CA2174722A1

CA2174722A1 - Detergent compositions which provide dye transfer inhibition benefits

Info

Publication number: CA2174722A1
Application number: CA002174722A
Authority: CA
Inventors: Rajan Keshav Panandiker; William Conrad Wertz; Larry James Hughes
Original assignee: Individual
Current assignee: Procter and Gamble Co
Priority date: 1993-11-10
Filing date: 1994-10-11
Publication date: 1995-05-18
Also published as: AU7931994A; EP0728184A1; PH31449A; WO1995013354A1; BR9408024A; US5466802A; CN1139954A; JPH09505096A

Abstract

Disclosed are detergent compositions and methods which are suitable for washing colored fabrics in aqueous washing solution with little or no transfer of dye between fabrics. The compositions utilized comprise detersive surfactant, detergent builder, certain selected polymeric dye transfer inhibiting agents and certain selected hydrophilic optical brighteners. The polymeric dye transfer inhibiting agents are polyamine N-oxides such as poly(4-vinylpyridine-N-oxide), i.e., PVNO and/or copolymers of N-vinylpyrrolidone and N-vinylimidazole, i.e., PVPVI. The optical brighteners are selected from certain stilbenedisulfonic acid salts.

Description

WO9511335~1 21~722 PCTIUS94/11509 DETERGENT COI~OSITIONS WEIICH PROVIDE
DYE T~ANSFER I~HIBITION BENEFITS

FIELD OF T~ INVENTION
This invention relates to laundry detergent . , ~ which can be used to wash dye-containing colored fabrics and which contain additives that inhibit dyetransfer bet veen fabrics during laundering operations.
BACKGROUND OF THE I~VENTION
One of the most persistent and l~v~bl~v~ problem-causing events which arises during modern fabric laundering operations is the tendency of some colored fabrics to release dye into the laundering solutions. Such dye is then frequently transferred onto other fabrics being washed in the sarne aqueous washing solution.
One approach in attacking the dye transfer problem in laundering operations has been to complex or adsorb the fugitive dyes washed out of dyed fabrics before such dyes have the v~,po- t~y to become attached to other articles in the wash solution. Certain polymeric materials, for instance, have been suggested as being useful laundry detergent additives which can complex or adsorb fugitive dyes in aqueous washing solutions. For example Abel, U.S. Patent 4,545,919; Issued October 8, 1985 describes the use of carboxyl-containing polymers in fabric laundering operations. Waldhoffet al; DE-A-2 814 329, Published October 11, 1979discloses the use of N-vinyl- ' ' polymers and Cracco et al; GB 1,348,212;
Published March 13, 1974 discloses the use of 15-35% of a copolyrner of pvl~.' Jl~".., ' ' ~ and acrylic acid nitrile or maleic anhydride within a washing powder. Clements et al; EP-A-265 257; Published April 27, 1988 describes detergent ~ comprising an ~ " " . ' carboxy-metal 30 ca.l,uA~ ,lh,: " ' , a ~ ".., ' ' ~ polymer and a E;~ UA~' ' polymer . ' ' g prior art attempts to solve the dye transfer problem during fabric laundering, there is a continuing need to identify detergent . ~ ;n.. "
d~tergent v .~ - additives and fabric laundering methods which are especially effective against dye transfer. Accordingly, it is an object of the present invention to 35 provide detergent ~ v~ which contain ingredients that eliminate or at least minimize dye transfer between fabrics when such, , - are used in fabric laundering operations.

2~ 4 . ~ . PCTIUS94111r~09 It is a further object of the present invention to provide such especiaily effective dye transfer-inhibiting detergent ~ in either granular or liquid form.
It is a further object of the present invention to provide a method for laundering colored fabrics in aqueous washing solutions which are formed from the detergent5 ~ .O~ c herein and which thereby contain materiais that eliminate or at least minimize dye transfer between fabrics beirlg washed therein.
SUM~ARY OF T~F. INVENTION
The present invention is directed to laundry deterBent ~ which 10 provide especially effective inhibition of dye Iransfer between fabrics being laundered in aqueous washing solutions that are formed from these detergent i Such detergent ~ . ~ comprise from about 1% to 80% by weight of a detersive surfactant, from about 0.01% to 80% by weight of a detergent builder '`'~ r '~ from about 0.01% to 10% by weight of certain polymeric dye transfer inhibiting agents and from about 0.005% to 5% by weight of certain hydrophiiic optical brightener ~ li The poiymeric dye transfer inhibiting agents can be polyamine N-oxide polymers, ~,o~.u~ of N .;..,~ ' ' and N .- ,' ' '- or;
of these polymers and cu~ The hydrophiiic opticai brighteners used are 20 those having the formula:

