CA2006527A1 - Enzymatic liquid detergent compositions - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

The invention pertains to enzymatic liquid detergent compositions in which the enzymes comprise a mixture of lipolytic enzymes and proteolytic enzymes. The storage stability of lipolytic enzymes in these proteolytic enzymes containing liquid detergent compositions is enhanced therein by the inclusion of a lower aliphatic alcohol such as ethanol and a salt of a lower carboxylic acid such as sodium formate and by providing for a detergent-surfactant system therein which predominantly consists of a nonionic detergent.

The lipases are fungal lipases ex Humicola lanuginosa or Thermomyces lanuginosus. The proteolytic enzymes are preferably of the subtilisin type.

Description

c~ l l EDZY~at1C Llquid Det~ ~eQ~6 ~omp7sltlon~

BACKGROUND OF THE INVENTION
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P I E L D O F ~ H E I N V E N T I O N

The present inventlon relate~ to enzymatic liquld detergene composltions comprlsing llpolytic enzymes e~ numlcola lanu~inosa or Thermomyces ... .
lanu~lnosus and pro~eolytic enzymes D E S C R I P T I O N O F T H E R 1~ L A T E D A R T
._) ' ' ' 'enzymatlc }lquid detergent composlti~o~ are well-know?~ in the artO ~ost of the prlor proposals are howe~er concerned ~ith enzy~atlc llquld detergent composltlons whlch contain a pro~eolytlc enzywe lngredlent, or a mixture thereof wlth amylolytlc enzymes.

One of the problems, lnberent to the use of enzy~es ln l~quld detergent compositions i8 their stabillty ln suich liquid detergent co~positions. The art i8 crowded wlth a varlety of proposals to improve the ~csbllley o~
enzyme3, particularly proteolgtic and/or ~mylolytlc enzr~es i~ liquid tetergent co~position3. Thu~, ~or example, ln European Patent Speclflcation~ 28,865 and 28,866 lt has been prop~sed to ?~tablllze enzym ln llquld detergent compositions by the Inclusion therelo of a certain amount of enzyme-sccesslble calclum and n certaln amount of a short chain carboxyllc acld or a salt thereof, ?3uch a8 sodlum formate. ~he enzy~es are preferably proteolyeic e~zymes.

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.- ZOal~iS~:7 r~he art ls far less concerned with lipolytic enzymes in liquld deeergent composltlons. Although lipases have recently been proposed for Inclusion in detergent compositions, see e.g. U.S. Pa~ent 4,707,291 ~Tho~ ot ~
they have been malnly consldered for inclu~lon in particulate detergent compositlons. In Europesn Patent Appllcatlon 0258,068 a partlcular llpase e~ ~u~icola lanuglnosa ~s proposed a~ a detergent nddltlve, also for lnclusion ln liquid detergent compositlon~. Accordlng to ehis reference, l, 2 - propanediol and calclum salts Improve the 6tabillty of thls lipase in liquid systems. Sorbitol has only ~ sllght ~tabillzlng effectO

The present lnventioa ls particularly conoerned with the sbov2 llpa~es ex -j Humicola lanuginosa or Ther~o~ces lanuginosus! herelnafter collectlvel~
re~erred to as ex Hu~icola lanuginosa.

Since these llpases, like all enzyme~, are proteir~, they are suscept~ble to proteolytic attack by proteolytlc enzy~e~, which further reduce8 the ~tabllity of these llp~ses in co~positions also comprislng proteolytlc enzymes.

It is therefore an ob~ect of the present inventlon ~o i~prove th~ seorage st~bility of these llpolytlc enzyQes e~ Hu~icol~ lanuglnosa or Then~omyces lanuRinosus ~n llquld detergent co~posltions which al80 co~prise proteolytic enzy~es.

SUMMARY OF TH~ INVENTION
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It bas no~ been found, that the lnclusion of ~ lo~er alipha~lc ~Icohol aod '.. ..

