CA2196423A1 - Detergent composition - Google Patents

Abstract

The present invention relates to bleach detergent compositions providing improved cleaning performance, comprising a builder and a surfactant system present at specified ratios greater than those conventionally employed, wherein the detergent composition has a specified lower pH value range.

Description

~ WO 96/05283 r ~ . 7n DETERGENT COMPOSITION

Field of the InvPntitm The present invention relates to detergent compositions COllluli~il g a bleach, a builder system and a snrf~nt~nt system having improved overall cleaning pclru--..ance on a range of soils, particularly oily soils and bleachable soils.

Bac~ uul~d of the Inv~ntirm In~ commonly employed in the detergent comrocitinnc for fabric washing are surfactants, dc~ .cy builders and bleaches. Builders serve a number of functions such as assisting in the control of mineral hardness, pepti7~tifn and pH control. The level of builder required in granular comrocitirmc for example is typically in the range of from 10%
to 90% by weight of the detergent cnmrociti~n and builders are commonly employed at levels up to 50% .

However, there are a number of disad~all~dges related to the use of high levels of builders in detergent comrocitionc Firstly, certain types of builders such as c~.l,u--a~es and silicates form insoluble salts with the calcium or m!lpn~cillm hardness ions present in the wash solution.
Dependant on the nature of the composition at least a proportion of these insoluble salts are cllbseq~ ntly deposited upon the fabric and may also be deposited onto the heater elements of the washing machine. Secondly, in terms of weight ratio with respect to certain other ingredients such as en_ymes, soil release polymers and surfactants, an increase in the builder WO 96/05283 r~ C ~~

levels beyond a certain level does not ~ignific~ntly increase the bleachable stain removal p. .rullllance of the composition. The presence of high levels of builders therefore reduces the formula space that might with advantage be filled by other COlll~ Glll~t of more value to the stain removal pc.rullllallcc capability of the composition.

There is accoldill~ly a need for a detergent composition Culll~ illg a builder system at a reduced level to that conventionally employed, that provides improved cleaning pc.rullllance on everyday body soils, greasy soils and bleachable stains.

It has now been surprisingly found that this aim may be achieved by the use of a bleach detergent composition colll~ g a builder system in cnmhin~tinn with a ~,.., r~ ,.l system wherein the weight ratio of the surfactant system to the builder system differs from that conventionally employed and wherein the cu",l,o~ "~ has a specific lower pH range.

One advantage of the present invention is that the p~,.rullll~ c of certain dGL~.~",ncy enzymes is also improved thus resulting in an )lu~G~ llL of the removal E~c.rulllldllce of enzymatic stairls.

Another ad~.llL~.~,e of the present invention is the overall improved bleaching pe.rullll~.llce of the hydluphobic peracids in the compositions of the present invention at pH 8 to 9.8, despite the reduction in the rate of perhydrolysis.

Furthermore, the fu~ liull of unsightly dark polyphenolic stains produced by the complexation between polyphenol anions and metal ions is reduced at lower pH values.

A further a-lv~llL~,e is that the amount of soaps formed from hardness ions and soils CUIIIAhI;IIg fatty acids is reduced by the use of the compocitir)nc of the present invention.

The use of various builder and ~ulr~ L~Ill systems in detergent comrocitionc has been extensively described in the art. For example EPO
313 143 describes non rho~ph~tP ~hlminncilir~t~ built detergent bleach ~ W096/05283 2 1 9 6 4 2 3 F~ c, -~n compositions having effective cleaning and stain removal p-,lru~ ncc at 40~C. The ct7mrncitionc may ~rlitinn~lly comprise 5-40% detergent active and are described as alkaline pH 8-10.5, preferably 8-9.

DE 42 42 185 relates to granular wash- and cleaning compositions having a high S",r~ l~"l content and a high density. The culll~u~ilio-ls comprise 20-55% anionic and nonionic ~ulraulallL~ and optionally soap and may optionally comprise builders, bleach and enzymes. The pH value of the compositions are not tliccios~t~

EPO 219 314 relates to granular detergent colllpo~i~iolls having improved solubility. The compositions comprise 30-85 % linear alkyl sulrhon~t~ (LAS) and alkyl sulphate (AS), alkali metal silicate, wherein the ratio of LAS/AS to silicate is 1.5:1 to 6:1, 15-60% sulphate and 0-20% phocrh~t,~ Optionally the cu~ o~:l;n~c may comprise bleaching agents and other d.,t~ .,n~,y builders. The examples disclose compositions in which the ratio of total builder to snrf~rt~nt is high. The pH of the compositions are not ~icclosed European Patent Application number 94914042.0 relates to layered silicate builders in cu~l)hl~l;ol~ with secv--d~..y alkyl sulphates to minimise ~iepncition The compositions may 2~1~ition~11y comprise 5-30%
nnninnicc, percarbonate bleach and have a pH of 7.5-11.

Broad pH ranges which ~llculll~a~S the pH range of the present invention have been disclosed in the art. However, the pH range typically utilised in laundry detergent co~ oji~iulls and ~Y~mplifi~d in the prior art has a highly alkaline pH value and is typically in excess of 10. Indeed it is known that a high pH value is generally required for the ~lli~; .... ~l of overall peLrullll~lllce and fabric compatibility. In contrast the colll~o~iliolls of the present invention have pH ranges which are less alkaline.

Detergent compositions having lower pH values than are commonly employed in detergent compositions have been described in the art. For example WO 95/02673 discloses low pH (8-9) granular detergent comrrlSitione having improved biodegradability. The cu~ l-o~;~innC
comprise 5-50% detergent surfactant, 5-50% non phosphorous builder 3 1'~ 5N' -~n~

and 0-5 % enzymes. All the exemplified comrociti~nc contain a high builder to aul L~ ratio. European Patent Application number 91201057.6 also relates to low pH (~-9.3) granular detergent compositions comprising a low level of chlorine scavenger which ",i"i"~;crS fading of fabric colours. The composition cull"uli~es 15-25%
linear alkyl 5111rhon~t~ and alkyl sulphate, 20-30% alumino silicate, 1-3%
alkali metal silicate, ~10% citric acid and 5-20% alkali metal carbonate.
The compositions may also comprise 5-50% detergent surfactant and 5-95% det~ cy builders. All of the exemplified compositions comprise high builder to surfactant ratios.

However in contrast to the present invention, none of the identified prior art docllmr~ntc disclose a detergent composition co...l,i. i-.g a surfactant system and a builder system at ratios greater than cull~ iondlly employed and having a specific lower pH level range.
r,~lLll~,llllole, none of these docnm~nte provide any teaching as to the p~lr~ .llce benefits that the comr~ citionc of the present invention deliver.

S--mm ~ry of the Invention The present invention is a granular detergent cullluù~;~iOn cOlll~uliaihlg a bleach system, a builder system and a ~l~lrac~ system, wherein the ratio of said surfactant system to said builder system is 0.8:1.0 or greater, ch~l.a~t~,.ised in that the pH of a 1% solution of said composition at 20~C is from 8 to 9.8.

All amounts, weights, p~ .-Lges and ratios are given as a %
weight of the detergent composition unless otherwise stated.

D~t~ilP~ Description of the Invention Surfactant system According to the present invention the detergent composition culll~uli~es as essential COlllluOl1~.lL~ a surfactant syste~. The term ~."I~ system as used herein refers to a system which cu'lllll;cr c at WO 96105283 1~ n s least one surfactant selected from anionic, nonionic, cationic, zwitterionic, ~mphotpri~ surfactants and any mixhures thereof. Preferably the sllrf~t~nt system is selected from anionic, nonionic, cationic surfactants and mixtures thereof, more preferably from anionic and nonionic ~ ~, rA~ According to the present invention said sllrf~rt~nt system is preferably a non soap ~.,. r~ ...l system.

According to the present invention the detergent compn~ifion Co~ iscs at least 1% of a sulrd~;ldll~ system, preferably from 10% to 50%, more preferably from 15% to 35%, most preferably from 20% to 30% of a sllrf~rt~nt system.

Aninni~ Snrf:lrt~nt~

Anionic i,... r.~ useful herein include the coll~ iulldl primary, branched-chain and random C1o-C20 alkyl sulphates ("AS"), the C10-C18 s~c~llddly (2,3) alkyl sulphates of the formula CH3(CH2)x(CH~SO3~M+) CH3 and CH3(CH2)y(CHOSO3~M+) CH2CH3 where x and (y + 1) are integers of at least about 7, p~r.,ldbly at least about 9, and M is a water-solubilizing cation, especially sodium, Ull~dlUIdll d sulphates such as oleoyl sulphate, the C1o-C1g alkyl alkoxy sulphates ("AEXS"; especially EO 1-7 ethoxy sulphates), C1û-Clg alkyl alkoxy cdlbo~yldt~,~ (especially the EO 1-5 ethoxycarboxylates), sulphated C1o-C1g alkyl poly~;lycosilles, and C12-C1g alpha-~ h,.. ~Ird fatty acid esters.

