CA1228275A - Soil release promoting liquid detergent - Google Patents

Abstract

SOIL RELEASE PROMOTING LIQUID DETERGENT

ABSTRACT OF THE DISCLOSURE:

A soil release promoting liquid detergent comprises a detersive proportion of a synthetic organic nonionic detergent or a mixture of such nonionic and synthetic organic anionic detergents and a soil release promoting proportion of a particular type of soil release promoting copolymer of polyethylene terephthalate and polyoxyethylene terephthalate in an aqueous medium which contains no more than 2% of water soluble ionizable salt (which is not an anionic surface active agent) or equivalent ionizable species, and which is at a pH
in the range of 6 to 9.
The described liquid detergent, which is preferably clear or translucent, may preferably include a proportion of enzyme sufficient to enzymatically hydrolyze soils on fabrics dur-ing washing, and a stabilizing proportion of stabilizer for the enzymes. Also preferably, there may be present a fabric softening proportion of a quaternary ammonium salt fabric softener. Such a detergent is found to be non-separating and of improved stability on storage, with substantial retention of soil release promoting characteristics, so that laundry containing polyester materials is made effectively soil releasing after washing with the liquid detergent.

Description

~22~2t~

~ his invention relate~ to liquid deter~ent composi-tions. ~ore particularly, it rel~te3 to ~uch compo~itions which ~ontain a 80il relea~e promoting polymer ~hich ~ep~sits on poly~sters ~nd polyester blend materials ~uring ~shing there-S of and promotes the relea~e from them of ~ubs~qu~ntly ~ppliedllpophilic ~oil8. Preferably the liquid det2rgent may include ~n enzyme t~ a0sist in cleaning, with a ~abilizer for ~he enzyme, and may also include a fabric ~o~tening co~pound, ~uch ~8 a quaternary ammonium ~alt. Surprisingly, tbe in~ented compositions are physically ~nd functionally ~table on ~torage, even when they contain the enzyme(s) ~nd f~bric ~oftener(s).
Liqu~d det~rgents have been omploy~d ~or the washi~g of household laundry items in washing m~chines ~nd have often been applied to ~oiled areas of the l~undry, such a~ shirt collars, be~o~e washi~g. ~he ~mploy~ent o~
copolymers of polye~hylene terephthalate ~nd p~lyoxyethylene terephthalate in detergent composition~ ~s oil r~l~ase promoting agents has ~een described in variou6 pa~ents, ~ome of which related to liguid preparations. However, the liquid deter~ents described ~re ~ot o~ the type of the present in~en- -~ion because those of the patents con~in triethanol~mine and/or ionizable, w~ter ~oluble alts (other tban anioni~
detergents) which tend ~o cause separation of the liquid detergent and destabilize the soil release promoting polymer on ~torage 50 that it becomes less effective ~or promotins ~vil relea~e afterward.

- 2 -B~75 In liqu$d detergent~ ~nzymes tend to lo~e ~ctiv$1ty on ~tor~ge Ul~1e8B stabilized, ~ ~y ~alt~, e~g., ~odium for~te, glycols, Q.g., propyl~ne 5j~1yt:91, or othQr lluch Du~terial~ owever the ~entioned ~alt~ t~nd to ~ t~bilize 5 quat~rnary ammonium halide ~abric softene:r~ ar~d t~ae copolymer ~o~l release pro~oting zlgent~ which are desi~able oomponent~
of the present liquid deteryents, and ~uch destabilizatisn of the ~oil ~elease ~lqent 1~ ~specia) 1y bad in ~he presence of ~ower z~lkanolamines c~r ~al~s thereo~, ~uch el8 'criethanol-10 amlne tTEA~, the pre~ence of which will ~ avoided~ ~hereore it was suxpri~ing ~hat t:h~ pre~ent liquid detergent~
~ould be Dlade 1n clezlr and stable non-separ~ting ~orm, with ~he variou~ ~unctional components thereof b~inq ef~ective a~er storage at elevated temp~ratures.
In accordance with the pr~ent invention ~ ~oil re1ea~e promoting liquid detergent comprise~ ~ d~t~r~ive proportion of nonionic detergent or a ~ixture of nonionic and anionic detergent~, a ~oil rele~se prom~ting proportion o~
~ soil re1ease promoting polymer of po1yethy1ene tereph~halate 2D and polyoxy~thy1ene terephth~l~te ~nd an a~ueo~ ~edium, in w~ic~ the pH i~ ~n ~he range of 6 to 9 and ~n which th~re i8 contaiaed ~o more ~h~n 2% of non (anionic ~ur~we ~ctiv~ water so1ub1e ionizab1e ~alt, Al30 withi~ the inven-tion i5 a ~ethod of nanufac~uring ~he described c.ompo~ition~,

3 --27~i Preferred ~uch liquid compo~itions also contain enzymes and en~yme ~tabilizer~, more pref~rably with ~abri~
~oftener ~180 being pre~ent~ Thus ~ stable enzyme-containing llguid detergent compri~e~ a deter6ive proportion of ~ nonio~ic detergent, a detergent ~upplementing and fluore8~ent brightener ~ubstantivity increasing proportion of a higher fatty ~lcohol polyethoxylate sulfate detergent, a ~oil release promoting proportion of a ~oil release prom~ting polymer of polyethylene ~ereph~h~la~e ant polyoxy~thylene ter~phth~la~e, a proport~on of ~nzyme ~uffi~ient to ~nzymatically hydrolyze pro~ein~ceou~
~nd/or ~mylaceous ~oils ~n fabric~ during wa~hing thereof wi~h ~n aqueou~ washing solution ~f the liquid detergent, a ~tabilizing proportion Df a ~tabilizer ~or ~he enzyme(s), and ~n a~ueous medium, in which She p~ i8 in the range of ~bout 6 to 9 and ~n which there i8 present no more ~han 2~ o~ water ~oluble ionizable material other ~han the higher fa~y ~lcohol polyethoxylate ~ulfate detergent. Similarly a ~table fabric ~ofteni~g, ~oil relea~e promoting, enZ~me-oont~ining liguid detergent compri~e~ a deter~ive proportion of nonionic detergent, ~ 80il ~lea~e promoting proportion of ~
~oil ~elease promo~ing polymer of polye~hyl~ne terephth~l~te and polyoxye~hylene texephtha~.a~e, a 60ftening proportion o~
a quaternAry ammon~um ~alt fabric softener, a proportion o e;nzyme 3u~icient to ~nzy~atical~y hydroly~ proteina~eou~
~n~or ~ylaceous ~oils, on fabri~s during wa~hing ~h~reo~

~2~3~75 w$th an ~queou~ w~hing ~ollltion of ~he liquid ~t~rsl~nt~
stabll~zing proportion of~ er sor tho ~n~y~(~), . and am Aqueou~ ~e~ium, ~n which ~e pH ~ ~n l~ e of about 6 to 9 ~nd ln which there i8 present ~o ~or~ n 24 5 c~f wat~r 80~ e ionizable material, ~uch el3 ~al'w u~d/or ~rieJch3nolamine .
Al~hough various ~ynthetic organic Ao-aion~c deter-gent~ of ~ati~factory phy~ical characteri~ti~ ay be ut~lized, inc~uding condensation pxod~cts c>f ~thyl~ne ox~de ~nd pxopylene 10 oxide with each other and with hydroxyl-contAining bases, ~uch a6 nonyl phenol and Oaco-type alcc~hols, for ~e~t ~e3ult~
it i~ highly pre~erred that the n~nionic detergent l;~e ~
condensation produc~ of ethylene oxide ~nd highea: ~atty ~lcohol. I~ such produc~s ~he higher fatty ~lcohol i~ of 10 to 20 carbon atoms, preferably 12 to 15 or 16 ~arbon a~om~, ~nd the nonionic d~tergent conSains ~EOm 2 or 3 ~o 20 ox 30 e~hylene oxide groups per mole, p~e~e~bly from 6 to 11 or 12. ~ost preferably, the nonionic d~ergent wlll be one in which the higher fatty alcohol i8 of about 12 to 15 or 12 to 14 carbon atoms and which ~ontains rom 6 or 7 to 11 ~ole~
of ethylene oxid~, ~.9., 7. Among 8uch deterg~t~ ~ Al~n~
1214-60Ct ~old by ~he Conoco ~ivi~ion of E.I. ~uPont ~e _ 5 ~2~ 7~5 Nemour~, ~nc., ~ N~odol ~ 23-6.5 ~nd 25-7, ~vail~ble ~om ~hell Chemical Ccmpany. ~mong th~ir espe~ially ~ttractive properti~, in ~ddition o good d~ergency with æ~pect ~o oi~y ~nd greasy ~oil depo~its on good~ to ~e ~ash~d~ ~nd excellent compatibility with the pre~ent polymeric soil release promoting agents, are compatibilities with ~oluble ~nionic detergents o~ he linear hi~her alkylbenzene 6ulfonate and higher ~atty alcohol polyethoxylate ~ulfate types, enzymes, enzyme ~tabilizer~, fabric softener~ and other components of the present compositions, and long term viscosity stability in aqueous and aque~us ~lc~hol$c ~lutions.
The anionic detergent which may be employed in the li~uid detergents within the broader aspects of the inven-tion is preferably a higher linear alkylbenzene sulfonate or a higher fatty ~lcohsl polyethoxylat~ ~ul~t~. ~o~m~lly, wat~r soluble 6a~t~ of such mat~rial~ ~re preferred, 6uch a~ the alkali metal salts, and of the~ sodium salts ~re u~ually pre~errea over the pota~sium ~lt~. ~hen the anionic detergent i5 a ~odium higher ~lkylbenzene ~ul~onate the 2~ higher alkyl will nsrmally be ~f 10 to 18 carbon ~tom~, preferably 12 ~o 16 carbon atom~ ~nd ~ore preferably 12 or 13 carbon atom~, eig., 12. When zuch anionic deter~e~t i~ a higher ~atty alcohol polye~hoxylate sulfate, a~ i~ the case with the enzyme-containing liguids, in which the d~tergent inerease~ detergency and pxomotes an increase in ~ub~tantivity of ~luore~ent brighten~r pEe~ent, ~he higher ~atty alcohol will be o~ 10 ~o 20 ~arbon ~tom~, prefer~bly 12 ~o 16 c~rbon . ~toms ~nd more pre~er~bly 12 to 13 02 12 to 15 ~rbon ~toms, 7~i ~nd ~h~ polyethoxylate will include 1, 2 or 3 to 20 ethoxy group~, pref~rably 3 to 10 thereof, and more preferably 3 to 6 or 7, ~.g., 3, 6.5 ox 7. While not preforred, mixtures o~ ~ch ~ionic detergent~ may be employed in the non-enzyme ~ompositions usually in ratios o~ 1:10 to 10;1~ ~uch as 1:2 t~ 2:1. Anionic detergents and ~rfactants will n~rmally be omitted ~rom the fabric ~oftening li~uid detergents.
The ~oil relea~e promoting polymer, which i~ ~n e~en~ial component of ~he c~mpositions of thi~ invention, 10 i8 ~ polymer of polyethylene terephthalate ~nd polyoxy-ethylene terephthalate which is soluble (preferred)or disper-sible in water and is depo~itable from wash w~ter containing the detergent (5) onto ~ynthetic organic polymeric fibrous ... .
material~, e~pecially polye~ters ~nd polyeste~ blend3, ~o to impart ~oil release properties to them, whil~ ~aintain-ing them comfortable to a wearer o~ clothing m~de ~Eom ~uch ~terials and not preventing or ~ignificantly inh~biting vapor t~ansmi~sion through such clothing. Such polyester6 have ~l~o b~en ~ound to po~ses~ anti-redeposit~on p~operties and ~en ~s~ist ~n removing 8tain8 ~r~m ~ub~trated.
They te~d to maintain ~oil~ e~p~cially oily or ~rea3y ~oil, di~per~ed ~n wa~h water duri~g washing ~nd rinsing, ~ that it i8 no~ red~p~si~ed on the laundry. U~eful ~uch product6 are ~opolymer~ of e~hylen2 glycol or other ~uit~hl~ 30urce ~ ~hylene oxide moiety, polyoxye~hylene glycol ~n~ ~ere phthalic ~cid or ~uitabl~ ~ource of th~ terephthallc ~oiety.
The c~polymers ~ay al~o ~e con~i~e~ed to ~e c~ ns~t~n produ~ts o~ polyethylone terephthal~t~, which ~ay ~metime~
be refe~r~d ~o ~ ~n othylene ~erephthalate polymer, ~nd polyoxyethylene t~reph~halate. While ~he ~e~eph~halic 7~

