CA2006527A1 - Enzymatic liquid detergent compositions - Google Patents

Enzymatic liquid detergent compositions

Info

Publication number
CA2006527A1
CA2006527A1 CA 2006527 CA2006527A CA2006527A1 CA 2006527 A1 CA2006527 A1 CA 2006527A1 CA 2006527 CA2006527 CA 2006527 CA 2006527 A CA2006527 A CA 2006527A CA 2006527 A1 CA2006527 A1 CA 2006527A1
Authority
CA
Canada
Prior art keywords
composition
detergent
weight
lower aliphatic
liquid detergent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA 2006527
Other languages
French (fr)
Inventor
Martin S. Cardinali
Jack T. Mc Cown
Thomas Weber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Original Assignee
Martin S. Cardinali
Jack T. Mc Cown
Thomas Weber
Unilever Plc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US292298 priority Critical
Priority to US29229888A priority
Application filed by Martin S. Cardinali, Jack T. Mc Cown, Thomas Weber, Unilever Plc filed Critical Martin S. Cardinali
Publication of CA2006527A1 publication Critical patent/CA2006527A1/en
Application status is Abandoned legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease, amylase
    • C11D3/38663Stabilised liquid enzyme compositions

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
-- ~ :

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.

.

.- 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
''~
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~
.

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.

.

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.

"',: ~"

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.
~ .
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.

', ' ' : ':
"

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. .~

') ' ' ' .;, ' ' '"
~ 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.
`.

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

. . ~

,^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. ~ -:: .

,) '' ~ ~

., I ~ ,.

:`"'''''','' ' _) ~ ;' '

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.
CA 2006527 1988-12-30 1989-12-22 Enzymatic liquid detergent compositions Abandoned CA2006527A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US292298 1981-08-12
US29229888A true 1988-12-30 1988-12-30

Publications (1)

Publication Number Publication Date
CA2006527A1 true CA2006527A1 (en) 1990-06-30

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Family Applications (1)

Application Number Title Priority Date Filing Date
CA 2006527 Abandoned CA2006527A1 (en) 1988-12-30 1989-12-22 Enzymatic liquid detergent compositions

Country Status (6)

Country Link
EP (1) EP0376705A1 (en)
JP (1) JPH02227500A (en)
AU (1) AU4724989A (en)
BR (1) BR9000010A (en)
CA (1) CA2006527A1 (en)
ZA (1) ZA8909957B (en)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69121059D1 (en) * 1990-11-14 1996-08-29 Procter & Gamble Lipase and protease-containing liquid detergent composition
EP0583383B1 (en) * 1991-04-30 1995-12-13 THE PROCTER & GAMBLE COMPANY Liquid detergents with an aryl boronic acid
WO1993004158A1 (en) * 1991-08-21 1993-03-04 The Procter & Gamble Company Detergent compositions containing lipase and terpene
JP3244700B2 (en) * 1991-12-04 2002-01-07 ザ、プロクター、エンド、ギャンブル、カンパニー Citric acid, cellulase, and boric acid to inhibit proteolytic enzymes - liquid laundry detergent containing the diol complexes
US5442100A (en) * 1992-08-14 1995-08-15 The Procter & Gamble Company β-aminoalkyl and β-N-peptidylaminoalkyl boronic acids
US5354491A (en) * 1992-08-14 1994-10-11 The Procter & Gamble Company Liquid detergent compositions containing protease and certain β-aminoalkylboronic acids and esters
DE4344154A1 (en) * 1993-12-23 1995-06-29 Henkel Kgaa An enzyme-containing liquid detergent
US5474701A (en) * 1994-01-21 1995-12-12 Buckman Laboratories International, Inc. Enzymes for recreational water
US5691295A (en) * 1995-01-17 1997-11-25 Cognis Gesellschaft Fuer Biotechnologie Mbh Detergent compositions
DE19515072A1 (en) * 1995-04-28 1996-10-31 Cognis Bio Umwelt Cellulasehaltiges detergent
US6165966A (en) * 1996-09-24 2000-12-26 The Procter & Gamble Company Liquid detergents containing proteolytic enzyme and protease inhibitors
DE19605688A1 (en) * 1996-02-16 1997-08-21 Henkel Kgaa Transition metal complexes as activators for peroxygen compounds
CA2266525A1 (en) 1996-09-24 1998-04-02 Charles Winston Saunders Liquid laundry detergent compositions containing proteolytic enzyme and protease inhibitors
BR9712111A (en) * 1996-09-24 1999-08-31 Procter & Gamble Liquid detergents containing proteolytic enzyme and protease inhibitors.
WO2003035712A1 (en) 2001-10-22 2003-05-01 Henkel Kommanditgesellschaft Auf Aktien Cotton active, dirt removing urethane-based polymers
JP2008094726A (en) 2006-10-06 2008-04-24 Thales:Kk Composition for microbubble cleaning, method for microbubble cleaning and apparatus for microbubble cleaning
JP5913781B2 (en) 2009-11-12 2016-04-27 有限会社ターレス Method for cleaning hair with braided hairstyle
CA2783972A1 (en) * 2009-12-21 2011-07-14 Christian Adams Detergent compositions containing thermobifida fusca lipase and methods of use thereof
EP2551335A1 (en) 2011-07-25 2013-01-30 The Procter and Gamble Company Enzyme stabilized liquid detergent composition

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5811196B2 (en) * 1979-11-09 1983-03-01 Procter & Gamble
DE3068554D1 (en) * 1979-11-09 1984-08-16 Procter & Gamble Stabilised aqueous enzyme composition containing formate and calcium ions
AT110768T (en) * 1986-08-29 1994-09-15 Novo Nordisk As Enzyme-containing detergent additive.

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BR9000010A (en) 1990-10-09
AU4724989A (en) 1990-07-05
EP0376705A1 (en) 1990-07-04
ZA8909957B (en) 1991-08-28
JPH02227500A (en) 1990-09-10

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