NZ241641A - Detergent composition comprising a surface active agent, a quaternary amine and a lipase enzyme - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £41 641 '4 1641 Priority Date(s): Compote Specification Filed: Cl»^-<>h— Publication Dote: .... 2 S - JUL' 4995' I P.O. Journal. No- • • • AC DRAVM NEW ZEALAND PATENTS ACT, 1953 COMPLETE SPECIFICATION r 18 FEB IC32 PEC_I\—» DETERGENT COMPOSITIONS CONTAINING LIPASE AND WATER-SOLUBLE QUATERNARY AMMONIUM COMPOUNDS He, THE PROCTER & GAMBLE COMPANY, a corporation organized under the laws of the State of Ohio, United States of America, located at One Procter & Gamble Plaza, Cincinnati, Ohio 45202, United States of America hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- (followed by page la) - la - 241641 DETERGENT COMPOSITIONS CONTAINING LIPASE AN_D WATER-SOLUBLE QUATERNARY AMMONIUM COMPOUNDS TECHNICAL FIELD The present invention relates to detergent compositions having ennanced soil removal properties, particularly of triglyceride-containing soils.

BACKGROUND OF THE INVENTION Enzymatic detergent compositions are wed Known in tne an. In particular, lipases have been descnbed as possible enzymes from aetergent compositions m several patent publications; reoresentatlve of sucn disclosures are US 4 011 169. describing tne use of lipases in the preparation of additives for washing agents, as well as EP-A- 205 208, EP-A-206 390 or EP-A-341 9S9, all relative to specific detergent compositions containing lipase as a soil-removai agent.

The production of lipase from certain micrcorganismes nas Deen aescnbea m e.g. EP-A-214 761 and EP-A-258 068. 2 2 4 1 6 4 t On tne other nana, tno use of certain water-soiuble quaternary ammonium compounds m detergent compositions exmbitmg textile cleaning ana softening properties is known n particular, EP-A- 26 529 descrioes sucn cetergent compositions. where the presence of certain water-soluble quaternary ammonium compounds provides benefits m terms of fabric cleaning ana softening.

It has now Deen found that the combination ot lipase enzymes with certain water-soluble Quaternary ammonium compounas. unexpectedly increases the removal of trigiyceride-contaming sous from fabrics, ana provides soil-anti-'eaeposftion effeas not previously achievable from the use of either or the combined species above.

SUMMARY OF THE INVENTION The present invention relates to detergent comoositions comprising a Surface-active agent, and a water-soluble quaternary ammonium compound of the formula: (i) R1R2RaR4N^ X* wherem R-j is Cg - C-ig aikyi or is R5-T-C-R5, wherein T is 0, NH or N-C1.4 & aikyi, R5 is a aivaient Ci-C3 alkyiene group or wherein m is a number from 1 to8, and r& is c12-c14 aikyi, each of R2, R3 and R4 is independently C1 • C4 aikyi or hydroxy! aikyi, oenzyi, or - (C2H40)XH wnere x has a value from 2 to 5. not more than one of R2. R3 or R4 oema benzyl, and X* is an anion; or ,'ii) (CH-) _ / \ S 2 Q% wherein n is 2.3. or 4, preferaoly 2 , q is ch, ch., or n, ^ C r2 R-j ana R2 are the same as in formula (i), i-i x * and X* Is an anion ; nharactenzed-in that the compositions additionally contain a lipase enzyme.

The quaternary ammonium salts above are oreferably selected from species m which R119 C-.2-C15 alkyl ano R2, R3 ana R4 are preferaoly selected from methyl ana hyaroxyetnyl groups.

