CA2245561A1 - Autodishwashing method using cellulose ether as a soil release agent - Google Patents

Abstract

There is provided the use of cellulose ether material as agents enabling the improved removal of soils from tableware in automatic dish washing methods.

Description

CA 02245561 l99X-08-05 AUTOOISHWASHING METHOD USING CELLULOSE ETHEPs AS A SOIL RELEASE
AGENT.

Te~ Field The present invention relates to the use of cellulose ether m~t~ril 1~ as agents enabling the ~mproved release of soils from tableware in automatic dish washing methods.

kpround to the Invention A con~i~tent effort is made by delergent manufacturers to provide detergent compositions which have the ability to clean and/or rinse even the hardest to remove soils, fior example tea, coloured vegetable soils and starch-based soils, from tableware.
Effort invested in finding a solution to this problem is reflected by the large number of patent ~pplit~tions filed in this area.

Soil release agents have traditionally been described in laundry applications where the s~il release agent adheres to the surface of fabrics by way of hydrophobic interactions between the fabric and the soil release agent.

The most commonly used soil release agents inco~ dled into detergent compositions have been derivatives of Terc~h~ t~ and more recently poly~ch~n~le ethers. US 4 795 584 and EP 253 567 disclose soil release polymers comprising ethyleneoxy L~ tf~ and polyethyleneoxy k;~;pl~ t~ monomer units. Poly.~rch~ri<1P! ethers, such as c~ll-llose ethers, have been deswibed for example in GB 1 534 641, which~i~rlc~sPs m~niQniC. s~ t~nt detergent col,-~silions comprising cellulose ether soil release agents as al}yl and hydroxyalkyl c~ s~o, ethers.

The Procter & Gamble pending UK patent application number 9424291.4 (attorney docket number CM 850F) discloses the use of terephth~l~te and cellulose ethers as soil release ~gents in laundry detergent compositions, providing increased soil removal ~,e. ~,....ance.

J~p~n~se patent N~ 5,078,69~ describes an automatic dishwashing detergent composition cont~ining a sodium or potassium salt of carboxy methyl cellulose, showing bactericide activity.

The problem underlying the present invention is the provision of a dishwashing detergent col--~nent that provides improved soil removal from tableware.

It is the surprising finding of this invention that cellulose ether soil release agents applied in a dishwashing method can enable the improved release of soils from said tableware.

The soil release agent une~c~cteAly adheres to the surface of the tableware, forming a barrier layer on which soils deposit. The soil release agent and ~tt~hP~ soil are released in the subsequent wash cycle.

C~e~ k~se ether m~t~ri~l.c are known as soil release agents as ~les~rihe~l above. Cellulose ether mat~ 1.c are also hlown in dishwashing. However, the use of celll-lose ether m~tPri~lc as soil release agents in dishwashing has not been previously docum~n~P~l.
Neither the problem underlying the present invention nor the subsequent solution, as inAic~ed above, have been addressed in the prior art.

~n additiont a further advantage of the present invention is the non-toxic nature of the cçlhlEQsP ether soil release agents. The soil release agent, being a component of a dlishwashing form~ tion, adheres and remains on the surface of the tableware. It is the.~fo.,~ prefPr~hle that the soil release agent be edible and harmless to hnm~nc when concllmefl The soil release agent is ~l~ft:lably invisible to the naked eye, to minimicP
nn~e~ y Cons~lmt~r concern.

S--lrnmsry of the ;"~..lion l he present invention provides the use of a cellulose ether material as an agent enabling the impr~ved release of soils from tableware when employed in a method comprising the steps of ~ i) applying a coating of said cellulose ether to said tableware;

~ii) 'in use' soiling of the coated tableware; and (iii) washing of the tableware, thereby removing said coating and soils.

I~etailed Desc. .~lion of the Inven~ion A~ent enabl~n.~ the improved removal of soils According to the present invention a cellulose ether material is used as an agent enabling the improved release of soils from tableware.

The ce~ se ether soil release agent is believed to adhere to the surface of the tableware providing a prot~Li~/e layer coating the surface of the tableware. Thepl~te~ re coating layer acts as the outermost surface of the tableware onto which soils will be adsorbed. The cellulose ether soil release agent and ~tf~h~ soil are removed from the surface of the tableware, and it is believed that a new protective coating layer is de~o~i~, during the washing step.

C:ellulose Ether Material By cPIllllose ether m~tPn~l herein, it is meant a polymeric material having cellulose ether monomer units, preferably comprising only cellulose ether monomer units.

The polys~rl~. ;de cf~ ()se ether m~tPri~l is preferably selPctecl from the group having the general formula as shown below.

0~
''~\
o 1''' OR OR n WO g7128908 PCT/US97/02144 R is either hydrogen, an alkyl or carboxy alkyl group n is between 100 and 10 000 The c~ os~- ether is more preferably methyl c~ k)se, where R is C~3, or carboxy methyl cellulose, where R is CH2COO~Na+. Preferably the cellulose ether has a degree of substitution of between 0.0 and 3.0, preferably between 0.5 and 2.5 and a molecular weight of between 20 000 and 150 000. According to the present invention the cel~ulose ether m~t.~n~l has a degree of polymerisation of more than 100, pler~ldbly between 100 and 10 000. As used herein, the term 'degree of polymerisation (dp)' is the ratio of the weight average molecular weight to average molecular unit weight, i.e.
d~ = MWW/MUW. The weight average molecular weight (MWW) is obtained by ~lda~-l analydcal methc ds as described in Polymer handbooks. A ~l~,Çe~llcd method is light sr;.~ g from polymer solutions as originally defined by Debye.

For eY~mpl~, the average mole~ r unit weight (MUW) for methyl cellulose ether may be d~ t~LI,lilled from the sum of the molecular weight of the unsubstituted cellulose unit and the product of the degree of polymPri~tion and the molecular weight of the sulls~ nl less the hydrogen mass (1).

i.e. MUW=162 + (15-1)* ds - for methyl sllhstit~lçntc found in methyl cellulose ethers.

MUW may also be d. te~"~ined from the " % methoxyl content" value (mc) also used by manufactures of methyl celllllose ethers instead of the degree of substitution, such that;

MUW = 100 - ~(mol.wt. of CH2/mol.wt. of OCH3)*mc]

~pplication Ste~

Cellulose ether materials are applied as a coating to the surface of the tableware.
App~i~ation of the cellulose ether material can be done by p~inting-on~ spraying-on, application with a cloth or other applicator. The ~ Gll~ d method of application is by way of so~kin~ and/or rinsing in a d~e~ solution collt~ining between 0.0001% and0. 1%, piefe.~lbly 0.0005% and 0.005%, most preferably 0.001 % and 0.01% by weight active cellulose ether. The detergent solution cont~inTng cellulose ether may be provided by way of a block of poorly water-soluble material impr~n~tp~ with cellulose ether, which is then suspended in the interior of the dishwasher machine. Materials similar to those used in the formation of commonly known 'toilet blocks' could find utility in this execution. Altematively, the delel~,cnl solution can be provided by dissolution of a granular or tablet form detergent coluposition, as is typically a step in the washing of tableware.

