CA2179010A1 - Use of polymers in liquid detergent compositions containing brighteners for preventing fabric spotting - Google Patents

Abstract

The present invention relates to the use of a polymer selected from polyamine N-oxide containing polymers and/or N-vinylimidazole Nvinylpyrrolidone in liquid detergent compositions for inhibiting fabric spotting associated with detergent compositions containing brighteners.

Description

2 1 790 1 o PCT/US95/00396 USE OF POLYMERS IN LIQUID DETERGENT COMPOSITIONS
CONTAINING BRIG~ITENERS
FOR PREVENTING FABRIC SPOTTING

Technical Field The present invention relates to liquid detergent compositions co.l.pl ising optical brightenPrs. More in particular, the present invention relates to the use of polyamine N-oxide cGnl~;n;ng polymers and/or N-vinylimidazole N-vinylpyrrolidone copolymers in detergen~
compositions co~ ;ning brightPners for reducing fabric spotting associated with the use of said bri~ tc nc . ~.

Background of the Invention Optical bright~PnPrs, also known as fluorescent whitening agents, are commonly used in liquid laundry additives.
BrightenPrs deposit onto fabrics where they absorb ultraviolet radiant energy and reemit it as blue light.
This reduces or ~ s any yellowish cast to fabrics and gives them a bright appealal1ce.
A specific problem ~csori?ted with liquid detergent compositions conl~;n;~g brightpnprs is their un~ 1t~Pd app~ tiQrl on textiles, on which high bl;gl.lcnrr conce~l~alion bccGll~es visible as a whilener spot.

The present invention is based on the discovery that polyamine N-oxide conl~ining polyrners and/or N-vinylim;~ole N-vinylpyrrolidone copolymers inhibit the fabric spotting of bri~htPnPrs. Said polymers are used to col"plc~ or absorb the fugitive dyes washed out of dyed fabrics before they have the opportunity to become att~ched to other articles in the wash.
Copending EP Patent Application 92202168.8 describes dye transfer inhibiting compositions comprising polyamine N-oxides cor~l~inil~g polymers. N-vinylimid~7ole N-vinylpyrrolidone copolymers are described in prior art documPnt~ such as DE 2 814 287-A
which relates to detergent compositions comprising 0.1 to 10 wt% water-soluble or water-WO95/19419 ` ~ ` O I O PCT/US95/00396 dispersible N-vinyl imidazole homo- or copolymer in combination with anionic and/or nonionic surfactants and other detergent ingredients. EP 372 29l relates to a process for washing discolouration-sensitive textiles. The wash liquor contains anionic/nonionic surfactants and watersoluble polymers e.g. (co)polymers N-vinylimid~7ole, N-vinyloxazolidone or N-vinylpyrrolidone. EP 327 927 describes a granular detergent additive co~ ;ng water-soluble polymeric compounds based on N-vinylpyrrolidone and/or N-vinylimidazole and/or N-vinyloxazolidone and cationic compounds. DE 4027832-A discloses electrolyte-free liquid detergent compositions comprising zeolite A, nonionic surfactants and dye transfer inhibiting polymers. The dye transfer inhibiting polymers are homo-and copolymers selected from N-vinylpyrrolidone and/or N-vinylimidazole and/or N-vinyloxazolidone.

According to the present invention, a liquid detergent composition comprising a brightener is provided which reduces or eliminates the fabric spotting of brighteners upon pr~l.ea~l"enL.
Summary of the Invention The present invention relates to the use of a polyamine N-oxide conl~ini~-g polymers and~or N-vinylimidazole N-vinylpyrrolidone copolymers in liquid detergent compositions for inhibiting fabric spotting associated with detergent compositions containing brighteners.

Detailed description of the invention The compositions of the present invention comprise as essenti~l elernent~ a brightener and a polymer s~lected from polyamine N-oxide contail ing polymers and/or N-vinylimidazole N-~inylpyrrolidone copolyrners.

(a) Polyamine N-oxide COIl~ill;llg polymers The cGI~po~ ions of the present invention comprise as an essenti~l element a polymer selected from polyamine N-oxide co~llA;~ polymers which contain units having thefollowing structure formula:
p I

(I) Ax R

wherein P is a polymerisable unit, whereto the N-0 group can be ~tt~ched to or wherein the N-0 group forrns part of the polymerisable unit or a coll~b;nd~ion of both.