~ ~ ~ C=c~ N
P2 503M 50311 j~
30 wherein Rl can be arliiino, N-2-' hJ.l~u~,lh~l or NII-2 h~ u~ l, R2 can be N-2-bis ~ u~,lhyl~ N-2 h,.' u~ l.yl 2: b~ u.l' "' , chloro or amino and M can be any sait-forming cation.
In its method aspects, the present invention provides a method for laundering colorod fabrics with little or no dye transfer between fabrics taking place. Such a 35 method comprises contacting such fabrics in an aqueous washing solution formed from an effective amount of the laundry detergent r 1, herein.
_ _ . _ _ . _ _ WO 95/13354 2 1~' ~ 7 2 2 PCT/US94111509 ~, DETAILED DEsci~rpTloN OF THE INVENTION
As noted, the laundry detergent ~ u~ herein essentiaiiy contain detersive surfactant, detergent builder, certain polymeric dye transfer inhibiting agents and certain opticai ~ ,,' Each of these essentiai ~ . as weii as S optional ingredients for such r~. ~p~ and methods of using such .,o are described in detail as follows:
A) Detersive Surfactant The detergent ~ ;r,--- herein comprise from about 1% to S0% by weight of a detersive surfaetant. Preferably such . comprise from about 5% to 10 50% by weight of this surfactant. Detersive surfactants utilized carl be of the anionic, nonionic, L~.-'' , ampholytic or cationic type or can comprise compatible mjxtures of these types. Detergent surfaetants useful herein are described in U.S.
Patent 3,664,961, Norris, issued May 23, 1972, U.S. Patent 3,919,67g, Laughiin et ai., issued Deeember 30, 1975, U.S. Patent 4,222,905, Cocicrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980. Ali ofthese patents are ~JUl~tlXi herein by reference.
Of the ~llrfsrtsntc, anionics and noniorlics are preferred and anionics are mostpreferred. Such preferred anionic surfaetants can themselves be of severai different types. For exampie, water-soluble saits of the higher fatty acids, i.e., "soaps", are 20 useful anionie surfaetants in the , - herein. This includes aikaii metai soaps sueh as the sodium, potassium, . and ~ c' saits of higher fatty aeids eontaining from about 8 to about 24 earbon atoms, and-preferably from about 12 to about 18 earbon atoms. Soaps ean be made by direct r ' of fats and oiis or by tho ' of free fatty aeids. r~ ,uLI~ useful are the 25 sodium and potassium saits of the mixtures of fatty acids derived from coeonut oii and taiiow, i.e., sodium or potassium tailow and eoeonut soap.
Additionai anionie surfaetants whieh suitable for use herein inelude the water-solublesaits, preferably the aiicaii metai, ammonium and " ~' ' saits, of organie suifurie reaetion produets having in their moleeular strueture an aiicyl group 30 eontaining from about 10 to about 20 earbon atoms and a suifonie aeid or suifuric aeid ester group. (Ineluded in the term 0aikyl" is the alkyl portion of aeyl groups.) Examples of this group of synthetie surfaetants are a) the sodium, potassium and' ' - aiicyl sulfates, espeeially those obtained by suifating the higher aieohols (C8 C 18 earbon atoms) sueh as those produeed by redueing the giyeerides of tailow 35 or eoeonut oii; b) the sodium, potassium and ~ ' ' aikyl pU1~_1llUA~' suif~tes, ~ ,ukul~ those in whieh the aiicyl group eontains from 10 to 22, preferably from 12 to 18 earbon atoms, and wherein the ~r~ u~l~Lc: chain WO9S/13354 21~ ~722 PCT/US9~/llS09 0 contains from I to 15, preferably I to 6 ethoxylate moieties; and c) the sodium and potassium al~ll,.,.u ~ sulfonates in which the allyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain . S ~ e.g., those of the type described in U.S. Patents 2,220,099 und 2,477,383. Especially valuable 5 are linear straight chain ~ ~ ..e sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, al~ ;d~d as C11-13 LAS.
Preferred nonionic surfactants ue those of the formula Rl(OC2H4)nOH, wherein Rl is a C10-Cl6 alkyl group or a C8-C12 alkyl phenyl group, and n is from 3 to about 80. r~ ULI~ preferred are ' products of C12-C15 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., C12-C13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol. Additionalsuitable nonionic surfactants include PCI~J.' VAy fatty acid unides ofthe formula o R~
R~ z wherein R is a Cg 17 alkyl or alkenyl, Rl is a methyl group und Z is glycityl derived from a reduced sugar or alkoxylated deriva~ive thereo Examples are N-methyl N-l-d~Ay~lu~,;L~I cocoamide and N-methyl N-l-d~uA~,.uc;lyl oleunide. Processes for making pc,lyh,l~uA~ fatty acid amides ue known und can be found in Wilson, U.S.
Patent 2,965,576 und Schwar4 U.S. Patent 2,703,198, the disclosures of which areii.cu. ~,u~ i herein by reference.
B) Deter~ent Builder The detergent ~c .l.~ herein also comprise from about 0.1% to 80% by weight of a detergent builder. Preferably such , in liquid form will comprise from about 1% to 10% by weight of the builder ~ ~-r ' Preferably such in grunular form will comprise from about 1% to 50% by weight of the builder ~ , - Detergent builders ue well known in the ut und cun comprise, for example, phosphate salts as well as vuious orgu~ic and inorganic ,' ,' u~
builders~
Water-soluble, ,'-,' orgulic builders useful herein include the vuious alkali metal, ammonium and substituted ammonium pùl~ce~..a,~, CalbUA~' , PGI~ bUA~ und ~c~l~h, ~IAy sulfonates. Exumples of polyacetate und ~ul~_~l.uAyldte builders ue the sodium, potassium, uthium, unmonium and substituted unmonium salts of ethylene diamine tetraacetic acid, ' ~ ~ acid, UA~' ' acid, mellitic acid, benzene pOI~_a l~UA~" acids, ud citric acid. Other suitable ~vly~,~bu~ld~ for use herein ue the polyacetal ~a buA~' described in U.S. Patent 4,144,226, issued March 13, 1979 to CrutchlSeld et al, und U.S. Patent 4,246,495, issued Much 27, 1979 to CrutchiSeld et al, both of which ue _ ~W095~13354 2~7~ PCTIUS94/115()9 i,.cc"~JulaLc:l herein by reference. Particularly preferred poly~,~buA~: builders are the ~y,' - and the ether carboAylate builder c~ -r comprising a ;u ~ of tartrate ~ and tartrate disuccinate described in U.S.
Patent 4,663,071, Bush et al., issued May 5, 198~, the disclosure of which is S ;~cù~ùl~Lcd herein by reference.
Examples of suitable , ' -, ' - u~, inorganic builders include the silicates, ~' ' , borates and carbonates. Particularly preferred are sodium and potassium carbonate, 1.;.,~ , ~s~u;.,.u~ , tetraborate ' ' ~ LC, and silicates having a weight ratio of SiO2 to alkali metal oxide of from about 0.5 to 10 about 4.0, preferably from about 1.0 to about 2.4. Also preferred are - ' including zeolites. Such materials and their use as detergent builders are more fully discussed in Corkill et al, U. S. Patent No. 4,605,509, the disclosure of which is ~uldt~,l herein by reference. Also, crystalline layered silicates such as those discussed in Corkill et al, U. S. Patent No. 4,605,509, ;..~,ull ' herein by 15 reference, are suitable for use in the detergent ., , - of the invention.
C. Polymeric ~ye Transfer Inhibitin~ ntC
The detergent, , herein also comprise from about 0.01% to 10% by weight of certain types of polymeric dye transfer inhibiting agents. Preferably the detergent ~.. ~,.. -:~;.. ~c herein comprise from about 0.05% to 0.5% by weight of these polymeric dye transfer inhibiting materials.
The selected dye transfer inhibiting polymeric materials can be certain polyamine N-oxide polymers, certain co~ul~ of rT ~ and N-~, ," ' '- or ' ~ of these types of materials. Each of these two ~ol~ ,o~.vl~ types is described in greater detail as follows:
O Polyamine N-oxide Polymers The polyamine N-oxide polymers suitable for use herein contain units having the structural formula:
P
~x ., wherein P is a ~ul~ ' ' unit to which a N-O group can be attached or the N-O
30 group can form part of the pGI~..-.,.;~lJl~, unit or the N-O group can be attached to both units; A is one of the following structures:
O o WO95113354 2~ 4~2 6 PCTIUS94/11509 x is O or l; and, R comprises aliphatic, ethoxylated aliphatic, aromatic, I~c:..u,,~G~, or alicyclic groups or any ~ thereof to which the nitrogen of the N-O
group can be attached or the N-O group is part of these groups.
The N-O group can be ~cl,-c ~ Cli by the following general structures:
o (R~x--N~ N--(R,i~
(R3)z wherein Rl, R2, R3 are aliphatic, aromatic, ~ u.~.,L, or aGcyclic groups or, 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 d[UI ' groups. Purther, the N-O
group can be part of the p~ unit (P) or can be attached to the polymeric backboneora~ ofboth.
Suitable polyamine N-oxides wherein the N-O group forms part of the p~l,..l_.~l,l~ unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or l..,t~,.u.,~.,li., groups. One class of such polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O15 group forms part of the R group. Preferred polyamine N-oxides are those wherein R
is a ~ t.,~u~ group such as pyrridine, pyrrole, irnidazole, pyrrolidine, piperidine and derivatives thereo Another class of the polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group is attached to the R-group. Other 20 suitable polyamine N-oxides are the polyamine oxides in which the N-O group is attached to the p~l~ ' ' unit. A preferred class of these polyamine N-oxides are the polyamine N-oxides having the general for~nula presented above wherein R is an aromatic, h_t~,.u.,~ . or an alicyclic group and the nitrogen of the N-O functional group is part of the R group. Examples of these classes are polyamine oxides 25 wherein R is a k_t~.u~ , compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the polyamine oxides having the general formula presented above wherein R is an aromatic, h~ lul,~,lG, or alicyclic group and the nitrogen of the N-O functional group is attached to the R
30 group(s), 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 atnine oxide polyrner formed is water-soluble and has dye transfer inhibitmg propenies.Examples of suitable polymeric backbones are poly~inyls, pul~ , polyesters, polyethers, polyamide, polyimides, p~ and mixtures thereo _ _ _ _ _ _ _ ~VO 95~13354 2 1 7 ~ 7 2 ~ PCTNS94/11509 The amine N-oxide polymers useful in the detergent ~u~ ;o ~ of the present invention typically have a ratio of amine to the amine N-oxide of lO:l to l:l,ûOO,OOû. However, the number of arnine oxide groups present in the polyamineoxide polymer can be varied by a~"..up.i~le ~,u~ .._.iLaliun or by an ~,lul degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 3: l to l:lOOûOûû. The polymers useful in the detergent , of the present invention actuaUy encompass random or block Cu~Gl~ . where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
The amine oxide unit of the polyamine N-oxides has a pKâ <lO, preferably pKa lû <7, more preferred pKa <6. The polyamine ovides can be obtained in almost any degree of pGI.~ - The degree of pu~., is not critical provided the material has the desired water-solubility and d~ power. TypicaUy, the average molecular weight is within the range of 500 to l,000,000; more preferredl,000 to 500,000; most preferred 5~000 to lO0,000.
l[he most preferred polyamine N-o~ide use&l in the detergent .
herein is poly(1 ~ ~J~p.~ ~ -N-oxide) which has an average molecular weight of about 50~0ûû and an amine to amine N-oxido ratio of about 1:4. This preferred material can be al~ ;alcd as HPVNOH.
The polyamine N-oxides useful in the present invention can be synthesized by ~ul~ ~ thc amine monomer and oxidizing the resulting polymer with a suitable oxidizing agent or tfie amine oxide monomer may itself be pGI,~ ' to obtain the desired polyamine N-oxide. Such reaction schemes are well known and within the scope of those persons skiUed in the art.
Co~olymersofN.- ~ ûl~andN . ,~ r The detergent, . of the present invention may also utilize a copolymer of N .- ~ ' ' and N . ~' ' ' (also ~ ............ i herein as "PVPVI~). It has been found that co~ul~ . of N .- ~'p~ ' ' and N-~ ,' ' " can provide excellent dye transfer inhibiting ~f A when utilized in the l~ of this invention.
3û In a preferred ' ~ ' t, the copolymer of N .- ,'~.. ~ " ' and N-' polymers has an average molecular weight range from 5~000 to l,000,000, more preferably from 5~000 to 200,000. A highAy preferred copolymer for use in detergent; . according to the present invention has an average molecular weight range from 5,000 to 50,000, more preferably from 8,000 to 30,000 and, most preferably from lO,000 to 20,000. The average molecular weight range is determined by light scattering as described in Barth J. H. G. and Mays J. W.