The cellulose ether material may alternatively be ~-lminictPred by way of a rinse-aid composition preferably co~ ining cç~ lose ether, non-ionic surf~rt~nt~ and/or hydluL~ )es~ Rinse-aid co~ ositions are added during the rinsing cycle of the dishw~ ing m~chinP sepaldlely~ and in addition to the delclgel~l coll~osition employed in the main wash cycle(s). The rinse-aid is ~iS~n~ by way of a standard rinse-aid pen~ing system at levels of between O.5g and lOg of rinse-aid co-llposilion per rinse cycle. Rinse-aid compositions enh~nf~e rinsing of the tableware and tend to prevent spot and film rol~ndtion.

'In-use' SoilinF Step The term 'in-use' soiling can be inlel~lclcd as in~lic~ting everyday use of the tableware for example as a carrier or container for foo~t--ff~, but may also include p~in~ing-on, spraying-on or ap~lication of a soil with a cloth or other applicator. The variety of soils may include any food soil. Particularly good removal of soils in accord with the invention can be achieved on boiled ~p~ghetti solution, egg, cheese and highly coloured tea stains.

Washin~ St~

The soiied tableware, described above, is washed in a detergent solution. Any method for w~shing or r~e~ning soiled tableware can be implemented. The l~lc~cllcd method of washing or r7~ning is a m~r,hine dishwashing method A ~lc~llcd m~rhine dishwashing method may be pclr~llned using any m~-hinP dishwasher commonly available on the market at a tc~ dl~llc of between 50 and 60~C. Said ~lcÇellcd rn~rhine dishwashing method compri~Ps treating soiled tableware, se1ect~ from crDckery~ g~idssware, hollowware, silverware and cutlery and mixtures thereof, with an WO 97/28908 PCT/US9711~2144 aqueous liquid having dissolved or ~ pçnsp~ therein an effective amount of a m~ch;n dishwashing de~ e"t composition. By 'an effective amount of machine dishwashing coll~posilion' it is meant from Sg to 60g of product dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical product dosages and wash solution volumes commonly employed in conventional rr ~ ine dishwashing methods.

In a p lc~Çe,l.,d aspect the wash solution contains cellulose ether material, preferab}y delivered as a colll~ollent of the detel~en~ col"posiLion, at a concentration of from 0.00()1% toO.1%, preferablyO.0005% toO.01%, mostpreferablyO.001% toO.005%
by weight active cell~lose ether. Reapplication of a cellulose ether coating to the .
tableware can thus occur in the washing step, concurrently with the removal of the 'old' coating together with soils.

Delel~nt Gompositions DeLe~cllt co,llpo~iLions are employed in the washing step as described above. The c~-11--1c se ethers are ~leÇ~,.dbly present as co~l~ponents of the delelge~"t composition at levels of between 0.2% and 10%, preferably 0.5% and 2% by weight active cellulose ether. The deltl~cnt co~ osi~ion may contain various components including surf~Pnt~, ble~hing agents, deL~l~.,nt builders, ~lk~linity sources, lime soap di~.sanL~, organic polymeric co.l,~unds in~lu~ling polymeric dye transfer inhibiting agents, crystal growth inhibitors~ heavy metal ion sequestrants, enzymes and enzyme stabilizers, corrosion inhibitors, suds :~u~l~lt;55~ 1~, solvents, and hydlo~ es.

Surfa~~-t~nt A highly ~ref~.n d co.~ e.-L of the compositions used in this invention is a surfactant system comprising surfactant sele~t~d from anionic, cationic, nonionic ampholytic and zwitt~rioniC ~ t~nt~ and mi~lulcs thereof. Automatic dishwashing m~- hint~ products should be low foaming in character and thus the foaming of the surfactant system must be ~llwl~ssed or more preferably be low foaming, typically nonionic in character. The surfactant system is typically present at a level of from 0.2% to 30% by weight, more prcfel~dbly from 0.5% to 10% by weight, most preferably from 1% to 5% by weight of the coll,l)osiLions.

WO 97/28908 PCT/US97/n2144 A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Heuring on December, 30, 1975. A list of suitable cationic surf~t~ntc is given in U.S.P.
4,259,217 issued to Murphy on March 31,1981. A listing of surfactants typically included in automatic dishwashing detergent compositions is given for example, in EP-A-0414 549 and PCT Applications Nos. WO 93/08876.

Nonionic surfactant F~enti~lly any nonionic surfactants useful for detersive purposes can be included. in the co,l,po,itions. Preferred, non-limiting classes of useful nonionic surf~çt~nt~ are listed below.

Nonionic ethoxylated alcohol surfactant The alkyl ethoxylate con~-n~tion products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the ~liph~til' alcohol can either be straight or b~.~n~h~, primary or secondary, andgenerally contains from 6 to 22 carbon atoms. Particularly pl~ell~d are the con~ nc~tion products of alcohols having an alkyl group cont~inin~ from 8 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.
Nonionic ethoxylated/propoxylated fatty alcohol surfactant The ethoxylated C6-Clg fatty alcohols and C6-Clg mixed ethoxylated/propoxylated fatty alcohols are suitable surf~t~nt~ for use herein, particularly where water soluble.
Preferably the ell.o~ylated fatty alcohols are the Clo-CIg ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most piereidbly these are the C12-C1g ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40. Preferably the " mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of plo~o~y}ation of from 1 to 10.

Nonionic l~O/PO condçns~tes with propylene glyco}

The con~i~n~tion products of ethylene oxide with a hydrophobic base formed by the conden~tion of propylene oxide with propylene glycol are suitable for use herein. The hydrophobic portion of these compounds preferably has a molecular weight of fromabout 1500 to about 1800 and exhibits water insolubility. Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, m~rk~t~d by BASF.

Nonionic EO condensation products with propylene oxide/ethylene di~nine adducts The con~len~tion products of ethylene oxide with the product rPslllting from thereaction of propylene oxide and ethylene~i~mine are suitable for use herein. Thehydrophobic moiety of these products cor~ t~ of the reaction product of ethylen~ minç and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. Examples of this type of nonionic surfactant include certain of the co..~ll,c.~ially available Tetronic~M com~o~ ds, Illalhe~ed by BASF.

(:)xy~en-rçle~sin~ ble~chin~ system An optional feature of the compositions of the present invention is an oxygen-rP~ ing ble~hing system. In one ~l~f~ ;d aspect the b~ hin~ system cont~in~ a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The prc~llction of the organic ~,v~yacid occurs by an in situ reaction of the precursor with a source of hydrug~ n peroxide. P~fe,led sources of hydrogen peroxide include inorganic perhydrate bl~ h~s. In an allell,dLi~re ~lerelled aspect a ~ rulllled organic peroxyacid is incol~,dted directly into the compo~ition- Compositions col.l;tinin~ mixtures of a hydlui2en peroxide source and organic peroxyacid precursor in combination with ae~l.,-ed organic ~l~ydcid are a~so envisaged.

=_ g Inorganic perhydrate bleaches The compositions in accord with the invention preferably include a hydrogen peroxide source, as an oxygen-rel~ing bleach. Suitable hydrogen peroxide sources include the inorganic perhydrate salts.

