CA2184364A1 - Detergency composition comprising zeolite map and protease enzyme - Google Patents

Abstract

A detergent composition is disclosed which comprises a surfactant selected from anionic, nonionic, cationic, amphoteric and zwitteronic detergent-active compounds and mixtures thereof; a detergency builder comprising zeolite P having a silicon to aluminium ratio not greater than 1.33 (zeolite MAP); and a proteolytic enzyme having an isoelectric point below 10. Alcalase is exemplified. Preferably the composition is free of enzymes having an isoelectric point above 10.

Description

WO 9S/27030 PCT/US~5~7~

DETERGENCY COMPOSITION COMPRISING ZEOLITE MAP AND PROTEASE ENZYME

The present invention relates to a delerg~ll composition and, in particular, to improvem~nt~ in the detergel.cy performance of laundry detergent compositions comprising zeolites as a sequestering agent for water hardness.

Detcrgent compositions for fabric washing conventionally contain detergency builders which lower the conce~ ion of calcium and magnesium water hardness ions in the wash liquor and thereby provide good delergellcy effect in both hard and soft water.

Conventionally, inorganic phosphates, such as sodium tripolyphosphate, have been used as builders for laundry detergcnts. More recently, alkali metal ~ minosilicate ion-exchangers, particularly crystalline sodium ~lmninosilicate zeolite A, have been proposed as replacements for the inorganic phosph~tes.

For example, EP 21 491A (Procter & Gamble) discloses detergenl compositions co..t~;..;..~ a b~liltlin~: system which includes zeolite A, X or P(B) or a ln,~ e thereof. EP 384070A (Unilever) discloses specific zeolite P materials having an especially low silicon to ~ll....;.~i..." ratio not ~eaterthan 1.33 (hereinafter rere.led to as zeolite MAP) and describes its use as a delergellcy builder. To date, however, zeolite A is the ~re~-led ~lllminosilicate de~rgency builder in commercially available products.

Detergent compositions col-t~ g proteases are well-known in the art. By using a protease in a de~clgent, it is possible to hydrolyze the proteins, present in stains and soil on the clothes, to such a degree that they become readily soluble in water.

It is equally well recognised that the relative ability of each protease to meetvarious pclrollllance criteria is dependent on the composition of the detergent matrix. As a consequence, the detergelll forrmll~tor is faced with a 21 ~4364 WO 95t27030 ` PCI/US9S~27~

difficult task of providing detergent compositions cont~ining a protease, wherein said protease has an excellent detergency pelrol.llance.

EP 384070A (Unilever) suggests that zeolite MAP has advantages as a detergency builder over other zeolites. We have found, however, that detergenl compositions comprising zeolite MAP as detergency builder have a marked incomp~tibility with printed cotton fabrics as colllpaled with conventional detergent compositions comprising other zeolites such as zeolite A. In particular, it has been found that detergent compositions co.~l~i";,~g zeolite MAP tend to lead to the removal of printed pigment from a printed cotton fabric surface as co~ ed with dele~ compositions comprising zeolite A. The presence of certain proteolytic enzymes, in particular those having a high isoelectric point, has been found to exarcebate this effect.

We have surprisingly found that this problem can be ameliorated by incorporating in the deterg~ll composition a proteolytic enzyme having an isoelectric point below 10.

The present invention is thus based on the unexpected fintlin~ that the printed cotton fabric care profile of a detergent composition comprising zeolite MAP and co..t~;..;..g a protease having an isoelecLtic point below 10 is superior to that of comyalable compositions co~t~...i..g other proteases having an isoelec~ic point of higher than 10.

Exarnples of suitable proteases according to this invention having an isoelectric point below 10 incl~l~le Alcalase (Trade Mark), Maxatase (Trade Mark), Optimase (Trade Mark) and Primase (Trade Mark). Examples of proteases which have an isoelectric point of higher than 10 and which have been found not to afford such a superior printed cotton fabric care profile in zeolite MAP co.-~;n;.-g compositions are Savinase (Trade Mark), which is disclosed, in EP 384070A (Unilever) Opticlean (Trade Mark), Maxacal (Trade Mark), Purafect (Trade Mark), and Esperase (Trade Mark).

This fin~ling allows the form~ tion of delergcnt compositions providing both excellent cleaning and printed fabric care properties on cotton fabrics.

