CA2167372A1 - Detergent compositions inhibiting dye transfer in washing - Google Patents
Detergent compositions inhibiting dye transfer in washingInfo
- Publication number
- CA2167372A1 CA2167372A1 CA 2167372 CA2167372A CA2167372A1 CA 2167372 A1 CA2167372 A1 CA 2167372A1 CA 2167372 CA2167372 CA 2167372 CA 2167372 A CA2167372 A CA 2167372A CA 2167372 A1 CA2167372 A1 CA 2167372A1
- Authority
- CA
- Canada
- Prior art keywords
- ppm
- dye
- binding polymer
- dye binding
- amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3707—Polyethers, e.g. polyalkyleneoxides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3792—Amine oxide containing polymers
Abstract
The invention relates to a dye transfer inhibiting composition comprising: (a) dye binding polymers selected from polyvinylpyrrolidone, polyamine N-oxide containing polymer, N-vinylimidazole, N-vinylpyrrolidone copolymer, and mixtures thereof; and (b) polymeric agents selected from alkoxy containing polymers, cellulosic derivatives, and mixtures thereof; where the ratio of polymeric agent to dye binding polymer on a ppm basis delivered in the wash solution is from about 2:1 to about 250:1. The invention also relates to a detergent composition which contains the dye transfer inhibiting composition in addition to surfactants, builders and other conventional detergent ingredients, where the level of dye binding polymer in the detergent composition is from about 0.001 % to about 10 % by weight, and the 1evel of polymeric agent in the detergent composition is from about 0.1 % to about 15 % by weight. The amount of dye binding polymer delivered in the wash solution is from about 0.01 ppm to about 120 ppm, and the amount of polymeric agent delivered in the wash solution is from about 1 ppm to about 100 ppm.
Description
~1 67372 DETERGENT COMPOSITIONS INHIBITING DYE TRANSFER IN WASHING
Related Application Field of the Invention The present invention relates to a composition for inhiL,iling dye transfer between fabrics during washing.
Backaround of the Invention One of the most per~islent and troublesome pr~b!en,s arising during modem fabric laundenng operations is the tender,cy of some colored fabrics to release dye into the laundering solutions. The dye can then be transferred onto other fabrics being washed therewith.
rolyv;nylpy"~'idone and other dye binding polymers have been used to inhibit dye transfer betvlecn fabrics during laundering operations. However it has now been found that certain polymeric agents such as polyethylene glycol or carboxymethylcellulose cG",bined with certain dye binding polymers in specific raffos provide an un~ eclæd improvement in the dye transfer inhibition pe,toi",ance of deleryen~ ~",posi~ions. This cG",bnation of ingredients is very effective in reducing the amount of dye transfer that occurs during a launderingope,alion.
Accordingly the present invention provides a dye ll anster inhibiting cG",posilion which exhibits optimum dye l,anster inhibiting p,~,pe,lias.
Summary of the Inve. ~tiGn The invention relates to a dye l-dnster inhibiting ~",position cG",prising:
(a) dye binding polymers selected from polyvinylpy". ;done polyamine N-oxide conbining polymer N-vinylil"~ 'e N-vinylpy"~ one copolymer, and mixtures thereof; and (b) polymeric agents selected from alkoxy containing polymers cellulosic derivatives and mixtures thereof; where the ratio of polymeric agent to dye binding poly~"er on a ppm basis delivered in the wash solution is from about2:1 to about 250:1. The invention also relates to a detergenl cG",position whichcontains the dye l,anster inhibiting composition in addition to surfactants builders and other conventional deteryenl ingredients where the level of dye binding polymer in the deteryent cG",position is from about 0.001% to about 10% by weight and the level of polymeric agent in the detergel1t co",posilion is from about 0.1% to about 15% by weight. The amount of dye binding polymer delivered in the wash solution is from about 0.01 ppm to about 120 ppm and the amount of polymeric agent delivered in the wash solution is from about 1 ppm to about 100 ppm.
Related Application Field of the Invention The present invention relates to a composition for inhiL,iling dye transfer between fabrics during washing.
Backaround of the Invention One of the most per~islent and troublesome pr~b!en,s arising during modem fabric laundenng operations is the tender,cy of some colored fabrics to release dye into the laundering solutions. The dye can then be transferred onto other fabrics being washed therewith.
rolyv;nylpy"~'idone and other dye binding polymers have been used to inhibit dye transfer betvlecn fabrics during laundering operations. However it has now been found that certain polymeric agents such as polyethylene glycol or carboxymethylcellulose cG",bined with certain dye binding polymers in specific raffos provide an un~ eclæd improvement in the dye transfer inhibition pe,toi",ance of deleryen~ ~",posi~ions. This cG",bnation of ingredients is very effective in reducing the amount of dye transfer that occurs during a launderingope,alion.
Accordingly the present invention provides a dye ll anster inhibiting cG",posilion which exhibits optimum dye l,anster inhibiting p,~,pe,lias.
Summary of the Inve. ~tiGn The invention relates to a dye l-dnster inhibiting ~",position cG",prising:
(a) dye binding polymers selected from polyvinylpy". ;done polyamine N-oxide conbining polymer N-vinylil"~ 'e N-vinylpy"~ one copolymer, and mixtures thereof; and (b) polymeric agents selected from alkoxy containing polymers cellulosic derivatives and mixtures thereof; where the ratio of polymeric agent to dye binding poly~"er on a ppm basis delivered in the wash solution is from about2:1 to about 250:1. The invention also relates to a detergenl cG",position whichcontains the dye l,anster inhibiting composition in addition to surfactants builders and other conventional deteryenl ingredients where the level of dye binding polymer in the deteryent cG",position is from about 0.001% to about 10% by weight and the level of polymeric agent in the detergel1t co",posilion is from about 0.1% to about 15% by weight. The amount of dye binding polymer delivered in the wash solution is from about 0.01 ppm to about 120 ppm and the amount of polymeric agent delivered in the wash solution is from about 1 ppm to about 100 ppm.
Detailed DescriPtion of the Invention It has now been discovered that the combination of certain polymenc agents and certain dye binding polymers, in specific ratios, delivers unexpectedly improved dye transfer inhibition relative to the dye binding polymers alone As aresult, the dye transfer inhibition performance of a detergent composition can be dramatically enhanced.
The dye binding polymers are selected from polyvinylpyl, ulidone, polyamine N-oxide contain: ~9 polymer, N-vinyli",;d 'e N-vinylp~".lidone copolymer. and mixtures thereof. These dye binding polymers are described in o more detail hen,inbelow.
PolYvin~/lPY- ~li d o nc The dye binding polymer can be a polyvinylpy.,~'.done (nPVP") having an average ~ CUI^- weight of from about 5,000 to about 400,000, preferdbly from about 5,000 to about 200,000, more p.eferably from about 5,000 to about 50,000, and most preferdbly from about 5,000 to about 20,000. Suitable polyv;n~lpy(..!ldones are cG""ne.cially available from GAF Co-~,Gralion, New York, NY and Mo.~beal, Canada underthe product names PVP K-15 (average ",~lec~
weight of ~0,000), PVP K-30 (average ".~12~ r weight of 40,000), PVP K~0 (average ",o'e~ a~ weight of 160,000), and PVP K-90 (average ",o'e~ weight of 360,000). PVP K-15 is also available from ISP Co, ~ordtion.
rolyv;nylpy.--' dones are known to persons skilled in the debrgent field; see, for example, EP-A-262,897 and EP-A-256,696. The amount of polyvinylpy..c':done used in the pmësent detcryent compositions is p~ferably from about 0.001% to about 5% by weight of the dcte~5~ant, more prefer~bly from about 0.01% to about 4% by weight, more ptere~ably from about 0.05% to about 3% by weight, and most p--ef~5-ably from about 0.1% to about 2% by weight. The amount of pol~r;nylp~ l;done delivered in the wash solution is prefe,dbly from about 0.1 ppm to about 75 ppm, more plefeldbly from about 0.5 ppm to about 50 ppm, and most pr~f~rably from about 1 ppm to about 25 ppm.
