oomposition. Tho particul~r ¦
build~r sub~tituta3 mentioned her~in are hydrox~ralkyl ~ethyl9 propyl and butyl) ethers o~ mono- and di~saccharlde~O ~aowover, thera i~ no msntion herein Or guar gum or gu~r gum deri~atl~e~
nor Or ~oAm utabili ~tivn~
ll ; ~9~ 1.
It ha~ now b~en found that the ~ddition of ~me.ll amount~ !
Or a nonionio hydrox~propyl gu~r gum dariYat~Y~ ~OoOl~ ) to g.
light duty llquid d~tergenk comprising a tornary mixturo o~ ~ ¦
n~cyl e~h~no~r eth3r ~ul~a~e~ an alkyl ~ul:~t0 and a betaine, .
.
~ 4_ ~
Significantly improves the foam stability, cleaning efficiency and consistency of said liquid detergent.
Accordingly, the present invention provides a light duty, liquid detergent composition consisting essentially of between about 0.1% -to about 1.0% by weight, preferably between about 0.1% to about 0.6% by weight, of a nonionic hydroxypropyl guar gum derivative in an aqueous vehicle containing a maximum of 40% by weigh-t of a detergent active system comprising a mix-ture of a water-soluble salt of an anionic C8-Cl8 alkyl ethenoxy ether sulfate surfactant containing l to 12 ethenoxy groups in the molecule and a water-soluble salt of a C8-Cl8 alkyl sulfate surfactant, the weight ratio of said alkyl sulfate to said alkyl ethenoxy ether sulfate being from 1:29 to 29:1, and 2% to 5% by weight of a zwitterionic betaine surfactant of the formula:
lR2 Rl - N - COO
wherein Rl is an alkyl group having lO to 20 carbon atoms or the amido radical o H
Il 11 R - C -- N - (CH2) wherein R is an alkyl group having 9 to l9 carbon atoms and a is an integer from l to 4; R2 and R3 are Cl-C3 alkyl; and R4 is an alkylene or hydroxyalkylene group having l to 4 carbon atoms and, optionally, one hydroxyl group; said composition exhibiting enhanced foaming properties as compared with the same composition without said nonionic guar gum.
In another aspect, the present invention provides a method of preparing the liquid detergent as defined above, which comprises the steps of first preparing an aqueous solution of the ternary mixture of surfactants by mixing a-t a temperature up to a maximum of 100C; thereafter slowly adding said guar gum in the foYm cf particles having a slze such that a minimum of 90% passes through a 140 mesh U.S. standard sieve in the presence of agitation; and continuing said agitation until said guar gum is solubilized therein.
The novel liquid detergent composition preferably contains a reduced amount of detergent active ingredients and has improved foaming and cleaning performance.
Preferably the invention attemp-ts -to provide a novel liquid - 5a -,!, ---- . A
detergent with enhanced foaming properties and a viscosity oE at least 100 centipoises, comprising the ternary mixture of an alkyl ether sulfa*e, an alkyl sulfate and a betaine.
The invention will be further set forth in part in the des-cription which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention.
Broadly, the present invention is a novel light duty liquid detergent composition comprising a ternary mixture of the surfactants alkyl ethenoxy ether sulfate, alkyl sulfate and betaine and about 0.01-1%, prefera~ly 0.1 - 0.6% of a nonionic hydroxypropyl guar gum derivative.
Accordingly, the present invention relates to a light duty liquid detergent composition having good foam stability consisting essentially of 0.01 to 1%, preferably 0.025 - .6% and most preferably 0.1 to 0.6% by weight of a nonionic hydroxypropyl guar gum derivative, iJI an aqueous vehicle containing a maximum of 40%, preferably a maximum of 35% by weight of a detergent active system comprising a water soluble ternary mixture of a C8-C18 alkyl ethenoxy ether sulfate, a C8-C18 alkyl sulfate and a betaine. Formulations containing as low as 22%
active ingredients are capable of maintaining foaming and cleaning performance in the presence of small amounts of the hydroxypropyl guar gum derivative.
The foam booster utilized in instant invention which also functions as a thickening agent is a nonionic hydroxypropyl guar gum derivative. Aforesaid derivative is prepared by hydroxy-propylating the guar molecule, which is a straight chain mannan branched at quite regular intervals with single membered gal-11~l165~ . ~
actio~ urllt~ on ~ltarn~.};e manrlos~ un:Lta ~5 a~ discloa~d in arore-sald Jaguar catalogue by the Steln-:Hall Comp~ny" Tha hydro~
proyylated guar gum rler:Lvatlva~ utlliæed ln the pregent lnvcIl~iou i ara water ~loluh~ , dr~ partî.culAte~, earbohydrata material~ havlng a part:Lcle ~i.ze su-.h ~:hak a mlnimu:m of 90,~ pa~e~ throu~h a 140 ma~h U~ S,, ~3t;~ndard 9i~9ve amd en MS (molr3a o:~ aubst:ltutlon) value ¦
in the range of V~92 to oO8, prefsxably :rxom 0~3 to 0.~5"
Genelrally,, 1~ aqlleou~ solu~lon~; ther~or hav~ ~ p~ ln the range o:~ 5 to 11 and a vl~co~ tyr of about 3000 to 4000 cps m~asured on ~ Brookrl01d nvF~ v:l~r,omet~r u~ing ~ NoO 3 spindle rotatin~
at 20 RPM at ~ tempa~ature o~ 25G, and the resul~ant ~olution~
aro thixotroplc as v:Lscoslty changes with ~hearlng 3tres3 Suitable hy~droxypropyl guar gum dcrivatives may be obtainod rrom Steln-~all Company under tha name~ Jaguar~R~HP 6û9 Jaguar( ~I~P
f~d ~aguar(~ P 119 wl~lch u~clually co~ta~n 5~13,~" pre~erab~y 8-10,~ Or mo~tura ~ r~c~ived~ j The, hydroxypropyl Kuar gl3m darlYat,iv0~ ~re kno~n ~o ha~re thlckaning prop~r~les in aquoou~ solutionss, ~lowe~rer, a thick~ning agorlt i~ no~t generally known to improve the ~oaming propert~a3 o~
aqueou~ 301ution~ contalning sur~actants, wh~rea~ the hydroxy~ ¦
propyl guar g~n darlvative ds~ined above~ both increase~ tho viacosity of a detargent ~ormulatlon as w~ll ag improve~ it~
foamin~ per~`o~Rnco~ Sinc0 ~o~m volume and fo~n stablllty are o~tcn u~ed to gauga tho cleaning er~-l cisncy~ it is desirable to rormulate a datergent compo~itlon with improved ~o~ming pcr~or~anceO
Another advantage3us ~e~ture o~ instant novcl detergent com- ¦
po~itions contalning ~aid hydro~ypropyl guar gum deri~ativa~ !