According to the present invention suitable alkyl or hydroxyalkyl alkoxylated sulphates for use herein are of the formula RO(A)mSO3M, wherein R is an nn~llbstihltpd Cll-C24 alkyl or hydroxyalkyl COIl~
preferably a C12-C20 alkyl or hydroxyalkyl, more preferably a C12-C1g alkyl or hydroxyalkyl co..lpun~ l, A is an ethoxy or propoxy group, m is from 1 to 15, more preferably from 1 to 10, and M is H or a cation which may be selected from metal cations such as sodium, puL~siu~u, lithium, calcium, mslgnPei~lm ~.... ,.. i"... or ~h~ Specific examples of ~ s~ d ~"........ "i,., .cations include methyl-, dimethyl-, trimethyl-~..,---"-.i---.- and quaternary ~ .n,~ .. cations such as tetramethyl-:~mmoni--m, dimethyl piperidium and cations derived from WO 96105283 E~,l/u~. _ JG2q~

alkanolamines, e.g. monoethanolamine, diethanolamine and tri~qthqnnlqmin~ and mixtures thereof. EAe~ IaIY surfactants are C12 C1g alkyl polyethoxylate (2.25) sulphate, C12-C1g alkyl polyethoxylate (3) sulphate and C12-Clg alkyl polyethoxylate (4) sulphate wherein M is selected from sodium or pu~ c;~ C12-C14 alkyl sulphate which has been ethoxylated with an average of from 0.5 to 4 moles of ethylene oxide per molecule is especially preferred.

Other suitable anionic surfactants for use herein include salts (e.g.
alkali metal and qmmonillm salts) of Cll-C24, preferably C12-C20 alkyl sdlcosilldl~s, linear alkylaryl s~lrhnn-qtf~s, particularly linear alkyl benzene slllrh~mqt~c, primary or secondary alkane sulphonates, alkene snlrhnnqtfs such as o-olefin snlrhonDt~c, ether sulphonates, snlrhnnqtfd polyl ~ JoAylic acids, oxyalkane 5nlrhon-qtf s (fatty acid ;~r~ tf ~), acylamino alkane s~lphnnqt~s (taurides), alkyl glycerol slllrhonqt~s and Cl-lrhqtf s, fatty acyl glycerol slllrhonqt~s, fatty oleoyl glycerol s--lphnnDt~s, and any mixtures thereof. Also suitable as anionic 5--rfqrtqntc are fatty acids and the salts thereof, particularly mono~.ll,oAylic fatty acids and the salts thereof. Preferred anionic ~ulr~u~ ~ for use herein are alkyl snlrhqfP~, alkyl alkoxylated sulphates and mixtures thereof.

According to the present invention the colllposiliùlls comprise from 3% to 30%, preferably from 10% to 20%, most preferably from 12% to 18 % of a anionic surfactant.

Noninnin S", r;.~ Ii."~

According to the present invention another CGIllpOn,-ll of the .~, r~ 1 system is a nonionic cllrfP~ tqnt Nonionic condensates of alkyl phenols The polyethylene, poly~.u,uylt;nc, and polybutylene oxide cnn~f ncqtf s of alkyl phenols are suitable for use herein. In general, the polyethylene oxide con~ifncqtes are preferred. These compounds include the cnn~enc-qtion products of alkyl phenols having an alkyl group 2 1 9 6 4 2 3 ~ J s ~ n C~JIII;I;II;IIg from about 6 to about 12 carbon atoms in either a straight chain or branched chain cnnfigl-r~ n with the alkylene oxide.

W0 96/05283 1.~

Nonionir Pth~xylated alcohol surfactant The alkyl ethoxylate co.~ c~ n 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 aliphatic alcohol can either be straight or branched, primary or secul.da~y, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the c~-n~nC~tion products of alcohols having an alkyl group Çl~ll(A;II;IIg from 8 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.
Most preferred are the CI III~ products of alcohols having an alkyl group C.lJIIIA;II;IIg from 8 to 15 carbon atoms with from about 3 to about 9 moles of ethylene oxide per mole of alcohol. FY~mrl.oc of CO~lllll~,.~ ially available nonionic surfactant of this type include TergitolTM 15-S-9 (the çon~ nc~tion product of C11-C1s linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the contllong~til)n product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow mo!Pc~ r weight di~llibuliull), both marketed by Union Carbide Col~ulaliûn;
NeodolTM 45-9 (the cO,l~f ~c~l;nn product of C14-C1s linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-6.5 (the c-m~onc~tion product of C12-C13 linear alcohol with 6.54 moles of ethylene oxide), NeodolTM
45-7 (the con~lPnc~tinn product of C14-C1s linear alcohol with 7 moles of ethylene oxide), NeodolTM 45 4 (the con~PnCAtion product of C14-C1s linear alcohol with 4 moles of ethylene oxide), NeodolTM23-3 (the c~n~oncAtinn product of C12-C13 linear alcohol with 3 moles of ethyene oxide) marketed by Shell Chemical Company, KyroTM EOBN (the CO~ product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter ~: Gamble Company, Dobanol 91 and Dobanol 25 marketed by the Shell Chemical Company and Lial 111 marketed by Enichem.

Nonioniç EO/PO c~ (rS with propylene elycol The conti~nc~tion product~s of ethylene oxide with a hydrophobic base formed by the col~ cAI;on of propylene oxide with propylene glycol are suitable for use herein. ~mpl~s of cul.l~oullds of this type include certain of the c~,llllll~.cially-aYailable PluronicTM
marketed by BASF.

W0 96/05283 2 1 9 6 4 2 3 r~ J c ~ .

Nnni~mir E0 con~lensatjon products with propylene oxide/ethylene tli~minr adducts ~ The c o ~ . . products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethyl~ ~e~ ..,;n~ are suitable for use herein. FY~mrleS of this type of nonionic mrf~t~nf include certain of the co.,..ll~.cially available TetronicTM c~....l.o~",.1c, marketed by BASF.

Nonionic ~lkylpoly-g~rrh~ride ~ulr~

Suitable alkylpolysaccharides for use herein are disclosed in U.S.
Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group crnt~inin~ from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a poly~ic~
e.g., a polygly~oside, hydrophilic group c..~ ;";,-g from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 g~r,rh~ri~lr units. Any reducing cq~rhqri~lr crlnt~ining 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be ~b~ d for the glucosyl moieties.
(Optionally the hyd.u~hob:c group is attached at the 2-, 3-, ~, etc.
positions thus giving a glucose or galactose as opposed to a glucoside or g~l~rtoci~le ) The hl~ r,~ e bonds can be, e.g., between the one position of the q~lrlitit)nql ~c:?rch~ri~le units and the 2-, 3-, 4-, and/or ~
positions on the pl~ccdillg ~~nll~ units. The preferred alkylpolyglycosides have the formula R20(CnH2nO)t(glYC~sYl)x wherein R2 is selected from the group c~-ncicting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, x is from 0 to 10 preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 and t is from 0 to 10. The glycosyl is preferably derived from glucose.

W 0 96/05283 2 ~ 9 6 4 ~ ~ F~ 520 ~

Nonionic f~tty acid amide surfactant Fatty acid amide surfactants suitable for use herein are those having the formula:
o R1 wherein Rl is H or a C1-C4 hydluc~llbyl, 2-hydroxy ethyl, 2-hydroxy propyl and R2 is a CS-C31 Lydluc~.lbyl and Z is a polyhydroxyhydrocarbyl having a linear lly~llu~ ~llbyl chain with at least 3 hydroxy groups directly connect~d to the chain or an alkoxylated derivative thereof. Preferably R is a methyl, R is a straight chain C11-C15 alkyl or alkenyl such as coconut alkyl or mixtures thereof and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose in a reductive amination reaction Other polyllydluxy fatty acid amides suitable for use herein are gemini polyllyd~ y fatty acid amides having the formula:

I--X--I
O= l l =O
R R' wherein: X is a bridging group having from about 2 to about 200 atoms; Z
and Z' are the same or different alcohol-c-,..;~;";,.g moieties having two or more hydroxyl groups (e.g., glycerol, and units derived from reducing sugars such as glucose, maltose and the like), or either one (but not both) of Z or Z' is hydrogen; and R and R' are the same or different L.ydlul albyl moieties having from about 1 to about 21 carbon atoms and can be saturated, branched or ull~ ul~lted (e.g., oleoyl) and mixtures thereof.

Preferred X groups are selected from ~ub~ t~ or u~
branched or linear alkyl, ether alkyl, amino alkyl, or arnido alkyl moieties having from about 2 to about 15 carbon atoms. Preferred alkyl moieties WO 96/05283 P',~ ?/1 are nn~bstihltpd) linear alkyl moieties having the formula -(CH2)n-, wherein n is an integer from 2 to about 15, preferably from 2 to about 10, and most preferably from 2 to about 6; and also nngllhstihlt~p~l~ branched alkyl moieties having from 3 to about 15 carbon atoms, preferably from 3 to about 10 carbon atoms, and most preferably from 3 to about 6 carbon atoms. Most preferred are ethylene and propylene (branched or linear) alkyl moieties. Also preferred are .~ h~ "~d~ branched or linear ether alkyl moieties having the formula -R2-(O-R2)m-, wherein each R2 is in-lPpen-lPntly selected from C2-Cg branched or linear alkyl and/or aryl moieties (preferably ethyl, propyl or colllbilldlio.ls thereof) and m is an integer from 1 to about 5. X may also be nn~llhstihltpd~ branched or linear amino and/or amido alkyl moieties having the formula -R2-(N(R3)-R2)m-, wherein each R2 is i~ lly selected from C2-Cg branched or linear alkyl and/or aryl moieties (preferably ethyl, propyl or combinations thereof), m is an integer from 1 to about 5, and R3 is selected from hydrogen, C1-Cs alkyl, and -C(o)R4-, wherein R4 is C1-C21 alkyl, including -C(O)R. The X moiety may be derived from cullllll~.ci~lly available amine compounds such as, for example, J~rr~ll.i..~,sR (supplied by Texaco) such as JED600, JEDR148, JEDR192, JED230, JED2000, J-D230 and J-D400.