Polyamine N4xide Containino PolYmcr The dye binding polymer can also be a polyamine N-oxide containing polymer which conbins units having the fc"ow,ng structure fommula (I):
p I
(I) Ax I
R
wherein P is a polymerisable unit, whereto the R-N-O group can be attached or wherein the R-N-O group forms part of the polymerisable unit or a combination of WO 95/033gO PCTIUS94/06849 both;
O O O
Il 11 11 wherein A is NC CO C -O- -S- or-N-; x is 0 or 1; and s wherein R are aliphatic ethoxylated aliphatics aromatic heterocyclic or alicyclic groups or any combination 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 represented by the following general structures:
O O
(R1)X N- (R2)Y =N- (R1)x I
(R3)z wherein R1 R2 and R3 are aliphatic groups aromatic heterocyclic or alicyclic S groups or combinations thereof x and/or y and/or z is 0 or 1 and wi,er-~in the ni~ogen of the N-O group can be attached or wherein the nitrogen of the N-O
group forms part of these groups.
The N-O group can be part of the poly."eiisable unit (P) or can be atla- hed to the poly."enc bac~ one or a combination of both.
Suitable polyamine N-oxides wl,erl in the N-O group forms part of the poly."ensable unit co"~pnse polyamine N-oxides v.~,e.- in R is sele~æd from aliphatic ."o,nalic alicyclic or h~er~c.yclic groups.
One class of said polyamine N-oxides cG",prises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. R,èfe,.-~d polyamine N oxides are those v ha.- ;n R is a he~er~ ~clic group such as pyridine pyrrole imidæole pyrrolidine piperidine quinoline acridine and derivatives thereof.
Another class of said polyamine N-oxides cG",prises the group of polyamine N-oxides wl,-r_in the r,:Logen of the N-O group is dllached to the R-group.
Other suitable polyamine N-oxides are the polyamine oxides wherèto the N-O group is dUacl.Gd to the poly.-,erisable unit. A p~fell~J class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) ~h,:rein R is an a-~"~ tic, heterocyclic or alicyclic group wherein the ni~ogan of 3S the N-O functional group is part of said R group.
Examples of this class are polyamine oxides wl,ere;n R is a heteroc~clic compound such as pyridine pyrrole i",~ e and derivatives thereof.
Another prafe..ed class of polyamine N-oxides are the polyamine oxides having the general forrnula (I) wherein R are ar~",atic hetertJcyclic or alicyclic 216~372 groups wherein the nitrogen of the N-O functional group is attached to said R
groups.
Examples of this class 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. E~a",F es ofsu t-~le polymeric backbones are polyvinyls polyalkylenes polyesters polyethers polyamide polyimides polyacrylates and mixtures thereof.
The polyamine N-oxide containing polymers of the present invention lo 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 N-oxide containing polymer can be varied by appropriale copoly,,,cfi~alion or by app~priale degree of N-oxidation. rlefer~bly the ratio of amine to amine N-oxideis from 2:3 to 1:1000000. More pref~rably from 1:4 to 1:1000000 most prcferably from 1:7 to 1:1000000. The polymers of the present invention actually enco",passrandG", or block copolymers where one ",onG"~er type is an amine N-oxide and the other ",GnG"~er type is either an amine N-oxide or not. The amine oxide unitof the polyamine N-oxides has a PKa c 10 p,efefably PKa ~ 7 more prcfel,æd PKa ~ 6.
The polyamine N-oxide conbining polymer can be obtained in almost any degree of poly",eli~a~on. The degree of poly."a"~ation is not critical provided the " ,aterial has the desired water-solubility and dye-suspending power.
Typically the average ",o ee~ weight of the polyamine N-oxide containing poly."ar is within the range of 500 to 1 000 000; p,cfe,~bly from 1 000 to 50 000 more p,cf~,ably from 2 000 to 30 000 most p,cfe~ably from 3 000 to 20 000.
The amount of polyamine N-oxide containing poly."er used in the present deter~ent c4.,-FQ~itions is pr~ferably from about 0.005% to about 5% by weight of ~e det~rgent, more prefe.ably from about 0.01% to about 3% by weight and most p~ef --ably from about 0.02% to about 1.6% by weight. The amount of polyamine N-oxide cQntaining poly."er delivered in the wash solution is prcfe,ably from about 0.01 ppm to about 30 ppm more prefcrdbly from about 0.05 ppm to about 20 ppm more p,eferably from about 0.1 ppm to about 10 ppm and most preferably from about 0.1 ppm to about 5 ppm.
35 N-v;n~liu.id--ole Nl v;nYl~ lid~ Col~olYcr The dye binding poly. "er can also be an N-vinyli" ,~ e N-vinylp~",. .done copolymer having an average ",olec~ weight range from about 5000-1 000000 pfeférably from about 20000-200000. Highly pr~fe"~d polymers having an excellent overall detergency pe,ro""ance 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 average molQcul~r weight range was determined by light scattering as described in Barth H.G. and Mays J.
W. Chemical Analysis Vol. 113 "Modem Methods of Polymer Characleri~alion".
The N-vinyli,r,id-~ole N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinyli.,. ~ 'e to N-vinylpy"~lidone from 1 to 0.2 more preferably from 0.8 to 0.3 most preferably from 0.6 to 0.4. The N-vinyli",i N-vinylp~ lid~ne copolymers can be linear or branched.
The amount of N-vinyli",.~-cle N-vinylpy"-'.d~ne poly."er used in the o present deteryenl compositions is prefê(ably from about G.005% to about 5% by weight of the detargellt more prefe...bly from about 0.01% to about 3% by weightand most prefêrably from about 0.02% to about 1.6% by weight. The amount of N-vinylimidazole N-vinylpy,.~l,done polymer delivered in the wash solubon is preferably from about 0.01 ppm to about 30 ppm more prefe.dbly from about 0.05 ppm to about 20 ppm more preferdbly from about 0.1 ppm to about 10 ppm and most p.eferdbly from about 0.1 ppm to about 5 ppm.
The polymeric agents which are cG,nb.ned with the dye binding poly."era in the p,esen~ cG",positions are select~d from alkoxy containing poly."e.a cellulosic derivatives and mixtures thereof. These polymeric agents are desc.ibad in more 20 detail hereinbelo~.
AlkoxY Containino Polv."~ . ~
The alkoxy containing polymen (i.e. polymers having alkoxy "DieLes) can includecopoly."eric blocks of ethylene ~erèphU,alale and polyéU,~le~ne oxide or poly~,rupylene oxide t~réphU,ald~e and the like. The most p(erelled alkoxy 2~ containing poly.-,e.a include poly~thJlena glycol or poly~ pJlene glycol and derivatives thereof. Particularly pref~..ed is poly~thJlena glycol (~PEG") having an av~.~gc .n~'e~ weight from about 500 to about 100,000 p,~ferably from about 1,000 to about 50 000 more p,~fe.dbly from about 1 500 to about 10 000 and most prefe.dl,ly from about 1 500 to about 4 000. rolyelhJlan.. glycol is prepa,ed 30 in a known ,-,annEr by subjecting etl"rlene glycol to a polycondansation p,ucess;
thus the poly_U"~l~na glycol may be .ega--Jed as the condensdtion poly."er of ethylene oxide or 0~,yl~na glycol with water. The general structure is: HO-(-CH2-CH2-O)n-H. Suitable poly_ll,ylene glycols are cG"""a~ially available from Union Carbide Chemicals and rlastics Co. Inc. Danbury CT. The polyethylene glycol 3s can be added as a sepa,alè ingredient or as part of a combined ingredient (e.g. a co-flake containing about 99% polyethylene glycol and about 1% suds suppressGr).