i~ that thls roam boo~tor has a thlckenin~ ~unction which allows reduc~lon in the activo ineredlent level Or ~ rormulationr yet m~int0,1~ os~n p~r~ormanee~ thl3r~b~ e~ct:lng ~ ~a~lng ln the co~t o~ m~k~g thls :Light duty liquicl deter~e~t produetO
~111 ~other ~d.v~ntP.~ o '~ ~ ~h~t ~mQller ~mount~ Or thls ~v~m boo~lter (0"01-1% ~18 oppos~d to 3D6~ are n~eded ~omp~red to ~o~
~e3lt~0nal ~o~a boo~ter~9 ~urgher rsdu~ing the ~oat Or ~aid d~t~rgont produat "
It ha~ addlt$onally boen ~ou~d that th0 nonionlc hy-dro~rpropyl guar gum deriY t~.Yo nmcl;iona ~9 a fQ~ ~t,~bllizor ror certain detergent ~y3t,e~ nd ha~ no e~re~t on the ~oam per~ormallca o~ o~her ~y~tems such a~ llnaar alkyl b~nzen,3 ~ul~o~-~t~/sllcyl ~th~r ~ulrake, or lirl~ar alkyl be~ene ~ulronate/~
other oul~te/l~llrlo-~yristio mono~thanol aD~deO Acoordingly, it h~s been round that the p~rtiuular detergent ~y~tem ~heroisl ¦
~oar~ p~rro~mance 1~ ~ignifi~antly impro~0d by the presence o~ ¦
~a~d ~onionl~ guar gu~ dsri~rativ~ i8 a ternary mixture co~pr~n~ I
8~ alk~l ~theno~:y ether sul~ate, a~ alkyl sulf~t ~ and a bet~ine O
Thu~ it ls e~ldant that the ~pec~fi~ deterg~nt ~ystem utll~ed wlth the nonionic hydro~propylated gu~r ~;um derlvati~0 is orltl~al in ordar to obtain a l~ght duty liquid detergent ha~ing ~igni~icantl~ impro~ed ~oam porformulce.
m~ e~ential oo~ponsllt~ Or thi~ llght du~y llq~aid dat3:rgent e~prlse a water s~luble C8-C18 alkyl etheno~ ether ¦.
sul~ate ~nd an ~mmonium or alk~li metal ~alt o:e a C8 Cl8 alkyl sulrat0, both o~ w}l~ah ~ra ~ioni~ ~Ur~G~nt~; and a beta~e, . ' , . I
prerer~bly ~ fl~ldobatalna, which ~ 3 zwitterloxlic ~urr~lct~nt, dis~olved in 1n aq,ueou8 vehlcl~ " Th~ betai~e ~ompo~nt consti-t;Ut39 about 2~-3,~ and ~ot more th~n 5,9~ by ~rei~ht o~ tha llquld d~tergerlt ~ompo~itlon,9 a~d tho snionlc ~urfactants 50~stituli0 prerer~bly ~bout 20~ 30% by w~ight Or the llquid compo~ltlon ~ith the ratio o~ alkyl ~th~no~r ether ~ulra~s to aL~yl ~ul~a~e b~g noxl~criti¢al,, ~atios o~ 1/29 ~o 29/1 o~ the ~lkyl sulr~te to alkyl eth~no~ her sulrate, and pre~erably 17/13 to 12~J8 r~p~ctl~ , may be utilizad in pre~nt in~ention l~e anionlc 3ur~au~ants ~hich mEIy ba ussd ln the det0rgent co~rposi tion o~ the invention include at lea~t one ~ur~act~t ~lected ~ror~ the group &onsi~t$ng Or water noluble ~lt~, a.gO, the ~odium~ potass~um" ammoniun~ ~nd alkanolR~o ~alt~, Or a CB-C18 ~lkyl sul~t~ and prerer~bly C12- C16 and C12-C15 alkyl sulr~t~s. 9 ~uch a~ the lau~yl ~ulfates" ~rri~tyl 3ul~ate~ Qnd the lîke 9 and at .l~a~t one ~ur~actant ~elocted ~rom the group con~i3ting o~ the water ~oluble alkyl ethenoxy ~ther sulrAte~ ha~r~ng the general ~o:~mula R(C~i2CE~20 ) oso3h , I
whereln R ~ an alkyl radi~al ha~ 18 ~arbon ~tom~, n ~ a~ ¦
integer ha~in~ th3 ~alu~ oî 1-12 and pro~r~bly 1-5,, ~
an alk~ll matal, ar~oniu~ or ~:lkylolammonium" suLch as lauryl trietheno~ th~r 8ul~at3 " tridecyl alcohol tr~ ~theno:~ ether sulf~t0, and the llke~ Other anionio ~urract~ts ~uch as the . ~ , ~odium lauryl ~arco~i.nato~ 9 alkyl ~ul~onake3 3 alkyl bonzeno sulfonate~ and laur~l alcohol ~ul~ate s)r the liko cannot b0 :~ub~3tituted :eor ei th~r o~ the ~bov~ ~wo group~ Or a~ionîc {~ur-r~Otant~ a~ a cornponnnt ~ the terll~ry deterg~nt ~y~tem o~ pre~ont I
. lnventio~ o produce a liqu$d product with impro~ed foam p~r- j ~o~anC~- !