The ccmcositions herein are in granuiar form, compact granular :crm or liquid 24164 DETAILED DESCRIPTION OF THE INVENTION the water-soluble quaternary ammonium compound The water-sotuOle quaternary ammonium compounds useful tne preseri composition have tne formula: (') R-^RafUN^ X- wnerem Ri is Cg - C16 a'ty' or is Rs-T-C-Rg, wnerein T is 0. NH or N-C-* .4 aikyi. R5 is a oivalent C1-C3 aikylena group or (CoH40)m, wherein m is a numoer from 1 to 8, and Rfe is C12-C14 aikyi, each of Ro, R3 and R4 is independently Ci - C<t aikyi or nyaroxyi aikyi, cenzyi, or - (C2H40)XH where x has a value from 2 to 5. not more than one cf R2. R3 or R4 oemg benzyl, andX- :s an anion: cr (•') /(CH2)n R2 Q% wherein n is 2.3, or 4, preferably 2, q is ch, ch2, or n C + r2 Ri and R2 are tne same as in formula (i), R-i X* and X* Is an anion.

The oreferred alkyl chain length for R1 is C-12 - C15 particularly where the aikyi group is a mixture of chain lengths derived from coconut or palm kernel fat or is oertveo synthetically by olefin build up or 0X0 alcohols synthesis.

Preferred groups for R2.R3 and R4 are metnyi and hyoroxyethyl grouos and the anion X may be selected from hatide. metnosuipnate. acetate and chosphate ons.

Examples of suitable quaternary ammonium compounas of formulae (i) for u.se herein are: coconut trimethyl ammonium cnloride or bromide coconut methyl dihydroxyethyl ammonium cmoride or oromide decyl trietnyl ammonium chloride necyi dimethyi hydroxyethyl ammonium cnioride or bromide Ci2-i5d'metfJy' hydroxyetnyl ammonium chloride or bromioe coconut dimethyl hydroxyethyl ammonium chloride or bromide nyristyi trimethyl ammonium methyl sulphate auryi dimethyl benzyl ammonium chloride or cromide \ 241 5 1 lauryi cimetnyi (ethenoxy)4 ammonium cnionde or bromiae cnoime 69ters (compounds of formula (i) wherein is -CH2-0-C-Ct2--..; aikyi ana R2R3R4 are metnyi) 0 al-aikyi imidazolines (compounds of formula (ii)l.

The acove water-soluble cationic components of the compositions of the cresent invention, are capable of existing in cationic form in a 0.1% aqueous solution at pH 10.

The water-sciuole cationic compounas are present in an amount of from 0.1 to *. 0% by weight of the detergent comoositions.

The lioaae enzvme The oresent composition comonses a lipase enzyme whicn can be chosen from among a wide range of lipases: ;n particular the lipases aescrlbed In for example the following patent specifications, EP 0 214 761, EP 0 258 068. EP 0 205 208. EP 0 2C6 390. Suitable in particular are for example the following commercially available lipase preparations: Novo Lipoiase9, Amano lipases CE, P. 8, AP. M-AP, AML, and CES. and Meito lipases MY-30, OF, and PL. also esterase MM, Upozym, SP225, SP285. Saiken hoase, Enzeco lipase, Toyo Jozo •case ana Diosyntn lipase (Trade MarKS).

Genetic engineering cf the enzymes can oe achieved by extraction cf an approcriate lipase gene. e.g. the gene for noase from Humicola lanuginosa or *rom 0 mutant thereof, and introouction ana expression of the gene or derivative thereof m a suitable producer organism such as an Aspergillus. The techniques cescrioed n WO 88/02775 (Novo), EP 0 2*3 338 (Labofina) and EP O 268 452 ^Genencor) may be applied and adeDted.

The lipase is present in the oresent composition at levels of from 10LU to 500CLU /g of composition. 1LU is the lipolytic activity which releases 1 micrcmole titrataDle butyric acid wtmm 1 minute under the following concitions: Temo: 30°C pH: 7.0 Substrate: triputyrm (Details published in NOVO publication AF S5.4/1).