Another suitable alkoxy containing polymer is a copolymer having random blocks of ethylene ~erep~,ll,alate and polyethylene oxide (PEO) terephtala~e. More specifically these polymers are comprised of repeating units of ethylene terephthalate and PEO terephthalate in a mole ratio of ethylene terephthalate units to PEO terephthalate units of from 25:75 to 35:65 said PEO terephthalate units containing polyethylene oxide having molecular weights of from 300 to 2000.
The molecular weight of this polymer is in the range of from 3 000 to 55 000.
Another s~litable alkoxy containing polymer is a polyester with repeating units of ethylene terephll ,alale containing 10-15% by weight of ethylene ~ereph~l ,alate units together with 90-80% by weight of polyoxyethylene ~erephthalate units derived from a polyoxyethylene glycol of average ",o es~
o weight 300-5 000 and the mole ratio of ethylene terephll,alate units to polyoxyethylene tertphtl,alate units in the poly."eric compound is bet~ecn 2:1 and 6: 1.
Other alkoxy containing polymers are compounds of fommula:
O O O O
ll ll ll ll X-(OCH2CH2)n [oC-R1-Co-R2)U(-oc-R3 - CO-R2)V]
O O
Il 11 oC-R4-C~(CH2CH20)n-X
wherein the R1 ",o.et;es are all 1 4-phenylene ",~iet;es; the R2 ",0 et:es are essentially ethylene ",D;eLes 1 2-propylene ,.,o:eLes or mixtures thereof; the R3 .-,~.e~es are suhstit~ted 1 3-phenylEne ."o ~Les having the s~hstituent O O O
Il 11 11 2s -CO [(R2-oGR4-Co] w (CH2CH20)n-X
at the S posiUon; the R4 ".o.et:es are R1 or R3 -,o et;es or mixtures ll,ereof each X is ethyl or pr~fel~tly methyl; each n is from 12 to 43; when w is 0 u + v is from 3 to 10; when w is at least 1 u ~ v ~ w is from 3 to 10. ~efellèd block polyestersare those where v is 0 i.e. the linear block polyestqrs. For these p,dfe..ed linear 30 block polyesters, u typically ranges from 3 to 8, especially for those made from dimethyl t~r~phU-alab ethylene glycol (or 1 2-propylene glycol) and methyl capped poly~lhylene glycol. The most water soluble of these linear block polyestcrs are those where u is from 3 to 5.
Other alkoxy containing polymers suitable for the present invention are 3s alkoxyldted polyamines. Such malèrials can conveniently be represented as ",o!e~u les of the empirical stnuctures with repeating units:
[N R] n Amine form I
(alkoxy)y and R 1 s [N+ R! n nX~ Quaternized form (alkoxy)y Wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms; R1 may be a C1-o C20 hydrocarbon; the alkoxy groups are ethoxy, propoxy, and the like, and y is 2-30, most prefe,dbly from 10-20; n is an integer of at least 2, preferably from 2-20, most p~efe(ably 3-5; and X~ is an anion such as halide or methylsulfate, resulting from the quate" ,i~ation reaction.
The amount of alkoxy containing polymers used in the present de~ergenl 15 compositions is prefcrably from about 0.2% to about 8% by weight of the detergan~, more prèferably from about 0.3% to about 6% by weight~ and most p,ete,dbly from about 0.4% to about 4% by weight. The amount of alkoxy containing polymers delivered in the wash solution is pfeferdbly from about 3 ppm to about 90 ppm, more pmëfelclbly from about 5 ppm to about 80 ppm, and most 20 prefe,c,bly from about 10 ppm to about 70 ppm.
Cellulosic De.i~at;~/~s The cellulosic derivatives for use as polymeric agents in the present dye bc".sfer inhibiting co,.,F~s;tions are water-soluble cellulosic derivatives which include the alkali metal salts of a ca,l,oxy lower alkyl cellulose having up to 3 25 ca,L,ons in the alkyl group, such as the sodium and pot~ssium salts of c~.Lox~meU-~lcellulose or of c~,Lo~.~U jl~e"ulose. Sodium ca,boxjmethylcellulose is p~efelled. Suitable water-soluble cellulosic derivatives also include the lower alkyl cellulose ethers, e.g., methyl cellulose and ethyl cellulose; hydroxyalkyl cellulose ethers, e.g., hydroxyethyl cellulose; cellulose 30 ethane sulfonic acid; and cellulose glycollic acid.
The amount of cellulosic derivatives used in the present detergant CGI I ,positions is prefe, ably from about 0.2% to about 8% by weight of the de~aryênt, more prèferably from about 0.3% to about 6% by weight, and most p~ferably from about 0.4% to about 4% by weight. The amount of ce"~l~sic 35 derivatives delivered in the wash solution is prefe,..bly from about 3 ppm to about - 90 ppm, more preferably from about 5 ppm to about 80 ppm, and most preferably from about 10 ppm to about 70 ppm.
As discussed above, it has su" ,isingl~ been discovered that by co",bin ~9 the polymeric agents with the dye binding polymers in certain ratios, an WO 95/033g0 2 1 6 7 3 7 2 PCT/US94/06849 unexpected improvement in dye transfer inhibition is obtained. -The ratio of polymeric agent to dye binding polymer on a ppm basis delivered in the wash solution is from about 2:1 to about 250:1. When polyvinylpyrrolidone is used as the dye binding polymer the ratio of polymeric agent to dye binding polymer on appm basis delivered in the wash solution is preferably from about 2:1 to about 50:1 more preferably from about 3:1 to about 20:1 more preferably from about 3:1 to about 10:1 and most preferably from about 4:1 to about 8:1. When polyamine N-oxide containing polymer and/or N-vinyli ,~ -!e N-vinylp~".!,done copolymer are used as the dye binding polymer the ratio of polymeric agent to o dye binding polymer on a ppm basis delivered in the wash solution is preferably from about 3:1 to about 150:1 more prefe(ably from about 3:1 to about 100:1 and most p~ferably from about 4:1 to about 75:1.
The present dye l,ansfer inhibiting co"~posi~ions are conveniently used as additives to conventional deter~ent cG",posilions for use in laundry oparations.The present invention also enco,npasses deterg-~nt composi~ions containing the dye ~ansfer inhibiting co",pGsitions along with corventional dete.~ent ingredients.
ret~rao~t l~a.~.~ s~ta A w;de range of su,ra~.lants can be used in the deteraent composilions. A
typical listing of an ~n ~ non on - a,.,pholytic and ~J i:lenon.~ classes and species of these su,faclants is given in U.S. Patent 3 664 961 issued to Norris on May 23 1972.