21D~52:7 salt of a lower csrboxyllc acld In a proteolytic enzyme contaioing llquid detergent compo~ition whlch co~prlses a detergen~ active ~y~e~ ~hieh consist~ predomlnantly of ~ nonionlc detergene signlficantly i~proves the storage stabillty of lipolytic enzymes ex Humlcola lanuginosa in ~u~h liquid detergent compositions in the presence of proteolytic enzy~e~

Consequently, in lts broade~t aspect the present lnvention relaees to a pro~eoly~ic enzy~es containing liquld detergent composlt~on co~prlsing a detergent-active system which consist~ predominantly of a nonionic detergene, ~nd furthen~ore comp~isl~g a lipolyeie enzy~e e2 ~umicola lanuginosa, a l~wer aliphaelc alcohol and a salt of a lower carbo~ylic acid as the e~sentlal co~po~ene~

DETAILED DESCRIPTION OF THE INVENTIO~
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The flrst essentlal componqnt of the liqu~d detergent compos1tlon Is the nonlonlc detergen~. Nonlo~c detergents are ~ell known ln ehe ~rt. They are normally reaction products of co~pouod~ haYing a hydrophoblc group a~d a reactive hydrogen atom, for exsmple allph~tic alcohol~, acid~, amldes or alkylphenols uith alkylene oxides, especlally ethylene oxide either ~lone or witb propylene oxlde. Typlcal e~a~ples of ~ultsble non10nlc detergenes ~re alkyl (C6-C22) phenol-ethylene oxlde condensatlo~ products, wieh gener~lly 5-25 ~ole~ of ethylene oxide per ~ole of alkylphenol, the condensation products of sliphatie Cg-C18 pri~ary or aecond~ry, linear or branched chain ~lcohols with generally 5-40 moles of ethylene oxlte, ~nd products ~ade by eondensatIon of ethylene o~ide and propylene sxide ~ith eehylenedlamlne. Other nonlon~c detergents lnclude the block cop~ly~ers of . . :~ `:~; ' ' " . ~: L. ~ t~ -f ~thylene oxide and propyle~e ox~de, a ~ylpolyglycosldes, tertiary amine-oxide~ and dlalkylsulphoxld~ The condensatlon products of the alcohols with ethylene oxlde are ~he preferred nonIonic deter~ents.

In the presene inventlon, one of the sbove nonionlc detergents ~ay be used as well as mlxture~ thereof. The nonionlc detergent or detergents ~ay form the sole detergent-actlve system ln the llquid detergent compo~ition, or they ~ay be in admixture ~lth oeher deeergene-active compounds such ~9 snlonlc, catlon~c, zwitterlonic or ampholytlc de~ergeotoactive compounds9 i~8 long a~ the nonlonic detergent const~tutes ehe ~a~or psrt of the detergent-actlve sy~te~. The nonionic detergent should for~ a~ leasL 502, .
usually at least 60Z, prefersbly at least 70X by velght-of the detergent-act~ve system. The total a~ount o~ detergent-actlve compound ln the composltlon ranges from lO-90, usually from 15-70Z b~ welght.

The second essential lngredlent of the presene lnventlon 18 the llpolytlc enzyme. This llpolytlc enzy~e ls a fungal llpase produclble bg Humicola lanuginosa and Ther~o~Yces lanuginosus.

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Examples of fungal lipi~es as defined above are the lipases e~ ~uMlCOla ~ :~
lanuginosa as de~cribed ln the a~oresald European Patene Appllcatlon 02S8,068 (NOVO), as well a~ tbe lipase obtalned by ~loning the ge~e ro~
Humicola lanu~inosa and expres~ing this gene in Asperglllu~ oryzae, commerclally nvallable from NWO Indu~tri AIS under the trade naoe ;
~Llpolase~ . Thls Llpolase ls n preferred llpase for use ln the pre~ent -lnvention.