The inorganic perhydrate salts are normally incol~oldted in the form of the sodium salt at a level of from 1% to 40% by weight, more preferably from 2% to 30% by weightand most preferably from 5 % to 25% by weight of the compositions.

~xamples of inorganic perhydrate salts include perborate, ~l-;~uI,onate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without ~ddition~ utc~;lion. For certain perhydrate salts however, the ylc~ferlcd ecutions of such granular co,-l~o~ ions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.

Sodium pc-bu-dte can be in the form of the monohydrate of nominal formula NaB02H202 or the tetrahydrate NaB02H202.3H20.

Alkali metal ~e.c~l,onates, particularly sodium ~call,onate are plcrt;llcd perhydrates for inclllcion in coll,po~iLions in accordance with the invention. Sodium pe,~d.bonate is an ~d~lition colll~ound having a formula co--c~ollding to 2Na2C03.3~202, and is available coll,lllc.~iially as a crystalline solid. ~o ~ m ~lc~hl,onate, being a hydrogen peroxide addition collly~ulld tends on ~icsol~ltion to release the hydrogen peroxide c~uite rapidly which can increase the ten~ncy for localised high bleach concentrations to arise. The p~uLol~a~e is most plcfcldl)ly inco-~.dled into such compositions in a coated form which provides in- product stability.

A suitable coating m~tf~.ri~l providing in product stability comprises mixed salt of a water soluble alkali metal sulphate and ~d L,onate. Such co~tingC together with coating processes have previously been described in GB-1,466,799, granted to Interox on 9th March 1977. The weight ratio of the mixed salt coating material to percarbonate lies in the range from 1: 200 to 1: 4, more preferably from 1: 99 to l: 9, and most -preferably from 1: 49 to 1: 19. Preferably, the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2SO4.n.Na2CO3 wherein n is from0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.

Other co~tin~c which contain silicate (alone or with borate salts or boric acids or other inorganics), waxes, oils, fatty soaps can also be used advantageously within the present invention.

Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility in the co",~o5iLions herein.

Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be l~r,sented as o ~1 X-C--L

where L is a leaving group and X is ecc~nt~ y any functionality, such that on perhydrolysis the structure of the peroxyacid produced is o Il X-C-OOH

Peroxyacid bleach precu.:,o- compounds are preferably incorporated at a level of from 0.5Yo to 20% by weight, more preferably from l ~o to 10% by weight, most preferably from 1.5% to 59~ by weight of the compositions.

Suitable peroxyacid bleach ~ or compounds typically contain one or more N- orO-acyl groups, which ~lc~;ul;~or~ can be sel~tPd from a wide range of classes. Suitable classes include anhydrides, esters, imides, I~.t~mc and acylated derivatives of imi~l~7oles and oximP,s Examples of useful m~t~.ri~i.c within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798? 1147871, 2143231 and EP-A-0170386.

~ Leavin~ groups The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle).
However, if L is too reactive, this activator will be difficult to stabilize for use in a ble~çhing co"~l,osition.

Pl~Ç~ d L groups are se1e~te~1 from the group conci.cting of:

--0~ --O~Y, and --0 1~l /~ 1~l R3 ~ . R3 Y

--O--CH=C--CH=CH2 --O--C H=C--C H=CH2 -O--C--R1 CH2-C --N~ ~NR4 ~ O

--O--C=CHR4 , and N S--CH--R4 R O

and mixtures thereof, wherein RL is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R3 is an alkyl chain co,~ -g from 1 to 8 carbon atoms, R4 is H
or R3, and Y is H or a solubilizing group. Any of Rl, R3 and ~4 may be substituted by çscenti~lly any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ~mmonium or alkyl ammonium groups The l~lere.led solubilizing groups are -S03 M+, -C02 M+, -S04 M+, -N+(R3)4X-and o<--N(R3)3 and most ~l~feldbly -S03 M~ and -C02 M+ wherein R is an alkyl chain co~ in~ from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
Preferably, M is an alkali metal, ammonium or substitl-te~l ammonium cation, with sodium and pot~ccil-m being most p~ ed, and X is a halide, hydroxide, methylsnlf~te or acetate anion.

PelLell~oic acid l?l~UI:~OI

Pell~ll20ic acid plC~;Ul~Ul co~ oullds provide perbenzoic acid on perhydrolysis.
Suitable O-acylated l)e~bel-zuic acid ~l~u-~or compounds include the sul.s~ituLed and ~~llsllbs~ilu~d ben~oyl oxybenzene sulfonates, in~ln(ling for exarnple benzoyl ox~ 7~P, sulfonate:
o ~o~S03-Also suitable are the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, in~ lin~ for example:

OAc AcO~o ~,OAc OAc OBz Ac = COCH3; Bz = Benzoyl Perbenzoic acid ~ulaor compounds of the imide type include N-benzoyl succ-inimi~P, tetrabenzoyl ethylene ~ mine and the N-benzoyl substituted ureas. Suitable imitl~7ole type perbenzoic acid ~l~ulaula include N-benzoyl imirl~7.cl1e and N-benzoyl ben7.imicl~7ole and other useful N-acyl group-cont~ining ~lbellzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyrogl~lt~mic acid.
Other ~lI,enLoic acid pl~;UlaOl~ include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the c~ pound having the formula:
O O
~0' O~'cOOH

Phthalic anhydride is another suitable perbenzoic acid p.~lllaor compound herein:
O

~0 Suitable N-acylated lactam perbenzoic acid ~ laOIa have the formula:

CH2~cH2 ]n wherein n is from 0 to 8, ~erc~-~ly from 0 to 2, and R6 is a benzoyl group.

Perbenzoic acid derivative precursors re~benzoic acid derivative precursors provide substituted perbenzoic acids on perhydrolysis.

Suitable substituted ~lbe~ ic acid derivative plC~;U1501:~ include any of the herein disclosed ~l,cn~oic precursors in which the benzoyl group is substituted by escenti~lly any non-positively charged ~i.e.; non-cationic) functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.

A p-~r~-ed class of s~b~ d perbenzoic acid plccul~r compounds are the arnide ~ubs~iLuL~d cc,~ ounds of the following general formulae:

Il l 11 1 11 11 O R5 O or R5 O O

wl~wein Rl is an aryl or alkaryl group with from I to 14 carbon atoms, R2 is an arylene, or alkarylene group cont~ining from 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group co~ 1 to 10 carbon atoms and L can be e~enti~lly any leaving group. Rl preferably con~ from 6 to 12 carbon atoms. R2 preferably cont~in~ from 4 to 8 carbon atoms. Rl may be aryl, sllbstitllt~ aryl or alkylaryl col-l ~;..i.~g b~ ng~ sub~Lilu~ion, or both and may be sourced from either synthetic sources or natural sources inclufling for example, tallow fat. Analogous structural variations are perrnissible for R2. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R~ is preferably H or methyl. R1 and R5 should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0 170386.

~5 Cationic peroxyacid precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids onperhydrolysis.