T~19 bet~ine component o~ i~st~t llquid det~rgent cor~positlon ha~ tho gen~ral ~ormuls:
l 1 4 F~3 wharoin R~ lkyl group hsving lO to about 20 carbo~ atoms, pr~rerabl~ 12 to 16 c~rbon atom~ or the ~m~ do radiS~al .
0~ ' R-&-~-(G~2) _ where$n R ~8 Rn alkyl group haYi~g about 9 to 19 carbon atoms and ~ la the integor 1 to ~9 R2 ~nd R3 are e~oh ~lkyl eroup~
havlng 1 3 oarbons snd pro~ersbly 1 Gsrbon; R4 19 an alkylene ~.~ '.' . -10-11~1.65~
or :hydroxyalk~lene group ha~.~g ~rom 1 ~o 4 carbon ato~ and~, optlonally7 orle hydro:~cyl group~, Typical Qlkyld~oth~l betaines in~lude dec~l dlm~ h~l betaln~ or 2~DI decyl-Ia9N-dim~khyl~
~onio~ acet~t~ ~oco dimeth~yl bot~l~s or 2~ 0~0-~911-diDIethyl-ammonlo) ac~teD myrl~tyl dlmothyl beta:~ne9 palmityl d~u~thyl bet~ine; ~auryl d~ thyl bet~ e g ~tyl dlm~thyl bet aine " ~tearyl almeth~l bet~ e~ etG~ The ~m:Ldobotaine~ simllarly lnclude coGoam~doeth~l betaina9 eocoamidopropyl bet~in~,~ and the lik~ao All o~ the afore~aid conapc~n~rata ln thl~ ligh~ duty detorgent are ~r~t~r ~oluble and remal~ wat9r solubl3 dur~g ~tor~ee9 Thi~ partl ~ular cQmbi natlon Or anlo~lc sulrs.te~ ~d bsta~ne provldes a ternary detePgo3lt ~y~tem which ~oa~to with th0 nonionio hydro~propyl g~ar ~5U~ derl Yati~3 to pro~uce ~ ;
li~uid d~tePge~ cvmpo~ltion with de~irabl~ fo~ming~ roam ~t~b~
ity, dster~l~e prop~rtias ~ w81~ a~ d~ir~bl~ co~l~y chaP~t- ¦
er:~tios~, m~ re~ult~nt homog3neous liquld detergent e~hiblts suporior foam p0rrormanGe a~ co~p~red ~o ~he same detergent ~om- !
posltion wlthout th~ no~ionlo guar gwn deriYatiLY~ Rg -~hown ln ~he ~ollowing Table I,, usl~g ~he T~rgoto~etor ~o~m te~, ~8r9i~
soiled pl~hota [1" diamot~r R:~d l/Bn hlg~ ), e~h cont~
on~ gr~m Cri300 SOllg ~r~ ~dded in tlmed in~r0mDnts ~eYe~y . I
minutes), to a 0.1% aqueous test solution of 150 ppm hardness as CaC03 (Ca/~lg = 2/1), and 100 ppm alkalinity as HC03 , at a temperature of 50C, and agitated at 75 rpm for one minute. The foam level is recorded when the agitation is turned off after each addition of planchets, and the -total number of planchets required to kill the foam is recorded.
TABLE I
Number of Planchets Detergent Formulation Washed 1. 17/13/3 AEOS/ALS/Betaine 19
2. 17/13/3/0.3 AEOS/ALS/Betaine/Jaguar HP-60 22
3. 12/8/2 AEOS/ALS/Betaine 16
4. 12/8/2/0.5 AEOS/ALS/Betaine/Jaguar HP-60 19 AEOS = Ammonium C12-Cls Alkyl ~2 4 )3 ALS = Ammonium Lauryl Sulfate Betaine = Coco Amido Propyl Betaine Jaguar HP-60 = hydroxypropyl guar gum derivative ~9% H20) In addi~ion, the addition of the Jaguar HP-60 to formula 3 increased its viscosity by 18 times,from 22.5 to ~07.5 cps using a Brookfield Viscometer RVF, Spindle No. 1, 20 RP~I and a solution temperature of 25C. Furthermore, soil removal perform-ance, as an evaluation of cleaning efficiency was not adversely affected by the presence of said guar gum derivative thickening agent as shown in Table II, using a static soaking test. A soil-containing planchet (0.5 g soil), as in the afore defined foam performance test, which has been aged for 1 1/2 min. is soaked for 30 sec. in a warm ~50C) aqueous test solution of 150 ppm hardness and 100 ppm alkalinity and containing 0.1% detergent and is immediately transferred to an ice-water bath to stop the soil removing process. The unremoved soil is solidified on the planchet which is air dried and % SR (soil removal) is calculated as:
Amount of Soil Removed % SR = X 100% .