~oiety i~ pr¢~erred ~18 ~che ~s)le ~ib~ic w~d Dloiety ~n th~
poly~er ~t ~ within ~he i~verltion to utilize x~l~tively ~mali prc~portion~ of i~ophthalic ~cid ~na~or ortbophthallc ~cid (and ~ometime~ o1:her dibasic acids, too) ~co ~aify ~he properties of the polymer. ~owever, the propsrtion~ of ~uch ~cids or ~ources of such ~upplemes~tal ~oie~ eharged to any reac~ion mixO and the cor~espos~di~g prope~r~on~ in ~he ~ al polymer wlll normally ~e le~ than 10~ o~ch ~f the to~c~l phthalic moietie~ pre~ent, ~nd pre~erably Irill be l~ss than 54 thereof.
~he molecular weight of the pDlymer will l:~e in the range of about 15,000 to 50,00Q, pref~rably being ~ t 19,000 to 43,000, more preferably being ~bout 19~090 to 25,000, e.q., about 22,00û. Such mol~cular weigh~ ~re weight ~verage molecular weights, as di~tingui~hed ~rs)m nwnber aver~ge molecular w~ight~, wllich, ~n the o~ o~ the present polymers, are ~f~en lower. In t~he poly~er~ utilized the polyoxyethylene will be of a molecular weight ~n ~he r~nge of ~bout 1,000 to 10,000, pref~rably ~bout 2,5Q0 to 5,000, more prefera~ly 3~000 to ~,000, ~ out 3,400.
In ~u~:h polymer~ ~he mol~r r~tio of polyethylen~ tore-phth~late to polyoxyethylene ~cerephthalate unit~ on~idgring ~OCH2CH2O-C- ~ -C~ and ~ (0~2CH2 ) n~ C ~) ~
~a ~uch urlit~) will b~ wi~hin the range o~ 2:1 to 6sl, ~ghly preferably 5: 2 to 5 s 1, ~ven allore pree~ bly 3 :1 to ~ : 1 , e . g., about 3 : 1 ,. q;he ?roEsortion of ethylone ox$de to phthalic ~ieky in the polymer will be ~t l~t 10:1 ~nd o~terl will be 20:1 or læore~ pref~r~bly being withln the S ran~e o~ 20:1 to 30:1 and ~more pre~erably ~einy ~bout 22 1.
~hus, it is seen that the p~ly3ner ~ay be c~n~dea~ed as being es~entially a m~dified ethylene oxide pDlymer, ~th the phthal~c ~oiety being only a minor c:omponent ther~o~, wh~ther ~alculated on a ~olar or weight ba~i6. Tt $8 consid~re~d ~urpri~ing that wi~h ~uch ~ 8ma11 proportion o ethylene ter~pbthala te or polyethylene terephthalate $n the polymer the polymer i~ sufficien~ly similar to the polymer c>f th~s polye~ter fiber ~ubstrate (or other polymer~ ~o which it may be adherent, ~uch as polyamides 3 s to be retained ther~on durisag the washing, rin~ng and drying operation~. Yet, as ~hown by comparatiYe experimerlt~ and variou~ wa~hing tests in which ~oil rel~a~e i~ ~neasured, the described pol~aer~ ln the present detergent co~positionst i~ ef~ective to depo~it on wa~hed ~ynth~tics, especially polye~ter~, 80 a8 to ~ke 'chom be ter able to be wa~hed ~ree o~ oily ~oil by o. li~uid rlonionic detergen~ compc~ition or otheE detergent p~oduc~.
It ~s con idered ~hat the polymer ' 8 ~r~cr~a~ed hydrophil~ity, ~ttri~ut~ble ~o the large proportion of hydrop~ilic e~hylene oxide nloieties therein, may be ~spon~ibl~ ~or ~he oxc:ellent ~oil ~elea~e properties ~or relea~ing lipophil~c: 80~1~) which ~2~27~

lt ~mpar~ to the ~er~l upon which it 1~ depo~t~d~ and ~uch ~y al~o help ~t to ~oact with ~he 11~ nonion~c . d~t~rg~nt.product compon~nt~.
Y~riou~ lit~ratur~ ~rticle~, texts ~nd patents di~close methods for the ~anufac~ure of the pr~nt polymer6, $ncluded sm~nq which are Journal of Pol~mer S~ence, Vol. 3 pages 609-630 (1948) and Vol. 8, pages 1-22 (1951).
Althou~h suitabl~ methods or ~aki~g the instant potymers are de cribed in ~uch re~erences it i~ con~id~red that none o~ them di~clo~es the particular polymer~ which ~re ~til~z~d in the pr~ent ~nvention ~but ouch ~ro ~Yail~ble ~o~merci~lly) and none di~clo~e~ the pre~ent detergent oompo3itions. Such polymers may be considered a~ having been randomly constructed ~xom polyethylene terephthalate and polyoxyethylene terephthalate moieties, such ~ ~ay be obtained by reacting polyethylene ~erephthalate (e.g., spinninq grade) and polyoxyethylene tereph~hala~e or reacting the e~hylene glycol, polyoxyethyle~e glycol and acid tor ~ethyl ~ste~) prec~r~or~ thereof. Yet, it ~ al~o within the invention to utilize more or~ered ~opo~y~er~, au~h as those made ~y reacting componen~ of predetermined or known ~hai~ leng~hs or molecular wei~ht~, ~o a~ to produce wha~

~ ~0 _ 275~

~lght ~e r~erx~3~ ~ as block c:opol3n~r~ or ~Dn-rAaldo2n ~:opoly~er~. ~;raft polymer~ m~y ~l~o b~ practica~le.
- The described ~ater~al~ ~re available ~ ariou~
s~u~ces, the prc>du~t~ of one ~ which w~ll be ~c~d in ~ore detail here. U~eful ~opolymers ~Eor the Dlanu~cture of the detergent ~ompositi3s~s of thi~ invention ~r~ m~rketed by Alkaril Chemical~, Inc. ~ and commerci~l produet~ of ~uch company thA~ have be~n ~ucces~fully employed to produce s~ti~actory ~oil ~r~le~se p~omotlng det~gont eo~npo~ltiosl3 are tho~e ~old by them under the tr~demarks Alkaril QCJ and - A13caril QCF, ~ormer;ly Quaker QCJ ~nd Quaker QCF. Product~
available from them in limited quantiti~s, d~ignRted by them a~ 2056-34B and 2056-41, have al~o been ound to be ~cceptable. The QCJ product, ~ormally ~upplied ~s ~n ~queous di~per~ion, of abc:~ut 14 or 15% conc~ntration in w~ter, 2~nd prefer~bly used to make the present liquid ~letergents, is al~o available as an es~entiaïly dry solid (QCF). In both ~uch types of products the molar ratio of ethylene oxide to phthali~
moiety ~ out 22~ n a 16~ pQr~ion 1~ w~ QCJ, the viscosity ~t 100C., i~ ~bout 96 cent~tokes. ~he 2056-41 polyJoer is like a hard, l~gh~ brown wax ~nd in ~t the hyd~ophile: hydrophobe r~t~o i~ ~out 16 to 1, wi~h the v~sco~ity being abou~ 265 centi~toke~ he 2056-34E~ polyme~
~ppears to be a hard brows~ waxt wi~h a hydrophil8"hydl~rophobe ratio of about 10.9sl and ~ viwosity, uu~der the oa3~e ~ondition~ ~ pr~viou~ly ~n~ioned, ~ ~bout 255 cQnti~tokes.
~he higher the ~olecular w~gh~ ~f ~h~ polym~r the lnwex the hydrophile:hydrophobe ~ol~r rat~o ~ay b~ ~h~r~in ~nd ~till ~e~ult ~n ~ati~factory 80il rele~e pro~otion ~y the 1nvented ~tergent compo~i~ions~ ~he QCJ and QCF polym2rs h~ve ~elting points (by dif~erential thermal ~naly8i8) ~ a~t 50 to 60C., a carboxyl analy~is of 5 to 20 or 30 equivalent~/106 grams and ~ pH o~ 6 to B in distillo~ wat~r at 5~ Gon~entr~tio~.
The molecular weight~ ~weight ~verag~) ~re in the range o~
20,000 to 25,000 and the ethylene terephthal~te:polyoxy-ethylene terephthalate unit~ ~ol~r ratio i~ about 74:26. All of the mentioned trademarked prod~ct~ ar~ w~tor ~olubl~ ~n warm or hot water (at 40 to 70C.) or ~t least are readily di~per ibl~, and may be characterized as of high molecular weight, over 15~000, generally in the range of 19,000 to ~3,300, often p~eferably 20,noo to 25,000, e.g., ~bout 22,00~.
The enzymes employed in ~ome of the invented com-positions include b~th proteolytic ~nd ~mylolytic ~nzymes, ~uch a5 the alkaline proteases (~ubtili~in) and alpha-l `
amylase. ~mong preferred enzyme pxeparations that ~re u~e~ul are ~lcala~e 2.5L ~2.5 Anson unit~ per gr~m~ and ~, . . . . ..
Term~myl 120L, bo~h ~anufa~tured by Nov~ I~dust~i~ AOS.
Howev~r, other ~uitable prot~olytie and nmylolytic enzyme preparation~ may be u~ed, too. The mention~d ~o~po~ition~
~e ~ liguid form ~nd con~ain 54 o~ ~ct~ve ~n~y~e in comhina-tion wath 65~ o~ propylene glycol and 30~ o~ ~a~or. In ~hi8 de /Y~ar~

7~i ~pecification proportions referred to are of the ~ctive ~nz~met ~ in the preparat~n~.
~ he ~t~bil~zer o~ ~ mixture of ~ ~biliz~r~ or ~he ~nz ~ ~ ~o~t pre~srably sDdium fo~m~te or i~luæe~ ~uch S ~alt, but other w~t2r ~oluble format~s, ~uch a~ potasaium fonmate, can al~o be ~mployed and acetate6 may ~ be u~eul, a~ m~y be o~her equivalent salt~ or mixture~ oP æ~ch ~alt~ ~nd alkali ~etal ~orma~e.
The quaternary ~mmonium 8alt fabri~ ~oftener that i~ employed in some of the invented liquid detergent composi-tions ~ay be ~ny suitable su~h material which is ~table in the present ~ompositions. In some instances, known imidazo-linium halides of ~atisfactory stability may be u~ed instead o~ the u ual quaternary ammonium halides. However, ~he quater-nary ammonium halides are pre~erred. Such compounds will prefer-~bly b~ chloriae~, although bromid~ ~nd ~odid~s ~ay be u~e~ul. O~ the ~our ~ubstituent~ on the qu~er~ary nitrogen at least one,and prefera~ly two, w~ll be a long chain ~ub stituent ~uch as higher linear or fatty alkyl, and ~ore preferably, ~wo ~uch ~ub~titue~ts will bs higher ~tty alkyl~ $he chain l~ng~h w~ll unually be ~o~ 10 ~o 20 carbon a~oms, pre~erably 12 to 18 carbon ~t~ms, w~h ~hain lenqths o~ 12 to 14 carb~n ~toms or mixtures thereof, ~uch a~ coco alkyl (derived from coconut oil or equivalent feed ~tock), being ~t preferred. The other 5ub~tltuent~ on - 13 ~