Typically, cationic peroxyacid precursors are formed by substitllting the peroxyacid part of a suitable peroxyacid precursor co.u~ulld with a positively charged functional group, such as an ammonium or alkyl ammonium group, preferably an eehyl or methyl ammonium group. Cationic peroxyacid pr~ ol~ are typically present in the conlyosiLions as a salt with a suitable anion, such as for example a halide ion or a methylsulfate ion.

The peroxyacid ylc~;ulSOl compound to be so cationically ~b~;tu~e~ may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hc~ befole. ~ltern~tively, the peroxyacid yl~;~l~or compound may be an alkyl y~lcalbo~ylic acid yl~Ul:~Ol cc,.l-~u--d or an amide substituted alkyl peroxyacid precursor as des, lii~ed hereinafter Cationic -yeroxyacid yl~ul~Ol~ are described in U.S. Patents 4,904,406; 4,751,015;
4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594;
EP 475,512, 458,396 and 284,292; and in JP 87-318,332.

Examples of l.lGrt;ll~d cationic peroxyacid Ill~U~:~Ul~ are described in UK Patent Appli-~tinn No. 9407944.9 (attorney's docket no. CM642F) and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 081298906 (attorney's docket nos. 5413 to 5416).

Suitable cationic peroxyacid ~r~ul~o,~ include any of the ~mmonium or alkyl ~mm-~nil-m substituted alkyl or benzoyl oxybenzene sulfona~s, N-acylated caprol~t~m~ and monobenzoyltetraacetyl glllcose benzoyl peroxides.
-A L,iefe.led cationically substituted benzoyl oxybenzene sulfonate is the 4-~trimethyl ammonium) methyl derivative of benzoyl ox~L~enz~ne sulfonate:

~_~o~S03-\N+
/ ~

A ~ re.led cationically substituted alkyl oxyb~on7~ne sulfonate has the formula:

, N ~ o ~ l ~

Preferred c~tionic peroxyacid pl~Ul:~olS of the N-acylated caprolactam class include the trialkyl arnmonium methylene benzoyl caprol~t~m~, particularly trimethyl ammonium methylene bt:l.zoyl caprol~ct~m-O

/ N ~ ~"~ ~
Other l)refc.led cationic peroxyacid pl~;C~ Ol~i of the N-acylated caprolactam class include the triaLIcyl ~mmonillm methylene alkyl capro~ t~m~:
O O
)~ N ~l ~N+ ~ (CH2)n V

where n is from 0 to 12, particularly from 1 to 5.

Another ~lcf~lled cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.

CA 0224556l l998-08-05 _ Alkyl percarboxylic acid bleach precursors Alkyl percarboxyiic acid bleach precursors form percarboxylic acids on perhydrolysis.
~ Preferred precursors of this type provide peracetic acid on perhydrolysis.

Preferred allcyl ~r~ulJoxylic precursor compounds of the imide type include the N-,N,NlNl tetra acetylated alkylene ~ mines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those col,lpounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetr~ etyl ethylene ~i~mine (TAF~) is particularly f~ d.

Other ~l~fel,ed alkyl ~l.;~boxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acet~yl,enzene sulfonate (ABS~ and penta acetyl glucose.

Amide substituted alkvl peroxyacid yl~ul~

Amide subsLiLuled alkyl peroxyacid precursor compounds are also suitable, including those of the following general formulae:

R1 C N ~2--C L R1 N C R2 C
Il l 11 1 11 11 O R5 0 or R5 0 0 wherein R} is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group collt;~inillg from 1 to 14 carbon atoms, and R5 is H or an alkyl group conl;.il-ing 1 to 10 carbon atoms and L can be ess~nti~lly any leaving group. R1 preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. Rl may bestraight chain or branched alkyl containing br~nçhing, substitution, or both and may be sourced from either synthetic sources or natural sources incl~l-iing for example, tallow fat. Analogous structural variations are permissible for R2. The substitution can include alkyl, halogen, nillogen, sulphur and other typical substituent groups or organic compounds. R5 is prefeldbly H or methyl. Rl and R5 should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

Benzoxazin or~anic peroxyacid precursors Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:

C
1~ 48--R1 inclu-ling the substituted benzoxazins of the type R4~N~

wl,e.~ Rl is H, alkyl, alk~ryl, aryl, arylalkyl, and whe~ein R2, R3, R4, and R5 may be the same or dirrelent sul~ Pntc SPlPctpfl from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (wherein R6 is H or an alkyl group)and carbonyl functions.

An e.spe~i~lly ~lGfGlled precursor of the bç~-7. .~,.;n-typG is:

[~N ~

P'~efc,l",ed or~nic peroxyacid The organic peroxyacid ble~hing system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach p~;ul~or compound, a preformed organic WO 97128908 PcT/us97lo2144 peroxyacid, typically at a level of from 0.5% to 25% by weight, more preferably from 1% to 10% by weight of the composition.

A ~l~f~;lled class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:

R1 C N- R2 ~ OOH R1 N C R2 C- OOH
Il l 11 1 11 11 O RS O or R5 O O

wherein Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group co~ ;ng from 1 to 14 carbon atoms, and RS
is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. ~l preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms.
Rl may be straight chain or br~nçll~A alkyl, sllbstit-lt~A aryl or alkylaryl co~ .;ng br~nclling, ~Litlllion, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R5 is preferably H orrnethyl. Rl and RS should not contain more than 18 carbon atoms in total. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, es~i~lly di~o~y~od~n~Aioc acid, di~lu~cytetr~d~n~lliQc acid, and di~~ yh~Y~c~ neAioc acid. Dil)enLo~l peroxide is a pl~r~ d organic peroxyacid herein. Mono- and di~dLelaic acid, mono- and dipe.l,ld~rlic acid, and N-phthaloylaminoperoxicaproic ac~d are also suitable herein.

Water-soluble bismuth compound The compositions used in this invention may contain a water-soluble bismuth compound, preferably present at a level of from 0.005% to 20%, more preferably from 0.01% toS%, mostp-~f~-dblyfrom0.1% to 1% byweightofthecompositions.

The water-soluble bismuth compound may be essentially any salt or complex of bismuth with essentially any inorganic or organic counter anion. Pl~fel~;d inorganic bismuth CA 0224.7F76 l l 998 - 08 - OF7 - -salts are sele~tPcl from the bismuth trih~ , bismuth nitrate and bismuth phosphate.
Bismuth acetate and citrate are ~lerelled salts with an organic counter anion.

Water-soluble sulfate salt The co.,.positions may optionally contain a water-soluble sulfate salt, preferably present at a level of from 0.1% to 40%, more ~fc;l~bly from 1% to 30%, most preferably from 5 % to 25 % by weight of the compo~ition~.

The water-soluble sulfate salt may be e~nt~ y any salt of sulfate with any coun~er cation. Preferred salts are sel-~ctP~ from the s--lf~tPs of the allcali and ~Ik~lin~ earth metals, particularly sodium sulfate.

Additional corrosion inhibitor com~ound The com~ositil ns may contain ~ ition~l corrosion inhibitors preferably selP~ctP~l from organic silver coating agents, particularly p~r~ffin, nil-.~gen-containing corrosion inhibitor co.,.~ounds and Mn(II) co-l.~vunds, particularly Mn(II) salts of organic ligands.