2 1 8 4 3 6 4 PCT/US55J~27~

Thus, the present invention provides a detergent composition comprising:

a) a surfactant selected from anionic, nonionic, cationic, amphoteric and zwitterionic detergent - active compounds and ~ res thereof;

b) a detergency builder comprising zeolite P having a silicon to alul~liu~
ratio not greater than 1.33 (zeolite MAP); and c) a proteolytic enzyme having an isoelectric point below 10.

In a ~le~lled embodiment of the invention, the detergcnt composition is free of any proteolytic enzyme which has an isoelectric point greater than 10.

In another llrefc,led embodiment the detergent composition according to the invention is fonmll~ted to be especially useful in the l~lm~ering of coloured fabrics and l le~rably is subst~nti~lly free of bleach. According to another aspect of the invention, the composition is subst~nti~lly free of an optical bri~htçn~r.

The detergent composition according to the invention contains, as an essçnti~l ingredient, one or more surfact~nts selected from anionic, nonionic, cationic, amphoteric and zwitterionic dct~ge.lt-active compounds and mixlules thereo Such surf~ct.~nts are well known and described in the literalule, for example, in "Surface-Active Agents and Detergen~s", Volumes I and II by Schwartz, Perry and Berch.

Examples of suitable anionic surfactants include alkylbenzene sulphon~tes, particularly sodium linear alkylbenzene sulphon~tes having an alkyl chain length of C8-C15; C12-C15 primary alkyl sulphates; olefin sulphonates;
alkyl xylene slllphon~tes; dialkyl sulphosuccinates; and fatty acid ester slllphon~tes. Sodium salts are generally prefe,led.

Examples of suitable nonionic surfactants include alkoxylated adducts of fatty alcohols co~.t~ il-g an average of less than S alkylene oxide groups per molecule, for example less than 4 alkylene oxide groups per molecule e.g.

WO 95/27030 i . ~ PCT/U3~ 27~

3.5 and usefully 3 alkylene oxide groups per molecule or less and usefully also greater than 0.5, or l, or 2 alkylene oxide groups per molecule.

A particularly ~refe,led aliphatic alcohol ethoxylate is a primary alcohol having an average of 12 to 15 carbon atoms in the alkyl chain condensed with an average of three ethoxy groups per mole of alcohol.

Specific examples of suitable alkoxylated adducts of fatty alcohols are Synperonic A3 (ex ICI), which is a C13-C1s alcohol with about three ethylene oxide groups per molecule and Empilan KB3 (ex Marchon), which is lauric alcohol 3EO.

Another class of nonionic surf~Gt~nt~ comprises allcyl polyglucoside compounds of general formula RO(CnH2nO)tzx wherein Z is a moiety derived from glucose; R is a sa~ ed hydrophobic alkyl group that cont~in~ from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds including less than 10%
unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
Compounds of this type and their use in detelgelll compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 0094118.

The surfactant will generally be included in the detergent composition in an amount of 1 to 60% by weight, prefe,ably 5 to 40% by weight and most ~refel~bly from lO to 25% by weight of the composition.

According to the present invention the detergency builder system is based on zeolite MAP, optionally in conjunction with one or more supplementary builders. The amount of zeolite MAP employed may range, for example, from 1 to 80 wt%, more ~,refe,ably ~om 5 to 60 wt%, most ~refeiably from 15 to 40 wt%.

Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to allllnil~iwll ratio not greater than 1.33, prefelably within the range from 0.9 to 1.33 and more p~erc~ably within the range of from 0.9 to 1.2.

Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.

Zeolite P having a Si:Al ratio of 1.33 or less may be prei)ared by the following steps:

(i) mixing together a sodium allmnin~te having a mole ratio Na20:A1203 within the range of from 1.4 to 2.0 and a sodium silicate having a mole ratio SiO2:Na2O within the range of from 0.8 to 3.4 with vigorous stirnng at a temperdlule within the range of from 25C to boiling point usually 95C, to give a gel having the following composition;
A12O3: (1,75-3,5) SiO2: (2,3-7.5) Na2O :P (80~50)H20;

(ii) ageing the gel composition for 0.5 to 10 hours, l.~fe,~bly 2 to 5 hours, at a tempe,~lure within the range of from 70C to boiling point, usually to 95C, with sufficient stirring to m~int~in any solids present in suspension;

(iii) sepa~al-~g the cryst~lline sodium ~lllminosilicate thus formed, washing - to a pH within the range of from 10 to 12,5, and drying, l~refe.ably at a templ ,alllre not excee~ling 150C, to a moisture content of not less than 5 wt%, P~efelled drying methods are spray-drying and flash drying, It appears that oven drying at too high a tempelalu~e may adversely affect the calcium binding capacity of the product under certain circllm~t~nces.