32~

. _._ . . .
th~ ni~og~n will be lower ~l~ylt usually o~ 1 to 3 ca~bon ~to~, ~nd o~ ~uch ~he mo~t pre~erred ~ ~ethyl. Thus, ~lt!hough other Sluatern~ry a~omon~ lide~ can ~l~o be u~e~ul, ~t lea~t w~q3n ~y con~titu~e os~ly a~ o lt~ae S qu~texna~y~oftener, that which ~ t p~ er~0d ~nd o~
highe~t stability in ~h~ pre~ent liquid ~ erge~t~ is di-~oco d~methyl ~monium chlQride. Such product i& availa~le a~ a liquid c:~mpri ing 753 ~ctive ingr~dient, 14~ o~ o-prop~s~ol ~nd 11% of water.
The aqu~u~ ~dium Qmployed include~ wA~r ~nd pre~er-~bly also include~ a lower allcanol. The watex i~ desirably deionized water bu~ city water o~E a hardness content up to ~b~ut 300 p.p.m., as calcium carbonate (~h~ hardnes~ i8 u~ually of mixed magnesium and calcium ions) may be employed, 1~ æl~hough it is preferabl~ ~r the hardne~s content to be le~ than lOC p. pOm. to help to av~id ~ny de~ta~iliz4tion o~ ths li~uid detergent or ~eparation6 o~ pax~ ~h~r~of. Some ... . _ _ water ~y be from the ~tar~ing material~, ~uch ~o a~ueous ~oil r~lea~e pr~moters, ~nzyme prepara~ions~ ~oteners, alkanol~, and dyes. The lower alkanol ~ay be ~ny:of ethanol, i~propanol or n-propanoltbut ethanol i~ ~uch pref~red. When ethanol ~8 employed it will normally be ~8 a dena~ured ~lcohol, such a~ 3~, which in~lud~s ~ 8mall proportion o~ water plus denatura~t. Small AmOU~B ~f compatible dissolved 6alts may al~o b~ pr~e~ he aque~u~ ~edium but normally ~uch will be ~v~ to the ~xtent feasible~

7~i ~ nother l~quid that may desir~bly be e~ployed in ~o~ o the present li~uid detergent~, ~uch ~ ~ho~ contain-i~g enzy~es and abric ~oftener~,ix ~ lower glycol, ~uch as on0 of 3 to 6 ~arbon ~toms in ~he alkyl group thereof. While hexylene gly~ol may be utilized in ~ome for~ul8tions, in ~ome o~hers it ~an promote instability, ~o propyl~ne glyc~l iB preferred.
Various ~u~t~bl~ ~djuvant~ m~y ~e p~ent ln ~he lnvented liqu~d detergents, ~uch ~B fluo~e~cent ~ye~, ~olorants (aye~ and w~ter disper~ible p~gm~nts, ~uch ~
ultramarine blue), bacteri~de~, fungicides ~nd por~umes.
Co~centr~tions of such components will usu~lly b~ k~pt low, often le~ than 1~ ~nd prefer~bly less than 0.7%. Thua, the per~ume concentration will usually be less than 1~, preferably 0.2 to 0.6~, e.g., 0.44. Fluorescent brightenexs ~r optical .

bl¢ach ~ompoun~s ~ay be pre3e~ in ~he ligul~ deto~A~ ~ ~n ~xt~nt of 0.02 ~o 2%, prefer~bly 0.1 to 1~ ~nd more pre~rably 0.2 to 0.54. The per~entaqe~ given are o~ ~he co~erci~lly s~ppli~d material~. Such brig~ner~ are known a~ cotton br~hten~r~, bleach ~luble brightener~, polyamide ~right~ner~
and polye~ter brigh~eners ~nd generally mixtur~s ~h~r~ e ~mploy~d ~o ~ to ~ake the detergent u~ul ~or brightaning w~de ~ariety o~ mat~rials ~ei~g ~a6hed, includlng eotton ~d ~ynthet~c~. Exemplary of ~u~h good briqhtener~ 4re ~h~e ~dentified ~5~ ~A; DM; DME~; DDEA; DMDDEA; BS; ~S~ ~I; AC;
DP; B80; ~OS; ~nd N~SA, in ~ ~ell known arti~lo ~n~t~d ~2~ 7~i ~ ~ by Per S. 8ten~by, publishe~ ~ in ~pril, ~5ay, ~y~ ~ugla~t and Sep~ er, 1967. ~ur~her di~cu3~ion~ o~
t:he fluc~r~cent brighteners ~ay ~e found in ~n ~3rticle entitled 5 ~ ~ by P.G:~ Yill~ume, ~ppe~rir~g in ~ J ~
~October 1958), Vol. 35, No. 10, pp. 558-566. U~eful fluores-cs~lt ~r ighteners ~re ~old undes the trade names: CalcoXluor W21ite AL~ ar~can Cyanamid) 7 ~ N (American Cyanamid); 80F
10 A-2001 (CI~); CWD ~Hilton D~vis); Pho~wi e RXH (Verona) ~ CSL, powder, acid ~American Cyan~nid); FB 766 ~Verona); Blancophor PD (~F~; UNPA (3;eigy); ~ pal RBS (Geigy); ~nd RBS 200 (Geigy), The v~riou~ brighteners ~re normally pr~ent ~8 their watex ~oluble ~alts bu~ ~ay also be employed in the corresponding ~cid forms. ~ost ~uch m~erial~ are u~eful ~or brighte~ing cotton and are of the stilbene ~ulfo~ic acid (or salt) or ~minostilbene types, herein re~erred to as stilbene bright-eners, and a preferred ~uch brightener i~ Tinopal 5~M Extra Conc., from CIBA-Geigy. ~or the fabric 80~t~ning detergent the pr~ferred content of briqhtener will be from 0.05 to 0.25~, preferably 0.05 to 0.15~, e.g., 0.1~. Colorants, such as Polar Brillian~ Blue, will be from 0.001 to 0.03~, pre~er~bly 0.002 to 0.2% of the li~uid detergent, e.g., 0.0025% or 0.01%, if present. The variou~ adjuvant materials ~ill b~ Gho~en ~or a ~omp~ibility with the other formula ~omponen~ and ~or non-~eparating aAd non-~et~ling ~bar~ct~ris- .
tics. Because water ~oluble ioni2able s~lt~0 wh~hor ~orqani~
or o~gani~, ar0 gener~lly inc~mpa~ible wi~h ~oil ~lea~e pr~oting ~gen~ h~ir pr~ence will u6ually be avo~d~d.

~2~ 5 ng ~uch ~ 6 ~ha~ ~re d~irsbly ~voided ~re ~odium ~ulf~te, pot~8~ium ~ulfate, ~odium ~hloride, pot~ium ~hlori~e, ~monium .hloride and ammonium ~ul~ate, but ~he~e ~r~ Qnly example~ of ~uch ~alts. While 30~iwm for~a~e ~hould ~l~o be omi~ted from many liquid det~rg~nt~, ~urpri~ing-ly, a l~mited proportion ~hereo~ has ~een found tv be csmpat~le ~ith t~e other aomponents o~ the pr~sent ~ormul~t~sn, in combination. The p~e~ence~ onizable ~peci~s, ~uch ~
tri~kh~nolamine (TEA), ~iethanola~ine, e~hanolamine, diiso-propanol~mine, n-propanolamine nnd o~ the lower m~no-, di-~tri- ~nd mixed lower ~lk~nolamines of 2 to 4 carb~n Qtom~
p~r ~lk~nol moiety will be ~voided becau~e, like the mentioned salt~, they de~tabilize ~he ~oil release promotlng polym~r and/or ~he li~uid de~ergent. Of these,TEA ~ppear~ ~o ~e the ~o~t de~tabilizing, causing ~evere ~eparations o~ the poly~$~.
In ~his specification ~uch ionizable ~pecies, which ~y Porm 8al t8 ~ ~hould be ~ounted as part~ of the permis~ible pr~por-tions of any.su~h 6alt~ that ~ay be pre~ent. Generally it will be de~ir~le ~o avoid the pre~ence~ of other ~diuv~nts than colorant6, perfume~, ~luore~cent brightene~, ~nti-oxidant~ and ~ny neutralizing agents that may ~e e~ployQd to adjust th~ pH of the liquid detergent ~o the st~ble ~a~ge.
It is pr~erred thBt any neutralizing ~gent whi~h ~ay ~e ~m~loyed O usually to increa~e the pH of the liquld dete~ent ~ixture, ~hould be ~lkali ~etal hydroxide, such ~ ~odiu~
~ydroxids, in ~queou~ ~olution at a conce~tr~t~o~ o~ ~ro~ S

- ~7 ~

~2~75 .. ..
to ~0~, ~3.g., 15 t~ 25~ ~specl~lly ~o bo ~Yoid~d ~re ~rle~hanol~mine ~alts ~nd f~ee ~ri~ nc>l~n~.
~!he liquid de'c~rçlen'c maae will b~ ~ a d~i;r~le ViBCi~ ity, c~ft~ in the r~n~l3e o~ 50 to ~5Q~ t~ o~t8, E~referably 100 ~o 200 centipoises, and tl~ 1160~1ty l~lay be ~djusted by Dl~odiiEying the proportion of l~wer ~Ikanol, within the range gi~ren. ~he li~uid det~r~n~ will be reaaily le lbu~ will ~es6 ~1 ~leRir@d "~dy". g!ho p~ ~h~resf will be ~n the range of 6 to 9, pre~er~bly 6.1 to 7.9 ~nd c~ften more preferably 6.5 to 7.5.
In the invenk~3d 80il r~lease proting liquid detergents of thi~ invention,which ~r~ of ~mp~ov~d Gtability on storage B0 that the ~oil relea~e pro~o ing poly~r ~nd enzyme(~) do not deteriorate and do not ~ep~r~te ~ro~ the ~est of the composi~ion, the propor~ion3 of ~h~ ~a~iou~
~ompon~nt will ~e ~ ~re giv~n b~low. ~11 the ~r~OU8 compone~s recited, ~lthou~h ~tated in the ~i~gul~r, include mixtures too. The propor~ions of componen~ that follow ~re for ~he broad invention, the enzyme-con~aining pr~duet ~nd ~he enzyme-and 60~tener-containing product, re~pectively.
The nonionic de~ergent (whi~h includes mixtures thereo~) or a mixture of nonionic and anionic dstergen~s (both being o ~he ~yn~hetic organic type) will be within ~he range o~ 25 ~o 50~ ~f the product, pre~er~bly being 20 ~o 40% ~or ~he 7~

~onionic ~eterg~nt ~Lnd 3 ts 15~ ~or tbe ~nioni ~terqent.
~re pre~erably, the prc~portion~ o~E sllch detergent~ will be 25 to 35~ ~d 5 ~o 10~ , ze~ t~vely , e . g ., ~bout 32~ ~nd ~ut 7~, ~o~pec~Yoly. ~h~ ~o~l ~eleA~e prom~tir~g polymer 5 will b~ ~bou~c 0. 5 to lû~, pre~erably 1 to 69~ and ~ro p~ePer-~ly 1 to 3~6 , e . g ., about 2~ . ~he lower alkanol cDntent will be from 3 to 15~, pr~erably 5 to 12~ and more pre~er-~bly S to 104, e.g., ~bout B~, and the water content, when lower ~lkan~ present, will be about 30 ts 60~, pre~Eer-~bly ~5 to 554, and if no lower ~lkanol i5 present ~uch ranges will be in~r~ased to ~llow ~or replacement o~ the lower alkanol with water. ~he content~ of ionizable water soluble salts, whether organic or inorganic, ~hould ~e kep~ low, u~ually being no more than 1~ o~ ~e 1~ liquid de~erges~, preferably le~ than 0.54 and ~re pr6!~er-~bly le~ than 0. 3~ d the cs:~ntes~t o~ tri~thanola~ine will ~imilearly be limi~ed, ~o ~Ivoid ~eparation o~ the soil release promoting polyTner, with ~he de~irahle limi~s being 0. 53, pr~3~erably 0.2% 2!md mo~t prefer~bly 09~. ~n som~ insta~ces 20 the ~alt eontent w~11 be held to l~mit~ lower than the allowed allc~nol~min~ con~ent ~ecau~e ~ome aal~ c~n be 2~ren D~ore det~imen~;~l to pr~du~t ~t~b~ y than the ~lkanoluaines. 0 eo~lr~e, the c:s~tent of ~nionic detergent pre~ent, whi~h ~ay be con~idered to be an ioni~ble ~alt, will no~ be included 25 ~Ln ~h~ limiting propor~ions o~ ~uch ~alt pre~ent bec~lase lt ~oes no~ appear to haYe the same l~ype o~ destab~l~z~ng 27 ~