Organic silver coating agents are described in PCT Publication No. WO94/16047 (atto~ney's docket no. CM497M) and copen~ling UK Application No. UK 9413729.6 (attorney's docket no. CM750F). Nitrogen-co.~ P corrosion inhibitor co-.-~ounds are ~ os~A in cu~nding Eun~ Application no. EP 932020g5. 1 (attorney' s docket no. CM571F). Mn(II) compounds for use in corrosion inhibition are described in copending UK Arpli~tion No. 9418567.5 (allulne~y's docket no. CM719FM).

Organic silver coating ~pents Organic silver coating agent may be inco~ dled at a level of from 0.05% to 10%, dbly from 0.1% to 5 % by weight of the total co~ o~ition.

~he filnt~fion~l role of the silver coating agent is to form 'in use' a protective coating layer on any silve.~ co...~onents of the washload to which the compositions of the invention ~re being applied. The silver coating agent should hence have a high affinity for ~tt~-~hment to solid silver surfaces, particularly when present in as a component of an aqueous washing and ble~hing solution with which the solid silver surfaces are being treated.
-Suitable organic silver coating agents herein include fatty esters of mono- or polyhydric alcohols having from 1 to about 40 carbon atoms in the hydrocarbon chain.

The fatty acid portion of the fatty ester can be obtained from mono- or poly-carboxylic acids having from 1 to about 40 carbon atoms in the hydrocarbon chain. Suitable examples of monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid, p~lmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, Valerie acid, lactic acid, glycolic acid and ~ dihydroxyisobutyric acid. Examples of suitable polycarboxylic acids include: n-butyl-malonic acid, isocitric acid, citric acid, maleic acid, malic acid and s~lccinic acid.

The fatty alcohol radical in the fatty ester can be ~,p~c3ellted by mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain. Examples of suita~le fatty alcohols ine~ e; behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, ethanol, isolJr~dllol, vinyl alcohol, diglycerol, xylitol, sucrose, ~ ol, pentaerythritol, sorbitol or 501 llil~Lrl.

Preferably, the fatty acid and/or fatty alcohol group of the fatty ester adjunct material have from 1 to 24 carbon atoms in the alkyl chain.

P~c;f~ d fatty esters herein are ethylene glycol, glycerol and so~ esters wherein the fatty acid portion of the ester normally comprises a species sele~t~d from behenic acid, stearic acid, oleic acid, p~lmitic acid or myristic acid.

The glycerol esters are also highly ~l~Çel,t d. These are the mono-, di- or tri-esters of gl~ycerol and the fatty acids as defined above.

Spec~fic examples of fatty alcohol esters for use herein include: stearyl acetate, palmityl dll-lactate, cocoyl isobutyrate, oleyl m~ t~, oleyl t~im~ te, and tallowyl proprionate.
Fatty acid esters useful herein include: xylitol monopalmitate, pentaerythritol monostealate, sucrose monostearate, glycerol mono:,le~dte, ethylene glycol monostearate, soll,i~n esters. Suitable sorbitan esters include sorbitan monoste~r~te, sorbitan p~lmit~t~, sorbitan monolaurate, sorbitan monomyristate, sorbitan mono~eh~n~te, sorbitan mono-oleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehen~t~Q-, su~ n dioleate, and also mixed t~llowalkyl sorbitan mono- and di-esters.

Glycerol mono~le~.,.te, glycerol mono-oleate, glycerol monop~lmit~te, glycerol monob~h~n~te, and glycerol distearate are ~le~ll~d glycerol esters herein.

Suitable organic silver coating agents include triglycerides, mono or diglycerides, and wholly or partially hyd,~,~e,lated derivatives thereof, and any mixtures thereof.
Suitab~e sources of fatty acid esters include vegetable and fish oils and animal fats.
Suitable vegetable oils include soy bean oil, cotton seed oil, castor oil, olive oil, peanut oil~ safflower oil, sunflower oil, r~se~d oil, g,~eseed oil, palm oil and corn oil.

Waxes, including Illicr~;l~stalline waxes are suitable organic silver coating agents herein. ~s~r~,. d waxes have a melting point in the range from about 35~C to about 110~C and co,-,p,ise generally from 12 to 70 carbon atoms. Preferred are petroleum waxes of the ~.~.Arr;-- and microcrystalline type which are composed of long-chain hydrocarbon co"lpou"ds.

~ in~te~ and gelatin are suitable organic silver coating agents herein.

Dialkyl amine oxides such as C12-C20 methylamine oxide, and dialkyl quaternary ammonium colnpuul~ds and salts, such as the C12-C20 methylammonium halides are also suitable.

Other s~ hle organic silver coating agents include certain polymeric materials.
Po~yvinyl~"olido~es with an average moiecul~r weight of from 12,000 to 700,000, polyethylene glycols (PEG) with an average molecular weight of from 600 to 10,000, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-viny1imiA~7Ole, and cellulose derivatives such as methylcellulose, carboxymethylcellulose and hylllo.,.yt;lllyk~ellulose are examples of such polymeric materials.

Certain ~,ru.~e mzlt~ri~ , particularly those demonstrating a high substantivity for mP~llio surfaces, are also useful as the organic silver coating agents herein.

Water-soluble builder compound The coln~o~;lion~ of the present invention may contain as a highly preferred component a water-soluble builder compound, typically present at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% byweight of the composition.

Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids.or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals s~p~.,.t~ from each other by not more that two carbon atoms, ca~bonates, bicarbonates, borates, phosph~tPs, and ~niALulc:s of any of the foregoing.

The carboxylate or polyc~rl,oAylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally ~r.;r~-led for reasons of cost and ~u~ ce.

Suitable carboxylates co~.l;~;~.i..~ one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates cont~ining two carboxy groups include the water-soluble salts of s~-cçinic acid, malonic acid, ~ethyl~n~ioxy~ ~tic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
POlycall-u~-ylates co.~ in~ three carboxy groups include, in particular, water-soluble citr~t~s, ~ni~ s and citraconates as well as succin~tP derivatives such as the carboxymethyloxy~ ;n~t~s described in British Patent No. 1,379,241, lac~i,.,ce;~ ., described in British Patent No. 11389,732, and aminosuccinates ~escribe~ in Neth~ n~lc Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.

Polycarboxylates col~ g four carboxy groups include oxydisuccinates disclosed inBritishPatentNo. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substitllent~ include the sulfos~lcçin~te derivatives ~ ç1ose~l in British Patent Nos.

1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.

Alicyc}ic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates, Z,2,5,5-tetrahy~lloru~ tetracarboxylates, 1 ,2,3,4,5,6-hexane - hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, m~nnisQl and xylitol.
Aromatic polyca boAylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives fli~clos~i in British Patent No. 1,425,343.

Of the above, the prefellt;d pol~calLo~ylates are hydroxycarboxylates cont~inin~ up to three carboxy groups per molecule, more particularly citrates.

The pa~ent acids of the monomeric or oligomeric polyca bo~-ylate chel~ting agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also coll~.l.plated as usefu} builder Conl~)o~ ls.