WO95/19419 2 ~ 790 1 0 PCT/US95/00396 O O O
Il 11 11 A is NC, CO, C, -O-,-S-, -N-; x is O or 1;

R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any col,lbination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
The N-O group can be r epresenled by the following general structures:

O O

(Rl)x -N- (R2)y .=N- (Rl)x I

(R3)z wherein R1, R2, and R3 are aliphatic groups, aromatic7 heterocyclic or alicyclic groups or colllbinalions thereof, x or/and y or/and z is O or 1 and wherein the nitrogen of the N-O group can be attac~ed or wherein the nitrogen of the N-O group forms part of these groups.

The N-O group can be part of the polymerisable unit (P) or can be att~c~ed to the polymeric backbone or a cGnlbinalion of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxide con~Aining polymers wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
One class of said polyamine N-oxide cGnlQin;ng polymers comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. ~refe"ed polyamine N-oxide cGn~il-ing polymers are those wherein R is a heterocyclic group such as pyridine, pyrrole, imid~701e, pyrrolidine, piperidine, quinoline, acridine and derivatives thereo Another class of said polyamine N-oxide co..l~inill~ polymers comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group is att~c~ed to the R-group.

Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.

WOgS/19419 2 1 790 1 o PCT/USg5/00396 Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general forrnula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group.
Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof.

Another prefe,~ed class of polyamine N-oxides are the polyamine N-oxide cont~ining polymers having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is attached to said R groups.
Examples of these classes are polyamine oxides wherein R groups can be aromatic such as phenyl.
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.
The amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1000000. However the amount of amine oxide groups present in the polyamine oxide co"lai"-ng polyrner can be varied by approp,iale copolymerization or by approp.ia~e degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 2:3 to 1:1000000. More preferably from 1:4 to 1:1000000, most plefc-ably from 1:7 to 1:1000000. The polymers of the present invention actually enco",pass random or block copolymers where one ",ow",~r type is an amine N-oxide and the other monomer type is either an amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a PKa <
10, preferably PKa ~ 7, more prcfcl, ed PKa < 6.
The polyamine N-oxide CGn~ g polymers can be obtained in almost any degree of pol~",e.isdlion. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-sus~endil-g power.
Typically, the average molecular weight is within the range of 500 to 1000,000; preferably from 1,000 to 50,000, more ~,-cÇc-~bly from 2,000 to 30,000, most preferably from 3,000 to 20,000.
The polyamine N-oxide cont~ining polymers of the present invention are typically present from 0.001 to 10%, more preferably from 0.01 to 2%, most prefclled from 0.05 to 1% by weight of the dye t- ~r,srcr inhibiting composition.
The present compositions are conveniently used as additives to conventional detergent compositions for use in laundry operations. The present invention also encompasses dye transfer inhibiting compositions which will contain detergent ingredients and thus serve as detergent compositions.

~ 2~ 79010 WO 95/19~19 PCT/US95/00396 Methods for making polyamine N-oxides:

The production of the polyamine-N-oxides may be accomplished by polymerizing theamine monomer and oxidizing the resultant polymer with a suitable oxidizing agent, or the amine oxide monomer may itself be polymerized to obtain the polyamine N-oxide.
The synthesis of polyamine N-oxide can be exemplified by the synthesis of polyvinylpyrridine N-oxide.
Poly-4-vinylpyridine ex Polysciences (mw. 50 000, 5.0 g., 0.0475 mole) was predisolved in 50 ml acetic acid and treated with a peracetic acid solution (25 g of glacial acetic acid, 6.4 g of a 30% vol. solution of H2O2, and a few drops of H2SO4 give 0.0523 mols of peracetic acid) via a pipette. The mixture was stirred over 30 minutes at ambient temperature (32 C).
The mixture was then heated to 80-85 C using an oil bath for 3 hours before allowing to stand overnight. The polymer solution then obtained is mixed with 11 of acetone under agitation. The resl~lting yellow brown viscous syrup fommed on the bottom is washed again with 11 of aceton to yield a pale crystalline solid.
The solid was filtered offby gravity, washed with acetone and then dried over P2O5.
The amine: amine N-oxide ratio of this polymer is 1:4.
The N-vi~.vli~..idazole N-vil~vllJvr~ olidone conolvmer The present invention comprises as an essenti~l detergent ingredient a polymer s~lected from the N-vinylimid~ole N-vinylpyrrolidone copolymers.
The N-vinylimidazole N-vinylpyrrolidone polymers have an average molecular weight range from 5000-1,000,000, preferably from 20 000-200,000.
Highly preferred polymers for use in detergent compositions according to the present invention comprise a polymer selected from N-vinylim~ 7ole N-vinylpyrrolidone copolymers wherein said polymer has an average molecular weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000.
The average molecular weight range was detem ined by light scattering as described in Barth H.G. and Mays J.W. Chemical Analysis Vol. 113. "Modem Methods of Polymer Characterization .
~rere" ed N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight range from 5,000 to 50,000, more preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000.