~nPiuenc~ on the pr~6ent ~ompo~itions. ~hile sui~abie ad~u~ant~ ~ay be pre~ent ln the liquid de~-ergent, ~uch ~8 the colorant, perfume ~d 1uorQs~ent br~ghtener, pre~i3~1y ~en~o~ed, ~rmally the conte~s o~ ~uch adju~nts wlll ~e 5 ~n~ized, u~ually being le~ than 24, p~efer~bly 1~8 than lS ~nd ~ore preferably less th~ 0.~, but the dye ~nd bright-~ner ~re not de~t~bilizing.
~or the enzyme-oon~aining pr4duct (without ~oftener) ~he By~thetiC organic nonionic detergent content will nonmally be within the range of 25 to 40~ o the product, pxeferably bei~g 28 to 36% and more preferably 30 to 34%, e.g., 32%. The ~atty ~lcohol alksxylate ~ulfate content will u~ually be 1 to 8~, preferably 2 to 7~ and more pre-ferably 2 to 6%, eOg., 3% or 5%. The fluore~cent bright-ener content i~ in the range of 0O 02 to 2~ and pre~erably0.1 to 1~, o.g., 0.~ or 0.4~. The perc~n~ge o~ ~ct~e ingredi~nt of t~e brigh~e~er m~y o~ten ~e 0.0~ to 1~, Duch ~8 0. 01 to 0~14. The 80il release promoting poly~er conten~
will ~e about 0.5 tG 5~, prefer~bly 0.8 to 3~ and ~ore ~re~erably 0.8 to 2.5~, e.g., about 1~ or 2% ton ~n active i~gredien~ basi~). The total enzyme content will u~ually be ~he range from 0.0005 to 0.154, preferably 0.025 ~o 0.1%, of which the protea~e ~ontent i~ 0.005 to 0.1~ ~nd ~he ~myla~e ¢onten~, if amyla~e i8 pre ent, is 0.005 ~o 0005~7 ~reerred con~ent~ o~ the enzymes are 0.01 to o.i~ ~d 0.01 - 20 ;

8~

~o O..û3~, r~ $-vely. ~lore ~xe~r~bly, 0.02 to O.OS
the pers:ent~ge oiE protease. ~;pec~:eic ~ormula per~ n'c~ge~
~re a~ t 0.03 and 0.02P~, r~llp~cti~ sly. The ~tabilia:3~r for the n2yme8, uRually an ~lkali metal ~al~ of ~1 lawer 5 ~l~phatic acid t~f 1 to 3 carbon ~toms, ~uch ~18 ~OdiU~I ormate, will u3ually be from 3.2 ~o 2~, preferably 0.5 ~ loSP~ ~d ~o~e pre~fe~ably 0.7 to 1.3~, e.g., 14. The lc~wer ~lkanc~l cont~n~ will be frolQ 3 lto 12~, pref~3rably 4 to 9P~ And ~ore prefer~bly 5 to IB%, e.g., 5.5 or 7.5%. ~he water content 10 will l~e ~bout 40 to 65~, pre~erably ~6 to 6296, ~or~ pr~es~ly 50 ts~ 604 , ~. g ., ~bout 54 or 55~ .
~ he con~ents of ~oniz~le water ~oluble ~lt~, whether organic or inorga~ic, ~hould be Icept low, 1~ n 2~, usually being no ~ore than 1~ of the liquid deterge~tO prefer-15 ~bly lefis than 0. 5% and Illore p~eferably le~s than 0. 3~, andthe ~or3tent of tri~th~nolamine will ~imil~rly ~e l~it~d to avoid ~ep~r~ios~ of ~he ~oil rol~a~e promot~ng polymer, with the de~irable li~its being 0.5~, pref~rably û.2~, ~nd ~t prefer~bly 0~ . In ~ome in~t~nces ~:he sal~ conter~t will 3; e 20 held to limits lower ~han the allc~wed alk~nol~mine con en~
be~auQe ~ome 8alt8 ~:an ~e even re detr~ental ~o product ~ability than the ~lkanolamine. E~ow2ver, in klle pr~ent comp~ ion~ th~ content~ c~f water ~olu~le ~lk~1~.~3t~1 . lower carbo;cylate, ~uch ~ ~odium forma~e, 311ay b~ up ~o 2%
25 bocause ~uch components ~tabilize ~he enzymes, and ~t ~uch concentrations, ~spe~ally ~t about 1~ or 1~il8, ~e~ co~npati~le w~th 'ch~ d e erg~ t pr~duc~ ~nd the ~ r~l ~a~e pr~ g polym~r, ~ 'cha~ polyme~ ~par~ti~r do~ no~ ~cour.

For the enzy~atic and 80ftenin9 liqul~ t~r~ents the _ . _ ~yr~th~tic o~ganic nonioni :: d~t~rgent ~w~h ~c~ xtures therec~) content will be within he ru~ge o:E 10 to 354 t~f the produr~, preexal:1y being 15 tc> 309~ aad a~Qre p~efer-~bly 20 ~o ~54 , e.g., 22~. ~he ~c~ elea~e promoting polyme~ s~ontent will ~e ~ut O.S to 5~, pref~sr~bly 0.7 l:o 2~ ~nd Dlore pre~er~ly 0.8 to 1.5~, e.g" ~out 1~, ~on an ~tive lngredier~t basi~). The ~:ontent o~ ~u~ternary ~o~pound will ~e 1 to lû~, preferably 3 to 8~ ~ore pr~ferably 3 'co 6~, e.g., 405%. The enzyme content m~y be ~rom 0.005 to O.lS~, preferably 0.025 ~o 0.05~, of which the protease co~tent is û . 005 tc~ 0.1~6 and the amyla~e co~tent, i~ yl~se is pre~ent, i~ 0. 005 to O . 053. Pre~er~ed cont~nt~ of the enzyme llre O . 01 ~o O . 05~ and 0. 01 to 0. 025~, re~pectively. ~or~ pre-ferably, ~h~ content of prot~a~e will ~e from 0.015 to O.û49~.
Specific: formula perc~n~age~ are ~bout 0.023 as3d 0.0154, i r~pectively. ~h~ sta~ zer f~r ~ zy~e~ we~
aliphatic ~cid salt, ~uch as sodiwa fonnate, will u~ually ~e . ~Erom 0.2 to 2~, pre~er~bly 0~5 to 1.5P~, ~d more p~or~ly 0.7 lto 1.39~, ~.g., 14, ~he ls~wer- ~lkanc~l ~ont~n~ will ~e ~rom 1 to lQ~, preforably l.S to 39~ and ~o~e l?ref¢rably 2 to 2.53, g.g. O X or 2.2%. ~he lower glycol corlt~t 1~ 2 to ~09~, preferably 3 ~o 8~, ~re pxe~3r~bly ~ to 7~ ., 69~.
~he wa~er conten~ will be about ~0 to 80~, pre~oro~ly SO
te~ 70%, ~ore prefQrably 60 to 65~, o.g., ~ut 63g.

- ~2 ~2~2~

.
The cc~n~ent~ o~ lonizable w~tex l~olubl~ ~alt~, ~rh~ther organic or inorgani~, ~hould be kept low, u~ually be~ l no D~ore th~n 1~6 sf the l~ql~id detexyent, px~f~ably l~$s than 0.54 ~nd ~ore proferably le~ an 0,3~, ~nd the S ~:ontent of trieth~nolamine will slmilarly be limited to ~-toid ~eparatic~n of the 80il release promoting polyDler, with the d~sir~le limit~ being 0.5~, preferably 0.2~, ~d ~o~t profe~ably 0~. In ~ome instance~ t:he ~alt $ontent will be held ~o l~Lt~ low~r th~n ~he ~Illowed ~lk~nolamine content 10 becau~e ~ome ~alts can be ~ven more detr~ental to product ~t~ ty than the ~lkanolamine. ~:lowever, in the pr~sent compo~itions the contente of w~ter tlolu3:~10 ~lkal$ D~tal lower oarboxyla~e, such as sodium fQrmate, may be up to 2%
becau~e ~uch components ~tabilize the enzymes, And ~t ~uch 15 oonee~trations, especially at about lX or les~, are compatible with the d~tergent product.
e invented liquid d~tergent~ ~y ~e ma~e by ~ixing ~he ~aric~us comporlent~ ther~of with the aqueou~
medium, pref~r~bly containing at least ~ome of the lc~wer 20 ~lkanol, until they di~s~ e ~t~r ~atisfactoriiy tili~peroe) ~her~in, or di~erent c:~mpc)nen~ may be ~electiv~ly di~solv~d in portions of the wato~ and/or lower ~l)canol ~nd/or lower glycol, and/or liquid ~oil relea~e promoting polymer prepa:ra-'cio~, and/or liquid enzyme preparatioF~, ~nd then the v~rious 25 liquid fractions may be mixed togetherO It will often be preferable ~o adjus~c ~he pH of the liquid to withi~l the o 6"1 to 7.9, o~en laore pre~e!sably 6.5 t~ 7D~ by ~3 ~2~ 7~;

~ddition of 2 111llit~ 3 ~3utsal~zi~as llgent ~nst ~iothanol-e~ which will Jlo~ haYe ~ dest~ z~ng ~Ja1uen~e o~ the ~oil rele~a~e promo~ing polymer, ~h~ os~xy~e(~ ot~ne~, ox ~he liquid produc~ containing ~hem, ~o th~at I~UIG~ nolt 5 de~eriorate ~nd will n~t ~eparzate from the ll~ otergent on ~crage, especially at elev~ted t~npera~ure. ~he pre~er~
~ed neutral~zin~ agent i~ queous ~olution o~ ~odium hyd~oxide, whach will no~ally be between lû ~ 0~ ~odium hydroxide, pr~~1ara~1y 15 to 25~, althouqh ~ore ~lilute 10 ~oncentr~tion~ ~ay ~ometi~es be de~rable. ~ eqllen1;1y, ~che vi~co~i~y of the p~o~uc~ may be ~d~u~ted by Deans of ~lkanc>l ~d/or water addition.
The invented liquid detergent co~posi~c>n may be u~ed to wash ~and treat) laundry containing ~yntheti~ fiber~, 15 ~uch a~ tho~ of polyester, e.y., Dacrc~n~), in thc nor~al m~nner u~ed in wa6hinq with other liquid de~rg~n~cs. ~owever, of the present product may be ~nployed l~ au~e of the ~oil relea~e promoting action thereof, ~nd in ~ny g:a~s the cleaning and ~oftening effe~t6 o~t~ined will be 3uperio~.
20 Different con~en~ra~iorl~ of the ll~au~ d~toxgsnt ~ay be used, normally being f~o~ ~bout û.02 or 0.04 tD 0.3 or 0.64, preferably 0 . 05 or 0 .1 to 0 .15 or 0 . 3~ ~, with the c~rlcentr~tion gen~rally being abol~t 1/2 cup per wash in a t~p loading ~nachine for the product c~ntaining ~oftener~ And ~bollt 1/~ cup per 25 w~sh for ~he ~ther two types of products. Generally, i~
will be ~dvised ~o use about 1/4 or 1~2 cup (~bou~ 60 or 120 ml.,) of the liquid detergen~ per ~tandard w~h load (~bou~