Preferred X moieties therefore include: -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -cH2cH(cH3)(cH2)3-~ -(CH2)2-0-(CH2)2-~ -(CH2)3-0-(CH2)3-, -(cH2)2-o-(cH2)3-~ -(CH2)2-0-(CH2)2-0-(CH2)2-, -(CH2)3-0-(CH2)2-0-(CH2)3-, -(cH2)2-o-(cH2)3-o-(cH2)2-~ -(CH2)2-NH-(CH2)2-, -(cH2)3-NH-(cH2)3-~ -(CH2)2-NH-(CH2)3-, -(CH2)2-N(C(O)R)-(CH2)2-, -(cH2)3-N(c(o)R)-(cH2)3-~ -(CH2)2-N(C(O)R)-(CH2)3-, -(cH2)2-NH(c6H4)NH4cH2)2-~ -(CH2)3-NH(C6H4)NH-(CH2)3-, -(CH2)2-NHCH2(C6H4)CH2NH-(CH2)2-, -(CH2)3-NHCH2(C6H4)CH2NH-(CH2)3-, etc.

Preferred Z and Z' groups are intlepçnriPntly selected from polyllydlu~yllydlu. ~.~byl moieties having a linear Lylllul all)yl chain with atleast 2 hydlùAyls (in the case of glycerol) or at least 3 Ly-lrù;~yl~ ( in the case of other sugars) directly connPcte~i to the chain, or an alkoxylated derivative (preferably t~hOxyla~d or propoxylated) thereof. Z and Z' preferably will be derived from a reducing sugar, more preferably Z and/or W096/05283 ~ J., C.C5~
2 ~ q642~

Z' is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, ~ q~tos~, mannose, and xylose, as well as glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilised as well as the individual sugars listed above. These corn syrups may yield a mix of sugar co~ lL~ for Z and Z'. It should be understood that it is by no means intended to exclude other suitable raw materials. Z and/or Z' preferably will be selected from the group c.on~ of -CH2-(CHOH)-p-CH20H, -CH(CH20H)-(CHOH)pl-CH20H, -CH2-(CHOH)2(CHORl)(CHOH)-CH20H, where p is an integer from 1 to 5, inclusive, and Rl is H or acyclic mono- or poly~ e, and alkoxylated d.,~ cs thereof. Most preferred are glycit-yls wherein p is 4, particularly -CH2-(CHOH)4-CH20H.

Preferred R and R' groups are inA~p~n~ntly selected from C3-C21 hydrocarbyl moieties, preferably straight or branched chain C3-C13 allyl or alkenyl, more preferably straight chain Cs-C11 alkyl or alkenyl, most preferably straight chain Cs-Cg alkyl or alkenyl, or mixtures thereof. R-CO-N< and/or R'-CO-N< can be, for example, cocqm~
oleamide, lauramide, llly~ ie~ c~ de~ rqimitqmi-lP, tallowamide, etc.

FYqmrl~s of such c~ ulllll1c therefore include, but are not limited to: CH3(CH2)6C(O)N[CH2(CHOH)4CH20Hl-(CH2)2-[CH2(CHOH)4CH20H]NC(O)(CH2)6CH3;
CH3(CH2)8C(O)N[CH2(CHOH)4CH20H]-(CH2)2-[CH2(CHOH)4CH20H]NC(O)(CH2)8CH3;
CH3(CH2)10C(O)N[CH2(CHOH)4CH20H]-(CH2)2-[CH2(CHOH)4CH20H]NC(O)(CH2)10CH3;
CH3(CH2)8C(O)N[CH2(CHOH)4CH20H]-(CH2)2-0-(CH2)2-o-(cH2)2 [CH2(CHOH)4CH20H]NC(O)(CH2)gCH3;
CH3(CH2)8C(O)N[CH2(CHOH)4CH20Hl-CH2CH(CH3)(CH2)3-[CH2(CHOH)4CH20H]NC(O)(CH2)gCH3;
CH3(CH2)8C(O)N[CH2(CHOH)4CH20H]-(CH2)3-0-(CH2)2-0-(CH2)3-[CH2(CHOH)4CH20H]NC(O)(CH2)gCH3;
CH3(CH2)3CH(CH2CH3)C(O)N[CH2(CHOH)4CH20H]-(CH2)2-[CH2(CHOH)4CH20H]NC(O)CH(CH2CH3)(CH2)3CH3;

WO 96105283 P'~
21 ~6423 CH3(cH2)6c(o)N[cH2(cHoH)4cH2oH]-(cH2)3-o-(cH2)2-o-(cH2)3 [CH2(CHOH)4CH20H]NC(O)(CH2)6CH3;
CH3(CH2)4C(O)N[CH2(CHOH)4CH20H]-(CH2)3-0-(CH2)2-o-(cH2)3 [CH2(CHOH)4CH20H]NC(O)(CH2)8CH3;
C6H5c(o)N[cH2(cHoH)4cH2oH]-(cH2)3-o-(cH2)2-o-(cH2)3 [CH2(CHOH)4CH20H]NC(O)C6H5;
C H3(c H2)4c(o)N[c H2(c H o H)4c H2o H]-(c H2) [cH2(cHoH)4cH2oH]Nc(o)(cH2)8cH3 -These CG~ UulldS can be readily ~yllLh~,;,;~ from the following disugar diamines: HN[CH2(CHOH)4CH2OH]-(CH2)2-[CH2(CHOH)4CH20H]NH; HN[CH2(CHOH)4CH20H]-CH2CH(CH3)(CH2)3-[CH2(CHOH)4CH20H]NH;
HN[CH2(CHOH)4CH20H]-(CH2)2-0-(CH2)2-o-(cH2)2-[CH2(CHOH)4CH20H]NH; HN[CH2(CHOH)4CH20H]-(CH2)3-0-(CH2)2-o-(cH2)3-[cH2(cHoH)4cH2oH]NH; and HN[cH2(cHoH)4cH2oH]-(cH2)3-[cH2(cHoH)4cH2oH]NH

Preferred nonionic snrf~rt~nf for use herein are polyl,yd.~Ayr~ly acid amides, ethoxylated alcohols, aikylpoly~ ro~:fie~ and miYtures thereof.

The compositions of the present invention comprise from 1% to 20%, preferably from 3% to 18%, more preferably from 5% to 15% of said nonionic surfactants.

According to the present invention the anionic and nonionic surfactant are present in the detergent composition at a ratio of from 1.0:9.0 to 1.0:0.25, preferably from 1.0:1.5 to 1.0:0.4 .

Cationic surfactant Cationic detersive surfactants suitable for use herein are those having one long chain hydrocarbyl group. FY~mrl~s of such cationic 5llrf~rf~n~c include the ~.""~-.li"lll surfactants such as alkyldil-.~ll,yl~,ll...--nillm h~lng~nillr~ and surfactants having the formula:

W0 96/05283 r~ 5--7a~
2~ q6423 [R2(oR3)y] [R4(oR3)y]2RSN + X-wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group cnn~icting of CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH20H)-, -CH2CH2CH2-, and m-ixtures thereof; each R4 is selected from the group cnncietin~ of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring ~IIUUIU1~
formed by joining the two R4 groups, -CH2CHOH-CHoHCOR5CHOHCH20H wherein R6 is any hexose or hexose polymer having a molecular weight less than about 1000 and hydrogen when y is not O; RS is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus RS is not more than about 18; each y is from about O to about 10 and the sum of the y values is from O to about 15; and X is any comp~tihle anion.

Preferred cationic sllrf~t~ntc are the water soluble llual~.l,aly allllllul.iulll compounds useful in the present comrocition have the formula:
Rl R2R3R4N + X-wherein Rl is a Cg-C16 alkyl, each of R2 R3 and R4 is in-lep~n~l.ontly C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl and (C2H40)XH where x has a value of from 1 to 5 and X is an anion. Not more than one of the R2, R3 or R4 should be benzyl.

The preferred alkyl chain length for R1 is from C12-C1s, particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived from synthetically by olefin build up or OXO alcohols synthesis. Preferred groups for the R2R3 and R4 are methyl and h~Yd1OA~ 1YI groups and the anion X may be selected from halide, m~thn5nlrh~t~, acetate and rlhn~l.h~lr ions.

~ xamples of suitable ~IU~,t~,lllaly a, .-n;~ cOIIIL)uulldS for use herein are: -coconut trimethyl ~.. -";"", chloride or bromide; coconut methyl dihydloA~ yl :1llllllnll;lllll chloride or bromide; decyl trimethyl ~mmnninm chloride; decyl dimethyl hydroxyethyl Allllllllllilllll chloride or bromide; C12-C1s dimethyl hydroxyethyl ~"",..-";~,., chloride or ~ W0 96/OS283 ~ C.'t, ''~l) bromide; coconut dirnethyl hydroxyethyl ~ ,., chloride or bromide;
myristyl trimethyl :~mmr)ninm methyl sulphate; lauryl dimethyl benzyl i1lllllll~llhllll chloride or bromide; lauryl dimethyl (ethoxy)4 ~"""""~
chloride or bromide and choline esters.