Original Amount of Soil TABI.E II
The Effect of Thickening Agent on Cleaning PerEormance Formulation Crisco % SR (Soil Removal) Tallow Keen (shortening) 1 94.4 77.2 50.6 2 96.0 78.0 50.6 3 94.8 80.4 52.6 4 96.6 78.4 51.6 6~i2 In addition to the previously mentioned essential constituents of the light duty liquid detergent, one may also employ normal and conventional adjuvants, provided they do not adversely affect the properties of the detergent. Thus, there may be used various coloring agents and perfumes; ultraviolet light absorbers such as the Uvinuls, which are products of CAF
Corporation; preservatives such as formaldehyde or hydrogen peroxide; pearlescing agents and opacifiers; pH modifiers;
hydrotropes such as ammonium or sodium xylene sulfonate, solubi-li~ers such as, ethyl alcohol; citric acid; etc. The proportion of such adjuvant materials, in totalg will normally not exceed 15% of the detergent composition. The percentages of most of such individual components will be a maximum of 5% and preferably less than 5%.
The present light duty liquid detergents such as dishwashing liquids are readily made by simple mixing methods from readily available components which, on storage, do not adversely affect the entire composition. However, it is essen-tial that the guar gum derivative be added slowly and with agitation to the preformed aqueous solution containing the ternary surfactant system. The ternary surfactant system is prepared by adding with agitation an aqueous solution of alkyl sulfate and then betaine to an aqueous solution of an alkyl ethenoxy z ether sulfate which may have been previously mixed with an agent such as ethyl alcohol and/or xylene sulfonate to assist in solubilizing said surfactants, and then adding with agitation the rest of the water to form the aqueous solution of the ternary surfactant system. The use of mild heating (up to 100C) assists in the solubili~ation of the surfactants. The viscosities are adjustable by changing the total percentage of active ingredients and by modifying the percentage of the thick-ening-foaming agent, hydroxypropyl guar gum derivative. In all such cases the product made will be pourable from a relatively narrow mouth bottle (1.5 cm. diameter) or opening, and the viscosity of the detergent formulation will not be so low as to be like water. The viscosity of the detergent should be at least 100 cps at room temperature, and up to about 1,000 centi-poises. Its viscosity may approximate those of commercially acceptable detergents now on the market. The detergent viscosity and the detergent itself remain stable on storage for lengthy periods of time, without color changes or settling out of any insoluble materials. The p~l of this formulation is preferably neutral, about 6 to 8.
Ihese products have unexpectedly desirably proper-ties. For example, the foam quality is superior to standard light duty liquid detergents while using a smaller active in-gredient content.
~; ~L18~S5Z
~r q~ne rollo~rlng e~mple~ are merely ~llu~tr~t~va o~ th~
invent iO:~l and are ~ot to be co~strued a~ l~ting th~reo~, O
. . .
~P 601 O OD~ g Citri~ acld O 1~,0 g Deionized b~er 36~06 g 34~56g All~l e~her ~ulrate ~AEOS~ 58D3% QI) 20"6 g 2V~6 g E~hyl al~ohol 5 g 5 g ~mmonlur~ ~lene sul~onate l40g AI) 5 g 5 g ~onium l~uryl 9U~ t;e ~L~" 30~ AIJ` 26,367 g 26.h78 Fooo~ldop:; ylbctaine ( 3 0% AI ) 6. 67 6 6. 67e 1 nonivnic hydro~propyl ~uar gu~ deriv~tlve (9% H20) 2 ammonil.~m G12-Cls ~3~yl ~C~40)3 9ul~at~
;, ~ he ratlo o~ th~ sur~a~tant~ ~EOS~LS~fBetaine i9 l~/B/20 ~ e ~OSg alcohol and ~o~ium xyl~n~ sul~enate ~rs ml~c~d tog~ther~ until ho~ogen~ou3 ~d ~lear,~ at room kempsrature . . I
.
I
or at ~llghtly eleYate~ temperaturo9 la max~mura O:e 100C)~ ~he ~onium lauryl .sul~ato and the bet~lna are then added with agitat:lon9 ~ollowed by th~ add~tlo~ e~ the wa; ~r9 ~hile a&itating the mi~ture to ~orm an agueou~ ~olu~ orl o~ the t~rnarg ~ur~ctant sy~emç, ID. ~ple 29 the guar gum deri~at~vs and citric a~
~h~ch a~ t9 lrl the dl~olution O;r ~ald guar g~nj, are addod l~tly and 810~1y wikh agitQtionO Th~ re~ult~t produ~t thi~ken~d ~olutlon with no sign o~ particulata s-lspan~ion or pra~ipit ~ iO~o Tergo-tometer ~oam t9~t9 on Cri9co ~oil uslng ta~t ~olutlons Or ~le3 ~ d 2 showed tha-t 16 planchet~ were wa~hed with the rormulstiQn o~ E~ple lg a~d 19 pl~n6hot~ ~sre ~a3hed with ~CQl0 2 ~con~aining the guar g~ deriY~ive)~
w~ich represeIltq a ~ ant impro~ement ~ the roamlng psr~
~o~nance ~the ~s~am la~ted until pla~chet 19~ It waq ~dditlo~
a~ oted that 80il~1 in th~ buckat~ conta~ning th~ ~o~po~itio~ ~
of 13x~mple 1 (~lthout th0 guar g~ deri~atiYe) ~tart3d ~o.~ppe~r on the top o~ the ~olution ~a~t~r ~a~ter th~ additloll o~ the 8~h planchet~ than iFl the bucket~ ~ontaining the ~olution o~
33~a~ple ~ l~e vls~oRit~ o~ l~nple 1 ls 2205 centipoi~o~
hîch is too ~at~ry îor a ~u~table oon~umer product; ~herea~
the vi3009ity 0~ }3~ipla 2 i~ 407~5 c~ntipoises9 ~ich la withln 1~ r go o~ ult~ble li~ht duty llquld dete~ gont product.
