Note: Descriptions are shown in the official language in which they were submitted.
~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,
-- 6
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,
-- 8 --
~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~
12
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~
- 14 -
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.
- 16 -
~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
- 18
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
-- 19 --
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$ng polymer.
In othex comparison~, when sub~tantial proportion~ o~ water
801uble ionizable ~al~, ~uch as 5% of s~dium ~ul~ate, or ~ore
than 1~ of triethanolamine or a salt thereo~, ~re present i~
the liquid detergent it i~ found that a~ter storage at
elevated temperature (43DC.) ~or ~wo weeks, s~mulati~g a
leng~hier ~torage at room tempera~ure, pha~es ~epar~te ~rom
the liquid detergent body and th~ ~oil ~ele~e promoting
properties of the polymer contai~ed ~herein are diminished,
a~ are the enzymatic and ~of tening activitie~, when ~uch
materials ~re in the formula. When the enzy~e stabilizer
i8 ~mitted enzymatic action i~ decreased ~ubstantially on
~torage. ~hus, ~he c~mpositions o~ thi~ invention ~re
imporkant because they ~re ~table, resulting ~n ~ore
ef~ective produc~s ~or the purpo~es intsnded, 80il rele~se
improvement, cleaDing e~fe~ts and 60~ten~y o~ the
- 26 -
27~
~br$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.
EXAMPLE 1
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
27 -
~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
- 28 -
~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
- 30 -
~2;~:~32~i
2301-1271
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~
33 -
~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.
EXAMPLE 5
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
- 34 -
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
35 -
~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
- 36
2301-1271
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
- 37 -
~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<ure, ¢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 .
3 8
2~ii 2301-1271
EXAMPLE 8
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.
- 39 -
"~
~2~ 7~ii
2301-1271
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
- 40 -
~2;~:827~
2301-1271
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.
- 41 -
;"
,.
~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
- 43 -
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.
- 44 -
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.
_ . _ . .. _ . . .__
EXAMPLE 11
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~
2301-1271
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.
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