Mixtures of anionic s~"fa~ lar,ts are pa ticularly suitable herein especially mixtures of sulphor.~te and sulphate s~"fac~--nls in a weight ratio of from 5:1 to 1:2 pl~fe.dbly from 3:1 to 2:3 more prefe.dbly from 3:1 to 1:1. P~efe,,ed 2s sulphonates indude alkyl benzen.5 sulphonat-~s having from 9 to 15 especially 11 to 13 carbon atoms in the alkyl radical and the alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a C12-C18 fatty source p,~r~fably from a C16-C18 fatty source. In each inslanca the cation is an alkalimetal prefcl~bly sodium. F~efe"ed sulphate su,r~ ts are alkyl sulphates having from 12 to 18 carbon atoms in the alkyl radical optionally in admixture with ethoxy sulphates having from 10 to 20 pr~ferdbly 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 0.1 to 9. Examples of plefe"ed alkyl sulphates herein are tallow alkyl sulphate coconut alkyl sulphateand C14.1s alkyl sulphates. The cation in each inslance is again an alkali metal3s cation preferc-bly sodium.
One class of non.on.o surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a su,faclant having an average hydrophilic 'ipoph 'is balance (HLB) in the range from 8 to 17preferably from 9.5 to 13.5 more preferably from 10 to 12.5. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of thepolyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hycl~phobic elements Fspeci~ly preferred nonionic surfactants of this type are Cg-C1s primary alcohol ethoxylates containing 3-9 moles of ethylene oxide per mole of alcohol, particularly the C14-C1~ primary alcohols containing 6-9 moles of ethylene oxide per mole of alcohol and the Ct2-C1s primafy alcohols containing 3-9 moles of ethylene oxide per mole of alcohol.
o Another class of non ~n ~ surfactants co,npnses alkyl polyglucoside compounds of general formula RO (CnH2nO)tZx wherein Z is a moiety derived from glucose; R is a saturated h~rdl~phO~ c alkyl group that contains from 12 to 18 ca bon atoms; t is from 0 to 10 and n is 2 or 3; x IS iS from 1.3 to 4, the compounds including less than 10% u(,-,ac~ed fatty alcohoi and less than 50% short chain alkyl polygluco~idcs Compounds of this type and their use in dehrgenl are ~;scl~sed in EP-B 0,070,077, 0,075,996 and 0,094,118.
Also suitab~e as non-~n.c surfactants are polyhy~l~o,~y fatty acid amide s~-- raclant~ of the formula R2-C-N-Z, Il I
o R1 æ.-,;n R1 is H, or R1 is C14 hlJ~ca,~l, 2~hydroxy ethyl, 2-hydroxy propyl or a miA~re thereof, R2 is C~31 h~d-oca.~l, and Z is a polyhyJ~Ayhydr~
having a linear l.~d~uc~.~Jl chain with at least 3 h~J~A~I~ direct)y conne.,led to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight C11.1s alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, se, in a reductive amination reaction.
The co.-.positions according to the p-`S'G.lt inv¢ntion may fur~er cG-np.ise a builder system. Any conve-~tional builder system is suitable for use herein including aluminosilicate ",at~rials, phas~l;Jt~s, silicates, polyc~oxylales, fatty acids, materials such as ell,~lencdid.nine t~ t~-, and mebl ion seques~.a,lts such as aminopolyphosphor,ates.
Suitable builders can be an inGryan c ion e3~hang~ ,.,atenal, ~""nonl~ an i.,o~an c hydrated aluminosilicate ,naterial, more particularly a hydrated synthetic zeolite such as hydrated zeolite A~ X, 8 or HS.
Another suitable ino,yanic builder material is layered silicate, e.g., SKS-6 (~loechs~). SKS~ is a crystalline layered silicate cûn3;~ting of sodium silicate (Na2Si2os) Suitable polycarboxylate builders for use herein include nitrilotnacetate (NTA); ethylenediaminetetracetic acid (EDTA); citric acid preferably in the form of a water-soluble salt; and 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 sl ~bstihlted with hydroxyl sulfo sulfoxyl or sulfone substituents. Specific exa",rles include lauryl succinate myristyl succinate palmityl succinate 2-~odecenylsuccinate 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts including 0 sodium potassium a"""on um and alkanola"""on -~m salts.
Especially for the liquid executiQn herein suitable fatty acid builders for use herein are saturated or unsaturated C10~18 fatty acids as well as the cG"-asponding soaps. rlefelled saturated species have from 12 to 16 carbon atoms in the alkyl chain. The prere"ed unsaturated fatty acid is oleic acid.
Another plefellèd builder system for liquid cG"~positions is based on dodecen~
succinic acid.
Prërellèd builder systems for use in granular CG",pOsit;ons indude a mixture of rJTA phosphate and zeolite.
Other builder materials that can form part of the builder system for use in granular cG",pGsitions for the purposes of this invention include ino,~an-c ",atenals such as alkali metal ca,LGnates bica,L,or,dtes silicates, and organic ",dtênals such as the organic pl,Gsphor,dtes amino polyalkylene phosphonates and amino polyca,l,oxylates. Other suitable water-soluble organic salts are the homo- or co-poly.--e ic adds of their salts in which the polyca,loxylic acid 2s cG."prises at least two ca,l,oxyl radicals separted from each other by not more than two carbon atoms. roly."era of this type are d;sclosed in GB-A-1 596 756.
Examples of such salts arr~ polyacrylates of MW 2000-5000 and their copolyme.a with maleic anhydride, such copoly",e. a having a ",o eou'-~ weight of from 20 000 to 70 000 especially about 40 000.
Builder~ are normally included in amounts of from about 10% to about 30%
by weight of the d&ter~ent CG",FCS tion p~eferably from about 20% to 70% and more prèfe,ably from about 30% to about 60%.
Other cG",ponenls used in d-~tergent cGIIlpGsitions may be employed such as suds booating or dep~esaing agents er,~."es such as proteases amylases or lipases e"~."e stabilizers or activators bleaching agents soil-suspending agents soil-release agents fabric softening agents optical bright~nera abrasivesbaclcri~d;~s tamish inhibitors c~, ~ ring agents and perfumes. Especially pr~fei,ed are comb.nations v~rith enzyme technologies which also provide a type of color care benefit for example cellulase for color maintenance/rejuver,alion.
WO 95/033g0 2 1 6 7 3 7 2 PCT~Sg4l0684g The detergent compositions according to the invention can be in liquid gel paste or granular forms. Granular compositions will generally have a density from about 300 9/l to about 900 9/l. "Compact" granular detergents can have a relatively higher density than conventional granular detergents; in such case the 5 detergent compositions will contain a lower amount of "inorganic filler salt" (e.g.
sodium sulfate) compared to conventional granular detergents typically not more than 20% filler salt.
The present invention also reiates to a process for inhibiting dye t,ansfer from one fabric to another of solubilized and suspended dyes encountered during o fabric laundanng opeldtions involving colored fabrics. The process co",pnses contacling fabrics with a laundenng solution containing the dye t~anster inhibiting cG",position of this invention. The process of the invention is conven enlly carried out in the course of the washing p,ucess. The washing process is prefeidbly carried out at 1C to 90C especially 5C to 60C. The pH of the ~edtl"en~
15 solution is ~referably from about 7 to about 12 especially from about 8 to abou~
11.
The following examples are meant h exemplify cGIllpGsitions of the presen~ invenbon but are not necess-~-ily meant to limit or oU,rrv,is~ define the scope of the invention said SCOpQ being determined according to claims which 20 follow.