~17-11165i2 Yariation~ ~n the abov0 ~ormulation~ may be made6, For e:c~mple, other ~lkyl ~ulr~to~ may bo 3ub~tltutcd for t~e ~mnonium l~uryl ~ulrat~ ~uch a~ aodlum l~uryl sul~ter pota~lum lauryl ~ulfate," the Qmmor~ odl~ ~d pot~ium myr~tyl ~ulrates and the likeO 51mllarl~J othor ~l~yl ethenox~ e~her sulr~es m~y b~ ~u~b~tikutod. ~or th~ ~mmonium ~lkyl eth~no~ ether ~ulrate such a~ 80d.1u!m ~nd pot~sium alkyl ethono~ ather sul~at~ a~d the like. Lîkewi3e, oth~r b~tainea may be substituted ~or th0 cocoamidopropyl b0taln~ ~uch R9 cocoamidoothylbot~ine~ cocobota~neI
~d the like O
In addltion, the smount~ of each of tha anlonlc com~
ponents ma~ b~ ~ariad pro~lded th3 aum to~l o~ ~aid ~peoi:~ic group~ o~ aniollle ~urf~tant~ ~on~tttutos abQut 20-30,~ by weight o:~ the ~ompo~ition. The ~mount O~e betaine may al~o be varied up to a maxlmum o~ aboul; 5~ by weight o~ the composition~ The amount o~ the nonionic hy~lro~ypropyl guar gwn d~rivatiYo ~y al90 be Yarled betw~on ODO1 to about 1,~ and prefor~bly Ogû25-0~,6%
by wei~ht o~ the ~ompo~ition" d~pending OI1 the d~3ir0d vi9009it9 o~ the r~sultant l~ d ~et~re:~t ~r~duct.. ~ CO~DO~ ~ con-taining 1% of said guar gum der~ va~ive has been :eound ~o resultin ~oo vi~ou3 a product~
The i~sntion has bsan des crlb0d wlth respact to various examples and embodiments but is not to be limit~d to Il 11~165~:
the~e be~auso it; ls e~ident th~t one Or skill ~Ln the art with th3 pre~nt ~pplicatio~ berore hi~ wlll b~ ~ble to utllize ~ub~titut~ ~.nd aqul~alsnt~ thout ~par~l~g from ~he ~plrl~
o~ the.l~ntionO
., . .
ll
Amount of Soil Removed % SR = X 100% .
Original Amount of Soil TABI.E II
The Effect of Thickening Agent on Cleaning PerEormance Formulation Crisco % SR (Soil Removal) Tallow Keen (shortening) 1 94.4 77.2 50.6 2 96.0 78.0 50.6 3 94.8 80.4 52.6 4 96.6 78.4 51.6 6~i2 In addition to the previously mentioned essential constituents of the light duty liquid detergent, one may also employ normal and conventional adjuvants, provided they do not adversely affect the properties of the detergent. Thus, there may be used various coloring agents and perfumes; ultraviolet light absorbers such as the Uvinuls, which are products of CAF
Corporation; preservatives such as formaldehyde or hydrogen peroxide; pearlescing agents and opacifiers; pH modifiers;
hydrotropes such as ammonium or sodium xylene sulfonate, solubi-li~ers such as, ethyl alcohol; citric acid; etc. The proportion of such adjuvant materials, in totalg will normally not exceed 15% of the detergent composition. The percentages of most of such individual components will be a maximum of 5% and preferably less than 5%.
The present light duty liquid detergents such as dishwashing liquids are readily made by simple mixing methods from readily available components which, on storage, do not adversely affect the entire composition. However, it is essen-tial that the guar gum derivative be added slowly and with agitation to the preformed aqueous solution containing the ternary surfactant system. The ternary surfactant system is prepared by adding with agitation an aqueous solution of alkyl sulfate and then betaine to an aqueous solution of an alkyl ethenoxy z ether sulfate which may have been previously mixed with an agent such as ethyl alcohol and/or xylene sulfonate to assist in solubilizing said surfactants, and then adding with agitation the rest of the water to form the aqueous solution of the ternary surfactant system. The use of mild heating (up to 100C) assists in the solubili~ation of the surfactants. The viscosities are adjustable by changing the total percentage of active ingredients and by modifying the percentage of the thick-ening-foaming agent, hydroxypropyl guar gum derivative. In all such cases the product made will be pourable from a relatively narrow mouth bottle (1.5 cm. diameter) or opening, and the viscosity of the detergent formulation will not be so low as to be like water. The viscosity of the detergent should be at least 100 cps at room temperature, and up to about 1,000 centi-poises. Its viscosity may approximate those of commercially acceptable detergents now on the market. The detergent viscosity and the detergent itself remain stable on storage for lengthy periods of time, without color changes or settling out of any insoluble materials. The p~l of this formulation is preferably neutral, about 6 to 8.