?~ 4~ 8 , ,~ ., Chemical Analysis Vol 113. "Modem Methods of Polymer t~ ", the disclosure of which is ;,.~,u- ~JUI~d herein by reference.
The Cu~lu~ of N ~; ylp.~.., ' ' and N .;..~'' ' ' '~ useful in the present invention can have a molar ratio of N .- .~'' '' ' to N .' ,!p.,." ''' from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. It should be understood that the copolymer of N ~ lp.~.., ' ' and N-,: ' ' can be either linear or branched.
D) O~oticalBrightener The detergent cc ~l c~ herein also essentially contain from about 0.005%0 to 5% by weight of a certain type of hydrophilic optical brightener. Preferably the herein will comprise from about 0.01% to 1% by weight of this optical brightener.
The hydrophilic optical brighteners useful in the present invention are those having the structural fommula:
R~ il R2 503~1 50 11 wherein Rl is selected from anilino, N-2-~ - h, ' UA~h,' and NH-2 hJJ~UA~ h,l, R2 is selected from N-2-1,;.. ~.,d-UA~ I, N-2 h,.' UA~ lyl N: ~' o, 1' ' , chloro and amino; and M is a salt-fomling cation such as sodium or 25 potassium.
When in the above formula Rl is anilino, R2 is N-2: h, ' UA~ h,l and M is a cation such as sodium, the brightener is 4,4, -bis[(4-anilino-6-(N-2~ , d~ uA~hJ )-s-tria2ine-2-yl)amino]-2,2- :"L ~ r acid disodium salt. This particular brightener species is "~ marketed under the t~adename Tinopal-UNPA-30 GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophiiic optical brightener useful in the detergent ~ ~ . herein.
When in the above fommula, Rl is anilino, R2 is N-2 h, ' u~,~h~' N-2-' ,' ' ~ and M is a cation such as sodium, the brightener is 4,4, bis[(4-anilino-6-(N-2 ~dlu~.~hJl N ' ,' )-s-tria2ine-2-yl)amino]-2,2 - " ' '~
35 acid disodium salt. This particular brightener species is l ' '1~ marketed under the tradename Tinopal 5BM-GX by Ciba-G~igy Corporation.