Borate builders, as well as builders cont~ining borate-forming materials that can produce borate under detergent storage or wash conditions can also be used but are not Çt~ d at wash conditions less that about 50~C, e~ lly less than about 40~C.

Examples of c~L~onate builders are the ~ linP earth and alkali metal carbonates,in~ lin~ sodium carbonate and ses~ui-~ubondle and mixtures thereof with ultra-fine c~k;-lm c~l,ollate as ~1ict~lQse~ in German Patent Application No. 2,321,001 published on November 15, 1973.

Specific eA~I.~les of water-soluble phospl~ , builders are the alkali metal tripo~ylJho~l.h~ lm, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.

CA 0224556l l998-08-05 Pa~i~lly soluble or insoluble builder compound The compositions of the present invention may less preferably contain a partially soluble or insoluble builder compound. Examples of partially water soluble builders include the crystalline layered cilic~t~s as ~icclosP~ for example, in EP-A-0164514, DE-A-3417649 and DE-A-3742043. Examples of largely water insoluble builders include the sodium alulllino~;lic~t~s7 including Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP, Zeolite HS and mixtures thereof.

,~?k~linity system The col,~)o~iLions preferably contain an ~Ik~lini~y system cont~ining sodium silicate having an SiO2: Na2O ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0, present preferably at a level of less than 20%, preferably from 1 % to 15%, most preferably from 3% to 12% by weight of SiO2. The alkali metal silicatemay be in the fc~rm of either the anhyd-rous ~It or a hyd~teA s~lt.

The ~lk~linity system also preferably cont~inQ sodium met~cilic~t~, present at a level of at least 0.4% SiO2 by weight. Sodium m~t~cilic~t~ has a nominal SiO2: Na2O ratio of 1Ø The weight ratio of said sodium silicate to said sodium met~cilic~tP, measured as SiO2, is pl~f~ably from 50: 1 to 5:4, more preferably from 15: 1 to 2: 1, most preferably from 10: 1 to 5:2.

Heavy metal ion se~ue;.llal,~

The d~ n~ co~ os;l;o--c LJl~relably contain as an optional component a heavy metal ion seqtlest7~n~ By heavy metal ion sequestrant it is meant herein components which act to sequester ~chelate) heavy metal ions. These coll-ponellL~ may also have calcium and m~neCi~lm chelation capacity, but p,cfclc,,Lially they show selectivity to binding heavy metal ions such as iron, m~nE~n~se and copper.

Heavy metal ion seque~Lld"~ are genpr~lly present at a level of from 0.005% to 20%, elably from 0.1% to 10%, more l~lefelably from 0.25% to 7.5% and most ere~dbly from 0.5 % to 5 % by weight of the co,lt~iLions.

WO 97/28gO8 PCT/USg7102144 Heavy metal ion sequestrants, which are acidic in nature, having for example phosphonic acid or carboxylic acid function~litips~ may be present either in their acid form or as a complex~salt with a suitable counter cation such as an alkali or ~Ik~line metal ion, arnmonium, or substituted ammonium ion, or any mixtures thereof.
Preferably any salts/complexes are water soluble. The molar ratio of said counter cation to the heavy metal ion sequestrant is preferably at least 1:1.

Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane l-hydroxy disphosphonates and nitrilo trimethylene phosphon~s~s Preferred among the abo~respecies are diethylene triamine penta ~methylene phosphonate), ethylene di~mine tri (methylene phosphon~t~) hPx~ethylene ~ mine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 tlirhocrhonate.

Other suitable heavy metal ion sequestrant for use herein include nitrilotri~cetic acid and poly~min~ boAylic acids such as ethylenPAi~minotçt~etic acid, ethyle~n ;~-..i..e pent~retic acid, ethyleneAi~mine ~ uccinic acid, ethylPnP~i~mine diglutaric acid, 2-hydroxypropylPnPAi~mine disuccinic acid or any salts thereof.

Fc~i~11y ~ f~llc;d is ethylf~-ne~ mine-N,N'-disuccinic acid (EDDS) or the allcali me~ 1k~ .o earth metal, ammonium, or substit~tecl ammonium salts thereof, or IllixLul~s thereof. Pl~fwled EDDS com~unds are the free acid form and the sodium or ..,~.,f-~;um salt or co,--l,lex thereof.

Crystal ~rowth inhibitor co,n~,onent ~e detc,,~ t co"l~,iLions ple~ldbly contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, incol~ol~led preferably at a level of f~m 0.01% to 5%, more preferably from 0.1% to 2% by weight of the compositions.

By organo ~ o~l.honic acid it is meant herein an organo diphosphonic acid which does not contain nitrogen as part of its chemical structure. This definitic n therefore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion seq~lçst~nt co"~ponell~s.

27 _ .

The organo diphosphonic acid is preferably a Cl-C4 diphosphonic acid, more preferably a C2 diphosphonic acid, such as ethylene diphosphonic acid, or rnost preferably ethane l-hydroxy-l,l-diphosphonic acid (HEDP) and may be present in partially or fully ionized form, particularly as a salt or complex.

~nzyme Another optional ingredient useful in the co,-lposilions is one or more enzymes.~ef~l~d enzymatic materials include the commercially available lipases, amylases, neutral and ~ ine proteases, esterases, cellulases, pectin~cçs, l~t~cçs and peroxidases conventionally incol~ol~,ted into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

P'Lcr~ d cc,.".,~el.,ially available protease enzymes include those sold under the t~-~P..~ llt'C Alcalase, Savinase, Primase, Durazym, and Lsperdse by Novo ~ndl-~tries AIS ~De.,--l~k), those sold under the t~ en~me ~Y~t~ce~ M~ l and Maxapem by Gist-Brocades, those sold by Genencor T~ ;onal, and those sold under the tr~çn~me Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incul~.dt~d into the compositions in acculdance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the co,.,~ ion.

P~cr~lcd amylases include, for eY~mple, a-amylases obtained from a special strain of B licheniformis, ~ps~nbe~1 in more detail in GB-1,269,839 (Novo). Pl~Çt;~
CQ~ eially available arnylases include for example, those sold under the tr~lçn~me Rapidlase by Gist-Brocades, and those sold under the tr~ n~me Termamyl and BAN by Novo Industries AIS. Amylase enzyme may be incol~laLed into the composition in accoldance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the co,.,~siLion.

Lipolytic c;llLyl..e (lipase) may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from0.0~1% to 0.5% by weight of the co---lJositions. The lipase may be fungal or bacterial in origin. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is described in Granted European Patent, EP-B-021X272.

WO 97~28908 PCT/US97/02144 An especially prefelled lipase herein is obtained by cloning the gene ~rom Humicola l~nuginosa and expressing the gene in Asper~illus orvza, as host, as described in Eulv~an Patent Application, EP-A-0258 068, which is commercially available from Novo Infl-lstries A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase iS also described in U.S. Patent 4,81(),414, Huge-Jensen et al, issued March 7, 1989.