E~a,.."le 1 A granular laundry de~ergent co",pesition of the p,..sent invention is as s:
Inaredient: Weioht r~ t Crutched Sodium C1~ ~ linear alkylL,anzene sulfonate 12.2%
Sodium C1~1~ alkyl sulfate 12.2%
Tetrasodium p~.oph~ sphat-~ 7.2%
Nitrilv0iace-~t.~s (active) 19.5%
Sodium ca~L~onJta 13 0%
Sodium silicate solids 6.1%
Optical Dr;~l ,tonar 0. 1 %
Zeolites (active) 4.7%
35 De-Dust Condensation product of C12 C13 linear alcohol with 6.5 moles 0.8%
ethylene oxide Dry-Adds Polyvinylpyrrolidone 0 5%
Polyethylene glycol 3 9%
Protease enzyme 0. 1 %
Perfume o 5%
S Zeolites (active) 1.2%
Cellulase enzyme 0 9%
The "cnutched" ingredients are mixed together with water in a crutcher to forrn a paste. This mixture is then spray dried to evapG,~le the excess moisture and form deteryenl granules. Then the de-dust is sprayed onto the granules. The "dry-add"10 ingredients are then ad",ixed to form the finished granular dete,yrn~ cGIllpGsiUon.
This co",position delivers in the wash solution about 37 ppm polyethylene glycol and about 5.1 ppm polyvinylpyrrolidone (a ratio of about 7.5:1 PEG:PVP).
The pH of a 1% aqueo~Js solution of the deter~enl co",position is 11.
ExamPle 2 The fo"~ing exa",r'e illustrates the invention and facilitates its unders~anding.
1. In a Miniwasher pot of 2 U.S. gallons of 35C water 61 grams of delergent are added. The mixture is agitated for 1 minute.
2. The dye source is added under agi~tion and allowed to mix for 1 minute.
20 3. A total of twelve tracer swatches are added to the Miniwasher pot and washed for 10 minutes. These swatches had previously been balanced by Hunter Colorimeter L,a b values so that all swatches of a specific type were starting unifommly for each ~at",en~
The dye binding polymers are selected from polyvinylpyl, ulidone, polyamine N-oxide contain: ~9 polymer, N-vinyli",;d 'e N-vinylp~".lidone copolymer. and mixtures thereof. These dye binding polymers are described in o more detail hen,inbelow.
PolYvin~/lPY- ~li d o nc The dye binding polymer can be a polyvinylpy.,~'.done (nPVP") having an average ~ CUI^- weight of from about 5,000 to about 400,000, preferdbly from about 5,000 to about 200,000, more p.eferably from about 5,000 to about 50,000, and most preferdbly from about 5,000 to about 20,000. Suitable polyv;n~lpy(..!ldones are cG""ne.cially available from GAF Co-~,Gralion, New York, NY and Mo.~beal, Canada underthe product names PVP K-15 (average ",~lec~
weight of ~0,000), PVP K-30 (average ".~12~ r weight of 40,000), PVP K~0 (average ",o'e~ a~ weight of 160,000), and PVP K-90 (average ",o'e~ weight of 360,000). PVP K-15 is also available from ISP Co, ~ordtion.
rolyv;nylpy.--' dones are known to persons skilled in the debrgent field; see, for example, EP-A-262,897 and EP-A-256,696. The amount of polyvinylpy..c':done used in the pmësent detcryent compositions is p~ferably from about 0.001% to about 5% by weight of the dcte~5~ant, more prefer~bly from about 0.01% to about 4% by weight, more ptere~ably from about 0.05% to about 3% by weight, and most p--ef~5-ably from about 0.1% to about 2% by weight. The amount of pol~r;nylp~ l;done delivered in the wash solution is prefe,dbly from about 0.1 ppm to about 75 ppm, more plefeldbly from about 0.5 ppm to about 50 ppm, and most pr~f~rably from about 1 ppm to about 25 ppm.
Polyamine N4xide Containino PolYmcr The dye binding polymer can also be a polyamine N-oxide containing polymer which conbins units having the fc"ow,ng structure fommula (I):
p I
(I) Ax I
R
wherein P is a polymerisable unit, whereto the R-N-O group can be attached or wherein the R-N-O group forms part of the polymerisable unit or a combination of WO 95/033gO PCTIUS94/06849 both;
O O O
Il 11 11 wherein A is NC CO C -O- -S- or-N-; x is 0 or 1; and s wherein R are aliphatic ethoxylated aliphatics aromatic heterocyclic or alicyclic groups or any combination 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 represented by the following general structures:
O O
(R1)X N- (R2)Y =N- (R1)x I
(R3)z wherein R1 R2 and R3 are aliphatic groups aromatic heterocyclic or alicyclic S groups or combinations thereof x and/or y and/or z is 0 or 1 and wi,er-~in the ni~ogen of the N-O group can be attached or wherein the nitrogen of the N-O
group forms part of these groups.
The N-O group can be part of the poly."eiisable unit (P) or can be atla- hed to the poly."enc bac~ one or a combination of both.
Suitable polyamine N-oxides wl,erl in the N-O group forms part of the poly."ensable unit co"~pnse polyamine N-oxides v.~,e.- in R is sele~æd from aliphatic ."o,nalic alicyclic or h~er~c.yclic groups.
One class of said polyamine N-oxides cG",prises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. R,èfe,.-~d polyamine N oxides are those v ha.- ;n R is a he~er~ ~clic group such as pyridine pyrrole imidæole pyrrolidine piperidine quinoline acridine and derivatives thereof.
Another class of said polyamine N-oxides cG",prises the group of polyamine N-oxides wl,-r_in the r,:Logen of the N-O group is dllached to the R-group.
Other suitable polyamine N-oxides are the polyamine oxides wherèto the N-O group is dUacl.Gd to the poly.-,erisable unit. A p~fell~J class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) ~h,:rein R is an a-~"~ tic, heterocyclic or alicyclic group wherein the ni~ogan of 3S the N-O functional group is part of said R group.
Examples of this class are polyamine oxides wl,ere;n R is a heteroc~clic compound such as pyridine pyrrole i",~ e and derivatives thereof.
Another prafe..ed class of polyamine N-oxides are the polyamine oxides having the general forrnula (I) wherein R are ar~",atic hetertJcyclic or alicyclic 216~372 groups wherein the nitrogen of the N-O functional group is attached to said R
groups.
Examples of this class 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. E~a",F es ofsu t-~le polymeric backbones are polyvinyls polyalkylenes polyesters polyethers polyamide polyimides polyacrylates and mixtures thereof.
The polyamine N-oxide containing polymers of the present invention lo 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 N-oxide containing polymer can be varied by appropriale copoly,,,cfi~alion or by app~priale degree of N-oxidation. rlefer~bly the ratio of amine to amine N-oxideis from 2:3 to 1:1000000. More pref~rably from 1:4 to 1:1000000 most prcferably from 1:7 to 1:1000000. The polymers of the present invention actually enco",passrandG", or block copolymers where one ",onG"~er type is an amine N-oxide and the other ",GnG"~er type is either an amine N-oxide or not. The amine oxide unitof the polyamine N-oxides has a PKa c 10 p,efefably PKa ~ 7 more prcfel,æd PKa ~ 6.
The polyamine N-oxide conbining polymer can be obtained in almost any degree of poly",eli~a~on. The degree of poly."a"~ation is not critical provided the " ,aterial has the desired water-solubility and dye-suspending power.
Typically the average ",o ee~ weight of the polyamine N-oxide containing poly."ar is within the range of 500 to 1 000 000; p,cfe,~bly from 1 000 to 50 000 more p,cf~,ably from 2 000 to 30 000 most p,cfe~ably from 3 000 to 20 000.