W095/13354 1 7~7~? PCTIUS9~/11509 When in the above formula, Rl i5 aniGno, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4, -bis[(4-anilino-6-~,lull ~ ~ r triazine-2-yl)amino]-2,2 ~lill.. . 1;~.,11~, acid, sodium salt. This particular brightener species is UU"~ ".y marketed under the tradename Tinopal AMS-GX by Ciga-Geigy S Corporation.
The specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition pf '- benefits when used inA with ehe selected polymeric dye transfer inhibiting agents 1~ e described. The ~ of such selected polymeric materials (e.g, PVNO andlor lû PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX Tinopal SBM-GX and/or Tinopal AMS-GX) provides ~ better dye transfer inhibition in aqueous wash solutions than does either of these two detergent c.. ,~ ;o~ . , ~ when used alone. Without being bound by theory, it is beGeved that such brighteners work this way because they have high affinity for 15 fabrics in the wash solution and therefore deposit relativdy quickly on these fabrics.
The extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient." The exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener ~ in the wash Gquor. F "' with 20 relatively hiBh exhaustion . ~- are the most suitable for inhibiting dye transfer in the context of the present invention.
E. O~tional Detergent Ingredients The detergent . of the present invention can also include any number of additional optional ingredients. These include . ' detergent ~..-~.. ~;..
25 ; , - such as suds boosters or suds ;.~ , anti-tarnish and ~...i;wllu~;u..
agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, e..L~
agents_~nd pe&mes. (See U.S. Patenl 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al., the disclosure of which is . ' herein by reference.) Additional dye transfer inhibiting agents and additional optical brighteners mayalso be included. For example, ~ul~ ' ' is a suitable dye transfer inhibiting polymer for use in the present detergent . . ~ F. ,' ~;, additional relatively h~d,~ r~ ~-~ brighteners optionally may be employed. However, the detergent u~ herein may also be . ' ~ free ûf ~.~d~ r' ' hrj~tPn.~rR
Chelating agents are described in U.S. Patent 4,663,071, Bush et al., from Column 17, line 54 through Column 18, Gne 68, I~u~ i herein by reference.
Suds modifiers are also optional ingredients and are described in U.S. Patents wo 95/1335~ ~ 2 1~ 4 ~ 2 2 ` PC~/US9~/11509