-- 2~ --17 gallons , for a top loading wa~hiny mach~ne), which is a gc~nc~ntr~tion of ~bout û . l or 0 . 24 of the liquid detergent in the w~sh water. ~3:>out the ~ne concentr~tion may be uRed when wa~hing i~ a fr~nt lcsadirlg ~ hine, ~lthough the w~ter 5 ~nployed i8 less ~so le s ~lstergent compo~itio~ i~ omployed).
Normally about 7 or 8 pounds (3 ~o 3.5 kg.), of lnundry will be charged ~o the washing ~nachir~e. ~he wa.h water temperature will preferably be 2~ lea~t 120F. (49C.) but good wa~hing and ~reatments by the ~c~il release proDIoting polymer, the enzymes 10 ~nd the ~o~tener in ~che liquid ~etergenl~, ~re obtairlable at t~perature~ in the range of ~about 40 ~c> 80~C., pre~erably 45 to 70~C:. ~he dry we~ght t~f ~ate~ eing wa~hed ~md ~r~at~d will l~ually be ~rom about 5 to 15 or 20~ o~ the weight o~ ~he ~queous washing medium, preferably a~out S to 15 10~ thereof. The wa~h will ~e conducted with ~git~t~on over ~ period o~ abc>ut ~ive mi~utes to one-hal~ hour t~r one hou~, o~ten ~rom 10 to 20 minute~. Ther~ the wa~hing ~t~rial~
will be rinsed, u~ually with ~everal rinse~, ~nâ will be ~ried, as in ~n ~utomatic la~andry dryer. Pre~erably, the 20 ~ir~t wa~hi~ of the m~terial ~o be tre~ted will b@ when ~h~t ~aterial ~8 ~ot unduly dir~y, ~o ~h~t the ~oil r~le~ase promo~ing polymer w~ll be ~lepo~ite~ on a6 ~le2~ ace a6 po~sible. ~oweves, thi~ o~ ~ce~sary, ~nd improv~ment~
he cleaning of 8Ub5~qUealtly ~oiled m terial~ ~nd ~w~kches 2~ will 3:~e ob~enred wh~o ~peci~l effor~ ~mad~ to ~Ave ~he IEir~ wa~hing b~ t.ha~ o~ a ~leaner ~ubstrat0. Up to - ~5 -~L~28~7~i . _ _ o~eti~e~ ~bout 3 or 5 ~r~a~ent~, plur~l washing~~it.h th~3 liquid dsa~ers~ellt of ~li8 inv~:nt$on incre~se t31e oil releasing properti~s o~E the treAte~ materi~
When polyest~r z~d pl~ly2 t~r/~o~ton a~ ~rics S aUr2 ~ra~h d in ~he manner described with the cso~ l'c$ons o~
thi8 ~ven~ion, and ~re ~heal soiled or sp~tted with dirty ~o or oil glnd wa~hed with a dete~gent o~ n~ention or znother commercial d~tergent k~ften of the builg: type), ~igni~icant remov~ll o~ the lipophilic 80il ~L~ noted, ~ompared 10 ~o 3iclilar treat~entli in whieh ~he liquid detergent e~plGyed .. .. . . . . ..................................... . . . . ~
lnitially did not ~ontain ~ny aoil relea~ pro t$ng polymer.
In othex comparison~, when sub~tantial proportion~ o~ water 801uble ionizable ~al~, ~uch as 5% of s~dium ~ul~ate, or ~ore than 1~ of triethanolamine or a salt thereo~, ~re present i~
the liquid detergent it i~ found that a~ter storage at elevated temperature (43DC.) ~or ~wo weeks, s~mulati~g a leng~hier ~torage at room tempera~ure, pha~es ~epar~te ~rom the liquid detergent body and th~ ~oil ~ele~e promoting properties of the polymer contai~ed ~herein are diminished, a~ are the enzymatic and ~of tening activitie~, when ~uch materials ~re in the formula. When the enzy~e stabilizer i8 ~mitted enzymatic action i~ decreased ~ubstantially on ~torage. ~hus, ~he c~mpositions o~ thi~ invention ~re imporkant because they ~re ~table, resulting ~n ~ore ef~ective produc~s ~or the purpo~es intsnded, 80il rele~se improvement, cleaDing e~fe~ts and 60~ten~y o~ the 27~

~br$c~ la~d~x~3d, ~and ~l~o ~ ult~alg ~n ~ r~ a~ ractive liqu~Ld ~let~rgent campoYition, w~ich doe~ not ~ep~ra~e on 8tor~g~, ~he ~ollowing ¢~xample~ illu~trate ~ ~rlv~JItion 5 13ut ~o not li;~ it. Unle~s otherwi~e in~lic~ted, ~11 parts ~e by weight and all temperatures are in 0C.

Component Percen~
, . .
Noc~dol 23-6 . 5 (condensation product of approximately 32 . O
6 . 5 mc)les o~ ethylene oxi~e ~nd a higher fatty alcohol averaging 12 ~o 13 carbon altoms per mole) E;od~um linear ~odeoylbenzenel 3~ulon~t~ tLDBS) 7.0 So~ ulat~ (~ccomp~niea the I.DBS) 0. 2 ~oil ~elease promoting polymer ~a copolymer o:E 14.3 polyethylene terephthal~te ~d polyoxy-~thylene texephthalAte of A molecul~
weigh'c of about 22,000 wherein the polyoxyethyl~ne ~ o~ ~ mole~ular we~ght of ~bout 3,~00, the mol~r r~t~o of poly-ethylene tereph~h~late to polyoxyethylen~
terephtllala~e un$t~ $~ ~bout 3: ~ ~md the E~roportion of ethylene oxide to phth~lic ~noiety ~n ~he polymer ~ about 22 ~ old by Alk~r11 Chemicals, Inc. ~ AlkJ~ril QCJ, ~IS ~ ~4~ solut~c~n ~n w~tex) Dena~ured eth~nol (3A) 8 . D
Fluorescent brlghtener (T~ne~pal SAM, E~tr~ Conc.) 9.24 Dy~ (Polar 2r~ nt Blue) 0.01 Per~ume 0 ~ 4 D~iOn~ed water q.8.
lûO. 00 ~22~7~ ~301-1271 The formula liquid detergent is made by mixing together a portion of the water with the nonionic and anionic dekergents, follwed by addition of the soil release promoting polymer, the ethanol, fluorescent brightener, dye and any remaining water.
Then, an acid or base (NaOH is preferred) may be used, if desired, to adjust the pH to within the desired range. In the above example the pH is 7.8 (undiluted). However, when the pH is lower than desired an aqueous solution of sodium hydroxide (20%) is used to raise it to the desired level, e.g., 7.5, and the proportion employed is small, e.g., about 0.2% or less NaOH.
Next, the formula proportion of perfume is added. The product made is tested by being stored at 43.3C. for two weeks, after which it is observed to be in a single phase, essentially like that first produced.
Shortly after making the liquid detergent it is used to wash a test load of clean fabrics, including some of polyester material and others of 65% polyester and 35% cotton material. The washing concentration is 0.1% by weight of the liquid detergent, on the basis of the weight of the wash water, and the swatches washed are about 5% by weight of the wash water~ After washing in a standard testing washing machine, using standard conditions previously described, is completed, the swatches are rinsed and dried. Subsequently each test swatch is stained with about three drops of dirty motor oil of a standard type used for ~u~h tes~ing ~ 8 wa~hed in ~ ~9 type c~f machine, a co~rcial detorgent. .A~ control~, ~wakche~ that wer~ ~ot previou ly ~eated with ~he pre~ent llqu~d deter~
ge~ ~re ~ployed. The wa~3hing-treating amd IIIII~S~OSlUOA~:
~ashing tempera~ures are the same in ~ aEest ~ing 499C., which $8 cc:~n~idered ~o ~e an optimum temperature for tre~-~e~t. ~n ~me experi~ent~, the Bubsequent wa~hing 1R with the invented liquid detergent cl~mposition. In ~11 ~xperiments the trested ~watches are ~igniflc~ntly whiter to . _ .
10 the eye ~nd by reflec:tom~ter teting than ~e control ~watches, ~howing that the ~oil relea~e promoting component oiE t.he liquid detergen~ c:omposition effectively aided in the ren~oval o~ ~uch applied Coil from the ~watches during the subsequent washings. Also, it is noted tha~ the xedepo~iti~n onto 15 un~oiled portions of the ~abrics of th~ dirty motor oil removed ~Erom the ~pG~ting application~ i8 dimin~sh~d when 80il release polymer i;~ applied to the ~abric be~ore ~e~t ~oiling thereof. Thus, ~he ~iquid de~erg~n~ containing ~oil relea~ promoting polyzner, in addition to ~iding ~emov~l o~
20 the ~oil, al~o help~ to maintai~ it ~u~pended, inhibiting deposit~on of $uch removed ~ il on t~ther partC o~ ~e te~t r~al.
When 2~ or 3g ~ triethanolamine i8 pre~ent ~n the liquid detergent of the ~rmula prev~ou~ly given, ~n re~plac:ement 25 of part of the wa~er ~her~D~, ~fter two we¢ks of ~orage ~t 43.3~C.
the ~ergent ~ found~ ~o haYe ~epar~ted. Separ~g~ also occur~

_ ~9 ~-~ 275 2301-1271 under such conditions when the triethanolamine is absent and 5% of sodium sulfate is present in the formula. Also, when the triethanolamine is present, the soil removal promoting action of the liquid detergent is significantly decreased, compared to the experimental formula of this invention after two weeks of elevated temperature aging at ~3.3C., followed by testing in the manner previously described. Furthermore, storage at room temperature also results in such diminution of soil release promoting activity of the formula containing triethanolamine, compared to the experimental formula.
When the amount of soil release promoting polymer is decreased to 1% or increased to 3% the same results reported above are obtained, with the modifications that the 3% release polymer formulation is more effective than the 2% formula in promoting soil release according to the tests described, and the 1% formula is slightly less effective, although at both 1% and 3% concentrations good and excellent results, respectively, are obtained.
When similar tests are made using other lipophilic soils, such as corn oil (red), butter, shoe polishl lipstick, French dressing and barbeque sauce, similar results are obtained, with the greatest improvements of the experimental over the control being with respect to the corn oil, lipstick and dirty motor oil. Release is lO0~ for the corn oil, butter, French dressing and barbeque sauce stains and is almost 100% for ~2;~:~32~i lipstick. Similar results are obtained when the test fabrics are single knit Dacron ~ , double knit Dacron and Dacron/cotton blends, and are also obtained with treatment temperatures above 32C. Such results are also obtained when a commercial or home laundry machine of the top loading or side loading type is employed instead of the laboratory testing washing machine.

EX~PLE 2 In the primary formula of Example 1 the sodium linear dodecylbenzene sulfonate is replaced with the corresponding tridecylbenzene sulfonate in one instance and with Neodol 25-3-S, which is the sodium salt of a sulfated condensation product of approximately 3 moles of ethylene oxide and a higher fatty alcohol averaging between 12 and 15 carbon atoms per mole, in another instance, and the nonionic detergent is replaced by Neodol 25-7 in both cases. When the compositions resulting are tested for elevated temperature stability and for storage stability, as described in Example 1, similar good results are obtained. Similarly, when more than 0.5% of triethanolamine is present in the compositions in place of an equal proportion of water and/or when 2% of sodium sulfate or other water soluble ionizable salt is present separation of components of the liquid detergent takes place. When the liquid detergents of this example are employed in washing polyester fabrics of the types mentioned in Example ~2;~ 7~i _ 1, ~f~r which tbe abri~ o ~o~l~d ~nd ~ub~equen~ly wa~hed, improv~d lipop~ilic 30il ~em~Yal~ result, compar~d to control~ which ~nt~in no ~oil r~le~se pro~t~n~ polymer o the type u~ed $~ the ~onmul~ of ~hi~ ~xnmpl~ o, when ~cr~ ~han 0.5~ ~ Sr~e~hanolamine ~nd/or 2% of water ~oluble lon~2~ble salt, such ~ ~odium ~ulfate, is pregent in each o~ the f~rmulas, ~f~er el~vated temperature or room temper~ture aging ~or pe~iods of two weeks and three months, respective-ly, if ~be ~par~t~d comp~ition ~ shake~ to di~per~e the 10 Yariou~ ~omponent~ thereof and i~ then used in the munner - previously described the ~oil release e~fect thereo~ i0 ~till dimini~hed ~ignific~ntly, compared to the ~xperim~ntal ~rmulas containing neither trietha~olamine nor ~uch ~lt.

E ~ PLE 3 ~he ~irst ~ormula of the inv~ntion giv~n ~n Example 1 i~ modi~ied by replacing the anionic detergent tAereof wi~h Neodol 25-7, 80 that the product con~ains 39~ of nGnion~c detergent, ~nd ~epla~inq the othanol with deion~z~d wa~er. The product is non-~parating on ~torage ~nd i8 0~
20 80il r~moving characteri~ticæ ~milar to those of the invented produc~ o~ Example~ d 2. Also, the ~xper~ont~l product 1~ ~table ~uring ~ccel~r~d ~gi~g a~ elevated t~mperature ~torage and during longer period9 of room temper~ture ~tor~ge, wherea~ a comparative produc~ containin~ 1% o~ txi-ethanolamin~ and/or 24 of ~odium sulf~te s~parat~ ilarly,~uch compara~ive product~ do not help to relea~ po~ited l~pophilic ~oil ~o th~ ~xtent ~hat ~ obtainable w~th the exper~mental product~ ~ thi8 ex~mp~.