The N-vinylimi~7O1e N-vinylpyrrolidone copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties while not adversely affecting the cleaning pe,ro-l"ance of detergent compositions formul~ted therewith.

WO95/19419 2 1 790 1 () PCTIUS95/00396 The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4 .
The N-vinylimidazole N-vinylpyrrolidone copolymers can be lineair or branched. The level of the N-vinylimidazole N-vinylpyrrolidone present in the detergent compositions is from 0.01 to 10%, more preferably from 0.05 to 5%, most preferably from 0.1 to 1% by weight of the detergent composition.
(b) Bri~htener An es~Pnti~l ingredient of the compositions according to the present invention is a bri&htener. Suitable brighteners include stilbene brighteners. Stilbene brighteners are aromatic compounds with two aryl groups separated by an alkene chain. They preferably have the following structural forrnula:

(SO3M) n tSO3M) n <~CH=CH ~

-m wherein Rl is hydrogen, halogen, alkyl, alkoxy or phenyl; R2 is hydrogen or alkyl;
M is hydrogen, an alkali metal or ammonium ion;
n = 0-2, but the formula must contain at least one SO3M group; and m = 1-2 and when m=l, the substituent on the linkage carbon is hydrogen.

Especially suitable stilbene brighteners for use herein are described in U.S. Patents 4,309,316, 4,298,490 and 5,035,825.

Bleach-stable anionic brighteners with sulfonic acid group(s) which work on cotton (cellulosics) are p, efel I ed.
The most pie~e-led stilbene brighteners for use herein, because it is bleach-stable, is TinopalR CBS-X, which is b~on7ene~ 1fonic acid, 2,2'-((1,1'-biphenyl)-4,4'-diyldi-2, 1-ethenediyl)bis-, disodium salt (CA Index Name). The forrnula for TinopalR CBX-X is SO3Na `~`cH~ ~ "'"' ~

Other brighteners that can be used are hydrophobic having the formula:

N~O~ I ~ ~H N~
R2 SO3Na NaSO3 R4 wl,erein Rl, R2, R3 and R4 represent, selected independently, anilino, cyclohexylamino, piperazino, phenylenedi~mino, toluene~i~mino, morpholino, and aminophenol, with the proviso that the brightençr con~ains not more than one morpholino group.
Suitable bright~rer species include any combination of the possible Rl 4 moieties.
F.Y~mples of prere" ed brightençr species are the tetra-anilino, tetra-pipe- ~z;no, tetra-cyclohexylamino and co."binalions thereof such as for example the di-anilinodip;l~l~no;
and the tli~nilino-dicyclohexylamino species.

Highly p,~re"ed for reasons of .~ .;ilg brightçnçr staining are the tetraanilio derivatives, having the following formula:
4,4 -bis (4-anilino-6-anilino-s-triazin-2-yl)amino)-2,2- stilbene disulfonic acid sodium salt (A). A prtfe.,ed bright~nPr system in the context of this invention co"la;ns at least 40% (by rer~ rence to the total amount of the detergent brightener) of the specific hydrophobic bright~rler leÇ~ ;d to hereinbefore in cGIllb;nation with a conventional detergent brightçnPr, e.g., a di-sulfonated ~ nilino, dimorpholino stilbene brightener.

Conventional detergent brightçners for use in combination with the hydrophobic species described hereinabove embrace common detergent brighteners inclusives of:

4,4 (2H-naphtho(1,2-d)triazol-2-yl)-2-stilbenesulfonic acid, sodium salt; (i) 4,41 -bis((4-anilino-6(N-2-hydrozyethyl-N-methylamino)-s-triazin-2-yl)amino)-2,2 1 stilbçnedisl-lfonic acid disodium salt; (ii) WOg5/19419 2 1 7 9 0 1 0 PCT/USgS/00396 4,41 -bis((4-anilino-6-morpholino-s-trizain-2-yl)amino)-2,21-stilbenedisulfonic acid, sodium salt; (jjj) 2,2-(4,41-biphenylene divinylene)-dibenzenesulfonic acid, disodium salt; (ivi) 4,41 -bis(4-phenyl-2H- 1,2,3-triazol-2-yl) disodium salt (vi) 4,41-bis(4-anilino-6-morpholino-1,3,5-triazin-2-yl)amino)-2-stilbene sulfonate sodium salt.

The weight ratio of polyamine N-oxide containing polymer and/or N-vinylimidazole N-vinylpyrrolidone to the brightener present in the detergent composition is from 1/20 to 20/1, preferably from 1/10 to 12/1, more preferably from 1/1 to 12/1, most preferably from 2/1 to 7/1.