According to the present invention the detergent composition may comprise from 0.1% to 6%, preferably from 1.0% to 3.5% of a cationic snl-fzlrt~nt The ~UIfa~ system of the present invention may also comprise ~fill~,,iul.ic and/or amphoteric surfactants such as C12-C1g betaines, sulphobetaines ("sultaines") and C1o-C1g amine oxides.

Builder systf m According to the present invention the detergent composition co.u~lises as an essential i..gl~,dil.ll a builder system. The term builder system as used herein refers to a system culll~ illg at least one builder selected from the builders defmed herein below and any mixtures thereof.

According to the present invention the builder system may comprise inorganic as well as organic builders and which are selected from the group cu"~;~l;"E of alkali metal silicates, layered silicates, minrl.cilic~tf~5, rl~ 5, citrates, ~IIC~,illa~ hpyorliq~tf~c and mixtures thereof.

Suitable rhosphotf builders for use herein include the alkali metal, i.l.. l.. "~;~."~ and alkanol~.. ,";"", salts of poly~hr~ h~l ~ (f~Y~mrlifi~ by the tripolyl.hn~l,h,,t .s, ~Jylophr~llh~ , olLhl)~hr~ f s and glassy polymeric meta-pl-r,~ At ,) and rhosrhfm~tf s Inorganic detergent builders include, but are not limited to, phytic acid, silicates and ~hlminr cili~tf c (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) and the so-called "weak" builders (as compared with pho~ c) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders.

WO 96/05283 I ~ u~

Examples of silicate builders are the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbl~vial~d herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain ~lnmini-lm NaSKS-6 has the delta-Na2Si2Os lllul~,holo~y form of layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSix~2x+1 YH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
As noted above, the delta-Na2Si2Os (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example mognPcillm silicate, which can serve as a ~ g agent in granular formlll~tinng, as a stabilizing agent for oxygen bleaches, and as a Culll~)ullC.Il of suds control systems.

~ hlmin~ci~ t~o. builders are useful in the present invention.
~IIlminncilir~tr builders are of great hll~Ollallcc in rnost currently marketed heavy duty granular detergent comrocitiûncJ and can also be a ci~nifir~nt builder hlgredicllt in liquid detergent fnrml~ firmc ~Alnmint)gilir~tP builders include those having the empirical formula:
MZ[(sio2)w(zAlo2)y] XH20 wherein w, z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.

Useful alnminncilic~tr ion exchange materials are collllll~.~;ally available. These ~lllminncilir~trs can be crystalline or dlllu-L,huus in structure and can be naturally-occurring ~hlminncilir~trc or synthetically derived. A method for producing ~lllminncilic~t~ ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, ~ W0 96/0~283 r~ . J~-7n 2 1 9~23 1976. Preferred synthetic crystalline alllminncilir~tr ion exchange materials useful herein are available under the d~;g,i~l;o,~ Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline :Ihlminncilir~tf ion exchange material has the formula:
Nal2[(A102)12(SiO2)12] XH20 wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehyd~d~f,d zeolites (x = O - 10) may also be used herein. Preferably, the ;~lllminncilic~tf has a particle size of about 0.1-10 microns in diameter.

Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are also useful as builders in the detergent compositions of the present invention, especially in combination with zeolite and/or layered silicate builders. Oxy~licllcçin~te s are also especially useful in such comrn~itionc and co l~ ;n ~

Also suitable in the detergent compositions of the present invention are the 3~3-dicarboxy-4-oxa-l~6-h~ oAlf~ and the related CO...1.U~
disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986.
Useful succinic acid builders include the Cs-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred cu.l.~uu..d of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, ~y~i~Lyl~ r~ palmitylcucrin~t~. 2-dodc;~ .yl~lccin~fP (preferred), 2-F~ 1e~f uyl~.lçcinotr, and the like.
Laury1cucrin~t.oc are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.

According to the present invention the builder system preferably cu...l...~ builders selected from alkali metal silicates, layered silicates, minrJ.cilir~t!~c, citrates, phn~ , s~lccin~tf s and mixtures thereof, more preferably selected from alkali metal silicates, layered silicates, nminncilir~tf s, citrates and mixtures thereof.

According to the present invention the compositions will typically comprise at least 1% builder, preferably 5% to 50%, most preferably WO 96/05283 2 1 9 6 4 2 3 r~ . 70~

from 15% to 35%, more preferably 18% to 28%. The ratio of said surfactant system to said builder system is 0.8:1.0 or more, preferably 0.9:1.0 to 4.0:1.0, more preferably from 0.95:1.0 to 3.0:1.0, most preferably from 1.0:1.0 to 2.0:1Ø

~ WO 96/05283 P'~

Bleach system - Bleachin~ A~ents :3n(1 Bleach Activators The detergent compositions herein comprise as an essential ingredient a bleach system. The term bleach system as used herein refers to a system co, I;lh~;,,g a bleaching agent and one or more bleach activators. Bleaching agents will typically be at levels of from 1% to 40%, more typically from S~c to 30%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from 0.1% to 60%, more typically from 0.5%
to 40% of the bleaching composition c~ g the bleaching agent-plus-bleach activator.

The bleach system used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.

PcrùA~ bleaching agents can also be used. Suitable p~.UAy~
bleaching cu~ uullds include sodium carbonate pero~yl.y~llal~ and equivalent "pel~ allJunàt~," bleaches, sodium ~y.ul,ho~ "
p~,lu1Lyllydldl~, urea P~lUAYI1Yd1al~ and sodium peroxide. Persulfate bleach (e.g., OXONE, m~mlf~tllred cullllllcl-;idlly by DuPont) can also be used.

A preferred p~ .albolldl~ bleach cu...~ cs dry particles having an average particle size in the range from about 500 IlliCIUIIIc;lu~ to about 1,000 Illi~,lulllct~.~, not more than about 10% by weight of said particles being smaller than about 200 ...i. .u..-~t. .~ and not more than about 10%
by weight of said particles being larger than about 1,250 mi.~ ,t~
Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Preferred coatings are based on carbonate/sulphate mixtures. Percarbonate is available from various cullllll~ idl sources such as FMC, Solvay and Tokai Denka.

Another category of h' ' g agent that can be used without restriction ~l-co---~a;~es p~ ll,oAylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include m~gn~illm WO 96/05283 2 1 q 6 4 2 3 monoperoxyphthalate hexahydrate, the m~qgnpcillm salt of metachloro p~lbell,u C acid, 4-nonylamino~-oxoperoxybutyric acid and diperoxy~orle.~ e.1i~-ic acid. Such bleaching agents are disclosed in U.S.
Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.

Mixtures of bleaching agents can also be used. Peroxygen bleaching agents, the p~lbo~ s, e.g., sodium perborate (e.g., mono- or tetra-hydrate), the p~,lcall,unaL~;" etc., are preferably combined with bleach activators, which lead to the in si~u production in aqueous solution (i.e., during the washing process) of the peroxy acid co--~ uolldi--g to the bleach activator. Various non limiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The nonanoylo~yl,~ ne sulfonate (NOBS) and L~ .dce~y! ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.

Highly preferred amido-derived bleach activators are those of the formulae:
R1N(R5)C(o)R2C(o)L or R1C(O)N(R5)R2C(o)L
wherein Rl is an alkyl group co"~ ,g from about 6 to about 12 carbon atoms, R2 is an alkylene c~ i.,."g from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl cr~ h~g from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a c~",~ ce of the mlr~l~ophilic attack on the bleach activator by the perhydroxyl anion. A
preferred leaving group is phenol sulfonate.

Preferred examples of bleach activators of the above formulae include (6-o~tqnqmi~o-caproyl)o~y~ fnmqt~
nr)n,qnqmirlocqrroyl)- oxyl,e ~ r~ fonqt~, (6-~ler~qn~qmir1r) WO 96/05283 p~ n caproyl)oxyb~ , nf ,,llfonate, and mixtures thereof as described in U.S.
Patent 4,634,551, incu.~o,at~ d herein by reference.

Another class of bleach activators COlll~ s the bc.~uAd~ type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference. A highly preferred activator of the b~ A~in-type is:

[~N"C~

Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams, acyl pyrolidone and acyl valerolactams of the formulae:
O O

R6--C--N~ CH2 R6--C--N~
CH2--CH2~ CH2--CH2 wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group c~nt~ining from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof.
See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, hlcOl~lat~i herein by reference, which discloses acyl ca~lùlacLall~, adsorbed into sodium perborate. Other preferred activators are cationic bleach activators.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilised herein. One type of non-oxygen bleaching agent of particular interest includes ph~L~ ivaLt;d bleaching agents such as the sulfonated zinc and/or ~IIlminillm phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, WO 96/05283 r~

detergent compositions will typically contain from 0.0259~ to 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.