3,933,672, issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gwlt et al., both ;IlCulyu~aL~i herein by reference. Suihblesmectite clays for use herein are described in U.S. Patent 4,762,645, Tucker et al, issued August 9, 1988, Column 6, line 3 through Column 7, line 24, Il~ yù~a~d 5 herein by reference.
While not essential to the detergent f''--~l'.J`I;'''' of the invention, it is preferable to include an enzyme: , Suitable enzyme ~. l,.,.,...:c are available from a wide variety of commercial sources. For example, suihble enzymes are available from NOVO Industries under prûduct names T-Granulate ~ and 10 Savinase, and Gist-Brocades under product names Maxacal and MaxataseT~.
Included within the group of enzymes are proteases, amylases, lipases, cellulases and mixtures thereo The enzyme; aL;ù.. preferably should be from about 0% to about 5%, more preferably from about û.1% to about 2.5%, and most preferably from about 0.2% to about 1%. Typically, proteases are used at an Activity Unit (Anson Unit) level of from about 0.001 to about 0.05, most preferably from about0.002 to about 0.02, while amylases are used at an amylase unit level of from about 5 to about 5000, most preferably from about 50 to about 500 per grarn of detergent F. ~etereentC:, r~ luldL;u~l The detergent , ~ according to the present invention can be in liquid, paste or granular forms. Such c- ~ ;..-, can be prepared by combining the essential and optional ~ . in the requisite a~;O..., in any suitable order and by an .. ' means.
Granular ~ . for example, are generally made by combining base 25 granule ingredients (e.g. surfachnts, builders, water, etc.) as a slurry, and spray drying the resulting slurry to a low level of residual moisture (5-12%). The remaining dry ingredients can be admixed in granular powder form with the spray dried gFanules in a rotary mr~ing drum and the liquid ingredients (e.g. enzymes,binders and perfumes) can be sprayed onto the resulting granules to form the Snished 30 detergent ~ . Granular :~ ~- according to the present invention can also be in ~compact form0, i.e. they may have a relativdy higher density than cu.... ' granular detergents, i.e. from 550 to 950 g/l. In such case, the granular detergent; . ~ according to the present invention will contain a lower amount of "inorganic filler saltn, compared to C(l..._.A;u.~dl granular detergents;
35 typical filler salts are alkaline earth mehl salts of sulphates and chlorides, typically sodium sulphate; "compact~ detergents typically comprise not more than 10% filler salt.

~W095113354 217~ 72 PCTIUS94111509 2 .~
-Liquid detergent ~O ~1 o~ can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide cc ~ containing cl. 1,.," - ~- in the requisite Liquid cc~ c;~ according to the present invention can also be in "compact form", in such case, the liquid detergent 5 .,, .1...~;l;~...~ according to the present invention will contain a lower amount of water, compared to . .. ' liquid detergents.
G. Fabric Launderin~ Method The present mvention also provides a method for laundering colored fabrics with little or no dye transfer talcing place. Such a method employs contacting these 10 fabrics with am aqueous washing solution formed from an effective amount of the detergent, , k.,.c;.,l,~,.';,~c described. Contacting of fabrics with washing solution will generally occur under conditions of agitation.
Agitation is preferably provided in a washing machine for good cleaning.
Washing is preferably followed by drying the wet fabric in a .,u..~. ' clothes dryer. An effective amount of the Gquid or granular detergent , in the aqueous wash solution in the washing machine is preferably from about 500 to about 7000 ppm, more preferably from about 1000 to about 3000 ppm.
EXAI~LES
The following examples illustrate the ~ , of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention.