Deter~ent ingredients In another embodiment of the present invention, a liquid detergent composition is provided comprising the dye transfer inhibiting composition mixed with detet~,en~ ingredients.
A wide range of surfactants can be used in the detergent composition of the present invention.

A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surf~ct~nts, is given in US Patent 3,664,961 issued to Norris on May 23, 1972.
Pler~,..cd anionic surfactants include the alkyl sulfate surfactants hereof which are water soluble salts or acids of the formula ROSO3M wherein R preferably is a Clo-C24 hydrocarbyl, pr~rt~ably an alkyl or hydroxyalkyl having a Clo-C20 alkyl component, more preferably a C12-C1g alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, pot~c~ m, lithium), or ammonium or substitllted ammonium (e.g.
methyl-, dimethyl-, and trimethyl a....-.onium cations and quate...a~y ammonium cations such as tel- a~cthyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). Typically, alkyl chains of C12-C16 are p.efe..ed for lower wash temperatures (e.g. below about 50C) and C16 18 alkyl chains are p.efe..ed for higher wash telll~Jc~alures (e.g. above about 50C).

Highly plefe.-ed anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)mS03M wherein R is an unsubstituted C1o-C24 alkyl or hydroxyalkyl group having a C1o-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-CIg alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.~ and about 6, more woss/ls4ls 2 1 7 ~ O ~ O PCTIUS95100396 preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations and quaternary a"""onium cations such as tt;~,~u..cli-yl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary surfactants are C12-CIg alkyl polyethôxylate (10) sulfate (C12-C18E(1 0)M), C12-Clg alkyl polyethoxylate (2.25) sulfate (C12-ClgE(2.25)M), C12-Clg alkyl polyethoxylate (3.0) sulfate (C12-CIgE(3.0)M), and C12-Clg alkyl polyethoxylate (4.0) sulfate (C12-ClgE(4.0)M), wherein M is conveniently selected from sodium and pot~csi~lm Other suitable anionic surfactants to be used are alkyl ester sulfonate surfactants inrhlding linear esters of Cg-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with ~seo~C
SO3 r ~ord;ng to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suit~le starting materials would include natural fatty subsl~nces as derived from tallow, palm oil, etc.

The prefe,lcd alkyl ester sulfonate surfactant, especially for laundry applications, comprise alkyl ester sulfonate surf~ct~nts of the structural fnrmula:
o R3 - CH - C - oR4 wherein R3 is a Cg-C20 hydroca.l,yl, prl,fe.~bly an alkyl, or cG...binalion thereof, R4 is a Cl-C6 hydroc~l,yl, prefe.ably an alkyl, or co,l.b;na~ion thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-fol"ling cations include metals such as so~i-lm~ pot~ccium~ and lithium, and substituted or unsubstituted z ...non ~m cations, such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, R3 is Clo-C16 alkyl, and R4 is methyl, ethyl or isopro~yl. F.speci~lly pre;fe~.led are the methyl ester sulfonates wherein R3 is Clo-C16 alkyl.

Other anionic surf~ct~nts useful for detersive purposes can also be inrluded in the laundry deter~ent compositions of the present invention. These can include salts (inr.luclin~, for example, sodillm~ pot~cs;~ ammonium, and substituted al,u"onhlm salts such as mono-, di-and trieth~nol~rnirle salts) of soap, Cg-C20 linear alk~,ll,e~ e,~llfonates, Cg-C22 primary of secondary ~Ik~n~5ulfonates, Cg-C24 olefinsulfonates, sulfonated polycarboxylic acids prepa,ed by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as 2? 7~0'0 WO 95/19419 PCT/US95/00~96 described in British patent specification No. 1,082,179, Cg-C24 alkylpolyglycolethersulfates (cont~ining up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether s~llf~tes, paraffm sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succ~ ates and sulfosuccin~tes, monoesters of sulfosuccin~tes (especially saturated and unsaturated C12-Clg monoesters) and diesters of sulfosuccin~tçs (especially saturated and unsaturated C6-C12 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonclllf~ted compounds being described below), branched primary alkyl 5lllf~tes, and alkyl po1yethoxy carboxylates such as those of the formula RO(CH2CH2O)k-CH2COO-M+ wherein R is a Cg-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 197S to T.~ughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by rerelence).

When included therein, the laundry detergent compositions of the present invention typically comprise from about 0.2% to about 40%, preferably from about 0.S% to about 20%
by weight of such anionic surfact~nts.