When tne tipase is UpoiaseR lOOkLU. tne levels typically range from Q&rfo 5% by weight of the total composition. / 24164 SURFACE ACTIVE AGENT A wice range cf surface-active agents can oe used in tne detergent compositions. A typical listing of anionic, nomonic. ampnolytic ana zwitteriomc classes, ana species of these surfactants, is given in US Patent 3.664.961 issuea to Norris on May 23.1972.

Mixtures of anionic surfactants are particularly suitable herein, especially mixtures cf suiDhonate ana sulphate surfactants in a weight ratio of from 5:1 tc 1:2. preferably from 3:1 to 2:3, more preferably from 3:1 to i .1. Preferred sulphonates mc:ude alky I benzene suiohonates having from 9 to 15, especially 11 to 13 carDon atoms in the elkyi radical, and aloha-suiohonated methyl fatty acid esters in wmcti the fatty acid is derived from a C12-C18 fatty source preferaoly from a C16-C18 fatty source. In each instance the cation is an alkali metal, selected from sodium mono or poiyethanoiamine or ammonium.

Preferred sulphate surfactants are alky! sulphates having from 12 to 18 carbon atoms in the aikyl radical, optionally in admixture with etnoxy sulphates naving from 10 to 20. preferably 10 to 16 carDon atoms in the aikyl radical and an average aegree of ethoxylatlon of 1 to 6. Examples of Dreferred aikyl sulphates herein are taiicw aikyl sulpnate, coconut aikyl 9uiphate, and Ci4_-j5 aikyl sulphates. The cation In each instance is again an aikaJi metal cation.

One ciass of nomonic surfactants useful in the oresent invention are conaensates cf etnyiene oxide with a hydrophobic moiety to provide a surfactant navmg an average hydrophilic-lioophillc balance (HLB) In the range from 8 to 17. preferaoly from 9.5 to 13.5, more preferably from 10 to 12.5. The hydrophooic (lipophilic) moiety may be aiiphatic or aromatic in nature and the length of the poiyoxyethylene grouD which is condensed with any particular hydroohooic grouo can oe readily adjusted to yield a water-soluole compound having the aesired degree cf balance oetween nyarophiiic and hydrophobic elements.

Especially preferred nomonic surfactants of this type are the Cg-C-| 5 primary alccnol ethoxyiates containing 3-8 moles of ethylene oxide per mole of aicohol. particularly the C-| 4-C15 primary alcohols containing 6-8 moie9 of ethylene oxide per moie of aicohol and the C-12-C14 primary alcohols containing 3-5 moies of ethylene oxide per mole of alcohol.

Another class of nomonic surfactants comprises aikyl polygiucosioe compounds cf general formula: RO (CflH2nO)tZx wherein Z is a moiety derivea from glucose; R is a saturated hydropnooic aikyl group that contains from 2 to 18 caroon atoms; t is from 0 to 10 ano n is 2 or 3. x is from 1.3 to 4, the compounds including less tnan 10% unreacted fatty aicohoi and less than 50% short chain aikyl pofygiuccsides. Compounas of this type and their use in detergent are cisciosed in EP-B 0 070 077, 0 075 996 and 0 094118.

Also suitable as nomonic surfactants are poiy hydroxy fatty acid amide surfactants of the formula R2 - C • N - 2. wnerem R1 sH, R1 -ydrocarbyi, 2-hydrcxy ethyl, 2-hydroxy propyl or a mixture merecf. R2 is C5.3. hydrocarpyi, ano 2 Is a polyhydroxynydrocaroyl having a linear hydrocarbyl cnam with at least 3 hydroxyls oirectly connected to the chain, or an aikoxyieted denvative thereof. Preferably, R1 is methyl, R2 is a straight ^ aikyl or atkenyi cnain sucn as coconut aikyl or mixtures thereof, and 2 Is denvea f'cm a reducing sugar sucn as giucose. fructose, maltose, lactose, in a reductive animation reaction.