If desired, the bleaching compounds can be catalysed by means of a mqng:~n~e compound. Such cu~ Juulld~ are well known in the art and include, for example, ~e ~ n~e-based catalysts disclosed in U.S.
Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat.
5,114,606; and European Pat. App. Pub. Nos. 549,271Al, 549,272A1, 544,440A2, and 544,490A1; Preferred examples of these catalysts include MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclonnnqn~ )2(PF6)2, MnIII2(u-0) 1 (u-OAc)2(1 ,4,7-trimethyl 1 ,4,7-triazacyclnnc.nqnP.)2 (C104)2, MnIV4(u-0)6(1,4,7-triaza~,y~,lollo~ c)4(Cl04)4, MnIIIMnIV4 (u-O)1(u-OAc)2 (I ,4,7-trimethyl-1,4~7-triazacyclonnnone)2(clo4)3~
MnIV(l ,4,7-trimethyl-1,4,7-triazacyclnnon~n~)- (OCH3)3(PF6), an mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of m~ng~n-oge with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; S,284,944;
5,246,612; S,256,779; 5,280,117; 5,274,147; 5,153,161; S,227,084.

pH of th~ com~osition According to the present invention it has been found that the pclrulllldilce of the comrosi~ion is improved by the use of specific pH
values. Thus it is essential to the present invention that the c~,lllpù~ s have a pH of from 8 to 9.8, preferably from 8.5 to 9.8, more preferably from 9 to 9.8, measured at 20~C at 1 % cunccll~l~,Lioll.

The required pH value of the comrncitionC of the present invention may be achieved by methods known in the art such as mo~lific~inn of the buffer system and/or hlcul~uidtion of acidic species. Typically the buffer system is based on carbonate, bicarbonates, protonic acids and/ or coordinatively unsaturated metals or non metals.

According to the present invention the detergent composition may comprise any number of optional ingredients commonly employed in . .

WO 96/OS283 2 1 9 6 4 2 3 r~ 5 -'~0 detergent compositions such as chelants, soil release agents, enzymes, suds :jU~)~)lt;SSUl:~i, softeners and brighteners and the like.

WO 96/05283 ~ 0~
21 ~ 6423 Ch~l~tinF Agents The detergent compositions herein may also optionally contain one or more iron and/or ~ g~l~fse chelating agents. Such chelating agents can be selected from the group concictin~ of amino carboxylates, amino phnsl)hn.~ .t~ " polyfilnrtinn~lly-~ Ih~ rd aromatic chelating agents and mixtures therein, all as hc,~ drL~. defined. Without intending to be bound by theory, it is believed that the beneflt of these materials is due in part to their eYceptiC)nol ability to remove iron and ,ll~ng~1llfce~ ions from washing solutions by formation of soluble chelates.

Amino carboxylates useful as optional chelating agents include ethy~ p~ h~rLldcetates~ N-hy-llu~yeLllylethyl~ P~ nGl1t~c~
nitriluLl;~r~l;.lrs, ethylPn~ min~ Lulla~lu~lionates, triethylenetetra-fllf ~ lrs, diethyl~ L,;~",;"~ I,. lh~ ;,t~ ,, and eth~nr'-l;~ly.;il.~,s, alkali metal, ~"""". ;""" and ~ Il.;;l~lrd ~mmnnillm salts therein and mixtures therein.

Amino phncrhnn~tPc are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethyl~ ll;ll hL-dkis (methyl~ hn~l,h-", .t. ~) as DEQUEST.
Preferred, these aminû rhocrholl~t~c tû nût cûntain alkyl or alkenyl groups with more than about 6 carbon atoms.

Polyfi-nction~lly-snhstihJtpd aromatic chelating agents are also useful in the comrocitinnc herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are ~lihyd~u7~y~ ulrub~ ,nes such as 1,2-dihydroxy-3,5-~licnlrub~ r A preferred biodegradable chelator for use herein is ethyl- ,r.l; ",;,~r ll;~lc~ r ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.

WO g6105283 P~ 520 2~ 96~23 If utilised, these chelating agents will generally comprise from 0.1% to 10% more preferably, from 0.1% to 3.0% by weight of such Co~ uO~iLiOI~S.

Polymeric Soil Release A~ent Any polymeric soil release agent known to those skilled in the art can optionally be employed in the cnmrn~itinn~ and processes of this invention. Polymeric soil release agents are chala~ ed by having both hydrophilic segments, to hydrophilize the surface of hydluuhob:c fibres, such as polyester and nylon, and hydrophobic segmPnt~, to deposit upon hydrophobic fibres and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segmfnt~ This can enable stains occurring 5nh~fqll~ont to treatment with the soil release agent to be more easily cleaned in later washing p~uCf lures.

The polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile COIII~UUII~ Cu~ lllg essentially of (i) polyoxyethylene segments with a degree of polymf~ri7~tinn of at least 2, or (ii) uAy~ulu,uylene or polyuA~.u~uylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not e '~ any oAylulu~ylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units c. ~ 'l" ;.~;- g oxyethylene and from I to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile culllpull-,.ll has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fbre surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably cuulpli~iulg at least about 25% uA~.,Lllylu-lG units and more preferably, especially for such Cu...pu..~,..L~ having about 20 to 30 uAy~ulu~ylene units, at least about 50% oxyethylene units; or ~b) one or more hydrophobe culllpu-lf,.l~ "o...~ i..g (i) C3 oxyalkylene terephth~l~t~ segm~ntc, wherein, if said hydlu,uhobe c.J",l.,:"~f ,l~ also comprise oxyethylene terf~phth~l~tf, the ratio of oxyethylene terephth~l~t~ C3 oxyalkylene terephth~ tf units is about 2:1 or lower, (ii) W0 96/05283 2 1 q 6 4 2 3 E ~ c ~c ~

C4-C6 alkylene or oxy C4-C6 alkylene segm~ntc, or mixtures therein, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl ether ~ ;l "~ , or mixtures therein, wherein said s~ll stih~nt~ are present in the form of Cl-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose deli~ati~ are qmphirhili~-, whereby they have a sufficient level of C1-C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon conventional polyester synthetic fibre surfaces and retain a sufficient level of LydiuAyl~, once adhered to such cull~ iullal synthetic fibre surface, to increase flbre surface hydrophilicity, or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO3S(CH2)nOCH2CH2O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.

Polymeric soil release agents useful in the present invention also include cellulosic dc.ivdLi~,s such aS hydroxyether cellulosic polymers, copolyrneric blocks of ethylene tererhtllqlqfl~ or propylene terephthql-t~
with polyethylene oxide or polypropylene oxide terephthqlqt~ and the like. Such agents are cull~ ;ally available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group conci~ting of Cl-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.

Soil release agents chala~ ed by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C1-C6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backl,ollcs. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al.
Collllllc.cially available soil release agents of this kind include the _ _ . . _ . ... .. . .. . .. _ .. . . .. . . . . . . .. . . ..

WO96/05283 21 96423 ~I/u -~n 21 ~7423 SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).

One type of preferred soil release agent is a copolymer having random blocks of ethylene terephth~l~tP and polyethylene oxide (PEO) terephth~ tP. The molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.

Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephth~l~tP units together with 90-80% by weight of polyoxyethylene terpphth~l~tp units, derived from a polyu~ l,ylene glycol of average molecular weight 300-5,000. FY~mphPs of this polymer include the coll,."~rc;ally available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.

Another preferred polymeric soil release agent is a s~lfon~tPd product of a substantially linear ester oligomer colll,ulii,ed of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone. These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents include the terpphth~l~tp polyesters of U.S.
Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric CUIIIIJUUIId~ of U.S. Patent 4,702,857, issued October 27, 1987 to GnccPlink Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to M:~lrh~n:~rlo et al, which discloses anionic, especially sulfoarolyl, end-capped terephth~l~tP esters.

WO 96/05283 2 1 q 6 4 2 3 P~""~ C.,,~ -7Q~

If utilised, soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.

Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulruisot..~,~hll-dloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The repeat units form the backbone of the oligomer and are preferably t~ lh~ ,d with modified i~ethion~t~ end-caps. A particularly preferred soil release agent of this type co~
about one sulruiso~h~llaloyl unit, S terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-eth~n~slllfonate.
Said soil release agent also co,.lp.ises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabiliser, preferably selected from the group cl~ h,~ of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.

As a practical matter, and not by way of limit~ti~n, the cu.~ c and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about I ppm to about 500 ppm, of the catalyst species in the laundry liquor.

Polymeric Dispersing A~ents Polymeric dispersing agents can advantageously be utilised at levels from 0.1% to 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric poly~dllJo~yldl.,;, and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric ~ E
agents enhance overall detergent builder pclru~ dnce, when used in combination with other builders by crystal growth inhibition, particulate soil release pepti7.~tion, and anti-redeposition.

WO 96105283 2 1 9 6 4 2 3 r~ c,620 Polymeric polycarboxylate materials can be prepared by polymerizing or copolyl--~ liGi..g suitable ~ d monomers, preferably in their acid form. U~ ulated monomeric acids that can be polymerised to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid""~ o"i,-- acid, citraconic acid and methyl~n~mrloni.- acid.
The presence in the polymeric polycarboxylates herein of m~ nnm~ric segmrntc, C91l~ no carboxylate radicals such as villyllll~lllyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.

Particularly suitable polymeric poly~dllJo~;ylal~i, can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerised acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ~mm~-,ninm and ~ ;l,.t~.d ~mm~,ninm salts. Soluble polymers of this type are known materials. Use of poly, c l.yl, t~ i, of this type in detergent compositions has been ~licclose~l, for example, in Diehl, U.S. Patent 3,308,067, issued march 7, 1967.