One class of nonionic surfactants useful in the present invention are cor-dçns~tes of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 6 to 17, prèfel ~bly from 8 to 17, more preferably from 9.5 eo 14, most preferably from 12 to 14; The hydrophobic (lipophilic) moiety may be ~liph~tic or aromatic in nature and the length of the polyoxyethylene group which is condenced with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elemPntc ~ lèf~.led nonionic surfactants include C9-C13 primary alcohol ethoxylates co~ ;n;.-g 3-30 moles of ethylene oxide per mole of alcohol.
Other nonionics that can be used are C13-C15 primary alcohol alkoxylates co..lainil-g polyethoxy blocks comprising 1 to 2 ethoxy groups and also col-~;l-ing polypropoxy blocks comprising 3 to 4 propoxy groups.
Especially p,efe~,ed nonionic surfactants are the Cg-Cls primary alcohol ethoxylates co..l~ 3-12 moles of ethylene oxide per mole of alcohol, particularly the C12-Cls primary alcohols co.~l~in;ng 5-8 moles of ethylene oxide per mole of alcohol.

Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula RO (cnH2no)tzx wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds incl~ldin~ less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polygl-lcosides Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.

Also suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula Il I
O Rl wherein Rl is H, or Rl is Cl~ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is Cs 31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. ~IcLably, Rl is methyl, R2 is a straight Cll l5 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducinE sugar such as glucose, fructose, mqltosel lactose, in a reductive amination reaction.
When included therein, the laundry detergent compositions of the present invention typically co-,.p.;se from about 0.5% to about 40%, plcfclably from about 0.5% to about 20%
by weight of such nonionic surfactans, highly p, erc,l ed from 0.5% to 10%.

The compositions according to the present invention may further comprise a builder system. Any conventional builder system is suitable for use herein inciu~in~ ~luminosilicate materials, silicates, polycarboxylates and &tty acids, materials such as ethylene~irmine tetrrrc.et~tç, metal ion sequestrants such as aminopolyphosphonates, particularly ethyle.ned;~...;.-e tcl~alll~lhylene phosphonic acid and diethylene triamine pe.llal"~,thylenephosphonic acid. Though less plefelled for obvious environmental reasons, phosphate builders can also be used herein.
Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated ~lllminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X B or HS.

WO95/19419 ~ 2 1 790 1 0 PCT/US95100396 Another suitable inorganic builder material is layered silicate, e.g. SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si2Os) Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R-CH(COOH)CH2(COOH) wherein R is C10-20 alkyl or alkenyl, preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents. Specific e,~alllples include lauryl succinate, myristyl succinate, palmityl succin~tP~-dodecenyl~ucGin~tç, 2-tetradecenyl sUcçin~te Succinate builders are preferably used in the form of their water-soluble salts, inrlu~ing sodium, pot~ssium, a"n)~onium and alkanolammonium salts.
Other suitable polycarboxylates are oxodisuc~in~tes and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
Especially for the liquid execution herein, suitable fatty acid builders for use herein are saturated or unsaturated C10-18 fatty acids, as well as the corresponding soaps. Plt:relled saturated species have from 12 to 16 carbon atoms in the alkyl chain. The plefelled unsaturated fatty acid is oleic acid. Another pref~ l ed builder system for liquid compositions is based on dodecenyl succinic acid.

Other suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.

Detergency builder salts are normally inçluded in amounts of from 2% to 80% by weight of the co"lpos;lion preferably from 20% to 70% and most usually from 30% to 60% by weight.

Detergent compositions according to the present invention may include bleaGhing agents. The ble?~c-hing agent suitable for the present invention can be an activated or non-activated bleaching agent.
One category of oxygen bleaçhing agent that can be used encompasses percarboxylic acid blea^hin~ agents and salts thereof. Suitable examples of this class of agents include m~gn~Sillm monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodec~ne~iioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, U.S. Patent Application 740,446, European Patent Application 0,133,354 and U.S Patent 4,412,934. Highly p~efel~ed bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551.
Another category of bleaching agents that can be used encomp~cses the halogen bleaching agents. Examples of hypohalite bleaching agents, for examplé, include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides. Such materials are normally added at 0.S-10% by weight of the finished product, preferably 1-5% by weight.

Preferably, the bleaches suitable for the present invention include peroxygen bleaches.
Examples of suitable water-soluble solid peroxygen bleaches include hydrogen peroxide rele~cin~ agents such as perborates, e.g. perborate monohydrate, perborate tetrahydrate, persulf~te~ percarbonates, peroxydisulfates, perphosphates and peroxyhydrates. Preferred bleaches are percarbQnates and perborates.
The hydrogen peroxide releasing agents can be used in col1,bi~-alion with bleachactivators such as tetraacetylethylenedi~ e (TAED), nonanoyloxybr.~,~;ne~llfonate (NOBS, described in US 4,412,934), 3,5,-trimethylhexanoloxybPn7çnPsulfonate (ISONOBS, described in EP 120,591) or pentaacetylglucose (PAG), which are perhydrolyzed to forrn a peracid as the active bleaching species, leading to improved bleaching effect. Also suitable activators are acylated citrate esters (ATC) such as disclosed in Copending European Patent ApplicationNo. 91870207.7.