Enzyme Stabili7inp Svstem Plert;ll~ enzyme-cont~;ning compositions herein may comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabili~ing system which is compatible with the detersive enzyme. Such stabilizing systems can comprise calcium ion, boric acid, propyleneglycol, short chain carboxylic acid, boronic acid, chlorine bleach scavengers and n~ ul~s thereof. Such stabilizing systems can also comprise reversible enzyme inl~ , such as reversible ~L~,lease inhibitors.

Or~nic po3yrneric compound Organic polymeric compounds may be added as ~.ef~ d components of the compositions. By organic polymeric compound it is meant e~enti~tly any polymericorganic ccll,l~ulld commonly used as di~ ,t~, and anti-redeposition and soil sllc~ncion agents in dcLe~gent co,.,~.~ n.~ Organic polymer compounds, however, have not been previously described as soil release agents in dishwashing. The use of organic polymeric con~ullds as soil release agents has not previously been described.

Organic polymeric compound is typically incol~oldled in the d~t~ r~,ent compositions of ~e invention at a level of from 0.1% to 30%, ~r~feldbly from 0.5% to 15%, most preferably from 1% to 10% by weight of the co",~osiLions.

~xamples of organic polymeric compounds include the water soluble organic homo~ or ~o-polyme~ic polyc~l,~ ~ylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals scp~ t~ from each other by not more than two car~on atoms. Polymers of the latter type are disclosed in GB-A-1,596,756.

-Examples of such salts are polyacrylates of molecular weight 2000-10000 and their copolymers with any suitable other monomer units including modified acrylic, fumaric, maleic, itaconic, aconitic, mes~ronic, citraconic and methylenPm~lonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any lu~es thereof. Plefelled are the copolymers of acrylic acid and maleic anhydridehaving a m~l~nl~ weight of from 20,000 to 100,000.

Pl~fel-ed coJ""~ cially available acrylic acid cont~ininE polymers having a molecular weight below 15,000 include those sold under the tr~-len~me Sokalan PA30, PA20, PA1~, PA10 and Sokalan CP10 by BASF GmbH, and those sold under the tr~ Pn~mP
Acusol 45N by Rohm and Haas.

Pl~,f~.led acrylic acid co~ E copolymers include those which contain as monomer units: a) from 90% to 10%, preferably from 80% to 20% by weight acrylic acid or its salts and b) from 10% to 90%, ~n,rt;lably from 20% to 80% by weight of a substituted acrylic mono",~,~ or its salts having the general forrnula -tcR2-cRl(co-o-R3)l-wi~ at least one of the ..u~ Pnt~ Rl, R2 or R3, prerelably Rl or R2 is a 1 to 4 carbon alkyl or i~ydnlAya'lkyl group, Rl or R2 can be a hydrogen and R3 can be ahyd.~,en or alkali metal salt. Most ~refelled is a substit~lt~A acrylic monomer wherein Rl is methyl, R2 is hydroge,l (i.e. a m~ . . ylic acid monomer3. The most pl~re~.. d copolymer of this type has a molecular weight of 3500 and conl;1;n~ 60% to 80% by weigi~t of acrylic acid and 40% to 20% by weight of m~th~rrylic acid.

TE~e polyamino co-l-~unds are useful herein inrh~-ling those derived from aspartic acid such as those ~ rlo~d in EP-A-305282, EP-A-305283 and EP-A-351629.

T.ime ~n:~ di~ l comL~u--d The co, l~oS;I;OnS may contain a lime soap di.~ L co,--~ound, preferably present at a leveloffromO.l~a to40% byweight, morepreferably 1% to20% byweight, most p.~re.~ly from 2% to 10% by weight of the co.-lpo~.itions.

A lime soap di .~. ~nt is a material that prevents the ~ tion of alkali metal, ~mmr~nillm or amine salts of fatty acids by r~lcil-m or magnesium ions. Pl~fell~d lime CA 0224556l l998-OX-05 _ .

soap di~~,~lt compounds are disclosed in PCT Application No. W093/08877 (attorney's docket no. CM466M).

Suds su~plessing system The co"-positions, when formulated for use in machine washing compositions, preferably co,nplise a suds s~le~.~.ing system present at a level of from 0.01% to 15%, ~Jl'e:f~ldl)ly from 0.05% to 10%, most l~lerc;l~bly from 0.1% to 5% by weight of the co.ll~o~.ition.

Suitable suds s~ es.,ng systems for use herein may comprise ~ssenti~lly any known iro~i~ co,..pou,ld, inc~ in~ for example siliconP- antifoam compounds, 2-alkyl and alcanol antifoam compounds. Preferred suds su~r~s~i"y~ systems and antifoam compounds are ~ losed in PCT ~pplic~tion No. W093/08876 and copending European .Ap~lir~tion No. 93870132.3.

Polymeric dye transfer inhibitin~ agents rhe compositions herein may also comprise from 0.01% to 10 %, preferably from 0.05 % to 0.5 ~o by weight of polymeric dye transfer inhibiting agents.

~e polymeric dye tr~n~f~r inhibiting agents are preferably sele~tPA from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimi~701e, polyvinylpyrr~ lonPpolymers or co~..bil-~tion~ thereof.

pH of the com~?ositions The dt;Lel~,el-~ compositions used in the present invention are preferably not formulated to nave an unduly high pH, in preference having a pH measured as a 1~ solution in tilled water of from 8.0 to 12.0, more preferably from 9.0 to 11.8, most preferably fromg.Sto 11.5.

Form of the compositions The detergent compositions can be form~ ted in any desirable form such as powders, granulates, pastes, liquids, gels and tablets, granular forms being ~lerelled.

The bull~ density of the granular detergent compositions in accordance with the present invention is typically of at least 650 g/litre, more usually at least 700 g/litre and more preferably from 800 gllitre to 1200 g/litre.

The par~icle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5 % of particles are greater than 1.4mm in rii~met~r and not more than 5% of particles are less than 0. lSmm in m--t~r.

Generally, if the com~o~ilions are in liquid form the liquid should be thixotropic (ie;
exhibit high viscosity when subjected to low stress and lower viscosity when subjected to high stress), or at least have very high viscosity, for example, of from l,000 to 10,000~000 ce..ti~oise.

CA 0224556l l998-08-05 E~amples The following examples illustrate the present invention.

In the co~ ions, the abbreviated co.. ~nent identifications have the following Nonionic : C13-C1s mixed ethoxylated/~,ol,oxylated ~atty alcohol with an average degree of ethoxylation of 3.B
and an average degree of propoxylation of 4.5 sold under the tr~en~me Plurafac LF404 by BASF GmbH
(low foaming) MPt~ t~ : Sodium m~t~silic~tp (SiO2:Na20 ratio = 1.0~

Silicate : Amorphous Sodium Silicate (SiO2:Na2O ratio = 2.0) Carbonate : Anhydrous sodium carbonate Pho~h~tP : Sodium tripolyphosphate 480N : Random copolymer of 3:7 acryliclmethacrylic acid, average molecular weight about 3,50 Citrate : Tri-sodium citrate dihydrate PB1 : Anhydrous sodium ~c.lGldle monohydrate CMC : Carboxy Methyl Cell-l1Ose (66% active) TAED : Tetraacetyl ethylene rli~mine CA 0224556l l998-08-05 Cationic ~ or Cationic peroxyacid bleach precursor salt of trialkyl ammonium methylene Cs-alkyl caprolactam with tosylate BzP : Dibenzoyl peroxide DETPMP : Diethylene triamine penta {methylene phosphonic acid), Ill~ke~ed by Monsanto under the tr~flf n~me Dequest 2060 .DP : Ethane 1-hydroxy-1,1-diphosphonic acid PM~ : 1-phenyl-5-me.cal lu-1,2,3,4-tetrazole T~iC~ l nitrate : Bismuth nitrate salt r~udrrln : Paraffin oil sold under the tr~den~m~ Winog 70 by Winlel~l,all.