Commercial sodium metasilicate pentahydrate dissolved in water and commercial sodium silicate solution (waterglass) are both suitable silica sources for the production of zeolite P in accordance with the invention The reactants may be added together in any order either rapidly or slowly.
Rapid addition at ambient temper~lure, and slow addition at elevated t~ p~alure (90-95C) both give the desired product, WO 95/27030 2 1 8 4 3 ~ 4 PCT/US95/02700 Vigorous stirring of the gel during the addition of the reactants, and at least moderate stirring during the subsequent ageing step, however, appear to be essential for the formation of pure zeolite P. In the absence of stirring, various n~ es of crystalline and amorphous materials may be obtained.

Zeolite MAP generally has a calcium binding capacity of at least 150 mgCaO per g of anhydrous aluminosilicate, as me~llred by the st~n~l~rd method described in GB 1473201 (Henkel). The calcium binding capacity is normally 160 mg CaO/g and may be as high 170 mg CaO/g.

Although zeolite MAP like other zeolites contains water of hydration, for the purposes of the present invention amounts and percentages of zeolite are expressed in terms of the notional anhydrous material. The amount of water present in hydrated zeolite MAP at ambient tempe~dl~e and hl~ lity is generally about 20 wt%.

A l.lere~led zeolite MAP for use accordin~, to the present invention has a dso of from 1.0 to 10.0 micrometres, for example 2.25 to 5 micrometres, more particularly 2.75 to 5 micrometres.

According to one embo~liment of the invention the zeolite MAP detergentbuilder is in powder form.

For convenience in h~n~lline however, the material may be gr~n~ te~l byconventional techni(lues such as spray drying or by a non-tower method to form larger particles.

The detc.ge,ll composition according to the present invention essentially comprises a proteolytic enzyme of isoelectric point below 10.0, more preferably below 9.0, most ~refe.ably below 7Ø

It has been found that det~,rge.ll compositions comprising zeolite MAP as detergency builder, when form~ te~l with a protease having an isoelectric point below 10.0, provide acceptable cleaning pe.rollnance and improved printed cotton fabric care pelrolmance in comparison with zeolite MAP

WO 95/27030 2 1 8 4 3 6 4 PCT/US55J~27~

cont~inin~ compositions having an isoelec~ic point higher than 10Ø

Suitable proteases include proteases represented by the genus of Subtilisin Carlsberg, producible by Bacillus lichel~iro~ is. Other suitable proteases include the proteases represented by the genus Subtilisin BPN', producible by B~Gj1111~ amyloliquefaciens. Other suitable proteases are proteases which show a positive il~".~"ological cross-reaction with the antibody of the proteases as described hereinabove. Highly l,re~led proteases are the proteases that are commercially sold under the tr~de~mes Alcalase (Trade Mark), ~ t~e (Trade Mark) Optimase (Trade Mark), Primase (Trade Mark) or mixtures thereof.

The proteases according to the present invention are l.re~lably present in an amount from 0.001% to 2%, more ~lefelably from 0.001% to 1%, more ~efe.ably from 0.002% to 0.5% of active enzyme by weight of the detergent composition.

In the granular delel~e.lt compositions according to the invention, thedetergency builder can be zeolite MAP alone or a combination of zeolite MAP with an organic or inorganic cobuilder.

Suitable organic cobuilders can be monomP,ric or polymeric carboxylatessuch as citrates or polymers of acrylic, methacrylic and/or maleic acids in neutralised form. Suitable inorganic cobuilders inclu~le carbonates, and amorphous and crystalline l~mPll~r sodium silic~tes.

Suitable silicates have the composition:

NaMSix02x+l, yH2o where M is sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20. Such materials are described in US
Pate.lls No. 4664839; No. 4728443 and No. 4820439 (Hoechst AG).
Especially p,efe.led are compounds in which x = 2 and y = O. The synthetic material is commercially available from Hoechst AG as ~-Na2 Si2Os (SKS6) and is described in US Patent No. 4664830.