The amount of polyamine N-oxide containing poly."er used in the present deter~ent c4.,-FQ~itions is pr~ferably from about 0.005% to about 5% by weight of ~e det~rgent, more prefe.ably from about 0.01% to about 3% by weight and most p~ef --ably from about 0.02% to about 1.6% by weight. The amount of polyamine N-oxide cQntaining poly."er delivered in the wash solution is prcfe,ably from about 0.01 ppm to about 30 ppm more prefcrdbly from about 0.05 ppm to about 20 ppm more p,eferably from about 0.1 ppm to about 10 ppm and most preferably from about 0.1 ppm to about 5 ppm.
35 N-v;n~liu.id--ole Nl v;nYl~ lid~ Col~olYcr The dye binding poly. "er can also be an N-vinyli" ,~ e N-vinylp~",. .done copolymer having an average ",olec~ weight range from about 5000-1 000000 pfeférably from about 20000-200000. Highly pr~fe"~d polymers having an excellent overall detergency pe,ro""ance 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 average molQcul~r weight range was determined by light scattering as described in Barth H.G. and Mays J.
W. Chemical Analysis Vol. 113 "Modem Methods of Polymer Characleri~alion".
The N-vinyli,r,id-~ole N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinyli.,. ~ 'e to N-vinylpy"~lidone from 1 to 0.2 more preferably from 0.8 to 0.3 most preferably from 0.6 to 0.4. The N-vinyli",i N-vinylp~ lid~ne copolymers can be linear or branched.
The amount of N-vinyli",.~-cle N-vinylpy"-'.d~ne poly."er used in the o present deteryenl compositions is prefê(ably from about G.005% to about 5% by weight of the detargellt more prefe...bly from about 0.01% to about 3% by weightand most prefêrably from about 0.02% to about 1.6% by weight. The amount of N-vinylimidazole N-vinylpy,.~l,done polymer delivered in the wash solubon is preferably from about 0.01 ppm to about 30 ppm more prefe.dbly from about 0.05 ppm to about 20 ppm more preferdbly from about 0.1 ppm to about 10 ppm and most p.eferdbly from about 0.1 ppm to about 5 ppm.
The polymeric agents which are cG,nb.ned with the dye binding poly."era in the p,esen~ cG",positions are select~d from alkoxy containing poly."e.a cellulosic derivatives and mixtures thereof. These polymeric agents are desc.ibad in more 20 detail hereinbelo~.
AlkoxY Containino Polv."~ . ~
The alkoxy containing polymen (i.e. polymers having alkoxy "DieLes) can includecopoly."eric blocks of ethylene ~erèphU,alale and polyéU,~le~ne oxide or poly~,rupylene oxide t~réphU,ald~e and the like. The most p(erelled alkoxy 2~ containing poly.-,e.a include poly~thJlena glycol or poly~ pJlene glycol and derivatives thereof. Particularly pref~..ed is poly~thJlena glycol (~PEG") having an av~.~gc .n~'e~ weight from about 500 to about 100,000 p,~ferably from about 1,000 to about 50 000 more p,~fe.dbly from about 1 500 to about 10 000 and most prefe.dl,ly from about 1 500 to about 4 000. rolyelhJlan.. glycol is prepa,ed 30 in a known ,-,annEr by subjecting etl"rlene glycol to a polycondansation p,ucess;
thus the poly_U"~l~na glycol may be .ega--Jed as the condensdtion poly."er of ethylene oxide or 0~,yl~na glycol with water. The general structure is: HO-(-CH2-CH2-O)n-H. Suitable poly_ll,ylene glycols are cG"""a~ially available from Union Carbide Chemicals and rlastics Co. Inc. Danbury CT. The polyethylene glycol 3s can be added as a sepa,alè ingredient or as part of a combined ingredient (e.g. a co-flake containing about 99% polyethylene glycol and about 1% suds suppressGr).
Another suitable alkoxy containing polymer is a copolymer having random blocks of ethylene ~erep~,ll,alate and polyethylene oxide (PEO) terephtala~e. More specifically these polymers are comprised of repeating units of ethylene terephthalate and PEO terephthalate in a mole ratio of ethylene terephthalate units to PEO terephthalate units of from 25:75 to 35:65 said PEO terephthalate units containing polyethylene oxide having molecular weights of from 300 to 2000.
The molecular weight of this polymer is in the range of from 3 000 to 55 000.
Another s~litable alkoxy containing polymer is a polyester with repeating units of ethylene terephll ,alale containing 10-15% by weight of ethylene ~ereph~l ,alate units together with 90-80% by weight of polyoxyethylene ~erephthalate units derived from a polyoxyethylene glycol of average ",o es~
o weight 300-5 000 and the mole ratio of ethylene terephll,alate units to polyoxyethylene tertphtl,alate units in the poly."eric compound is bet~ecn 2:1 and 6: 1.
Other alkoxy containing polymers are compounds of fommula:
O O O O
ll ll ll ll X-(OCH2CH2)n [oC-R1-Co-R2)U(-oc-R3 - CO-R2)V]
O O
Il 11 oC-R4-C~(CH2CH20)n-X
wherein the R1 ",o.et;es are all 1 4-phenylene ",~iet;es; the R2 ",0 et:es are essentially ethylene ",D;eLes 1 2-propylene ,.,o:eLes or mixtures thereof; the R3 .-,~.e~es are suhstit~ted 1 3-phenylEne ."o ~Les having the s~hstituent O O O
Il 11 11 2s -CO [(R2-oGR4-Co] w (CH2CH20)n-X
at the S posiUon; the R4 ".o.et:es are R1 or R3 -,o et;es or mixtures ll,ereof each X is ethyl or pr~fel~tly methyl; each n is from 12 to 43; when w is 0 u + v is from 3 to 10; when w is at least 1 u ~ v ~ w is from 3 to 10. ~efellèd block polyestersare those where v is 0 i.e. the linear block polyestqrs. For these p,dfe..ed linear 30 block polyesters, u typically ranges from 3 to 8, especially for those made from dimethyl t~r~phU-alab ethylene glycol (or 1 2-propylene glycol) and methyl capped poly~lhylene glycol. The most water soluble of these linear block polyestcrs are those where u is from 3 to 5.
Other alkoxy containing polymers suitable for the present invention are 3s alkoxyldted polyamines. Such malèrials can conveniently be represented as ",o!e~u les of the empirical stnuctures with repeating units:
[N R] n Amine form I
(alkoxy)y and R 1 s [N+ R! n nX~ Quaternized form (alkoxy)y Wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms; R1 may be a C1-o C20 hydrocarbon; the alkoxy groups are ethoxy, propoxy, and the like, and y is 2-30, most prefe,dbly from 10-20; n is an integer of at least 2, preferably from 2-20, most p~efe(ably 3-5; and X~ is an anion such as halide or methylsulfate, resulting from the quate" ,i~ation reaction.
The amount of alkoxy containing polymers used in the present de~ergenl 15 compositions is prefcrably from about 0.2% to about 8% by weight of the detergan~, more prèferably from about 0.3% to about 6% by weight~ and most p,ete,dbly from about 0.4% to about 4% by weight. The amount of alkoxy containing polymers delivered in the wash solution is pfeferdbly from about 3 ppm to about 90 ppm, more pmëfelclbly from about 5 ppm to about 80 ppm, and most 20 prefe,c,bly from about 10 ppm to about 70 ppm.