Acrylic/maleic-based copolymers may also be used as a preferred Cvlll~vll~,.ll of the di~ g/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average m~ cnl~r weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 90,000, most preferably from about 7,000 to 80,000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 70:30 to 30:70. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ~mmt-nillm and ~,l,sli~
~mmsnillm salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No.
66915, published December 15, 1982, as well as in EP 193,360, published Sc~ bcl 3, 1986, which also describes such polymers WO 96105~83 2 1 ~ 6 4 2 3 r~

Culll,ul;~L~g hydroxypropylacrylate. Still other useful disl,eL~ing agents include the maleic/acrylic/vinyl alcohol or acetate terpolymers. Such materials are also disclosed in EP 193,360, inrln~ing, for example, the 45/45110 terpolymer of acrylic/maleiclvinyl alcohol.

Another polymeric material which can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent p~.rull-lance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.

Polyamino acid ~ h~g agents such as polyaspartate and polyglutamate may also be used, especially in conjllnnti()n with zeolite builders. Dispersing agents such as polya~Jdl L~L~ preferably have a m~llrclll~r weight (avg.) of about 10,000.

Cl~y Soil R.orn-val/~nti-redeposition A~ents The comrclcitinnc of the present invention can also optionally contain water-soluble etho~ylated amines having clay soil removal and antire-deposition properties. Granular detergent colll~o~iLions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines.

The most preferred soil release and anti-redeposition agent is elLo~.ylat~;d ~ aelLyl~ l,,;nr Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, V~n-l~r~rer, issued July 1, 1986. Another group of preferred clay soil removal-~ h~d~,~o~iLiull agents are the cationic compolln(lc disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil removal/alllilcd~,o~iLioll agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the L~iLLeliullic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or anti WO 96/05283 2 1 9 6 4 2 3 ~ 7n redeposition agents known in the art can also be utilised in the compositions herein. Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.

W0 96/05283 2 ~ q 6 4 2 3 ~ ). 67q~

Dye Tr~ncfer Inhihi~in~ Agents The co,ll~os;lions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vhlyll~yllulidone and N-vhlyli~
5e phthalocyanine, pelù~idascs, and mixtures thereof. If used, these agents typically comprise from 0.01% to lO~o by weight of the composition, preferably from 0.01% to 5%, and more preferably from O.OS~o to 2%.

More specifically, the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-AX-P;
wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form part of the polyl-l~,iLdble unit or the N-O
group can be attached to both units; A is one of the following 2tLlU-,lU-~
NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated ~ .h~irs, aromatics, hct. .u~ ~ lic or alicyclic groups or any comhin~ion thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those wherein R is a h~,t~lu~ ~ lic group such as pyridine, pyrrole, imidazole, pyrrolidine, pilJ."idin~ and de,ivdli~,s thereof.

The N-O group can be l~ sc;,lled by the following general structures:
~l ~X 7 (R2)y; =N (Rl)x (R3)z wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the arOl~ ionf~d groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa <7, more preferred pKa <6.

~ W0 96105283 7 ~ f 2 3 r~ n Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, - polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000.
However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by dl)lUlU~ copoly""~;"~inn or by an a~,ululu~ degree of N-oxidation. The polyamine oxides can be obtained in almost any degree of polylll~ ation. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".

The most preferred polyamine N-oxide useful in the detergent compositions herein is poly(4-vhlyl~u.yli-lillc-N-oxide) which as an average mnleclllqr weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.

Copolymers of N-vh~ylluyllulidone and N-vinylimidazole polymers (referred to as a class as "PVPVI") are also preferred for use herein.
Preferably the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis, Vol 113. "Modern Methods of Polymer Cl--"- Ir,;,~ m", the clo;,.~, of which are hlcol,uul~.it;d herein by reference.) The PVPVI
copolymers typically have a molar ratio of N-vhlylilllid~ùle to N-vhlyl,uyllùlidone from l:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched. It has also been observed that q~-litinnql dye transfer inhibition benefits are provided by compositions COIll~ul i~hlg nonionic polysaccharide ethers and dye transfer inhibitors such as PVNO and PVPVI such as illustrated in Example 1, reference B and f )-mlllqfinn B. It is believed that a synergic effect due to the combination of poly~c~ s and dye transfer inhibitors provides the unP~rec~d wLil~lless ~ ,re p~lru~lllance benefits to white fabrics which have been subjected to repetitive washing.

The present invention compositions also may employ a polyvillyl~y-lulidone ("PVP") having an average molccnl~r weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000. PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696, hlcul~ol~.~td herein by reference.
Compositions cont~ining PVP can also contain polyethylene glycol ("PEG") having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.

The detergent compositions herein may also optionally contain from 0.005 % to 5 % by weight of certain types of hydrophilic optical bli~llt~,.l.l~ which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from 0.01% to 1% by weight of such optical bli~ ,n~

The hydrophilic optical brighteners useful in the present invention are those having the structural formula:

N~ ~C=C~NI ~NO<N

R2 SO3M SO3M Rl wherein Rl is selected from anilino, N-2-bis-hydlu~ ;llyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydlu~ yl-N-lll.,.llylalllillo, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or pU~ lsiUIII.

~ W096/05283 2 1 9 6423 r~ r~s.~

When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2 ,2 ' -stilh~nf ~ lfonic acid and disodium salt. This particular brightener species is co.. ~ially marketed under the tr~en~m~ Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical biikl~ . useful in the detergent comrociti~ nc herein.

When in the above formula, Rl is anilino, R2 is N-2-h.~ u~ l-yl-N-2-1llG~hylal~ o and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilh~n~ lfonic acid disodium salt. This particular brightener species is co------c.~ ially marketed under the tradename Tinopal SBM-GX by Ciba-Geigy Corporation.

When in the above formula, R1 is anilino, R2 is morphilino and M
is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilhPn.o~ 1fonic acid, sodium salt.
This particular brightener species is Collllll~l, ;ally marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

The specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition pGIru----allcc benefits when used in combination with the selected polymeric dye transfer inhibiting agents herein before ~crihçd The cclllbillation of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal SBM-GX and/or Tinopal AMS-GX) provides cignifi~ntly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition Culllpùll~,-lt~ when used alone. Without being bound by theory, it is believed that such h. ;~ work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics. The extent to which brighteners deposit on fabrics in the wash solution can be defined by a p,.. ,.. t", called the "çYh~lleti~n coeffficient". The eYh~nstion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial b.igl-t~,.-er c~1llcGIltldLion in the wash liquor. Bright~n~nc~

WO96/05_83 21 9 6423 r~ 70~

with relatively high f~h:lnctiQn coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.

Of course, it will be d~ ted that other, conventional optical bligl~ er types of compounds can optionally be used in the present compositions to provide conventional fabric "brightness" benefits, rather tban a true dye transfe} inhibiting effect. Such usage is conventional and well-known to detergent form~ tinnc ~zYm~

Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer, and for fabric ~ u~ The enzymes to be h.co.~ .t~,d include proteases, amylases, lipases, cf~ c,~c, and peroxidases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and prûteases~ and fungal ce~ ces Enzymes are normally hlcGl~oldt~ at levels sufficient to provide from 0.01mg to 5 mg by weight of active enzyme per grarn of the CGlll~o~ilioll. Stated otherwise, the csmpscitinnc herein will typically comprise from about 0.001% to about 5%, preferably 0.01%-1% by weight of a co.l....~ l enzyme preparation. Protease enzymes are usually present in such cGlllll..,.~ ;al preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of C~)1 l l1l95~

Suitable examples of proteases are the s~lb~ilicinc which are obtained from particular strains of B. subtilis and B. Iicl,c,liru..lls. Another suitable protease is obtained from a strain of Bacillus, having m~imnm activity throughout the pH range of 8-12, developed and sold by Novo ~ W0 96105283 F~ ,,5,~, -7n Tn~1llctriPs A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in British ~ Patent Sperifi~qfion No. 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are co.,l,..e,ci~lly available include those sold under the tra~lPnqmPc ALCALASE and SAVINASE by Novo Tn~ ctries A/S (Denmark) and MAXATASE by ~ntPnn~ti~mql Bio-Synthetics, Inc. (The Ne~lle.ldnds). Other proteases include Protease A
(see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985).

Amylases include, for example, oc-amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, TntPrn~tion~l Bio-Synthetics, Inc. and TERMAMYL, Novo ~n-lllctriPs Typically, bacterial amylases are present so as to provide from 0.001KNU to 1000KNU, preferably from 0.01KNU to 100KNU activity per gram of detergent composition. Fungal amylases if present in the compositions of the present invention preferably provide from 0.01FAU to 10000FAU, more preferably from 0.1FAU to 1000FAU (Fungal alpha amylase units) per gram of detergent composition.

The cellulase usable in the present invention include both bacterial or fungal cellulase. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Balbest~,a,.l et al, issued March 6, 1984, which discloses fungal cellulase produced from ~nmi~olq insolens and ~Tnmi-~olq strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hr~ p~ ,ds of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
CAREZYME (Novo) is especially useful. Typically cellulase enzyems are present in the detergent composition from 0.0001% to 2%, preferably from 0.01 % to 1 % as 1000CEVU active cellulase.