Ihese products have unexpectedly desirably proper-ties. For example, the foam quality is superior to standard light duty liquid detergents while using a smaller active in-gredient content.
~; ~L18~S5Z
~r q~ne rollo~rlng e~mple~ are merely ~llu~tr~t~va o~ th~
invent iO:~l and are ~ot to be co~strued a~ l~ting th~reo~, O
. . .
~P 601 O OD~ g Citri~ acld O 1~,0 g Deionized b~er 36~06 g 34~56g All~l e~her ~ulrate ~AEOS~ 58D3% QI) 20"6 g 2V~6 g E~hyl al~ohol 5 g 5 g ~mmonlur~ ~lene sul~onate l40g AI) 5 g 5 g ~onium l~uryl 9U~ t;e ~L~" 30~ AIJ` 26,367 g 26.h78 Fooo~ldop:; ylbctaine ( 3 0% AI ) 6. 67 6 6. 67e 1 nonivnic hydro~propyl ~uar gu~ deriv~tlve (9% H20) 2 ammonil.~m G12-Cls ~3~yl ~C~40)3 9ul~at~
;, ~ he ratlo o~ th~ sur~a~tant~ ~EOS~LS~fBetaine i9 l~/B/20 ~ e ~OSg alcohol and ~o~ium xyl~n~ sul~enate ~rs ml~c~d tog~ther~ until ho~ogen~ou3 ~d ~lear,~ at room kempsrature . . I
.
I
or at ~llghtly eleYate~ temperaturo9 la max~mura O:e 100C)~ ~he ~onium lauryl .sul~ato and the bet~lna are then added with agitat:lon9 ~ollowed by th~ add~tlo~ e~ the wa; ~r9 ~hile a&itating the mi~ture to ~orm an agueou~ ~olu~ orl o~ the t~rnarg ~ur~ctant sy~emç, ID. ~ple 29 the guar gum deri~at~vs and citric a~
~h~ch a~ t9 lrl the dl~olution O;r ~ald guar g~nj, are addod l~tly and 810~1y wikh agitQtionO Th~ re~ult~t produ~t thi~ken~d ~olutlon with no sign o~ particulata s-lspan~ion or pra~ipit ~ iO~o Tergo-tometer ~oam t9~t9 on Cri9co ~oil uslng ta~t ~olutlons Or ~le3 ~ d 2 showed tha-t 16 planchet~ were wa~hed with the rormulstiQn o~ E~ple lg a~d 19 pl~n6hot~ ~sre ~a3hed with ~CQl0 2 ~con~aining the guar g~ deriY~ive)~
w~ich represeIltq a ~ ant impro~ement ~ the roamlng psr~
~o~nance ~the ~s~am la~ted until pla~chet 19~ It waq ~dditlo~
a~ oted that 80il~1 in th~ buckat~ conta~ning th~ ~o~po~itio~ ~
of 13x~mple 1 (~lthout th0 guar g~ deri~atiYe) ~tart3d ~o.~ppe~r on the top o~ the ~olution ~a~t~r ~a~ter th~ additloll o~ the 8~h planchet~ than iFl the bucket~ ~ontaining the ~olution o~
33~a~ple ~ l~e vls~oRit~ o~ l~nple 1 ls 2205 centipoi~o~
hîch is too ~at~ry îor a ~u~table oon~umer product; ~herea~
the vi3009ity 0~ }3~ipla 2 i~ 407~5 c~ntipoises9 ~ich la withln 1~ r go o~ ult~ble li~ht duty llquld dete~ gont product.
~17-11165i2 Yariation~ ~n the abov0 ~ormulation~ may be made6, For e:c~mple, other ~lkyl ~ulr~to~ may bo 3ub~tltutcd for t~e ~mnonium l~uryl ~ulrat~ ~uch a~ aodlum l~uryl sul~ter pota~lum lauryl ~ulfate," the Qmmor~ odl~ ~d pot~ium myr~tyl ~ulrates and the likeO 51mllarl~J othor ~l~yl ethenox~ e~her sulr~es m~y b~ ~u~b~tikutod. ~or th~ ~mmonium ~lkyl eth~no~ ether ~ulrate such a~ 80d.1u!m ~nd pot~sium alkyl ethono~ ather sul~at~ a~d the like. Lîkewi3e, oth~r b~tainea may be substituted ~or th0 cocoamidopropyl b0taln~ ~uch R9 cocoamidoothylbot~ine~ cocobota~neI
~d the like O
In addltion, the smount~ of each of tha anlonlc com~
ponents ma~ b~ ~ariad pro~lded th3 aum to~l o~ ~aid ~peoi:~ic group~ o~ aniollle ~urf~tant~ ~on~tttutos abQut 20-30,~ by weight o:~ the ~ompo~ition. The ~mount O~e betaine may al~o be varied up to a maxlmum o~ aboul; 5~ by weight o~ the composition~ The amount o~ the nonionic hy~lro~ypropyl guar gwn d~rivatiYo ~y al90 be Yarled betw~on ODO1 to about 1,~ and prefor~bly Ogû25-0~,6%
by wei~ht o~ the ~ompo~ition" d~pending OI1 the d~3ir0d vi9009it9 o~ the r~sultant l~ d ~et~re:~t ~r~duct.. ~ CO~DO~ ~ con-taining 1% of said guar gum der~ va~ive has been :eound ~o resultin ~oo vi~ou3 a product~
The i~sntion has bsan des crlb0d wlth respact to various examples and embodiments but is not to be limit~d to Il 11~165~:
the~e be~auso it; ls e~ident th~t one Or skill ~Ln the art with th3 pre~nt ~pplicatio~ berore hi~ wlll b~ ~ble to utllize ~ub~titut~ ~.nd aqul~alsnt~ thout ~par~l~g from ~he ~plrl~
o~ the.l~ntionO
., . .