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2(~0652~
,-~he llpases of the present invention are included 1~ the liquld detergent .
composltion ln such an a~ount that the flnal compo91tlon has a llpolytic enzyme act~vlty of from 100 to 0.005 LUI~g, preferably 25 to 0.05 W/mg of the composltion.

A Lipase ~nlt (LD) is thst amount of lipase ~hich produce~ l/u~ol of tl~ratable fatty acld per minute ln a p~ stat. under the following conditions: te~perature 30C; pH = 9.0; substrate 1~ au e~ulslon of 3.3 w~.X of olive oll and 3.3X gum arsbic, in the presence of 13 mmol/l Ca and 20 ~molll NaCl ln 5 ~mol/l Tris-buffer.

Naturally, mixtures of the above llpase~ can be used. The lipase~ can be ~sed ln thelr non-purified form or ln 8 purlfled ~or3, e.g. purified ~i h the ald of well-known adsorption ~ethods, s~ch as phenyl ~epharose ad~orptldn technlques.

The third essentlal ingredient of the present lnven~ion ia the lower d lphatic alcohol. Thls alcolhol can be ~ethanol, ethanol, propanol ~nd isopropanol or mixeures thereof. A preferred alcohol i~ ethanol.

The a~oun~ of lower aliph~tic alcohol to be used ln ~he present iDveneion depend~ to Aome extent on the co~posltion of the llq~ld detergent, but in genersl It varle~ fro~ 1 - lO2 by welgbt, preferably fro~ 2 - 3Z by weight of the flnal co~posltion.

The fourth essential lngredlent of the present invention is the 6alt of the lower aliphatlc carboxyllc acid. Th~s scld contalns fro~ 1 - 3 carbon ; : : : i , . ~ , : .

2~527 iower al~phatlc ~arboxylic scid. Thls acld contaln~ from 1 - 3 carbon atoms, such as formlc acld, ~cetlc acid and proplonic acld. It ~y be lncIuded tn the llquld detergent composltlon as an acid, the ~alt b~
formed ln sieu there~n by methathesis, or the ~alt of the ~cld m~y be included in ~he llquid detergent co~posltion. Sultable ~alts are the water-soluble alkallmetal a~d mono-, dl- and triethanolamlne salts.
Particularly preferred i8 sodium formate. In general, tlle ~ount of the salt of the lower allphatlc carb~xyllc acld used ln the prese~t lnventlon ranges from 0.1 - 5X by weight, preferably fro~ 0.5 - 3.5% by ~elght of ~he final composieion. Naturally, mixture~ of salts of these lo~er aliphatlc carbo~yllc aclds can be u~ ed .

The flfth e~sentlal lngredlent of ehe p~esent lnventlon 18 the proteolytlc e~zyme. This enzyme can be of ~egetable, ani~al or ~icroorganism origln.
Preferably it lfl of the lateer or~gIn, which lncludes y2asts, fungi, ~old~
flnd bacterla. P~rtlculsrly preferred are bacterlal subtlll~ln type proteases; obtained fro~ e.g. partlcul~r stralns of B. ~ubtllls and B.
llchenifor~is. ~xamples of suitable co~mercially svallable pro~eases ~re Alcalase0, Savina6e, Esperase~ all of NOV0 Indu~tri A/S; Msxat~e~ and Maxacal~ of Gist-Brocades; Razusa~e of Sho~a Denko; BP~ and BPN' protenses and 80 on. The ~mount of proteolytic enzr~e, in~luded in the co~positio~, ranges from 0.}- 50 GU/mg, based on the fl~al composltio~. ~atur~lly, ml~ture~ of different proteolytic enzymes ~zy be u~ed.

CU 1~ a glycine unlt, uhich 18 the nmount o~ proteol~tic enzyme whlch under ~tandard lncubatlon conditions produces nn smount of termlnal ~H2-group~ equivalent to 1 microgramme/~l of glycloe.