A further class of surfactants are the semi-poiar surfactants sucn as amine oxides. Suitaoie amine oxides are selected from mono CS-C20. preferaoly C13-C14 N-a»kyl cr alkenyi amine oxides and"propylene-1,3-diamine dioxides wnerem the remaining N positions are suostituted by methyl, hydroxyetnyl or hydroxypropyi groups.

Anotner c:ass cf surfactants are amphoteric surfactants, sucn as poiyamine-casea soecies.

Mixtures of surfactant types are preferred, more especially anonic-nomonic. The detergent compositions can comprise from i%-70% by weight of surfactant, but usually the surfactant is oresent in the compositions herein an amount of from 1% to 30%. more preferably from 10-25% by weight.

I' 1 6 Preteraory, tne moiar ratio cf the water-soluble quaternary ammonium compounds herein to the anionic surfactant snould be Ie39 than 1:1 and desirably should be less than 1:1.5. In preferred embodiments of the invention such as heavy cuty launcry detergent formulations, the molar ratio should be less than 1:2.

Optional inoredienta The oresent ccrr.oosition will typically include cotlonai ingredients that normany form Dart of detergent comoositions. The present composition typically contains a aetergent fc jilcer.

Any conventional builder system is suitable for use herein including aiumircsilicate materia^, silicates, poiycarboxyiates and fatty acics. materials sucn as ethyienedtamme tetraacetate, metal ion sequestrants such as amincpolypnosphcnates, particularly ethyieneciamine tetramethyiene phospnomc acid and diethylene triamine pentamethylenepnosphonic acic. Though less preferred for obvious environmental reasons, phosphate builders can also be useo herein.

Suitable buiiders can be an inorganic ion exchange material, commonly an ^organic hydratea eiuminosincate material, mere particularly a hydrateo synthetic zeolite sucn as hycratea zeolite A. X, B cr HS.

Anotfier suitaole inorganic builder material,^ layered silicate, e.g. SKS-6 (Hoecnst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Sl205).

Suitable poiycarboxyiates builders fcr use herein incluae cstric acid. preferably in the form cf a water-soluble salt, derivatives cf succnic acid of the formula R-CH(COOH)CH2(COOH) wherein R is C10-20 aikyl or alkenyl, preferably C12-1S. or wnerem R can be substituted with nydroxyi, suifo sulfoxyi or suifone suostituents. Specific examples induce lauryi succinate, mynstyl succinate, oaimityl succinate2-dodecenylsuccmate, 2-tetradecenyl succinate. Succinate Curiders are preferably used in the form cf their water-soluble salts, including sodium, potassium, ammonium and aikanoiammonium salts.

Other suitable poiycarboxyiates ere oxocisuccinates and mixtures of tartrate monosuccimc ana tartrate disuccinic acid such as described in US 4,663,07":.

Esoecially for the liquid execution nerein, suitable fatty acid builders for use herein are saturated or unsaturate C10-18 fatty acids, as well as well as the corresponaing soaps. Preferrea saturated species have from 12 to 16 carbon atoms In the aikyi chain. The pref6rrea unsaturated fatty acid is oleic aad.

Preferred builder systems for use in granular compositions include a mixture of a water-insoiuDle atuminosilicate buiider such as zeoiite A, and a water-soluble carboxyiate chelating agent such as citric acid.

Other builder metenals that can fcrm par. cf the builder system for use in the compositions of the invention include inorganic materials such as aikan metal carbonates, bicarponates, silicates, and organic matenais such as the organic ohosDhonates, amino polyalkylene phosphonates and amino poiycarboxyiates.

Other suitable water-soluble organic salts are the homo- or co-potymenc acios or their salts, in which the polycarboxylic acid comprises at least two carDOxyi radicals separated from each other by not more than two carbon atoms.

Polymers of this type are Disclosed in GB-A-1,596.756. Examples of such saits are polyacryiates of MW 2000-5000 ana their copolymers with maieic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially aoout 40,000.

Detergency builder salts are normally included in amounts of from 10% to 30% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight.