A pre~lled bleaching agent is hydrogen peroxide.
The hydrogen peroxide may be present as such or may be present by adding an enzymatic system (i.e. an enzyrne and a substrate therefore) which is capable of generating hydrogen peroxide at the be~,h-l~;l-g or during the washing and/or rinsing process. Such enzyrnatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.Other peroxygen bleaches suitable for the present invention include organic peroxyacids such as percarboxylic acids.

Bleachinp. agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest inrludes photoactivated bleaching agents such as the sulfonated zinc and/or alumimlnn phthalocyanines. These materials can be deposited upon the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by h~nging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached. P.eîe..ed zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718. Typically, detergent compositions will contain about 0.0001% to about 1.25%, by weight, of sulfonated zinc phthalocyanine. In WO 9S/19419 PCT/US95tO0396 addition, it has been found that the polyamine-N-oxide containing polymers eliminate or reduce the deposition of said photoactivated bleaching agents onto fabrics resulting in substantial no fabric spotting upon pretreatment and/or in the wash.

Other detergent ingredients that can be included are detersive enzymes which can be included in the detergent formulations for a wide variety of purposes inrll1-1ing removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and prevention of refugee dye transfer. The enzymes to be incorporated include proteases, amylases, lipases, ce~ cec, 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.
Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.05 mg to about 3 mg, of active enzyme per gram of the composition.
Suitable examples of proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames Alcalase, Savinase and Esperase by Novo Industries A/S (Denmark) and Maxatase by International Bio-Synthetics, Inc. (The Netherlands) and FN-base by Ge.-el-cor, Optimase and opticlean by MKC.
Of interest in the category of proteolytic enzyrnes, especially for liquid detergent compositions, are enzymes referred to herein as Protease A and Protease B. Protease A is described in European Patent Application 130,756. Protease B is described in European Patent Application Serial No. 87303761.8. Amylases include, for example, -amylases obtained from a special strain of B.licl~enifolllls, described in more detail in British Patent Specification No. 1,296,839 (Novo). Amylolytic proteins include, for example, Rapidase, Maxamyl (International Bio-Synthetics, Inc.) and Termamyl,(Novo Industries).

The cçllul~ces usable in the present invention include both bacterial or fungal ce~ ce.
Plerelably, they ~,vill have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal celllll~ce produced from Humicola insolens. Suitable cçllul~ses are also disclosed in GB-A-2.075.028;
GB-A-2.095.275 and DE-OS-2.247.832.
EAamples of such cel~ ces are cçllul~cçs produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800, and celllll~ces produced by a fungus of Bacillus N or a celllJl~ce 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopanc-eas of a marine mollusc (Dolabella Auricula Solander).

WO95/19419 ; 2 1 7 9 0 1 0 PCT/US95/00396 Other suitable cel~ Aces are cPll~llAsec originated from Humicola Insulens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids. Such cellulAse are described in Copending European patent application No. 93200811.3, filed March 19, 1993.
Especially suitable celhllAce are the cellulase having color care benefits. Examples of such celll~lAces are cellul~ce described in European patent application No. 91202879.2, filed November 6, 1991 Carezyme (Novo).

Suitable lipase enzymes for detergent usage include those produced by microor~nicm~ of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases include those which show a positive immunoligical cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescen~ IAM 1057. This lipase is available from Amano PharrnAceuticAl Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter l~;rel.ed to as "Amano-P".
Fspeci~lly suitable Lipase are lipase such as M1 Lipase (Ibis) and Lipolase (Novo).
Peroxidase enzymes are used in co,.,bh~a~ion with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes of 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, lignin~ce, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-cor.~A;.-in~ detergent compositions are disclosed, for example, in PCT Internation Application WO 89tO99813 and in European Patent application EP No.
91202882.6, filed on November 6, 1991.
In liquid formulations, an en_yme stabilization system is p. ~r~. ably utili7~od Enzyme stabilization teçhn;~ues for aqueous detergent compositions are well known in the art. For example, one technique for enzyme stabilization in aqueous solutions involves the use of free calcium ions from sources such as calcium acetate, calcium formate and calcium propionate.
Calcium ions can be used in co-.,bination with short chain carboxylic acid salts, preferably formates. See, for example, U.S. patent 4,318,818. It has also been proposed to use polyols like glycerol and sorbitol. Alkoxy-alcohols, dialkylglycoethers, mixtures of polyvalent alcohols with polyfi~nctional aliphatic amines (e.g., such as ~iethAnolamine, triethanolamine, di-isopropanolamime, etc.), and boric acid or alkali metal borate. Enzyme stabilization techniques are additionally disclosed and exemplified in U.S. patent 4,261,868, U.S. Patent 3,600,319, and European Patent Application Publication No. 0 199 405, Application No.
86200586.5. Non-boric acid and borate stabilizers are pre~..ed. Enzyme stabilization systems are also desc.ibed, for example, in U.S. Patents 4,261,868, 3,600,319 and 3,519,570.