X0 [)65Z~
;` e liquid detergent composl~ons of the present lnvention can further~ore contaln one or more oeher, optional ingredlents. Such optional lngredients sre e.g. perfumes, includlng deoperfume~, colou~lng materlals, opsclf~s~
soll-suspendlng agent~, soil-release agents, sol~ents ~uch as prop~lene glycol, hydrotropes such a3 sodiu~ c~mene-~ toluene- and xylenesulphonate as well as urea~ alkallne Daterial~ such as ~ono-~ di- or eriethanol-a~lne, clays, fabric-softening agents and 50 on. The llquld detergent composition y be unbullt or bullt, snd may be aqueous or non-aqucous. If a built liquld tetergent composltlon ls reguired; tbe compositloD may contain from 1 - 60%, preferably 5 - 30Z by weight of one or more organlc andlor ~norganlc builder~ Typlcal examples of such builders are the alkali~etal ortho-, pyro- and trl- polyphospha~e~, al~allmetal csrbonates, elther alone or in admlxture wi~h calclte, alkalimetal cltrates, alkalimetal nltrllotrlacetates, carboxymethyloxy succlnates, zeolites, polgscetal carboxylates and 80 on.

It may also be advantageous to lnclude a certaln a~o~nt o~ a calciu~ salt to further lmprove the enzy~e ~tabillty. A e~pical example of 8 sul~able calclum salt i8 calclum chlorlte; the calcium salt should be ~dded lo 6uch an amount, that from 0.1 - 2 mlll~oles of enzyme-accessible free c81elu~
(i.e. calclum, not sequestrated by any o~ the ingre~ients of the co~posltlon, e.g. a bullder) is available per ~ilogr~me of the flnal co~poslt~on.

The co~positlons may ~urtbermore co~prl8e lather boosters, Soa~ depressors, antl-corro~lon agents, chelatlng ngents, uoel-~oll redeposltIon age~t3, bleachlng ~gents. other stabllizlng agents ~or the enzyme~, actlv8tDr8 ~or :

Z0()~527 the bleaching agents and 80 on. They ~ay al80 comprl~e enzymes other than ehe proteases ~nd lipase~, 8uch aB a~ylase~, o~idase8 and cellulaseq~ In - general, the co~positions ~ay comprise such other enzy~e8 ln an amount 4 O.Ol-IOZ by weight.

~hen the liquid detergent co~posleion i~ an aqueous eo~posltion, the ~alance of the formulstlon consls~s o nn aqueous ~edlum. ~hen l~ i8 ln the fonm of a non-aqueous composition, the above ingredlents together with ehe essentlal lngredients ~ake up for the whole ~ormnl~tlo~.

The inventlon wlll further be illustra~ed by way of ~xampleO ~ ~`
'~ ; ', ~: ' ~
' ` ~ .~ '", .: ' ' ' The stabil~ty of Llpola~e ln varlous aqueous ~yste~s was assessed nt 379C
over 27 days of storage. The aqueous systems all contained al80 8 proteolyt~c enzy~e Ssvinase 16.0 L ex NOVO, in An amount equlvalent to 30 GU/~l of the system. The aqueous systems contained either 4.9X e~ha~ol, or 2.7Z sodlu~ for~ate, or 16.5Z of a nonlonlc dete~gent which was a C12 - C15 ~`
llnear primary alcohol, condensed wleh 9 ~ole~ of ethylene oxide, or a mixture of 4.9X ethanol, 2.7Z sodium for~ate and 16.5Z of the no~loalc detergent.
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F~gure I shows ehe results of the~e stabllity tests. It csn be ~learly seen, that the ternary mixture ethano}/sodlum for~ate/nonlonic detergent produced ~n unexpectedly ~proved lipolyt1c enzy~e stsr~ge ~tability. ln co~parison ~lth the single co~ponen~s.