Other optional ingredients Include fabnc softeners agents sucn as smectite c.ays, additional polymers such as polyethylene oxides, polyvinylpyrrolidones, Dolyvinylalconoi, bieecnes, bleach activators, suas suppressors, as well as other enzymes selected from proteases, amylases cetlulases. peroxidases, oxidases. •16 Form of the composition The present composition can be in granular form, and in particular in compact form, i.e. they may have a relatively higher density than conventional granular detergent compositions according to the present invention will contain a lower amount of 'Inorganic filler salt*, comparea to conventional granular detergents: typical filler salts are alkaline earth metal salts of sulphates and chlondes, typically sodium sulphate; "compact" detergents typically comprise net mere than 10% filler sait.

The present composition can also be in uquia form, and comprises typical ingredients of such composition such as organic solvents, n particular ethanot. r 16 Examples Example 1 The following oetergent compositions were prepared % bv wrtaht inoredients K> 0 3 0 od CornoC Ex. 1 Linear dodccyl benzene sulphonaie sodium sail 6.5 6.5 65 65 TaIIow alcohol sulphate sodium salt 2.5 2.5 2.5 2.5 Fatty alcohol ( CI2-C15 ) ethoxyiated ( 7 EO ) .5 .5 5 55 Zeolite 4A sodium form .0 .0 .0 .0 Perborate 4H20 .0 .0 .0 .0 Tetra acetyl ethylene diamine 3.5 3S 3 5 3.5 Carbonate sodium salt .0 .0 .0 .0 Brightener 02 0.2 0.2 02 Carboxymeihylcellulose 05 05 0.5 0.5 Ethylene diamine tetra acetate 03 03 03 03 Copolymer of acrylic acid and maieic acid 2.5 2.5 Coconut dimethyl hydroxyethyl ammonium chloride * 1.5 - 1.5 Lipase (LipolaseR at 100 kLC) - - 036% 036% Sulphate sodium salt 93 9.3 93 93 Minors + water balance to 100 The above compositions were compared for % Soil Removal and Whrteneas Maintenance Effect.

The % Soil Removal is evaluated by comparing reflectance measurements of swatches sotlea with olive oii/Sudan red before and after wasning; the method is as follows: in oroer to improve the visibility of the olive oil removal, the olive oil Is stained with Sudan red (oil soluble dye). This allows to measure the % Soil Removal by reading tne reflectance values.

To verify that these reflectance values (Sudan red concentration) correlate with tne acoial removal of olive oil, the olive oii-ioaaed swatches were extracted before and after washing. Extracts were measured in two ways: gravtmetncally ana via infra red soectrcscopy (1735 cm-1).

Results are as follows: % Soil Removal Reflectance Gravimetrlcallv LB. 21 19.4 21.6 / "I — t 941 The Whiteness Maintenance Effect corresponds to the soil redeoosition as percent of removed soil. It is calculated as follows: % Soil RadeposiHon x ICO % Soil Removal To monitor this effect, the reflectance of unsoiied swatches is measured.

Teet condition* were as followm: Launderometer equipment 400 heat up cycle detergent concentration:6g/l water hardness: 2.5 mmol/1 wasn liquor: 200ml load: 6 polyester swatches of 7 x 7 cm (3g) of whicn 4 swatcnes soiled each with 50 microliter olive oil 2 unsoiied swatcned cycles: 2 Results were as follows: % Soil Removal Whiteness Maintenance Compositions: Effect A 57 26 B 62 23 C 71 31 Ex."! 78 18 Discussion of the results: The superiority of the comoosition according to the present invention (Ex.1) in terms of soil removal (triglycerides containing soils) and wniteness maintenance effect, is clearly demonstrated.

Synergistic effect: 11 24 1 641 The % Soil-Removal and Whiteness Maintenance Effect of Fx.t was compared to the sum of the results of Composition B ano Q Compoartlona Soil removal Whiteness Maintenance (differences versus treatment A) E*1 r 21 * 8 B + C *19 ^ 2 The above results show that the results of Ex. 1 are more than additive and do Demonstrate the exlstance of a synergy.