WO 95/133S4 : PCT/US94/llSU9 217~722 EX~IPLE I
Several liquid detergent ~ p~ are prepared. The fmm~ tion for these .J~:l;o.,~ are set forth in Table 1.
TABLE I
Lio~uid Deter,eent ~u ~
Wt %
Component A B C
C12-CIs Alicyl sulfate -- 19.0 21.0 --C12-CIs Aikyl eLl~ .L~i~ sulfate 23.0 4.0 4.0 25.0 10C12-Cl4N-methylglucamide 9.0 9.0 9.0 9.0 C12-C14 Fatty alcohol ethoxylate 6.0 6.0 6.0 6.0 C12-cl6 Fatty acid 9.0 6.8 14.0 14.0 Citric acid anhydrous 6.0 4.5 3.5 3.5 Diethylene triannine penta ethylene 15r~ . ~ acid (DTPA) 1.0 1.0 2.0 2.0 M~ .. FII.~ 13.2 12.7 12.8 11.0 P~ r 12.7 14.5 13.1 10.0 Ethanol 1.8 1.8 4.7 5.4 Enzyrnes (protease, lipase, cellulase) 2.4 2.4 2.0 2.0 20Terephtalate-based polyrner 0.5 0.5 0.5 0.5 Boric acid 2.4 2.4 2.8 2.8 2-butyl-octanol 2.0 2.0 2.0 2.0 DC 3421 R~l) 0.3 0.4 0.3 0.4 FF 400 R(2) 25Poly(1 .~ , ' )-N-oxide (PVNO) -- -- 0.5 0.5 N. yl~ . ," ' 1t copolymer - MW 10,000 (PVPVI) 0.3 0.3 --Tinop~l UNPA-GX Brightener 0.075 0.21 Tinopai 5BM-GX Brightener -- -- 0.21 0.075 30 Wat & minors ., to 100%
(I) DC 3421 is a siiicone oil . "~ available from Dow Corning.
(2) ;5 a siiicone giycol emulsifier available from Dow Corning.
The . ~ described in Table I are suitable for laundering colored fabrics in aqueous washing solution while providing exceUent dye transfer inhibition 35 benefits. Dye transfer irlhibition ~ provided by the ~ ' of the PVNO or PVPVI and the selected Tinopal brightener is ,, " l~, better than if thedye transfer inhibiting poiyrners or the opticai brighteners were used alone. Dye . .

~A~o 95/13354 1 7~ 722 PCTIUS9411 ISO9 transfer inhibition p.,.~ c~ for these co ~ ;u--- is also superior to that whichwould be provided if other cu..~,..iiu..~l relatively hydrophilic optical brighteners were to be substituted for the Tinopal brighteners employed.

-Wo9sll33s4 2~ 2~ - PCTII~S94111509 ~A~LE 11 C-- ~r' built heavy duty liquid detergent c, r "' are prepared having the GJ. Il~ulu~ a set forth in Table II.

Liauid Detergent C.,~ ;u~
Wt. %
Cc:, A B
C14-1s Alkyl ~(,IJ~ lu~e (2.25) sulfonic acid 23.00 12.50 C12-13 Linear alkyl benzene sulfonic acid -- 11.46 101,2 P,., ' ' 10.50 3.97 12.50 3.65 C12-13 Alkyl pGI),~,.llu~' (6.5) 6.00 1.78 Ethanol 3.80 1.75 r~ h.~ ,~ C12 14 fatty acid amide 9.00 --15C12 14Coconutfattyacid 9.00 2.60 Citric acid 6.00 6.04 DTPA 0.95 Sodium forrnate 0.14 --Boric acid 2.4 1.0 T~l.u~hJ' ---r ' ' ethoxylate (15-18) 1.00 1.44 Soil release polymer 0.46 --Enzymes (protease, lipase, cellulase) 2.55 2.27 Silicone antifoam , ~ 0.04 0.02 Poly(1 .: ,!,, ' )-N-oxide(PVNO) 0.10 0.10 25Brightener - Tinopal UNPA-GX 0.20 0.20 Waterand " ~ minors Balanceto 100%
The liquid ddergent .~ of Table II have dye transfer inhibition which are ' '1~ similar to those of Table I
., .

W~95/133S4 ~1 7q 722 ~ t PCTIUS9~/11509 EXA~LE III
Several compact granular detergent c~ are prepared. The " ",.,~ for these ~ - are set forth in Table m.
T~R~.F m 5 Granular Desergent C.,,~
Wt. /0 Component ~ B C
Cl l-C14 Linear alkyl benzene sulfonate 11.40 -- _ C12-CIs Alkyl ul:~u~l~ sulfate -- 10 00 --C12-C14 N-methyl glucamide -- -- 13.00 Tallow alkyl sulfate 1.80 1.80 1.80 C4s allyl sulfate 3.00 3 00 3.00 C4s alcohol 7 timescLI.uA.tl~lc~ 4.00 4.00 4.00 Tallow alcohol 11 times ethoxylated 1.80 1.80 1.80 Dispersant 0.07 0.0~ 0.07 Silicone fiuid 0.80 0.80 0.8û
Trisodium citrate 14.00 14.00 14.00 Citric acid 3.00 3.00 3.00 Zeolite 32.50 32.50 32.50 Maleic acid acryGc acid copolymer 5.00 5.00 5.00 Cellulase (actve protein) 0.03 0.03 0.03 ALcalase/BAN 0.60 0.60 0.60 Lipase 0.36 0 36 0.36 Sodium silicate 2.0Ct 2.00 2.00 Sodium sulfate 3.50 3.50 3.50 rV1~4 . Jl~., ' ) N oxide (PVNO) 0.10 0.10 N.- Jl~ N . ," ' '-copûlymer - MW 10,000 (PVPVI) - - 0.20 Brightener - Tinopal UNPA-GX 0.20 -- 0.20 Brightener - Tinopal 5BM-GX -- 0.20 Misc. (water, minors, dc) " ' tû 100%---------The c.... l.~ .;...c described in Table m are suitable for laundering colored fabrics in aqueous solusions while providing excellent dye transfer inhibition benefits.
Dye transfer inhibition I r provided by the: ' of the PVNO or 35 PVPVI and the selected Tinopal brighteners is ~, r ~,~ better than if the dye transfer inhibiting polymers ûr the optical brighteners were used alone. Dye transfer inhibition 1~ r fûr these . is also superior to that which would be wo 95/1335~ 2 1~ 4 ~ 2 2 PCT/US9411 ISO9 0 provided if other cu~ ....iu~dl relatively hydrophilic optical brighteners were to be substituted for the Tinopal brighteners employed.