ll
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A light duty, liquid detergent composition consisting essentially of between about 0.1% to about 1.0% by weight of a nonionic hydroxypropyl guar gum derivative in an aqueous vehicle containing a maximum of 40% by weight of a detergent active system comprising a mixture of a water-soluble salt of an anionic C8-C18 alkyl ethenoxy ether sulfate surfactant containing 1 to 12 ethenoxy groups in the molecule and a water-soluble salt of a C8-C18 alkyl sulfate surfactant, the weight ratio of said alkyl sulfate to said alkyl ethenoxy ether sulfate being from 1:29 to 29:1, and 2% to 5% by weight of a zwitterionic betaine surfactant of the formula:
wherein R1 is an alkyl group having 10 to 20 carbon atoms or the amido radical wherein R is an alkyl group having 9 to 19 carbon atoms and a is an integer from 1 to 4; R2 and R3 are C1-C3 alkyl; and R4 is an alkylene or hydroxyalkylene group having 1 to 4 carbon atoms and, optionally, one hydroxyl group; said composition exhibiting en-hanced foaming properties as compared with the same composition without said nonionic guar gum.
wherein R1 is an alkyl group having 10 to 20 carbon atoms or the amido radical wherein R is an alkyl group having 9 to 19 carbon atoms and a is an integer from 1 to 4; R2 and R3 are C1-C3 alkyl; and R4 is an alkylene or hydroxyalkylene group having 1 to 4 carbon atoms and, optionally, one hydroxyl group; said composition exhibiting en-hanced foaming properties as compared with the same composition without said nonionic guar gum.
2. A liquid detergent composition in accordance with claim 1 wherein the mixture of said alkyl sulfate and said alkyl ethen-oxy ether sulfate constitutes about 20-30% by weight and the betaine constitutes about 2-5% by weight of the composition.
3. A liquid detergent composition in accordance with claim 1 wherein said guar gum constitutes 0.1% to 0.6% by weight of the composition.
4. A liquid detergent composition in accordance with claim 1 wherein the zwitterionic surfactant is an amidobetaine.
5. A liquid detergent composition in accordance with claim 1, wherein the mixture of anionic surfactants constitutes about 20-30% by weight of the composition and said surfactants are present as an alkali metal, ammonium or alkanol ammonium salt.
6. A liquid detergent in accordance with claim 1, wherein the aqueous vehicle contains in addition about 1% by weight of citric acid.
7. A method of preparing the liquid detergent in claim 1, which comprises the steps of first preparing an aqueous solution of the ternary mixture of surfactants by mixing at a temperature up to a maximum of 100°C; thereafter slowly adding said guar gum in the form of particles having a size such that a minimum of 90% passes through a 140 mesh U.S. standard sieve in the presence of agitation; and continuing said agitation until said guar gum is solubilized therein.
8. A method in accordance with claim 7 wherein said aqueous solution of the ternary mixture of surfactants is prepared by mixing aqueous solutions of said alkyl sulfate and said alkyl ethenoxy ether sulfate surfactants followed by the addition with agitation of said betaine and then by adding with agitation the rest of the water.
9. A method in accordance with claim 7 wherein said aqueous solution of said ternary mixture of surfactants further includes a solubilizing agent and up to 1% by weight of citric acid is added slowly together with said guar gum to facilitate dissolution of said gum.
10. A liquid detergent composition in accordance with claim 1 wherein the nonionic hydroxypropyl guar gum derivative is between about 0.1% to about 0.6% by weight of the composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US29064081A | 1981-08-06 | 1981-08-06 | |
| US290,640 | 1981-08-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1181652A true CA1181652A (en) | 1985-01-29 |
Family
ID=23116929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000408825A Expired CA1181652A (en) | 1981-08-06 | 1982-08-05 | Foam enhancing agent for light duty liquid detergent |
Country Status (18)
| Country | Link |
|---|---|
| AU (1) | AU549004B2 (en) |
| BE (1) | BE894036A (en) |
| BR (1) | BR8204607A (en) |
| CA (1) | CA1181652A (en) |
| CH (1) | CH651585A5 (en) |
| DE (1) | DE3227981A1 (en) |
| DK (1) | DK341082A (en) |
| ES (1) | ES514763A0 (en) |
| FR (1) | FR2511030B1 (en) |
| GB (1) | GB2103236B (en) |
| GR (1) | GR77266B (en) |
| IT (1) | IT1149341B (en) |
| MX (1) | MX156340A (en) |
| NL (1) | NL8203129A (en) |
| NZ (1) | NZ201338A (en) |
| PH (1) | PH20472A (en) |
| SE (1) | SE453399B (en) |
| ZA (1) | ZA825065B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8311854D0 (en) * | 1983-04-29 | 1983-06-02 | Unilever Plc | Detergent compositions |