wo 95/19419 2 1 7 9 o ~ o PCT/US95/00396 Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in Copending European Patent aplication N 92870018.6 filed on January 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

Other components used in detergent compositions may be employed, such as soil-suspending agents soil-release agents, abrasives, bactericides, tarnish inhibitors, coloring agents, and perfumes. In addition, it has been found that the polyamine-N-oxide containing polymers elimin~te or reduce the deposition of coloring agents onto fabrics resulting in substantial no fabric spotting upon prel~tal~ent and/or in the wash.

The liquid compositions according to the present invention can also be in "concentrated form", in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, cG",IJared to conventional liquid detergents Typically, the water content of the concentrated liquid detergent is less than 30%, more preferably less than 20%, most prefe~bly less than 10% by weight of the detergent compositions.
The present invention has found to be extremely useful when the liquid detergents are in direct contact with the fabrics such as during p,el,eat",ent. However, the present invention is also very suitable for inhibiting fabric spotting encountered during fabric laundering operations.
The process of the invention can be carried out before or in the course of the washing process. The washing process is preferably carried out at 5C to 95C, especially 20C to 60C, The pH ofthe tre~tment solution is from 2 to 10.5, preferably from 3:5 to 10.5, more preferably from 2 to 6.
The process and compositions of the invention can also be used as laundry detergent additive products.
Typically, the laundry additive compositions contain no more than 10% by weight of a surfactant. The compositions according to the present invention have proven to be very useful when form~ ted in said laundry additive compositions.
Such additive products are intended to supplement or boost the pe,îo""ance of conventional detergent compositions.

The detergent compositions according to the present invention include compositions which are to be used for cle~ning substrates, such as fabrics, fibers, hard surfaces, skin etc., for example hard surface cleaning compositions (with or without abrasives), laundry detergent compositions, automatic and non automatic dishwashing compositions.

WO 95/19419 ; : ` 2 1 7 9 0 1 0 PCT/US95/00396 The following examples are meant to exemplify compositions of the present inventions, but are not necesc~rily meant to limit the scope of the invention.
A liquid detergent composition according to the present invention is p,epaled having the following composition:

(a) Poly ethoxy propoxy alcohol 1.00 Alkyl sulphate 1.00 BHT (Butyl hydroxy toluene) 0.03 Perfume(Miraflor) 0.10 Hydrogen peroxide 7.00 H2SO4 to pH 4 Distilled water % by weight of the total detergent composition The extent of reduction on brightener spotting was studied under di~rere.lt conditions co,l~s~,ond;ng to possible product usage conditions on 100% cotton fabrics.
These product usage conditions were as follows:

I) Product applied on fabric for 10 minutes and then washed in laundero-meter. (T:
40C / washing time: 25 min.) II) Product dried on fabric and then washed in laundero-meter. (T: 40C / washing time: 25 min.) III) Product applied on fabric for 10 minutes and then rinsed IV) Product dried on fabric and then rinsed The fabric spotting was ~csessed by visual inspection of the samples under sllnlight by a panel of expert graders, using the following scale.

psu 0 I am sure there is no brightener spotting psu 1 I seem to see a light spot but I am not sure psu 2 I am sure there is a light spot psu 3 I am sure there is a spot psu 4 There is a heavy spot EXPERIMENTAL CONDITIONS:

wo 95/19419 2 1 7 9 o ¦ o PCT/US95~00396 A: A detergent composition according to Table I which contains no brightener and no poly(4-vinylpyridine-N-oxide) B: A detergent composition according to Table I which contains 0.06% by weight of brightener (Tynopal CBS-X) and no poly(4-vinylpyridine-N-oxide) C: A detergent composition acco,ding to Table I which contains poly(4-vinylpyridine-N-oxide) which has an average molecular weight of about 10 000 and an amine to amine N-oxide ratio of 1:5 (determined by NMR) and no brightener.
D: A detergent composition according to Table I which contains brightener (Tynopal CBS-X) and 0.06% by weight of poly(4-vinylpyridine-N-oxide) which has an average molecular weight of about 10 000 and an amine to amine N-oxide ratio of 1:5 (determined by N~) The results were as follows:

A B C D

m 0 2 0 0 As can be seen from the above results, brightener spotting is sig~uficantly reduced by the addition of poly(4-vinylpyridine)-N-oxide.