BD/MA : Copolymer of but~ienP-/maleic acid as sold by Polysri~-nc~-s inc under the t~l~n~m~ reference no.

P~VL~Se : Proteolytic enzyme sold under the t~rlen~me Savinase by Novo Industries A/S (approx 2% enzyme activity).

Amylase : Amylolytic enzyme sold under the tr~den~me Termamyl 60T by Novo Industries A/S (approx 0.9%
enzyme activity) BSA : Amylolytic enzyme sold under the tr~len~m~ LE17 by Novo Industries A/S (approx 1% enzyme activity) WO 97~28908 Sulphate : Anhyd~ous sodium sulphate.

pH : Measured as a 1% solution in llicti~ water at 20~C.

In the following ~Y~mI~lçs all leve}s of enzyme quoted are e~lessed as % active enzyme by weight of the composition.

The following c~ -lnsP ether-con~in;ng m~,hin~ dishwashing compositions were ~ ar~d (parts by weight). Composition A is a co.ll~ala~i~e composition, compositionc B to G are in accord with the invention.

A B C D E F G

Citrate 15.0 15.0 15.0 15.0 15.0 15.0 480N 6.0 6.0 6.0 6.0 6.0 6.0 Carbonate 17.5 17.5 17.5 17.5 17.5 17.5 Phosphate - - - - - - 38.0 SilicatG ~as 8.0 8.0 8.0 8.0 8.0 8.0 14.0 SiQ~) Met~.cili~t~ 1.2 1.2 1.2 1.2 1.2 1.2 2.5 ~as SiO~
C M C - 1.2 0.6 2.4 1.2 1.2 1.2 PBl ~A v 0~ 1.2 1.2 1.5 1.5 1.5 2.2 1.2 TAED 2.2 2.2 2.2 - - 2.2 2.2 W O 97/28908 PCTrUS97/02144 Cationic - - 3 3 precursor Paraffin 0.5 0.5 0.5 0 5 0 5 0 5 0 5 .

Bismuth 0.2 0.2 0.2 0.2 0.3 0.4 0.2 nitrate BDiMA - - - - - - 0 5 PMT - - - ~ ~ ~ 0 5 Protease 0.04 0.04 0.04 0.04 0.04 0.06 0.04 Amylase 0.03 0.03 0.03 0.03 0.06 0.1 -BSA - - - - - - 0.03 D l~MP 0.13 0.13 0.13 0.13 0.13 0.13 P 1.0 1.0 1.0 1.0 1.0 1.0 Nonionic 2.0 2.0 2.0 2.0 2.0 2.0 1.5 Sulphate 23.0 22.8 22.4 22.7 22.2 21.5 0.3 misc inc moisture to b~l~nce pH ~1% 10.7 10.7 10.7 10.7 10.7 10.7 11.0 solution~

Test method T~e ~ility of the above delel~,ell~ compositions to improve soil removal when used in accord with the method steps of the present invention was ~CcPccp~l using the following tive test mPth~

CA 02245561 l99X-08-05 1. Aprli~ti~. step Glass and metal test sample slides were soaked in a concentrated solution containing carboxy methyl cellulose (CMC) at a level of 0.0034% active CMC
~y weight. The test sample slides were soaked in the above solution for 30 mins before being removed and allowed to dry ovelT ight 2. 'In-use' soiling step The pre-treated test sample slides were then soiled using a variety of soil types, inr~ din~ a boiled $p~gh~tti solution, egg and cheese soils. The sr~hPt~i solution, egg and cheese soils were painted onto the slides. In addition, 70 g of DI~ soil (comI)ricing Breakfast oats, PG (t~d~n~ml-) loose leaf tea, frozen spinach, UHT full cream milk, butter, Tyne Brand (tr~/-len:~rnt?) mince and onions in gravy, 12 eggs in 4 litres of New~astle city water) was added. The soiled test sample slides were accurately weighed using a Sartarius BA61TM electronic balance linked to a data h~n~lin~ package on an standard 486 co~-lpuLer for subsequent proceccing.

3. Washing step The test sample slides were then washed in a standard dishwashing n ~t~hini~, p,ef~ .bly Hotpoint 7883 (tr~len~me), on an economy wash cycle at 55~C
using N_..~lle City water of ha~ 9 grains per gallon (1.26 mmol Ca2~/litre). 20 g of deLe.E;cnl was added by way of a standard ~lic~ncf~r ~ cll:~nicm The test sample slides were removed after 1 wash and 1 rinse cycle and subsequently oven ~ried at l(lO~C. The test samples were then reweighed The percentage soil removal is c~ ss~l using the following formula:

Post-soilin~ wei~ht - Post-washin~ wei~ht x 100%
Post-soiling weight Soil Type D~t~ t A D~t~ ~L B

% Removal % Removal ~a~h~lli soil 78.7 97.7 Cheese soil 42.9 91.8 E~ 41.5 52.1 It is a~ ;nt from the above results that the inclusion of cellulose ether material in dele~ nt formulation B, increases the percentage removal of soil from the surface of tableware.

Claims (6)

WHAT IS CLAIMED IS:

1. The use of cellulose ether material as an agent enabling the improved release of soils from tableware when employed in a method comprising the steps of (i) applying a coating of said cellulose ether to said tableware;

(ii) 'in use' soiling of the coated tableware; and (iii) washing of the tableware, thereby removing said coating and soils.

2. The use according to Claim 1, wherein the cellulose ether material is selected from the group of general formula:
R is hydrogen, an alkyl or a carboxy alkyl group n is 100-10 000 degree of substitution (ds) is between 0 and 3.0 degree of polymerisation (dp) is more than 100 molecular weight of between 20 000 and 150 000

3. The use according to either Claim 1 or 2, wherein the cellulose ether is either methyl cellulose or carboxy methyl cellulose.

4. The use according to any of Claims 1 to 3, wherein the application step comprises soaking the tableware in a solution containing between 0.0001% and 0.1%, preferably 0.0005% and 0.01%, most preferably 0.001% and 0.005% by weight active cellulose ether.

5. The use according to Claims 1 to 4, wherein the application step comprises treating the tableware with a detergent solution additionally containing between 0.0001% and 0.1%, preferably 0.0005% and 0.01%, most preferably 0.001% and 0.005% by weight active cellulose ether.

6. The use according to any of Claims 1 to 5, wherein said washing of the tableware is by a machine washing method.