- 3~ -7~
, ~W~LE 4 , .
~ hen l;he con~er~t~ of lthe variou~ ~xperiment~l for~ul ~ of ~ nven~io~, giv~n ln Ex~plq~ 3 ~ varaed -10~ ~nd ~254, wh~le k~eping th~ oportior~l~ O~ th3 v~riou~ ,.
~terial~ within the range~ r~cited in the ~pec~c~ti~n and when, in ~uch ~orDIulatic:~n~ in~tead o employ~rlg the QC3 ~oll ~lease polymer (aqueous ~olutior~ of QCF lAllcaril S:heTniaal~ CAS 9016-88-0) and 12. 39~, of water are ~ub3tituted, ~rith the QCF ~ir~t being dissolved in t;he wae,erO ~ood ~
~elea~e promotirlg~ ~e~ult, like those desoril~ed ~n ~xDmples 1-3, and the productsmade ar~3 stable and non-~epar~ti~g on ~tor~e. S~lch i8 ~l~o the c~e when tha ~luorescent ~ye, colorant ~nd perfume are omitted ~rom ~he ~ormula~ of ~hi~
Qxample. Simil~rly, wher~ triethanolamine or ioniz;~ lt i~ present in ~uch $c~rmulas beyond the limit~ given the product becomes le~s 3table ~nd less effective in promoting 80il relea~e during wa~hir~g.
In other ~ari~tions in l;hi~ ~x~mple the no~ionic deterg~n~ a mixture of equal part~ of Neodol 25-7 ~nd Neodol 91-6 and the anionic detergent is Neodol 45 2. 25-S .
Re~ul~ Lke tho&e pr~vaou ly reported in Exa~pleæ 1-3 ~re obtainable in both te~ washing machirle ~snd ~ctual launder=
ing, employislg ei1:her top loading or ~ide loadi~3g co~ercial or hou~ehol~ wa~hing machine~. Su~h i~ o the ~it-aat~on ~5 when pH ~djuctment~ re with p~ta~ium hydroxi~e ~d ~he~

~2~7~ ~301-1271 such adjustments, made with sodium hydroxide or potassium hydroxide, are to pH's of 7.0, 6.6 and 7.4. Normally such pH adjustments will utilize less than 1% of sodium hydroxide solution, preferably less than 0.5% thereof and more preferably less than 0.2% thereof. In some instances the sodium hydroxide may be added as a formula constituent in said proportion as is known to give the desired pH control (based on past experience with the formula) but it will still be preferred for it to be added before the perfume, although such is not necessary.
Similarly, while a 20% sodium hydroxide solution concentration may often be preferable, other concentrations thereof may be employed, too.

Component Percent .
Neodol 25_71 32.0 Neodol 45-2.25S2 3.0 Alkaril QCJ soil release promoting polymer (15%) 13.4 Denatured ethanol (3A) 5.5 Sodium formate 1.0 Alcalase 2.5L3 0.6 Termamyl 120L4 0.4 Tinopal 5BM5 0.27 Dye (Polar Brilliant Blue) 0.0025 Perfume 0 4 Deionized water q.s.

100 . 00 7~

.1. Conderlsation prt~duct of apprc~ximat~iy 7 ~ol~
of ethyl~ne oxide ~nd ~ h~gher ~ty ~lcohol av~r~ging 12 to 15 carbon z~toms per le 2. Sodium ~alt of the ~uluriG ~cid ester Qf the nonionic conden ation product of higher f atty ~l~ohol ~Yeragis-g 14 ~o lS oarbon ~to~s, with 2 . 25 ~ole~ o e~thy3.one oxide _ _ 3 Proteoly~ic ~n~ , oold by Novo ~austri, A/S
(5~ enzyme act~ve ingredient, 65~ propylene glycol ~nd 30~ water)

4 . Amylolytic enzyme ~old by Novo Indu~ri ~ A/S
(5~ enzyme A.I., 65% propylene glycol and 30% wa~er)

5 A stilbene type f luores~ent brightene~, ~old ~y CI~A Geigy _ .. . _ . _ _ . . . . . ~ .
The formula liquid detergent i~ ~ade iirl a ~nanner 1i3ce ~hat of Example.l, ~y mixing toge~her a pc~rti~n cf the water with the ~nionic and nonionic detergents, followed by ndditit~ns of the ~oil relea~e promo~ing polymer, the ethanol, ~lu~re~ent bright ener (sometime~ dis~olv~d ~n eth~nol or ethanol~w~ter ~slution ) enzymes; $odium fonmat2 ~dis~olved in Rome water), ~ye, and any ~2~32~

ng w~te~. ~hen, an ~cid or bas~ (NaO~ i8 p~efe~ed) ~y be u~ed, ~ d~ired, ~o Adjust ~he p~ to w~thin th~
de~rod range, ~.y., 7~ When the pH is lower th~n ~ired ~n ~queous ~olution of ~odi~m hydroxide ~20%) ~ u~e~ to ~ e it to ~he desired lev~l~ The proportio~ a~ployed i~
~mall, e.g., abou~ 0.2% or less NaOH. ~ext~ the.fonmula pr~pQr~ion of perfume i~ ~dded. The product made i8 ~e~ted by bein~ ~tored a~ 43~3Vco for a w~ek, ~er which i~ i8 ob~erved to be a clear light blue li~uid in a ~t~ble aingle phase, ~entially l~ke that when it was ~de. ~he prot~a~e activity is bettex than that o~ ~ control liguid d~tergent containing 7~ ~odium dodecyl benzene sulfon~te, 2.8~ of t~i-ethanolamine (TEA) and no alcohol ~ther ~ulfate, and i~ much b~tter than in other compositions like the control but con~
t~ining no sodium ~o~mate in one ca3~ ~nd no TEA ln the other.
When bo~h the ~ormate ~d ~EA are omitted ~rom th~ ~ont2ol formula ~in ~11 ca~es the di~ferences are made up with wæter) ~o~h protease and 2myl~se ~ctivities ~e drastically g~duced.
The cont~ol and the firs~ tw~ variations ~re un~t~ble on 2D ~tor~ge, with the polymer ~ettling out.
Shortly after m~king the liquid deterg~t ~t ~8 us~d to wash ~ test load of clean ~brics, including sQ~e ~f polye~er material~ ~nd others of 65~ polya~ter ~nd 35~
co~ton material. ~he washing Gonditions are the ~ame ~8 those in Example 1 and the result~ are very similaxD ~xcep~ for the a~ditianal enzyma ic cleaning action obtained. .uch 7~
desirable activities are obtained despite the presence in the liquid of the sodium formate and any other salt(s).
When 2.8% of triethanolamine or TEA salt is present in the liquid detergent of the formula previously given, in replacement of part of the water thereof, after storage for a week at 43.3C. the detergent is found to have separated.
Separation also occurs under such conditions when the triethanolamine is absent and 5% of sodium sulfate is present in the formula. Storage at room temperature also results in such separation and corresponding diminution of soil release promoting activity of formulas containing the indicated proportions of triethanolamine and~or sodium sulfate, compared to the experimental formula.
Tests on the liquid detergent for enzymatic cleaning power are satisfactory, indicating that the proteolytic and amylolytic enzymes are functionally effective in the stable liquid detergent. This is so despite the fact that enzymes are often unstable in liquid detergent systems, especially at elevated temperatures.
~XAMPLE 6 In a modification of the formula of Example 5, when the proportion of Neodol 45-2.25S is increased to 5%, the proportion of ethanol is increased to 7.5%, 0.01% of Polar Brilliant Blue dye is used instead of 0.0025%, and the bright-ener is replaced by 0.24% of Tinopal 5BM and 0.1% of Phorwite BHC, a stable liquid detergent having soil release promoting properties, enzymatic effectiveness and detergency like that of the ~2~ 7~;

~c~mpo~it$s~ o~ Exa~nple 5, or better 9 re~ults . ~he liquid d~t~rgent ~ clear 3:~1uo ~d ~Ln tho ~oru:~ of dy~ i~y be of ~ l$yht oolor, ~o ghat ~ an be de~ir~bly ~:olor~d ~y use o~
o~r ~ye~, ~oo. Ir~ea!ld of the ;brightene~ ~y~tem ~ent~oned, e~slu~val-en~ proportion~ o~ Tinopal RBS-200, Tin~p~l 4226 .
tCIBA~Geigy) o~ ~ht~rwite RKH (~obay Chemic!al Company) ~d ~ixture~ ther~of ~y be ~ ltuted. In all ~uch ca~e~ the aub~t~ntivi~y of ~he fluor~scent l;>righte~er i~ ~proved due ~o ~che pre~ence ~ the ~igher fa~ty alcohol othoxylate 8ulfat~ and, unlike other ~$onic deterg~3nt~, ~uch ~ ~odiusn line~r ~lodecyl benzene Elul~on~te, the ~atty alcohol ~thoxyla~e ~ulfgl~e ~oes not de~t~bil$ze the polymer$c 60il rel~e promoting ~gent in ~he presence of enzyme and enzyme s~abilizer.
EXAMPLE ?
The formula 3f Ex~mple S i~ ch~nged ~o that 5% of Neodol 25-3S i~ pr~ent ~n~t-sd of the 3~ o~ ~e~dol 45-2.2SS. The produc~c made i~ ~ta3ble ~d clear ~ftQr ~torage at elevated temper&lture, ¢md the Alcalal3e and ~I!erDlamyl ~ilities ~qual those for the primary csntrol mentioned in Rxample $ . However, wh~n 2 . 8% of TE~ i~ alAo pres~n~ in the ~ormula the produ~t i~ ta~,o, w~th the QCJ ~oil r~
poly~Der 1Oce~1ating out ~fter ~tor~ge at 43C. ~or one w~ek .

2~ii 2301-1271 The contents of the various experimental formulas of this inven-tion given in Examples 5-7 are varied ~10% and -25%, while keeping the proportions of the various materials within the ranges recited in the specification.
~n such formulations instead of employing the QCJ soil release polymer (aqueous solution), 2% of QCF (Alkaril Chemicals CAS
9016-88-0) and 11.~% of water are substituted, with the QCF
first being dissolved in -the water. Also other enzymes, stabilizers, alcohols and colorants, as described in the speciflcation, may be employed within the proportion ranges given. The detergents resulting are clear, stable and non-separating and possess good soil release promoting, cleaning and brightening properties, like those described in Examples 5 7.. Such is also the case when -the fluorescent dye, colorant and perfume are omitted from the formulas of this example.
Similarly, when triethanolamine or ionizable sal-t is present in such formulas beyond the limits given, and when other anionic detergents, such as sodium higher alkyl benzene sulfonates, are substituted for the alcohol ethoxylate sulfate the product becomes less stable and less effective in promoting soil release during washing, and when the sodium formate is omitted the effects of the enzyme are lost after only a few days storage at the elevated test temperature.