The following laundry liquid detergent compositions were made:

II m IV

C12-C1s Alkyl sulfate - 19.0 21.0 C12-C1s Alkyl ethoxylated sulfate 23.0 4.0 4.0 25.0 C12-C14 N-methyl glucamide 9.0 9.0 9.0 9.0 C12-C14 fatty alcohol ethoxylate 6.0 6.0 6.0 6.0 C12-C16 Fatty acid 9.0 6.~ 14.0 14.0 Bri~ht~n~or 0.1 0.1 0.1 0.1 wo 95/19419 ` 2 1 7 9 0 1 ~ PCT/US95,00396 N-vinylimidazole N-vinyl- O 5 0 5 pyrrolidone copolymer Poly(4-vinylpyridine)-N-oxide - - 0.5 0.5 hydrogen peroxide 5 5 s 5 citricacid anhydrous 6.0 4 5 3.5 3.5 Diethylene lr;a,l"ne penta methy-lene phosphonic acid 1.0 1.0 2.0 2.0 Water & Minors ------up to 100%------The above compositions (I-IV) were very good at displaying detergent pe.rullllance with excellent color-care benefits without creating significant fabric spotting on the fabrics.

The following liquid laundry additives were made:

(a) (b) (c) (d) DobanolR 91-10 - - 3 3 DobanolR 23-3 - - 1 1 DobanolR 23-6.5 T.utçrl.~olR A030 Poly ethoxy propoxy alcohol Alkyl sulphate BHT (Butylhydroxytoluene) Perfi~me (Miraflor) Isofol 16 - - 0.2 0.2 N-vinylimid~7Ole N-vinyl- 0.3 - 0.3 pyrrolidone copolymer Poly(4-vinylpyrridine)-N-oxide - 0.3 - 0.3 gri~htPnPr 0.06 0.06 0.06 0.06 Hydrogen peroxide 7 7 7 7 H2SO4 to pH 4 The above compositions (a)-(d) were very good at displaying detergent pe,ro""ance with excellent color-care benefits without creating significant fabric spotting on the fabrics.

Claims (15)

1. Use of a polymer selected from polyamine N-oxide containing polymers and/or N-vinylimidazole N-vinylpyrrolidone copolymers in a brightener containing detergent composition for reducing brightener spotting.

2. Use according to claim 1 wherein said polyamine N-oxide containing polymer is poly(4-vinylpyridine-N-oxide).

3. Use according to claims 1-2 wherein the ratio of amine to amine N-oxide is from 2:3 to 1:1000000, preferably from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000.

4. Use according to claims 1-3 wherein the polyamine N-oxide containing polymer has an average molecular weight within the range of 500 to 1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.

5. Use according to claim 1 wherein said comprising N-vinylimidazole N-vinylpyrrolidone copolymer has an average molecular weight range from 5,000 to 50,000.

6. Use according to claims 1 and 5 wherein said copolymer has an average molecular weight range from 8,000 to 30,000.

7. Use according to claims 1 and 5 wherein said copolymer has an average molecular weight range from from 10,000 to 20,000.

8. Use according to claims 1-7 wherein the weight ratio of polyamine N-oxide containing polymer and/or N-vinylimidazole N-vinylpyrrolidone to the brightener present in the detergent composition is from 1/20 to 20/1, preferably from 1/10 to 12/1, more preferably from 1/1 to 12/1.

9. Use according to claims 1-8 wherein said brightener is a bleach stable anionic brightener.

10. Use according to claim 9 wherein said brightener is TinopalR CBS-X.

11. Use according to claims 1-10 wherein said detergent composition further comprises surfactants, builders, enzymes and other conventional detergent ingredients.

12. Use according to claims 1-11 wherein the pH of said detergent composition is from 2 to 6.

13. A detergent composition comprising (i) a polymer selected from polyamine N-oxide containing polymers and/or N-vinylimidazole N-vinylpyrrolidone copolymers;
(ii) a brightener;
(iii) less than 10% of a surfactant.

14. A detergent composition according to claim 13, further comprising hydrogen peroxide.

15. A detergent composition according to claims 13-14 which is a laundry detergent additive.