WO 9S/27030 2 1 8 4 3 ~ 4 PCT/u~g5l~27~n The total amount of detergency builder in the granular composition ranges from 1 to 80 wt%, more ~Jrefeldbly 5 to 60 wt%, most pre~l~bly 10 to 45 wt%.

Other materials which may be present in the detergent compositions of the invention include, for example, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, other enzymes, lather control agents, fabric so~-ning agents, pi~n~nt~, coloured speckles and perfumes.

The detergellt compositions of the invention may be l.lepa~ed by any suitable method. The particulate detergent compositions are suitably prepared by any tower (spray-drying) or non-tower process.

In processes based around a spray-drying tower, a base powder is first ~re~ ed by spray-drying a slurry then be sprayed on or admixed (post-dosed). The proteolytic enzyme wil! generally be post-dosed.

The zeolite MAP is suitable for inclusion in the slurry, although it may be advantageous for processin~ reasons for part of the zeolite MAP to be incorporated post-tower. The lamellar silicate, where this is employed, is also l~refeldbly post-dosed.

~l~çrn~tively, particulate detelgehl compositions in accordance with the invention may be pre~ared by wholly non-tower processes such as gr~mll~tis)n The granular deter~ compositions of the invention may be prepaled to any suitable bulk density. The compositions preferably have a bulk density of at least 400 g/l ~ref~l~bly at least 550 g/l, most ~e~l~dbly at least 700 gA
and, with particular l,refelellce at least 800 g/l.

The benefits of the present invention are particularly evident in powders of high bulk density, for example, of 700 g/l or above. Such powders may be ~lel)aled either by post-tower densification of spray-dried powder, or by wholly non-tower methods such as dry mixing and gr~mll~hon; in both cases WO 95/27030 2 1 8 4 3 6 4 PcTlusg5lo27on a high-speed mixer/gr~n~ tor may advantageously be used. Processes using high-speed mixer/gr~nl-l~tors are disclosed, for example, in EP340 013A, EP
367 339A, EP 390 251A and EP 420 317A (Unilever).

According to a further aspect of the invention there is provided a liquid deterg~llt composition, ~refeldbly a heavy duty liquid detergent composition comprising a surf~ct~nt as previously described, a detergellcy builder comprising zeolite MAP and a proteolytic enzyme having an isoelectric point below 10.

According to this embodiment the liquid detergent composition may be of any convenient physical foIm which may be aqueous or anhydrous. The term "liquid" used herein includes pasty viscous formulations such as gels.
The liquid detergent system comprises, as the detergellcy builder zeolite MAP optionally in combin~tion with other dete,gency builders such as fatty acids, citric acid or zeolite A.

A plefe..ed co-builder is a l~tnell~r sodium silicate such as SKS-6 which is particularly useful in pasty viscous foImulations such as gels or in non-aqueous liquid dete~e.lt~ such as those described in WO92/16608 (Henkel).

The liquid detelgellt composition generally has a pH of from 6.5 to 10.5.

The total amount of delerg~lcy builder in the liquid composition is prefeldbly from 5 to 70% of the total liquid composition.

I~efel~ed bleach free detergell~ compositions according to the invention are characterised by having a pH < 10.5, prefe~ably < 10.4, most pleferably 10.3. It has been found that compositions having a low level of reserve ~lk~linity are advantageous in that they have a lesser ten-lency to cause the removal of printed pigment from printed cotton fabrics. Reserve ~lk~linity is expressed as g of NaOH per l00 g of composition as det~ ed by acid titration of a sample, as 1% solution in distilled water to a pH of 9.5.
Plefe,led values of rese~ve ~lk~linity are < 8.0 g ~refe.~bly < 5.0 g, most prefel~bly < 3.0 g NaOH per 100g of composition.

W O 95/27030 21 84364 PC~rAUS95/02700 The invention is further illustrated by the following Example.

The following abbreviations have been used.