IWO 95/13354 PCIIUS9 ~/l lS09

4~12~
EXAMPLF IV
A, ~ heavy duty granular detergent product is prepared having the 4~ set forth in Table IV.
T~RI.F IV
Compact Granular DeterFent Comvonent Wt %
C14 15 Alkyl ethoxy sulfonic acid 5.44 C12 13 Linear alkyl sulfonic acid 12.70 C12 14 Alkyl ethoxylate 0.50 10Alumino silicate (76%) 25.40 r~ 3.12 Tinopal UNPA-GX brightener 0.27 PEG-8000 (50%) 1.53 Silicone suds suppressor 0.02 15Enzymes 1.29 Citric acid 3.50 Perborate 2.00 PVNO 0. 10 MJ;..~UIC/ " "` '~ .h~.t;~.~lNaCO3/
20minors, urlreacted material Balance to 100/0 The granular detergent - , of Table IV has dye transfer inhibition ~; I; which are ' '1~ sunilar to those of the Table m . . .
r,,

Claims

1. A laundry detergent composition that provides especially effective inhibition of dyc transfer between fabrics being laundered in aqueous washing solutions formed from such a composition, which composition comprises:
(a) from about 1% to about 80% of a detersive surfactant;
(b) from about 0.1% to about 80% of detergent builder component;
(c) from about 0.01% to 10% by weight of a polymeric dye transfer inhibiting agent selected from the group consisting of polyamine N-oxide polymers. copolymers of N-vinylpyrrolidone and N-vinylimidazole, and combinations of said polymers and copolymers; and (d) from about 0.005% to 5% by weight of a hydrophilic optical brightener having the formula:
wherein R1 is selected from the group consisting of anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from the group consisting of N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation.

2. A detergent composition according to Claim 1 wherein (a) the detersive surfactant is selected from the group consisting of anionic surfactants, nonionic surfactants and combinations thereof;
(b) the builder is selected from the group consisting of aluminosilicates, crystalline layered silicates, citrates and combinations thereof;
(c) the polymeric dye transfer inhibiting agent is a polyvinylpyridine N-oxide; and (d) the hydrophilic optical brightener is 4,4,'-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisufonic acid disodium salt.

3. A composition according to Claim 2 wherein the polyvinylpyridine N-oxide has an amine to amine N-oxide molar ratio of from about 3:1 to 1:1,000,000 and an average molecular weight of from about 1,000 to 500,000.

4. A composition according to Claim 1 wherein (a) the detersive surfactant is selected from the group consisting of anionic surfactants, nonionic surfactants and combinations thereof;
(b) the builder is selected from the group consisting of aluminosilicates, crystalline layered silicates, citrates and combinations thereof;
(c) the polymeric dye transfer inhibiting agent is a copolymer of N-vinylpyrrolidone and N-vinylimidazole having a molar ratio of N-vinylpyrrolidone to N-vinylimidazole of from about 0.8:1 to 0.3:1 and an average molecular weight of from about 5,000 to 200,000, and (d) the hydrophilic optical brightener is 4,4,'-bis[(4-anilino-6-(N-2-bis-hydroyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid disodium salt.

5. A composition according to Claim 4 where the dye transfer inhibiting copolymer has a molar ratio of N-vinylpyrrolidone to N-vinylimidazole of from about 0.6:1 to 0.4:1 and an average molecular weight of from about 10,000 to 20,000.

6 . A liquid laundry detergent composition that provides especially effective inhibition of dye transfer between fabrics being laundered in aqueous washing solutions formed from such a composition, which composition comprises:
(a) from about 5 % to 50% by weight of a detersive surfactant selected from the group consisting of i) sodium, potassium and ethanolamine alkylsulfates wherein the alkyl group contains from 10 to 20 carbon atoms;
ii) sodium, potassium and ethanolamine alkylpolyethoxylates sulfates wherein the alkyl group contains from 10 to 22 carbon atoms and the poyethoxylate chain contains from 1 to 15 ethylene oxide moieties;
iii) polyhydroxy fatty acid amides of the formula wherein R is a C9-17 alkyl or alkenyl and Z is glycityl derived from a reduced sugar or alkoxylated derivatives thereof;
(iv) alcohol ethoxylates of the formula R1(OC2H4)nOH wherein R1 is a C10-C16 alkyl group or a C8-C12 alkyl phenyl group and n is from about 3 to 80; and (v) combinations of these sulfates and amides;
(b) from about 1% to 10% by weight of a detergent builder component selected from the group consisting of carboxylate and polycarboxylate builders;
(c) from about 0.05% to 0.5% by weight of a polymeric dye transfer inhibiting agent selected from the group consisting of (i) polyamine N-oxides having an anionic to amine N-oxide molar ratio of from about 10:1 to 1:1,000,000 and having an average molecular weight of from about 500 to 1,000,000;
and (ii) copolymers of N-vinylpyrrolidone and N-vinylimidazole having a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of from about 1:1 to 0.2:1 and having an average molecular weight of from about 5,000 to 1,000,000; and (d) from about 0.01% to 1% of a hydrophilic optical brightener selected from the group consisting of (i) 4,4,'-bis[(4-anilino-6-(N-2-bis-hydroxyehtyl)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt;
(ii) 4,4,'-bis[4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid disodium salt; and (iii)4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid, sodium salt.