Cellulosic De.i~at;~/~s The cellulosic derivatives for use as polymeric agents in the present dye bc".sfer inhibiting co,.,F~s;tions are water-soluble cellulosic derivatives which include the alkali metal salts of a ca,l,oxy lower alkyl cellulose having up to 3 25 ca,L,ons in the alkyl group, such as the sodium and pot~ssium salts of c~.Lox~meU-~lcellulose or of c~,Lo~.~U jl~e"ulose. Sodium ca,boxjmethylcellulose is p~efelled. Suitable water-soluble cellulosic derivatives also include the lower alkyl cellulose ethers, e.g., methyl cellulose and ethyl cellulose; hydroxyalkyl cellulose ethers, e.g., hydroxyethyl cellulose; cellulose 30 ethane sulfonic acid; and cellulose glycollic acid.
The amount of cellulosic derivatives used in the present detergant CGI I ,positions is prefe, ably from about 0.2% to about 8% by weight of the de~aryênt, more prèferably from about 0.3% to about 6% by weight, and most p~ferably from about 0.4% to about 4% by weight. The amount of ce"~l~sic 35 derivatives delivered in the wash solution is prefe,..bly from about 3 ppm to about - 90 ppm, more preferably from about 5 ppm to about 80 ppm, and most preferably from about 10 ppm to about 70 ppm.
As discussed above, it has su" ,isingl~ been discovered that by co",bin ~9 the polymeric agents with the dye binding polymers in certain ratios, an WO 95/033g0 2 1 6 7 3 7 2 PCT/US94/06849 unexpected improvement in dye transfer inhibition is obtained. -The ratio of polymeric agent to dye binding polymer on a ppm basis delivered in the wash solution is from about 2:1 to about 250:1. When polyvinylpyrrolidone is used as the dye binding polymer the ratio of polymeric agent to dye binding polymer on appm basis delivered in the wash solution is preferably from about 2:1 to about 50:1 more preferably from about 3:1 to about 20:1 more preferably from about 3:1 to about 10:1 and most preferably from about 4:1 to about 8:1. When polyamine N-oxide containing polymer and/or N-vinyli ,~ -!e N-vinylp~".!,done copolymer are used as the dye binding polymer the ratio of polymeric agent to o dye binding polymer on a ppm basis delivered in the wash solution is preferably from about 3:1 to about 150:1 more prefe(ably from about 3:1 to about 100:1 and most p~ferably from about 4:1 to about 75:1.
The present dye l,ansfer inhibiting co"~posi~ions are conveniently used as additives to conventional deter~ent cG",posilions for use in laundry oparations.The present invention also enco,npasses deterg-~nt composi~ions containing the dye ~ansfer inhibiting co",pGsitions along with corventional dete.~ent ingredients.
ret~rao~t l~a.~.~ s~ta A w;de range of su,ra~.lants can be used in the deteraent composilions. A
typical listing of an ~n ~ non on - a,.,pholytic and ~J i:lenon.~ classes and species of these su,faclants is given in U.S. Patent 3 664 961 issued to Norris on May 23 1972.
Mixtures of anionic s~"fa~ lar,ts are pa ticularly suitable herein especially mixtures of sulphor.~te and sulphate s~"fac~--nls in a weight ratio of from 5:1 to 1:2 pl~fe.dbly from 3:1 to 2:3 more prefe.dbly from 3:1 to 1:1. P~efe,,ed 2s sulphonates indude alkyl benzen.5 sulphonat-~s having from 9 to 15 especially 11 to 13 carbon atoms in the alkyl radical and the alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a C12-C18 fatty source p,~r~fably from a C16-C18 fatty source. In each inslanca the cation is an alkalimetal prefcl~bly sodium. F~efe"ed sulphate su,r~ ts are alkyl sulphates having from 12 to 18 carbon atoms in the alkyl radical optionally in admixture with ethoxy sulphates having from 10 to 20 pr~ferdbly 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 0.1 to 9. Examples of plefe"ed alkyl sulphates herein are tallow alkyl sulphate coconut alkyl sulphateand C14.1s alkyl sulphates. The cation in each inslance is again an alkali metal3s cation preferc-bly sodium.
One class of non.on.o surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a su,faclant having an average hydrophilic 'ipoph 'is balance (HLB) in the range from 8 to 17preferably from 9.5 to 13.5 more preferably from 10 to 12.5. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of thepolyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hycl~phobic elements Fspeci~ly preferred nonionic surfactants of this type are Cg-C1s primary alcohol ethoxylates containing 3-9 moles of ethylene oxide per mole of alcohol, particularly the C14-C1~ primary alcohols containing 6-9 moles of ethylene oxide per mole of alcohol and the Ct2-C1s primafy alcohols containing 3-9 moles of ethylene oxide per mole of alcohol.
o Another class of non ~n ~ surfactants co,npnses alkyl polyglucoside compounds of general formula RO (CnH2nO)tZx wherein Z is a moiety derived from glucose; R is a saturated h~rdl~phO~ c alkyl group that contains from 12 to 18 ca bon atoms; t is from 0 to 10 and n is 2 or 3; x IS iS from 1.3 to 4, the compounds including less than 10% u(,-,ac~ed fatty alcohoi and less than 50% short chain alkyl polygluco~idcs Compounds of this type and their use in dehrgenl are ~;scl~sed in EP-B 0,070,077, 0,075,996 and 0,094,118.
Also suitab~e as non-~n.c surfactants are polyhy~l~o,~y fatty acid amide s~-- raclant~ of the formula R2-C-N-Z, Il I
o R1 æ.-,;n R1 is H, or R1 is C14 hlJ~ca,~l, 2~hydroxy ethyl, 2-hydroxy propyl or a miA~re thereof, R2 is C~31 h~d-oca.~l, and Z is a polyhyJ~Ayhydr~
having a linear l.~d~uc~.~Jl chain with at least 3 h~J~A~I~ direct)y conne.,led to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight C11.1s alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, se, in a reductive amination reaction.
The co.-.positions according to the p-`S'G.lt inv¢ntion may fur~er cG-np.ise a builder system. Any conve-~tional builder system is suitable for use herein including aluminosilicate ",at~rials, phas~l;Jt~s, silicates, polyc~oxylales, fatty acids, materials such as ell,~lencdid.nine t~ t~-, and mebl ion seques~.a,lts such as aminopolyphosphor,ates.
Suitable builders can be an inGryan c ion e3~hang~ ,.,atenal, ~""nonl~ an i.,o~an c hydrated aluminosilicate ,naterial, more particularly a hydrated synthetic zeolite such as hydrated zeolite A~ X, 8 or HS.
Another suitable ino,yanic builder material is layered silicate, e.g., SKS-6 (~loechs~). SKS~ is a crystalline layered silicate cûn3;~ting of sodium silicate (Na2Si2os) Suitable polycarboxylate builders for use herein include nitrilotnacetate (NTA); ethylenediaminetetracetic acid (EDTA); citric acid preferably in the form of a water-soluble salt; and 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 sl ~bstihlted with hydroxyl sulfo sulfoxyl or sulfone substituents. Specific exa",rles include lauryl succinate myristyl succinate palmityl succinate 2-~odecenylsuccinate 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts including 0 sodium potassium a"""on um and alkanola"""on -~m salts.
Especially for the liquid executiQn herein suitable fatty acid builders for use herein are saturated or unsaturated C10~18 fatty acids as well as the cG"-asponding soaps. rlefelled saturated species have from 12 to 16 carbon atoms in the alkyl chain. The prere"ed unsaturated fatty acid is oleic acid.
Another plefellèd builder system for liquid cG"~positions is based on dodecen~
succinic acid.