| US4681704A (en) * | 1984-03-19 | 1987-07-21 | The Procter & Gamble Company | Detergent composition containing semi-polar nonionic detergent alkaline earth metal anionic detergent and amino alkylbetaine detergent |
| US4555360A (en) * | 1984-06-22 | 1985-11-26 | The Procter & Gamble Company | Mild detergent compositions |
| GB2172298B (en) * | 1985-03-01 | 1988-11-23 | Procter & Gamble | Mild detergent mousse |
| US5002680A (en) * | 1985-03-01 | 1991-03-26 | The Procter & Gamble Company | Mild skin cleansing aerosol mousse with skin feel and moisturization benefits |
| US5096608A (en) * | 1985-05-13 | 1992-03-17 | The Procter & Gamble Company | Ultra mild skin cleansing composition |
| US5064555A (en) * | 1985-12-02 | 1991-11-12 | The Procter & Gamble Company | Mild skin cleansing soap bar with hydrated cationic polymer skin conditioner |
| US4820447A (en) * | 1985-12-02 | 1989-04-11 | The Proctor & Gamble Company | Mild skin cleansing soap bar with hydrated cationic polymer skin conditioner |
| US4946618A (en) * | 1988-11-02 | 1990-08-07 | The Procter & Gamble Company | Toilet bar composition containing cationic guar gum |
| DE3910652C2 (en) * | 1989-04-01 | 1997-12-18 | Benckiser Gmbh Joh A | Surfactant mixture for use in foaming body cleansers |
| DE4040887C2 (en) * | 1990-12-20 | 1994-05-19 | Goldschmidt Ag Th | Process for the preparation of flowable aqueous dispersions of betaines |
| CA2137636A1 (en) * | 1993-12-22 | 1995-06-23 | Manilal Dahanayake | Surfactant compositions characterized by improved foam height |
| US5968493A (en) * | 1997-10-28 | 1999-10-19 | Amway Corportion | Hair care composition |
| EP0916720A1 (en) * | 1997-11-17 | 1999-05-19 | The Procter & Gamble Company | Anti-bacterial liquid dishwashing detergent compositions |
| US20170283748A1 (en) | 2014-09-10 | 2017-10-05 | Basf Se | Encapsulated cleaning composition |
| EP3426757A1 (en) | 2016-03-09 | 2019-01-16 | Basf Se | Encapsulated laundry cleaning composition |
| GB202014070D0 (en) | 2020-09-08 | 2020-10-21 | Alborz Chemicals Ltd | Polymorph |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3748201A (en) * | 1971-10-08 | 1973-07-24 | Gen Mills Chem Inc | Thickening compositions containing xanthomonas gum and hydroxyalkyl ether of guar gum |
| US3950417A (en) * | 1975-02-28 | 1976-04-13 | Johnson & Johnson | High-lathering non-irritating detergent compositions |
| US3996146A (en) * | 1975-08-01 | 1976-12-07 | Warner-Lambert Company | Clear shampoo formulation |
| DE2616800A1 (en) * | 1976-04-15 | 1977-11-03 | Henkel & Cie Gmbh | COSMETIC CLEANING AGENTS |
| US4246131A (en) * | 1978-11-20 | 1981-01-20 | Inolex Corporation | Low-irritant surfactant composition |
-
1982
- 1982-07-15 GR GR68760A patent/GR77266B/el unknown
- 1982-07-15 ZA ZA825065A patent/ZA825065B/en unknown
- 1982-07-19 SE SE8204378A patent/SE453399B/en not_active IP Right Cessation
- 1982-07-20 NZ NZ201338A patent/NZ201338A/en unknown
- 1982-07-27 MX MX193774A patent/MX156340A/en unknown
- 1982-07-27 DE DE19823227981 patent/DE3227981A1/en not_active Withdrawn
- 1982-07-28 PH PH27640A patent/PH20472A/en unknown
- 1982-07-30 FR FR8213370A patent/FR2511030B1/en not_active Expired
- 1982-07-30 DK DK341082A patent/DK341082A/en not_active Application Discontinuation
- 1982-08-03 GB GB08222424A patent/GB2103236B/en not_active Expired
- 1982-08-05 ES ES514763A patent/ES514763A0/en active Granted
- 1982-08-05 BE BE0/208755A patent/BE894036A/en not_active IP Right Cessation
- 1982-08-05 IT IT48945/82A patent/IT1149341B/en active
- 1982-08-05 CA CA000408825A patent/CA1181652A/en not_active Expired
- 1982-08-05 BR BR8204607A patent/BR8204607A/en unknown
- 1982-08-05 AU AU86765/82A patent/AU549004B2/en not_active Ceased
- 1982-08-05 CH CH4730/82A patent/CH651585A5/en not_active IP Right Cessation
- 1982-08-06 NL NL8203129A patent/NL8203129A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| SE8204378L (en) | 1983-02-07 |
| BR8204607A (en) | 1983-07-26 |
| NZ201338A (en) | 1985-09-13 |
| ES8306174A1 (en) | 1983-05-01 |
| GB2103236B (en) | 1985-06-19 |
| ZA825065B (en) | 1984-02-29 |
| PH20472A (en) | 1987-01-16 |
| DK341082A (en) | 1983-02-07 |
| ES514763A0 (en) | 1983-05-01 |
| BE894036A (en) | 1983-02-07 |
| SE453399B (en) | 1988-02-01 |
| GB2103236A (en) | 1983-02-16 |
| DE3227981A1 (en) | 1983-02-24 |
| CH651585A5 (en) | 1985-09-30 |
| AU549004B2 (en) | 1986-01-09 |
| AU8676582A (en) | 1983-02-10 |
| FR2511030A1 (en) | 1983-02-11 |
| GR77266B (en) | 1984-09-11 |
| IT1149341B (en) | 1986-12-03 |
| NL8203129A (en) | 1983-03-01 |
| FR2511030B1 (en) | 1986-12-12 |
| IT8248945A0 (en) | 1982-08-05 |
| SE8204378D0 (en) | 1982-07-19 |
| MX156340A (en) | 1988-08-18 |
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