7. A liquid detergent composition according to Claim 6 wherein (a) the dye transfer inhibiting agent is poly(4-vinylpyridine-N-oxide) having an amine to amine N-oxide ratio of about 1:10 and an average molecular weight of about 10,000; and (b) the optical brightener is Tinopal UNPA-GX.

8. A liquid detergent composition according to Claim 6 wherein (a) the dye transfer inhibiting agent is a copolymer of N-vinylpyrrolidone and N-vinylimidazole having an N-vinylpyrrolidone to N-vinylimidazole molar ratio of from about 0.6:1 to 0.4:1 and an average molecular weight of from about 10,000 to 20,000; and (b) the optical brightener is Tinopal UNPA-GX

9. A liquid detergent composition according to Claim 6 which also comprises from about 0.1% to 2.5% by weight of an enzyme component selected from the group consisting of proteases, lipases, amylases, cellulases and combinations of said enzymes.

10. A granular laundry detergent composition that provides especially effective inhibition of dye transfer between fabrics being laundered in aqueous washing solutions formed from such a composition, which composition comprises:
(a) from about 5% to 50% by weight of a detersive surfactant selected from the group consisting of (i) sodium and potassium alkylpolyethoxylatesulfates wherein the alkyl group contains from 10 to 22 carbon atoms and the polyethoxylate contains from 1 to 15 ethylene oxide moieties;
(ii) sodium and potassium C-9 to C-15 alkyl benzene sulfonates;
(iii) sodium and potassium C8 to C18 alkyl sulfates;
(iv) polyhydroxy fatty acid amides of the formula wherein R is a C9-17 alkyl or alkenyl and Z is glycityl derived from a reduced sugar or alkoxylated derivatives thereof; and (v) combinations of these surfactants;
(b) from about 1% to 50% by weight of a detergent builder selected from the group consisting of sodium carbonate sodium silicate, crystalline layered silicates, aluminodilicates, oxydisuccinates and citrates;
(c) from about 0.05% to 0.5% by weight of a polymeric dye transfer inhibiting agent selected from the group consisting of (i) polyamine N-oxides having an anionic to amine N-oxide molar ratio of from about 10:1 to 1:1,000,000 and having an average molecular weight of from about 500 to 1,000,000;
amd (ii) copolymers of N-vinylpyrrolidone and N-vinylimidazole having a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of from about 1:1 to 0.2:1 and having an average molecular weight of from about 5,000 to 1,000,000; and (d) from about 0.01% to 1% of a hydrophilic optical brightener selected from the group consisting of (i) 4,4,'-bis[(4 anilino-6-(N-2-bis-hydroxyethyl)-s-triazime-2-yl)amino]-2,2'-stilbendisulfonic acid disodium salt;
(ii) 4,4,'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid disodium salt; and (iii) 4,4,'-bis[4-anilino-6-morphilino-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid, sodium salt.

11. A granular detergent composition according to Claim 10 wherein (a) the dye transfer inhibiting agent is poly(4-vinylpyridine-N-oxide) having an amine to amine N-oxide ratio of about 1:10 and an average molecular weight of about 10,000; and (b) the optical brightener is Tinopal UNPA-GX

12. A granular detergent composition according to Claim 10 wherein (a) the dye transfer inhibiting agent is a copolymer of N-vinylpyrrolidone and N-vinylimidazole having am N-vinylpyrrolidone to N-vinylimidazole molar ratio of from about 0.6:1 to 0.4:1 and an average molecular weight of from about 10,000 to 20,000; and (b) the optical brightener is Tinopal UNPA-GX.

13. A granular detergent composition according to Claim 10 which also comprises from about 0.1% to 2.5 %
by weight of an enzyme component selected from the group consisting of proteases, lipaases, amylases, cellulases and combinations of said enzymes.

14. A method for cleaning colored fabrics in the wash with little or no dye transfer between fabrics, said method comprising contacting said fabrics with a wash solution which contains an effective amount of a detergent composition according to Claim 1.

15. A method according to Claim 14 wherein the detergent composition used comprised PVNO and Tinopal UNPA-GX brightener.

16. A method for cleaning colored fabrics in the wash with little or no dye transfer between fabrics, said method comprising contacting said fabrics with a wash solution which contains an effective amount of a detergent composition according to Claim 6.

17. A method according to Claim 16 wherein the detergent composition used comprises PVNO and Tinopal UNPA-GX brightener.

18. A method for cleaning colored fabrics in the wash with little or no dye transfer between fabrics, said method comprising contacting said fabrics with a wash solution which contains an effective amount of a detergent composition according to Claim 10.

19. A method according to Claim 18 wherein the detergent composition used comprises PVNO and Tinopal UNPA-GX brightener.