Suitable lipase enzymes for detergent usage include those produced by microolga..is~..s of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also WO 96/05283 2 1 ~ 6 4 2 3 p~"~ 70~

Iipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Phal",~r~ ir~l Co. Ltd., Nagoya, Japan, under the trade name Lipase P
"Amano," hcl~in~.rl~r referred to as "Amano-P." Other co-ll---c~
lipases include Amano-CES, lipases ex Cl--. ",nba~lr~ viscosum, e.g.
Chromobacter viscosum var. Iipolyticum NRRLB 3673, COllllllCl- i~.lly available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Billrhkmir~l Corp., U.S.A. and Disoynth Co., The Nethkrl~n~lc~ and lipases ex Pseu(lnmrn~c gladioli. The LIPOLASE enzyme derived from Humicola l~mlginos~ and l ullllllcl~;ally available from Novo (see also EPO 341,947) is a preferred lipase for use herein. Typically the lipase enzymes are present at from 0.001LU to 100LU, preferably from 0.005LU to 10LU per milligram of detergent composition.

Peroxidase enzymes are used in combination with oxygen sources, e.g., pel.;~.ll,on~L~, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and hromo-p(,lùAiddse. PGlo~idase-cont~ining detergent compositions are ~1icclose~ for example, in PCT
Tnn~rn~tion:ll Application WO 89/099813, published October 19, 1989, by 0. Kirk, assigned to Novo Tnthlctrie$ A/S.

A wide range of enzyme materials and means for their hlcOl~ulalioll into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both.
Enzymes for use in detergents can be stabilised by various l~rl~ s Enzyme stabilisation tkrhnirlukc are disclosed and exemplified in U.S.
Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No.
86200586.5, published October 29, 1986, Venegas. Enzyme stabilisation systems are also ~Ik5cribet1, for example, in U.S. Patent 3,519,570.

~ W0 96/OS283 r ~ n Enzyme Stab;lic~rs The enzymes employed herein are stabilised by the presence of water-soluble sources of calcium and/or mA~nf-cillm ions in the finished culll~o~i~ions which provide such ions to the enzymes. (Calcium ions are generally SOlll~ ~L~.~ more effective than mognl~ci~m ions and are preferred herein if only one type of cation is being used.) Additional stability can be provided by the presence of various other art-disclosed stabilisers, especially borate species: see Severson, U.S. 4,537,706. The level of calcium or m,n~n~cillm ions should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, fatty acids, etc., in the c~ o~:i;nl~ Any water-soluble calcium or IllAgll/~;lllll salt can be used as the source of calcium or IllAgll~ II ions, inAhl~ing, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium fvrmate, and calcium acetate, and the c~ ollding mAgn- cillm salts. A small amount of calcium ion, generally from about 0.05 to about 0.4 millimo!Ps per litre, is often also present in the compocition due to calcium in the enzyme slurry and formula water. In solid detergent compositions the formulation may include a sufficient quantity of a water-soluble calcium ion source to provide from 1 to 30, preferably from 2 to 20 millimoles per litre in the laundry liquor. In the alternative, natural water hardness may suffice.

It is to be nn/1(~r.ctood that the foregoing levels of calcium and/or f~ ions are sufficient to provide enzyme stability. More calcium and/or IllAg~ ions can be added to the compositions to provide an "tl~1iti~nAl measure of grease removal pclr~ c Accoldill61y, as a general ~roposi~ion the COIIl~uO~i~iull:, herein will typically comprise from about 0.05% to about 2% by weight of a water-soluble source of calcium or IIIA~ IIIIII ions, or both. The amount can vary, of course, with the amount and type of enzyme employed in the composition.

The compositions herein may also optionally, but preferably, contain various A~iti~nAl CtAhili~rs, especially borate-type stabilisers. Typically, such stabilisers will be used at levels in the c~,...l~o~ oll~ from about 0.25% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 3%, by weight of boric acid or other borate compound capable of forming boric acid in the composition (cqlrnlqt~d on the basis of boric acid). Boric acid is preferred, although other c-~""l.u~ e such as boric oxide, borax and ~ther alkali metal borates (e.g., sodium ortho-, meta- and ~lylvbolale, and sodium perlLabvlal~) are suitable. S~ t~ d boric acids (e.g., ph~.lylbol~Jnic acid, butane boronic acid, and p-bromo ph~.lylboluilic acid) can also be used in place of boric acid.

Suds Suv~ressol~

Coul~vullds for reducing or ~U~ sillg the formation of suds may also be hlcOl~vlal~d into the comrr)citinnc of the present invention. Suds ~U~ sDiull can be of particular hllpul lancc in the so-called "high Co~ .. ,1 "~ n cleaning process" and in front-loading European-style washing mqrhin~s A wide variety of materials may be used as suds ::Iu~ lUl~, and suds bu~ ul~ are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopaedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of culllpuullds which may be employed for suds :,u~ iug benefits is fatty acids and the salts thereof, see U.S. Patent 2,954,347, issued Se~,t~ "I,e 27, 1960 to Wayne St. John. However, whilst such compounds may assist in suds suppression, for the purposes of the present invention such cv.ll~vu--ds are to be considered as COIll~vlle-lL~ of the s~rfqctqnt system.

The detergent cullll,o~ilivns herein may also contain non-~u.Lc~a.ll suds :~U~ Ul~. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C1g-C40 ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkyl",~lA",;"~s or di- to tetra-alkyldiamine chlo-l-ia~ es formed as products of cyanuric chloride with two or three moles of a primary or secondary amine COIIIA;II;IIg I to 24 carbon atoms, propylene oxide, and l~ t~A~yl ph~crhqtes such as W096105283 2 1 9 6 423 F~ n l~u~o~ l yl alcohol pho~hal~ ester and mon~lstP~ryl di-aL~ali metal (e.g., K, Na, and Li) phosphates and phocrh~te esters. The hydlu~allJolls such as paraffm and haloparaffm can be utilised in liquid form. The liquid hydrocarbons will be liquid at room t~ "l .,~",c and sfmocrhf~ric pressure, and will have a pour point in the range of about -40~C and about 50~C, and a minimum boiling point not less than about 110~C
(;Il,~n~l~hf .ic pressure). It is also known to utilise waxy hy-llu~ albons~
pl~r~lably having a melting point below about 100~C. The hydrocarbons constitute a preferred category of suds ~ yl~ vr for detergent comrocitionc Hydlu~ allJ~ll suds ~"U~l~.oSOl~ are desrrihe~l, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydlucall)ons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or "~l~Al"l,ll~d hydi~callJolls having from about 12 to about 70 carbon atoms. The term "paraffin," as used in this suds ,sul ~ - nn, is intended to include mixtures of true paraffins and cyclic hydlu-,all~Olls.

Another preferred category of non-surfactant suds ~ SVl:~
Cu~ fs silicone suds ~ sol~. This category includes the use of polyorganosiloxane oils, such as polydi---~.;llybiloxane, ~ ;u"c or PmlllQi~mc of polyu~ .an~,lnYsnP oils or resins, and combinations of polyv~ n~iloY~nf with silica particles wherein the polyorg~nocilo~np is cLe.--i~o-l ed or fused onto the silica. Silicone suds a~l~pl~ Sul:~ are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M.
S.

Other silicone suds ;~-I,u~ ,SOl~ are disclosed in U.S. Patent 3,455,839 which relates to comroci~iong and processes for tlPfosming aqueous solutions by hlcOl~ulalillg therein small amounts of polydi---~ll.yl~iloxane fluids.

Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in WO 96/OS283 2 1 q 6 4 2 3 . ~I/L _ ~ ~3 -~o ~

U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.

An exemplary silicone based suds suppressor for use herein is a suds p~JI. ;t~iug amount of a suds controlling agent congie~ins~ essentially of:
(i) poly~ .l.ylsiloxane fluid having a viscosity of from about 20 cs. to about 1,S00 cs. at 25~C;
(ii) from about 5 to about S0 parts per 100 parts by weight of (i) of siloxane resin cu...L"~sed of (CH3)3SiOl/2 units of SiO2 units in a ratio of from (CH3)3 SiO1/2 units and to SiO2 units of from about 0.6:1 to about 1.2:1; and (iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel.

In the preferred silicone suds supp..ssor used herein, the solvent for a c~ c phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary si}icone suds ~u~.cssu. is branched/crosslinked and preferably not linear.

The silicone suds ~uy~ su. herein preferably Colll~liscs polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room t~lllpclalul~ of more than about 2 weight %, preferably more than about S weight %.

The preferred solvent herein is pol~ ll-yl~lc glycol having an average IllO'~ l~r weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG
200/PEG 300. Preferred is a weight ratio of between about 1: 1 and 1: 10, most preferably between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol.

~ W096105283 2 1 9 6423 r~ c ~ n The preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.

Other suds bU~lpl'U~SOl:~ useful herein comprise the sccond.~ly alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secull-hly alcohols include the C6-C16 alkyl alcohols having a C1-C16 chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed suds ~U~ D5UI~ typically comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 5:1.