(The % Soil Removal is increased, and the % of redeposited soli Is decreased (WM). 12

Claims (7)

- 13 - 2416 41 the following detergent compositions are also prepared: Composition (% by weight) inaxaXww Ea.2: Gr» nul<f fa. a; CmrbmI EIL<: Liquid Granuur CU-L2 beazeae suifoaate 4 ■ 10 Tallow alcohol sulfate (Na) - Ci4_i5 aikyl sulfate (Na) 3 0 4 Tallow alcohol ethoxylate (EO^J 0.5 - - Fatty aicohol ethoxylate (EO-r) 3 4 - Ci2_l5 Dimethyl (hydroethyl) ammonium chloride 5 - -

1.S Coconut Dimethyl (hydrocthyl) ammonium chloride - Zeolite A 23 w Sodium aerate 6 Oleic fatty acid 1 Curie acid Cl4- L6 iuconwc 10 L2-Propanediol 3 Ethaaoi Na Metaborate Oaanydiate Polyethylene unde 0.3MN1 molecular weight 03 Sodium sulfite 15 1 Sodium carbonate 11 Sodium uiicaie 4 3 Sodium perborate (1 aq.j LS • ^ N.N.S.N-Tctraaceryiethylene diamine - 3 CMC 0J 0.3 Polyicrylate (VTW 4000-5000) 3 - Maleic-acrytic copolymer - A Lipase (LipolascK 100 kLU) 0.4 0.5 I Smectite/moatmorulonite ciay :o.5 12 X Admix and >pray-oo (perfumes, protease and/or amyiase. ceilulase, peroxidase, buffer, suds suirorrssors. misceLaaeous. moisture and minors) balance to 100 balance to 100 balance to 100 13 - 14 - 2 A 1 / j WHAT //WE CLAIM IS i 1 A detergent Composition comprising a surface-active agent and a water-soluble Quaternary ammonium compound of the formula: (1) R-|R2R3R4N+ X- wnerem R1 is Cq - aikyl or is R5-T-C-R5, wherein T is O, NH or N-C^ O aikyl. R519 a divalent C1-C3 alkylene group or (C2H40)m. wherein m is a number from 1 to 0, and R£ is aikyi, . 6 12 14 each of R2, R3 and R4 is independently C1 - C4 elkyt or hydro)cyl aikyl, benzyl, or - (C2H40)XH where x has a value from 2 to 5, not more than one of R2, R3 or R4 being benzyl, and X* Is an anion; or («) ,(CH2)n R2 Q, whereinn is2.3. or4. q is ch, ch2, or n, ^•'C + R2 Ri and R2 are the same as in formula (i), X* and X* Is an anion ; characterized in that the composition additionally contains a lipase enzyme.

2. A detergent composition according to claim 1, wherein n is 2.

3. A detergent composition according to claim 1 or 2, wherein the quaternary ammonium salts are selected from species in which R, is Cl2"Cl5 aikyl and R3 and R4 are selected from methyl and hydroxyethyl groups.

4. A detergent composition according to Claim 1, 2 or 3, wherein the level of said water-soluble quaternary ammonium compound is from 0.1 to 10% by weight, and the level of said lipase enzyme is from 10 LU to 500 LU.

5. A detergent composition according to any one of claims 1-4, wherein the surface active-agent comprises anionic surfactants, wherein the molar ratio of the anionic surfactant to the water soluble quaternary ammonium compound is greater thai>'l;l- £*H 0 H 1 - 15 -

6. A detergent composition according to any one of claims 1-S which is in granular form, compact granular form or liquid form.

7. A detergent composition substantially as herein described with reference to any embodiment disclosed in Examples 1-4. A. Vj : K ; F0U AGEJJJJi" " ""r ' T. •" "f-Lie ANTS • .--rrMr OFFICE f 8 NOV 199* I