"~

~2~ 7~ii In other variations in this example the nonionic detergent i5 Neodol 23-6.5 or a mixture of equal parts of Neodol 23-6.5 and Neodol 25-7, with the same total proportion being employed and a stable effective product results. Also, the alcohol ethoxylate sulfate may be an equal mixture of Neodols 25-3S and 45-2.25S, and good results are obtained.
With such variations results like those pre~iously reported in Examples 5-7 are obtainable in both test washing machines and household and commercial washing machines, which are either top loading or side loading. Such is also the situation when pH adjustments are made with potassium hydroxide and when such adjustments, made with sodium hydroxide or potassium hydroxide, are to pH's of 6.6, 7.4, 7.9, and 8.6. Normally such pH adjustments will utilize less than 1% of sodium hydroxide solution, preferably less than 0.5% thereof and more preferably less than 0.2% thereof. In some instances the sodium hydroxide may be added as a formula constituent, in said proportion as is known to give the desired pH control (based on past experience with the formula) but it will still be preferred for it to be added before the perfume, although such is not necessary. Similarly, while a 20% sodium hydroxide solution concentration may often be preferable, other concen-trations thereof may be employed too.
From Examples 5-8 and the preceding description it is seen that the present in~ention is of a stable ~2;~:827~

and attractive liquid detergent which contains various compon-ents that might have been expected to interfere with the stability of the final product~ Yet, surprisingly, a stable product is obtainable in accordance with the invention. Such product has desirable soil release promoting, soil decomposing, fluorescent brightening (when the brightener is present) and detergent properties. Several of the components of the invented compositions exert dual effects therein. For example, the alcohol ethoxylate sulfate aids detergency and helps to make the substrates (laundry fibers) more substantive so that the fluorescent brighteners are more effective. The sodium formate, which is a stabilizer for enzymes, does not destabilize the soil release agent, as would have been expected. The various components of these liquid detergents coact to produce a surprisingly attractive, stable and effective detergent composi-tionO Thus, it is seen that the present compositions represent an unpredictable advance in the art of making stable products which are preferably attractively clear (transparent or txanslucent), although in some instances opalescent and semi-clear or intentionally creamy products may be made.

;"
,.

~2~ 5 X~PLE 9 Percent ~eodol 25~7 22.0 Alkaril ~CJ ~oil relea~e promoting polymer (15~) 6.7 S ~dogen 4626 ~
Propylene glycol 5.0 Denatured ~thanol (3A) 2.2 ~odium formate 1.0 Al~ala~e 2.5L 0.45 10 ~ermamyl ~20L 0.3 Dye (~olar Brilliant Blue) 0O0025 Perfume 0.4 Deionized water q. 8 .
100. 00

6. Di-coco dimethyl ammonium chl~ride, ~ld by Sherex Industries (contains 75~ ~ctive ingredient, 14 i~opr~panol and 11~ water) ~ he ~ormula liquid detergent is made in a manner e~entially like ~hat u~ed for Examples 5 8 but i~cluding the ~abric softener and ~mitting anionic detergent. The product made i8 te~t~d by being stored ~t 43.3C. ~or ~ week, after which it i8 ob~erved to ~e a clear ligh~ bl~e liquid in a ~table single phas~, s~sen i~lly l~k~ that wh~n i~ was made. The protease ac~ivity i8 70~ of that ~hen ~he liquid detergent was made and the ~myla~e a~tiv~ty i~ ~5% ~f i~8 initial ~alue.

~2 -~ 275 2301-1271 Shortly after making the li~uid detergent it is used to wash a test load of clean fabrics, including some of polyester materials and others of 65% polyester and 35% cotton material. The washing concentration and the other conditions for that washing are the same as in Example 5 and the results are essentially the same, too, except for improved fabric softening being obtained in this example. Similarly, when 2%
or 3~ of triethanolamine or TEA salt is present in the liquid detergent of the formula previously given, in replacement of part of the water thereof, after two weeks of storage at 43.3C.
the detergent is found to have separated. Separation also occurs under such conditions when the triethanolamine is absent and 5% of sodium sulfate is present in the formula.
Also, when the triethanolamine is present, the soil release promoting action of the li~uid detergent is significantly decreased. Storage at room temperature also results in such diminution of soil release promoting activity of formulas containing the indicated proportions of triethanolamine and/or sodium sulfate, compared to the experimental formula. When the amount of soil release promoting polymer is decreased to 0.8%
or increased to 2~ the same types of results as given above are obtained.
Tests on the liquid detergent for fabric soften-ing and enzymatic cleaning power are satisfactory, indicating that the quaternary ammonium halide and the proteolytic and 122827~ 2301-1271 amylolytic enzymes are functionally effective in the stable liquid detergent. This is so despite the fact that enzymes and quaternary ammonium halides are often unstable in liquid deter-gent systems, especially at elevated temperatures. However, replacement of propylene glycol with higher glycols, such as those of 8 to 12 carbon atoms, will result in separation of the product into two phases. In the particular formula given a complete replacement of propylene glycol with hexylene glycol will also cause phase separation although hexylene glycol and amylene glycol are considered to be useful glycol components of the present type of li~uid detergent if employed in lesser proportions and if employed in conjunction with lower glycols, ~uch as propylene glycol. Similarly, if the di-coco dimethyl ammonium chloride is replaced by di-hydrogenated tallow dimethyl ammonium chloride, the li~uid detergent also separates into two phases, especially in the presence of the hexylene glycol (in replacement of propylene glycol). However, again, in some circumstances the di-hydrogenated tallow dimethyl ammonium chloride can be employed in a stable product, by decreasing the proportion thereof present and mixing it with di-coco dimethyl ammonium chloride or other di-higher alkyl di-lower alkyl quaternary ammonium halides wherein the higher alkyls are of 12 to 14 carbon atoms and the lower alkyls are of 1 or 2 carbon atoms. As an alternative, a more hydrophilic quaternary ammonium halide, such as ditallow dimethyl ammonium chloride, which possesses a greater degree of unsaturation and thus is more tolerant of electrolytes, may be successfully used.

8~

~hE 1 0 When, $n th~ primary formula o~ Example 9, the ~c~n~02l1c ~terg~t ~ pl~ by ~ioodol 23~6 ~ 5, ~. 01~
~f ~l~r 13rillla~t Ellue ~ye i~ u~ed lA~t~ad o~ 0.0025%, Imd a 5 ~ilbene 1uo~esoent barightener i~ present, e.9., T~nopal ~s-20a, T~nopal 5BM o~ Tinopal 4226 (all ~old by C~ Geigy), OE Phs~wite E~ o~ Phorwit~ ~BP ~old by Mobay Chemical Co.) ~o the e~xt~t of O.l~,a ~table ~md ~fectiv~ pr~luet which unction~
like that o~ Example 9 re~ult~ but it ha~ a grea~er ~hitening 1~ pow2r due ~co ~he presence o~ t~e brighten~, wh~h 1~ ~table ch~ product. The produc~ o~ this example 1~ alao o~ ~
~ttracti~re cl~ar sppear~nce and i6 ~table on ~to~açle.

_ . _ . .. _ . . .__ The contents o~ the experimental formulas of Example~ 9 ~nd 10 are varied +10% and +254, while keeping the props~rtions of the various materials within the r~nge~
re~ited in ~he speoification. In such formulation~ in~ead of ~mpls:>ying ~3 QCJ ~oil r~lease polym~r (~q~aeous ~s~lution), iE QCF ~Alk~ril Chemica~l CAS ~016 88-0) ar~d 5~74 of w~er 20 are substituted, with the QCF fir~t being dis~c~lved ~n the water. ~180 other 0nzyme~, 8tabilizer8, ~abri~ ~ofteners, Çllyc~l~, alcohol~ ~nd oolorants, as desc~ ed in ~ peci~ica tion, l~aay be ~mployed within ~he proportion r~nge~ given~ The ~letergent~ resul~ing are clear, ~table ~nd non-6epar~ti~ag and 25 po~e~l; good ~oâl releas~ promoting, softening, oleaning a~d brightesling propertie~ ce ~:ho8e descrLbed la ~x~mple6 9 ~nd 10.

- ~5 2~7~

.
~uch is Rl~o ~ ca~e when th~ ~luor~cent dy~, c:alor~t and pe~iE~ ~re omitt~d ~rom ~he ~ormula~ of thi~ ~ac~pl~.
8~1a~1y, when ~r~e~hanol~i~e or ~oniz~ al~ 1~ present ~ ~uch formul~f~ boyon~ the l~mit~ giv~n, the prc3duct b~comes 5 les~ 3table as~d le~ ecti~e in promo~ing ~oil rel~ase ~u~:~ng w~shir.g, ~nd when ~e ~oaium ~oa~ce ~d ~lycol ~e o~tt~d tlle ef~ec:~s o~ enzyme ~re lo~t a:l~ter only 2 f~w ~tor~ge. ~t the elev~ted testing t~peratureO
In other vari~tion~ ln ~hi8 ~xample the rlonionic detergent i8 a ~ixture of e~qual part~ o ~3eodol 23-6. 5 and N~odol 25-7, wi~h 1:he 6a~e total propor~iorl ~eing ~mployed.
Result~ like those previously reported in Example~ 9 and 10 . _ . _ . .
~re obt~inable in both test wa~hing ~achines Rnd hou~ehold ~nd commercial wa~hing machines, which are ei~her top loading 15 c~r ~ide loading. Such i~ also the situation when pH ~dju~t-ments are ~de with potas~ium hyd~oxide ~nd wherl ~ach ~d~ ust-m~nt~, ~ade wi~h ~odium hydrox$~1e or pol:2~58ium hydr~3xid~, are to pH'~ o~ 6.6, 7.4, 7.9, I~nd 8.6.
From Examples 9~ nd the preceàing examples, ~s 20 well as the ~e~cription, it i~ æeen ~at the present ~nven-tion i8 of a ~table and attractive liquid de~ergent de~pite the ~act ~hat it cont~in~ various co~ponents that ~i~ht h~ve been expected to inter~ere wlt~ the ~tability of ~:he final product. Yet, ~urpri~ingly, a ~table product i~. obtained, 25 which ha~ desirable ~oil release promoting, ~abric:

-- ~6 --

7~

softening, soil decomposing and detergent properties. Several of the components of the invented compositions exert dual effects therein. For example, the propylene glycol may help to solubilize lipophilic materials in the formulation while at the same time helping to stabilize the enzymes. The sodium formate, which is a stabilizer for enzymes, does not destabilize the soil release agent, as would have been expected. ~lthough some quaternary ammonium halides and some glycols can destabilize liquid detergent formulas like those of this invention, the present materials do not do so. This is surprising because hydrophobic quaternary ammonium halides, which are normally flocculated from solution by electrolytes, are stable in the invented liquid detergents. Thus, it is seen that the present compositions represent an unpredictable advance in the art of making stable li~uid detergents.
The invention has been described with respect to various illustrations and preferred embodiments thereof but is not to be limited to these because one of skill in the art, with the present specification before him, will be able to util-ize substitutes and equivalents without departing from theinvention.

Claims (17)

WHAT IS CLAIMED IS:

1. A soil release promoting liquid detergent comprising a detersive proportion of nonionic detergent or a mixture of nonionic and anionic detergents, a soil release promoting proportion of a soil release promoting polymer of polyethylene terephthalate and polyoxyethylene terephthalate and an aqueous medium, in which the pH is in the range of 6 to 9 and in which there is contained no more than 2% of water soluble ionizable salt which is not an anionic surface active water soluble salt.

2. A liquid detergent according to claim 1 wherein the proportion of nonionic detergent or a mixture of nonionic and anionic detergents is within the range of 25 to 50%, the proportion of soil release promoting polymer is within the range of 0.5 to 10% and the soil release promoting polymer is a polymer of polyethylene terephthalate and polyoxyethylene terephthalate of a molecular weight in the range of about 15,000 to 50,000, wherein the polyoxyethylene of the polyoxyethylene terephthalate is of a molecular weight in the range of about 1,000 to 10,000, with the molar ratio of ethylene terephthalate to polyoxyethylene tere-phthalate units being within the range of 2:1 to 6:1.

3. A liquid detergent according to claim 2 which comprises from 20 to 40% of nonionic detergent, which is a condensation product of a higher fatty alcohol of 10 to 20 carbon atoms and 3 to 20 moles of ethylene oxide per mole of higher fatty alcohol, from 3 to 15% of anionic detergent selected from the group consisting of sodium linear higher alkylbenzene sulfonate wherein the higher alkyl is of 10 to 18 carbon atoms, and sodium higher fatty alcohol polyethoxylate sulfate wherein the higher fatty alcohol is of 10 to 20 carbon atoms and the polyethoxy is of 3 to 20 ehoxy groups, and from 3 to 15% of a lower alkanol of 1 to 3 carbon atoms.