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Z00t~52~7 Example II

With the same systems a~ aboYe, as well as varlous combinatlon~ o~ th~
lngredient~, the half-life ti~e o~ the W polase was asses~ed. ~he followlng table glves ~he results System Initial pH~alf-life tlme ir~ ___&

water 7.1 1.5 nonionic . : ` -detergent 5.4 ethanol 5.8less ehan 1 day sodiu~ for~ate7.9 7 day~ :
elehBnol plu9 : .
nonionlc detergent 5.8 less ~han 1 day etbsnol plus ~odium formate7.9 11 nonlonlc detergent plus sodlu~ formate 6.4 8 nonlonic detergent plus sodlum formaee plus ethanol 6.5 17 ''' Example III , :

The followlng llquid detergent composltlo~ was testea as to the ~tabilit~
of ~lpolase thereln~ `

_ g _ 2 0 06 5 2 7 X by welght C12-C13 prlmary linear alcohol, condensed with 9 moles of ethylene oxide 22.6 Sodlu~ coconut alcohol diethyleneglycol-ethersulphate 5-3 :
Sodlu~ coconut aleoholsulphate 3.5 x Sodium formate 1.9 Ethanol 5.2 ~ ~:
Water q~s. .~

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~ The composltion aIso contalned Llpola~e and Sa~lna~e in ~nounts, yleldin8 ::~
an activity of 15W/ml re~p. 30 GU/ml at a dosage of the co~po~itio~ of 2 g/l. to a wash lIquor.
., ~`~.

The half llfe tlme at 37C of the llpolase was 7 day~. Increaslng the . ~,, , , . . .: .
a~ount of.sodlum formate to 2.7X ylelded a half-life tlme o~ the Llpola8e of ~ore than 1.5 ~onths.
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Exa~ple rv : .
~,) , The ~ame smount~ of Lipolase and Savlnase of ~xa~ple 3 were u~ed tn the ..
~ollowing liquld detergent compo~ltlon Z by weight C12-C15 llnear pr1~ary slcohol. condensed w5th 10 moles of ethylene oxide 16.5 -- 10- . "

i,: :::,,~ ., . ...;

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,^Sodlum d od ecyl benz e nesu 1 phona t e 3. 5 Polyethyleneglycol esCer 0.6 Sodium For~ate 2.7 Ethanol 4.9 Water qo5~ . ~

The half-l~fe at 37C tlme of the Lipolase was more than 1.5 ~nonths. ~ -:: .

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., I ~ ,.

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Claims (7)

1. An enzymatic liquid detergent composition comprising a) from 10-90% of a detergent-active system which consists for at least 50% of one or more nonionic detergent-active compounds. b) one or more lipases selected from the group consisting of fungal lipases obtainable from Humicola lanuginosa or Thermomyces lanuginosus , in an amount, such that the final composition has a lipolytic activity of 0.005-100 LU/mg, c) from 1-10% by weight of a lower aliphatic alcohol having 1-4 carbon atoms, d) from 0.1-5% by weight of a water-soluble salt of a lower aliphatic carboxylic acid having 1-3 carbon atoms.
and e) proteolytic enzymes in an amount such that the final composition has a proteolytic activity of 0.1-50 GU/mg.

2. The composition of claim 1, comprising 15-70% by weight of a), 0.05-25 LU/mg of b), 2-8% by weight of c) and 0.5-3.5% by weight of d).

3. The composition of claim 1, wherein the lower aliphatic alcohol is ethanol, the water-soluble salt of the lower aliphatic carboxlic acid is sodium formate, and the nonionic detergent-active compound is an ethoxylated C8-C18 primary, linear alcohol.

4. The composition of claim 1, wherein the lipase is a lipase, obtained by ?loning the gene from Humicola lanuginosa and expressing this gene in Aspergillus oryzae.

5. The composition of claim 1, wherein the proteolytic enzyme is a bacterial subtilisin.

6. The composition of claim 1, further comprising a calcium salt in such an amount that the composition contains from 0.1-2 millimoles of enzyme-accessible free calcium per kilogramme of the final product.

7. The enzymatic liquid detergent composition as claimed in claim 1 and substantially as described herein.