For any detergent c~ o~ u~c to be used in qntnmqti(~ laundry washing mqrhinoS, suds should not form to the extent that they overflow the washing machine. Suds s-,u~ul~Daul~, when utilized, are preferably present in a "suds ~u~u~ ,hlg amount. By "suds ~u~u~ul~i~aillg amount" is meant that the formulator of the comrociti~m can select an amount of this suds controlling agent that will 5nffi~i~ntly control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing m~rhinf~s The cullluosilions herein will generally comprise from 0.01 % to about 5% of suds ~U,U~ Ol. Silicone suds ~U~U~UI~DDOI~ are typically utilised in amounts up to about 2.0%, by weight, of the detergent compncitinn, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs lllh~;...;~e~1 and ~rrt;u~ ,D~ of lower amounts for effectively controlling sudsing.
Preferably from about 0.01% to about 1% of silicone suds ~u,u,ul~ur is used, more preferably from about 0.25% to about 0.5%. As used herein, these weight p~LcellLge values include any silica that may be utilised in combination with polyulg,...o~;loYqn~ as well as any adjunct materials that may be utilised. M~ yl rhocrhqte suds ~u~essvl~ are generally utilised in amounts ranging from about 0.1% to about 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically WO96/05283 21 96423 F~~ .,,r,~

utilised in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol suds ~u~e~ol~ are typically used at 0.2%-3% by weight of the finished compositions.

The compositions of the present invention may be used in laundry detergent compositions, fabric treatment compositions and fabric softening comrocitionc In particular the compocitionC of the present invention find particular utility in automatic laundry washing m~rhin~c The cnmrncitinnc may be formulated as conventional granules, bars, pastes or powders. The detergent compositions are ",-,..,r~.l",~ in conventional manner, for example in the case of powdered detergent compositions, spray drying, agglomeration or spray mixing processes may be utilised.

Preferably granular detergent co~ osi~iolls accurdil.g to the present invention have a density of from 400g/1 to 1200g/1, more preferably from SOOg/l to lOOOg/l, most preferably from 600g/1 to lOOOg/l.

F~m~ples ~hbrevi:ltinnc lle~l in FY~m~les Ln the detergent comrocitionc~ the abbreviated COIll!)On~ c~lio,~.c have the following ~ c~

XYAS : Sodium C1x - C1y alkyl sulphate XYEZ : A C1x - Cly predo"~ "~ly linear primary alcohol con~ nced with an average of Z moles of ethylene oxide XYEZS : Clx - Cly sodium alkyl sulphate con~ nced with an average of Z moles of ethylene oxide per mole TFAA : C16-C1g alkyl N-methyl gl--c~mi~e W096/05283 2 1 9 6 4 2 3 P~ G20 Silicate : Amorphous Sodium Silicate (SiO2:Na2O ratio = 2.0) NaSKS-6 : Crystalline layered silicate of formula ~-Na2Si205 Carbonate : Anhydrous sodiumcarbonate MA/AA : Copolymer of 30:70 maleic/acrylic acid, average mnlrc~ r weight about 70,000.

AA : Polymer of acrylic acid Zeolite A : Hydrated Sodium ~IIlminncili-Plti~ of formula Nal2(A102SiO2)12. 27H20 having a primary particle size in the range from 1 to 10 IlliCl u...~,t~

Citrate : Tri-sodium citrate dihydrate PelcdllJondle : Anhydrous sodium p~ ,albOIIal~ bleach coated with a coating of sodium silicate (Si2O:Na2O
ratio = 2:1) at a weight ratio of pc.~albulldl~
to sodium silicate of 39:1 Cellulase : Cellulolytic enzyme sold under the lla~:lcnalllc of Carezyme or Celluzyme by Novo Nordisk A/S

DETPMP : Diethylene triaminepenta (Methylene rhncrhnnit~ acid), marketed by Mnnc~nh:? under the Tradename Dequest 2060 DTPA : Diethylene triamine penta acetic acid WO 96/05283 2 1 9 6 4 2 3 r ~ n ~

Granular Suds : 12 % Silicone/silica, 18 % stearyl alcohol,70%
S~ ,sol starch in granular form LAS : Sodium linear C12 alkyl ber~7ene snlrho TAS : Sodium tallow alkyl sulphate Phosphate : Sodium tripolyphncrhqt~.

TAED : Tetraacetyl ethylene diamine Sulphate : Sodium sulphate EDDS : [s,s] ethylene diamine ~ic~l~cinqtf~.

PVNO : Poly (4-vinylpyridine)-N-oxide ~,opolyll-~,. of vinylh..id~ulillc and vhlyl~Jyllulidine having an average mrl~ lqr weight of 10000 DHAC : Dimethyl hydroxyethyl ammcrlinm chloride F~,qm,rle 1:

The following granular comrncitirlns of the present invention were prepared by COII~h ~ g the listed hl~l.,die.l~ in the given amounts.

% weight Ingredient I II III IV V VI VII vm PIIG~haI~ ' 14 - - - 13 Zeolite A 4 10 8 10 5 8 17.8 9 Sulphate 9 6 6 5 8 7 12.3 MA/AA 4 4 2 3 4 3 - 7.5 WO 96/05283 2 1 9 6 4 2 3 P~ 71~

AA - - - - - - 0.2 LAS - 2 4 - 4 2 10.5 26.4 Silicate 2 1 1 2 0.5 - 0.6 CMC
Brightener 0.3 0.3 0.3 0.3 0.3 0.3 0.17 0.2 DETPMP 0.3 0.3 0.3 0.3 0.3 0.3 24E3S 2 2 - 3 2 2 1.4 28AS 10 8 14 11 8 12 9 7.9 28E5 4 8 4 8 8 7 1.4 3.5 Granular suds 0.5 0.5 0.5 0.5 0.5 0.5 0.2 0.4 ~U~ Ol Perfume 0.4 0.4 0.4 0.4 0.4 0.4 0.2 0.3 Bicarbonate 12 14 10 12 12 13 12 14 Carbonate PBl - - - - 15 - 2.6 4.35 TAED& 6 8.5 6 7 5 6 4.5 4.5 activator Zinc 0.02 0.02 0.02 0.02 0.02 0.02 Phtalocyanine enr.~rs~ tp~
Savinase 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 protease(TM) (4.0 KNPU /
g) Lipolase lipase 0.4 0.4 0.4 0.4 0.4 0-4 CrM) (100.000 LU/I) Termamyl 0.3 0.3 0.3 0.3 0.3 0-3 amylase )TM) 60KNU/g Cellulase 0.2 0.2 0.2 0.2 0.2 0.2 0.2 PEG - - - - - - 1.2 0.9 DTPA - - - - - ~ 0-5 Na-SKS-6 - 8 10 8 3 12 - 12 r~Ca~ 16 14 18 18 - 15 Citrate - 2 2 WO 96105283 2 1 9 6 4 2 3 ~ n ~

DHAC - - - - - 4 - 0.5EDDS 0.4 0.4 0.4 0.4 0.4 0-4 PVNO - - - 0.1 - - - 0.25 Dry mixed 1 - 3 - 1 2 13 Sulphate Balance 100 100 100 100 100 100 100 100 (moisture &
micc~ n~:On~) Surfactant 1.30: 1.19: 1.24: 1.30: 1.16: 1.50: 1.21: 1.80:
system:builder system ratio All of the exemplified co.l~.u~ n~ above have a pH value of from 8 to 9.8 measured as a 1% solution at 20~C.

Claims (13)

WHAT IS CLAIMED IS:

1. A granular detergent composition comprising a surfactant system, a builder system and a bleach system, wherein the ratio of said surfactant system to said builder system is 0.8:1.0 or greater, characterised in that the pH of a 1% solution of said composition at 20°C is from 8 to 9.8.

2. A granular detergent composition according to claim 1, wherein the ratio of said surfactant system to said builder system is from 0.9:1.0 to 4.0:1.0

3. A granular detergent composition according to either of claims 1 or 2, comprising from 10% to 50% of said surfactant system and from 5% to 50% of said builder system.

4. A granular detergent composition according to any one of the proceding claims, wherein said builder system comprises builders selected from alkali metal silicates, layered silicates, aluminosilicates, citrates, phosphates, succinates and mixtures thereof.

5. A granular detergent composition according to any one of the preceding claims, wherein said surfactant system comprises anionic surfactants, nonionic surfactants, cationic surfactants and mixtures thereof.

6. A granular detergent composition according to claim 5, wherein said anionic surfactant is selected from alkyl sulphonates, alkylaryl sulphonates, alkyl sulphates, alkyl alkoxylated sulphates, alkyl sarcosinates, alkyl alkoxy carboxylates, sulphated alkyl polyglucosides, alkyl alpha sulphonated fatty acid esters and mixture thereof.

7. A granular detergent composition according to claim 5, wherein said nonionic surfactants are selected from polyhydroxy fatty acid amides, ethoxylated alcohols, alkylpolyglucosides and mixtures thereof.

8. A granular detergent composition according to any one of the preceding claims, comprising from 1% to 40% of said bleach system.

9. A granular detergent composition according to claim 8, wherein said bleach system comprises a peroxygen bleach and a bleach activator.

10. A granular detergent composition according to any one of the preceding claims, wherein the pH of a 1% solution of said composition at 20°C is from 8.5 to 9.8.

11. A granular detergent composition according to any one of the preceding claims, further comprising from 0.01mg to 5mg by weight of active detergency enzymes per gram of detergent composition.

12. A granular detergent composition according to claim 11, wherein said detergency enzyme is an amylase.

13. A granular detergent composition according to any one of the preceding claims, further comprising from 0.01% to 5% of a suds suppressor.