4. A liquid detergent according to claim 3 in which the nonionic detergent is a condensation product of a higher fatty alcohol of 12 to 15 carbon atoms and 6 to 11 moles of ethylene oxide per mole of higher fatty alcohol, the anionic detergent is sodium linear higher alkylbenzene sulfonate wherein the higher alkyl is of 12 to 13 carbon atoms, the soil release promoting polymer is of a molecular weight in the range of 19,000 to 25,000, the polyoxyethylene of the polyoxyethylene terephthalate is of a molecular weight in the range of 3,000 to 4,000, the molar ratio of ethylene terephthalate to polyoxyethyl-ene terephthalate units of the polymer is within the range of 3:1 to 4:1 and the molar ratio of ethylene oxide to phthalic moiety therein is from 20:1 to 30:1, the lower alkanol is ethanol, the content of water soluble ionizable salt other than anionic surface active water soluble salt is less than 0.5%, the liquid detergent contains less than 0.2% of triethanolamine and the proportions of nonionic detergent, anionic detergent, soil release promoting polymer, alcohol and water are within the ranges of 25 to 35%, 5 to 10%, 1 to 6%, 5 to 12% and 30 to 60%, respectively.

5. A liquid detergent according to claim 4 consisting essentially of about 32% of nonionic detergent which is a condensation product of a higher fatty alcohol of 12 to 15 carbon atoms and about 7 moles of ethylene oxide per mole of higher fatty alcohol, about 7% of sodium dodecyl-benzene sulfonate, about 2% of soil release promoting polymer of a weight average molecular weight of about 22,000, in which the polyoxyethylene of the polyoxyethylene terephthalate is of a molecular weight of about 3,400, the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate units of the polymer is about 3:1 and the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate units of the polymer is about 3:1 and the molar ratio of ethylene oxide to phthalic moiety therein is about 22:1, about 0.2% of fluorescent brightener, about 8% of ethanol, and about 51% of water, wherein the pH is about 7.8, which liquid detergent contains no triethanolamine and in which the content of any water soluble ionizable salt other than anionic surface active water soluble salt that may be present is less than 0.3%.

6. A process for making a soil release promoting liquid detergent which comprises mixing together a detersive proportion of a nonionic detergent or a mixture of nonionic and anionic detergents and a soil release promoting propor-tion of a soil release promoting polymer of polyethylene tere-phthalate and polyoxyethylene terephthalate in an aqueous medium and admixing with such mixture an aqueous neutralizing agent to adjust the pH of the detergent to within the range of 6.1 to 7.9, which detergent, after such neutralization, contains no more than 1% of water soluble ionizable salt other than anionic surface active water soluble salt.

7. A process according to claim 6 wherein the liquid detergent comprises 25 to 35% of a nonionic detergent which is a condensation product of a higher fatty alcohol of 12 to 15 carbon atoms and 6 to 11 moles of ethylene oxide per mole of higher fatty alcohol, 5 to 10% of anionic deter-gent which is a sodium linear higher alkylbenezene sulfonate wherein the higher alkyl is of 12 to 13 carbon atoms, 1 to 6% of a soil release promoting polymer which is of a molecular weight in the range of 19,000 to 25,000 and in which the polyoxyethylene of the polyoxyethylene terephthalate is of a molecular weight in the range of 3,000 to 4,000, the molar ratio of ethylene terephthalate to polyoxyethylene tere-phthalate units of the polymer is within the range of 3:1 to 4:1 and the molar ratio of ethylene oxide to phthalic moiety thereof is from 20:1 to 30:1, 5 to 12% of ethanol, 0.1 to 0.5% of fluorescent brightener and 30 to 60% of water, with the content of water soluble ionizable salt other than anionic surface active water soluble salt being less than 0.5% and the content of triethanolamine being less than 0.2%, and in which the neutralization is effected with an aqueous solution of sodium hydroxide.

8. A stable soil release promoting enzyme-containing liquid detergent according to claim 1 comprising a detersive proportion of a nonionic detergent, a detergent supplementing and fluorescent brightener substantivity increasing proportion of a higher fatty alcohol polyethoxylate sulfate detergent, a soil release promoting proportion of a soil release promoting polymer of polyethylene terephthalate and polyoxyethylene terephthalate, a proportion of enzyme sufficient to enzymatically hydrolyze proteinaceous and/or amylaceous soils on fabrics during washing thereof with an aqueous washing solution of the liquid detergent, a stabilizing proportion of a stabilizer for the enzyme(s), and an aqueous medium, in which the pH is in the range of about 6 to 9 and in which there is present no more than 2% of water soluble ionizable material other than the higher fatty alcohol polyethoxylated sulfate detergent.

9. A liquid detergent according to claim 8 wherein the proportion of nonionic detergent is within the range of 25 to 40%, the higher fatty alcohol polyethoxylate sulfate is a sodium salt and 1 to 8% thereof is present, the soil release promoting polymer is a polymer of polyethylene terephthalate and polyoxy-ethylene terephthalate of a molecular weight in the range of about 15,000 to 50,000, wherein the polyoxyethylene of the poly-oxyethylene terephthalate is of a molecular weight in the range of about 1,000 to 10,000, with the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate units being within the range of 2:1 to 6:1, and 0.5 to 5% thereof is present, the enzyme includes a proteolytic enzyme, and 0.005 to 0.1% thereof is present, and from 0.2 to 2% of stabilizer for the enzyme is present.

10. A liquid detergent according to claim 9 which comprises from 28 to 36% of nonionic detergent, which is a condensation product of higher fatty alcohol of 10 to 20 carbon atoms and 3 to 20 moles of ethylene oxide per mole of higher fatty alcohol, 2 to 7% of sodium higher fatty alcohol polyethoxylate sulfate wherein the higher fatty alcohol is of 10 to 20 carbon atoms and the polyethoxylate is of 1 to 20 ethoxy groups per mole, 0.02 to 2% of fluorescent bright-ener(s), 0.01 to 0.1% proteolytic enzyme, 0.005 to 0.05%
of amylolytic enzyme, 0.5 to 1.5% of stabilizer for the enzyme and from 3 to 12 % of a lower alkanol.

11. A liquid detergent according to claim 10 in which the nonionic detergent is a condensation product of a higher fatty alcohol of 12 to 15 carbon atoms and 6 to 11 moles of ethylene oxide per mole of higher fatty alcohol, the higher fatty alcohol polyethoxylate is one wherein the alcohol is of 10 to 15 carbon atom and contains 1 to 5 ethoxy groups per mole, the fluorescent brightener is a stilbene brightener, the soil release promoting polymer is of a molecular weight in the range of 19,000 to 25,000, the polyoxyethylene of the polyoxyethylene terephthalate is of a molecular weight in the range of 3,000 to 4,000, the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate units of the polymer is within the range of 3:1 to 4:1 and the molar ratio of ethylene oxide to phthalic moiety therein is from 20:1 to 30:1, the enzyme stabilizer is sodium formate, the lower alkanol is ethanol, and the proportions of nonionic detergent, higher fatty alcohol polyethoxylate sulfate, fluorescent brightener, soil release promoting polymer, proteolytic enzyme, amylolytic enzyme, sodium formate, ethanol, and water are within the ranges of 30 to 34%, 2 to 6%, 0.1 to 1%, 0.8 to 3%, 0.02 to 0.05%, 0.01 to 0.03%, 0.7 to 1.3%, 4 to 9%, and 46 to 62%, respectively.

12. A liquid detergent according to claim 11 which is clear and consists essentially of about 32% of a nonionic deter-gent which is a condensation product of a higher fatty alcohol of 12 to 15 carbon atoms and about 7 moles of ethylene oxide per mole of higher fatty alcohol, about 5% of sodium higher fatty alcohol polyethoxylate sulfate wherein the higher fatty alcohol is of 12 to 15 carbon atoms and the ethoxylate is of about 3 moles of ethylene oxide per mole of higher fatty alcohol, about 0.3% of stilbene fluorescent brightener, about 2% of soil release promoting polymer of a weight average molecular weight of about 22,000, in which the polyoxyethylene of the polyoxyethylene terephthalate is of a molecular weight of about 3,400, the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate units of the polymer is about 3:1 and the molar ratio of ethylene oxide to phthalic moiety therein is about 22:1, about 0.03% of proteolytic enzyme, about 0.02% of amylolytic enzyme, about 1% of sodium formate, about 5.5% of ethanol, about 0.4% of perfume and about 54% of deionized water.

13. A stable fabric softening, soil release promoting enzyme-containing liquid detergent according to claim 1 comprising a detersive proportion of a nonionic detergent, a soil release promoting proportion of a soil release promoting polymer of polyethylene terephthalate and polyoxyethylene terephthalate, a fabric softening proportion of a quaternary ammonium halide fabric softener, a proportion of enzyme suffi-cient to enzymatically hydrolyze proteinaceous and/or amylaceous soils on fabrics during washing thereof with an aqueous washing solution of the liquid detergent, a stabilizing proportion of a stabilizer for the enzyme(s), and an aqueous medium, in which the pH is in the range of about 6 to 9 and in which there is present no more than 2% of water soluble ionizable material.

14. A liquid detergent according to claim 13 wherein the proportion of nonionic detergent is within the range of 10 to 35%, the soil release promoting polymer is a polymer of polyethylene terephthalate and polyoxyethylene terephthalate of a molecular weight in the range of about 15,000 to 50,000, wherein the polyoxyethylene of the poly-oxyethylene terephthalate is of a molecular weight in the range of about 1,000 to 10,000, with the molar ratio of ethylene terephthalate of polyoxyethylene terephthalate units being within the range of 2:1 to 6:1, and 0.5 to 5%
thereof is present, the quaternary ammonium halide is a di-higher alkyl dimethyl ammonium halide and 1 to 10% thereof is present, the enzyme includes a proteolytic enzyme, and 0.005 to 0.1% thereof is present, and from 0.2 to 2% of the stabilizer for the enzyme is present.

15. A liquid detergent according to claim 14 which comprises from 15 to 30% of nonionic detergent, which is a condensation product of higher fatty alcohol of 10 to 20 carbon atoms and 3 to 20 moles of ethylene oxide per mole of higher fatty alcohol, 3 to 8% of quaternary ammonium halide, which is chloride and in which the higher alkyls are of 12 to 18 carbon atoms, 0.005 to 0.05% of proteolytic enzyme, 0.005 to 0.05% of amylolytic enzyme, 0.5 to 1.5% of a stabi-lizer for the enzymes and from 1 to 10% of lower alkanol.

16. A liquid detergent according to claim 15 in which the nonionic detergent is a condensation product of higher fatty alcohol of 12 to 15 carbon atoms and 6 to 11 moles of ethylene oxide per mole of higher fatty alcohol, the soil releasing polymer is of a molecular weight in the range of 19,000 to 25,000, the polyoxyethylene of the polyoxyethylene terephthalate is of a molecular weight in the range of 3,000 to 4,000, the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate units of the polymer is within the range of 3:1 to 4:1 and the molar ratio of ethylene oxide to phthalic moiety therein is from 20:1 to 30:1, the quaternary ammonium halide is di-coco dimethyl ammonium chloride, the enzyme stabilizer is sodium formate, the lower alkanol is ethanol, from 2 to 8% of propylene glycol is present and the proportions of nonionic detergent, soil release promoting polymer, fabric softener, proteolytic enzyme, amylolytic enzyme, sodium formate, ethanol, propylene glycol and water are within the ranges of 20 to 25%, 0.8 to 1.5%, 3 to 6%, 0.015 to 0.03%, 0.01 to 0.025%, 0.7 to 1.3%, 1.5 to 3%, 3 to 8%, and 50 to 70%, respectively.

17. A liquid detergent according to claim 16 which is clear and consists essentially of about 22% of a nonionic detergent which is a condensation product of a higher fatty alcohol of 12 to 15 carbon atoms and about 7 moles of ethylene oxide per mole of higher fatty alcohol, about 1% of soil release promoting polymer of a weight average molecular weight of about 22,000, in which the polyoxyethylene of the polyoxyethylene terephthalate is of a molecular weight of about 3,400, the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate units of the polymer is about 3:1 and the molar ratio of ethylene oxide to phthalic moiety therein is about 22:1, about 4.5% of di-coco dimethyl ammonium chloride, about 0.023% of proteolytic enzyme, about 0.015% of amylolytic enzyme, about 1% of sodium formate, about 2% of ethanol, about 6% of propylene glycol, about 0.4% of perfume and about 63% of deionized water.