C24AS - sodium C24 alkylcl-lph~te C25E4 ~ C12 - Cl5 ~ y aliphatic ethoxylated alcohol having an average of 4 ethoxy groups per mole of alcohol DETPMP - diethylene ~ le penta (methylene phosphonic acid) CMC - carboxymethyl celll-lose PVP - polyvinylpyrrolidone ~lr.~ e - Alcalase (trade mark) enzyme sold by Novo Nordisk A/S having an activity of 2% by weight Savinase - Savinase (trade mark) enzyme sold by Novo Nordisk A/S having an activity of 2% by weight WO 95/27030 2 1 8 4 3 6 4PcT/usgslo27on EXAMPLES

ComPonent Reference 1 Reference 2 (% Example (% by - (% by wt) by wt) wt) C24AS 6.0 6.0 6.0 C25E4 8.0 8.0 8.0 Zeolite A - 40.0 Zeolite MAP 40.0 - 40.0 Carbonate 7.0 7.0 7.0 Citrate 10.0 10.0 10.0 DETPMP 0.4 0.4 0.4 CMC 1.0 1.0 1.0 PVP 1.0 1.0 1.0 MA/AA** 4.0 4.0 4.0 citric acid 3.0 3.0 3.0 Savinase 2.0 2.0 Alcalase - - 2.0 Bri~hte~er* 0.2 0.2 R~l~nce Moisture and Miscellaneous to 100%

WO95/27030 2 1 8 4 3 6 4 PCT/U353/~2700 $Tinopal DMS ex Geigy **Sokolan CP5 M.wt 70,000 The detergent composition according to the invention which comprises Zeolite MAP and Alcalase shows good results in stain removal and lower printed cotton fabric damage as compared with a composition comprising Zeolite MAP with Savinase.

Claims (16)

CLAIMS:

1. A detergent composition comprising:

(a) a surfactant selected from anionic, nonionic, cationic, amphoteric and zwitterionic detergent- active compounds and mixtures thereof;

(b) a detergency builder comprising zeolite P having a silicon to aluminium ratio not greater than 1.33 (zeolite MAP); and (c) a proteolytic enzyme having an isoelectric point below 10.

2. A detergent composition according to claim 1, which does not contain any proteolytic enzyme of isoelectric point > 10.

3. A detergent composition according to claim 1 or 2, which is substantially free of bleach.

4. A detergent composition according to any of claims 1 to 3, which is substantially free of optical brighteners.

5. A detergent composition according to any one of claims 1 to 4, wherein the zeolite MAP has a silicon to aluminium ratio not greater than 1.15.

6. A detergent composition according to claim 5, wherein the zeolite MAP has a silicon to aluminium ratio not gleater than 1.07.

7. A detergent composition according to any of claims 1 to 6, wherein the zeolite MAP has a particle size dso of from 1 to 5 micrometres.

8. A detergent composition according to any one of claims 1 to 7, which comprises from 1 to 80% by weight of zeolite MAP.

9. A detergent composition according to any one of claims 1 to 8, which comprises the proteolytic enzyme in an amount to provide from 0.001%
to 2% active enzyme by weight of the detergent composition.

10. A granular detergent composition according to any of claim 1 to 9, which comprises from 5 to 60 wt % of component (a); from 10 to 80 wt% of component (b) and a proteolytic enzyme (c) in an amount to provide from 0.001% to 2% active enzyme by weight of the detergent composition.

11. A liquid detergent composition according to any of claims 1 to 9 which comprises from 5 to 60 wt% of component (a), from 5 to 40 wt% of component (b); and a proteolytic enzyme (c) in an amount to provide from 0.001% to 2% active enzyme by weight of the detergent composition.

12. A detergent composition according to any one of claims 1 to 11, which comprises the proteolytic enzyme in an amount to provide from 0.002%
to 0.5% active enzyme by weight of the composition.

13. A detergent composition according to any one of claims 1 to 12, wherein the enzyme having an isoelectric amount of below 10 is represented by subtilisin BPN1 protease.

14. A detergent composition according to any one of Claims 1 to 12 wherein the enzyme having an isoelectric point of below 10 is represented by subtilisin Carlsberg protease.

15. A detergent composition according to any one of claims 1 to 14, wherein the composition has a reserve alkalinity (expressed as g of NaOH per 100 g of composition as determined by acid titration of a sample as 1%
solution in distilled water to a pH of 9.5) of < 8.0 g.

16. A detergent composition according to claim 15, wherein the reserve alkalinity is < 5.0 g.