Prërellèd builder systems for use in granular CG",pOsit;ons indude a mixture of rJTA phosphate and zeolite.
Other builder materials that can form part of the builder system for use in granular cG",pGsitions for the purposes of this invention include ino,~an-c ",atenals such as alkali metal ca,LGnates bica,L,or,dtes silicates, and organic ",dtênals such as the organic pl,Gsphor,dtes amino polyalkylene phosphonates and amino polyca,l,oxylates. Other suitable water-soluble organic salts are the homo- or co-poly.--e ic adds of their salts in which the polyca,loxylic acid 2s cG."prises at least two ca,l,oxyl radicals separted from each other by not more than two carbon atoms. roly."era of this type are d;sclosed in GB-A-1 596 756.
Examples of such salts arr~ polyacrylates of MW 2000-5000 and their copolyme.a with maleic anhydride, such copoly",e. a having a ",o eou'-~ weight of from 20 000 to 70 000 especially about 40 000.
Builder~ are normally included in amounts of from about 10% to about 30%
by weight of the d&ter~ent CG",FCS tion p~eferably from about 20% to 70% and more prèfe,ably from about 30% to about 60%.
Other cG",ponenls used in d-~tergent cGIIlpGsitions may be employed such as suds booating or dep~esaing agents er,~."es such as proteases amylases or lipases e"~."e stabilizers or activators bleaching agents soil-suspending agents soil-release agents fabric softening agents optical bright~nera abrasivesbaclcri~d;~s tamish inhibitors c~, ~ ring agents and perfumes. Especially pr~fei,ed are comb.nations v~rith enzyme technologies which also provide a type of color care benefit for example cellulase for color maintenance/rejuver,alion.
WO 95/033g0 2 1 6 7 3 7 2 PCT~Sg4l0684g The detergent compositions according to the invention can be in liquid gel paste or granular forms. Granular compositions will generally have a density from about 300 9/l to about 900 9/l. "Compact" granular detergents can have a relatively higher density than conventional granular detergents; in such case the 5 detergent compositions will contain a lower amount of "inorganic filler salt" (e.g.
sodium sulfate) compared to conventional granular detergents typically not more than 20% filler salt.
The present invention also reiates to a process for inhibiting dye t,ansfer from one fabric to another of solubilized and suspended dyes encountered during o fabric laundanng opeldtions involving colored fabrics. The process co",pnses contacling fabrics with a laundenng solution containing the dye t~anster inhibiting cG",position of this invention. The process of the invention is conven enlly carried out in the course of the washing p,ucess. The washing process is prefeidbly carried out at 1C to 90C especially 5C to 60C. The pH of the ~edtl"en~
15 solution is ~referably from about 7 to about 12 especially from about 8 to abou~
11.
The following examples are meant h exemplify cGIllpGsitions of the presen~ invenbon but are not necess-~-ily meant to limit or oU,rrv,is~ define the scope of the invention said SCOpQ being determined according to claims which 20 follow.
E~a,.."le 1 A granular laundry de~ergent co",pesition of the p,..sent invention is as s:
Inaredient: Weioht r~ t Crutched Sodium C1~ ~ linear alkylL,anzene sulfonate 12.2%
Sodium C1~1~ alkyl sulfate 12.2%
Tetrasodium p~.oph~ sphat-~ 7.2%
Nitrilv0iace-~t.~s (active) 19.5%
Sodium ca~L~onJta 13 0%
Sodium silicate solids 6.1%
Optical Dr;~l ,tonar 0. 1 %
Zeolites (active) 4.7%
35 De-Dust Condensation product of C12 C13 linear alcohol with 6.5 moles 0.8%
ethylene oxide Dry-Adds Polyvinylpyrrolidone 0 5%
Polyethylene glycol 3 9%
Protease enzyme 0. 1 %
Perfume o 5%
S Zeolites (active) 1.2%
Cellulase enzyme 0 9%
The "cnutched" ingredients are mixed together with water in a crutcher to forrn a paste. This mixture is then spray dried to evapG,~le the excess moisture and form deteryenl granules. Then the de-dust is sprayed onto the granules. The "dry-add"10 ingredients are then ad",ixed to form the finished granular dete,yrn~ cGIllpGsiUon.
This co",position delivers in the wash solution about 37 ppm polyethylene glycol and about 5.1 ppm polyvinylpyrrolidone (a ratio of about 7.5:1 PEG:PVP).
The pH of a 1% aqueo~Js solution of the deter~enl co",position is 11.
ExamPle 2 The fo"~ing exa",r'e illustrates the invention and facilitates its unders~anding.
1. In a Miniwasher pot of 2 U.S. gallons of 35C water 61 grams of delergent are added. The mixture is agitated for 1 minute.
2. The dye source is added under agi~tion and allowed to mix for 1 minute.
20 3. A total of twelve tracer swatches are added to the Miniwasher pot and washed for 10 minutes. These swatches had previously been balanced by Hunter Colorimeter L,a b values so that all swatches of a specific type were starting unifommly for each ~at",en~
4. After the wash cyde is complete the tracer swatches are rinsed in cold water (7C).
. Steps 1-5 are r~pe~1-d seven Umes for a total of 8 wash cycles using a new measu,~..,Ent of dete.~ent a new dye source and the same 12 tracer swatches for each wash cycle.
6. After wash cycle number 1 4 and 8 the tracer swatches are dried for 1 hour and then L a b readings are taken on the Hunterlab C~!cri",eter and a delta E (dE) at that cycle is calculated.
DYe Source C46 Brown Swatch - 3 swatches of 2.5" x 2.5" square are added per pot per cycle.
35 Tracer Swatches 4 - 86% Conon/15% Polye:tcr Terry (loop yam is 100% Cotton) 4-100% Cotton Denim ~ 2 4 - 100% Cotton Interlock T-shirt Condition 8 grains per gallon water hardness 35C wash water temperature 5 7C rinse water temperature Miniwasher of 2 U.S. gallon capacity Results The f~l'ow;ng bble shows that when the PVP level is cut by approximately 25% in conjunction with the PEG level being increased by nine times, subslantialo dye t(ar,s~er inhibition is acl-:eved. Lower delta E (dE) readings represent less color change from the original fabric color.
Cl,an e ir dE on Terry Fabric T-e ~.. ent PEG 8000 PVP K-15 PEG-PVP dE
Ratio CYcle 1 CYCI~ 4 Cycle 8 A 5.1ppm 11.75ppm 1:2.3 1.63 7.06 11.52 B 46ppm 8.82ppm 5.2:1 0.81 1.51 3.14 As a result, it app;~a,~ that PEG:PVP ratios dominated by higher PEG amounts deliver more dye t,ansrer inhibition.
Fxa.-,-~le 3 The granular laundry detergent cG-"position of the present invenUon is made as described in Example 1, except that 3.9% sodium carboxymethylcellulose is used instead of 3.9% polyell ,ylene glycol as the poly..,eric agent.
. Steps 1-5 are r~pe~1-d seven Umes for a total of 8 wash cycles using a new measu,~..,Ent of dete.~ent a new dye source and the same 12 tracer swatches for each wash cycle.
6. After wash cycle number 1 4 and 8 the tracer swatches are dried for 1 hour and then L a b readings are taken on the Hunterlab C~!cri",eter and a delta E (dE) at that cycle is calculated.
DYe Source C46 Brown Swatch - 3 swatches of 2.5" x 2.5" square are added per pot per cycle.
35 Tracer Swatches 4 - 86% Conon/15% Polye:tcr Terry (loop yam is 100% Cotton) 4-100% Cotton Denim ~ 2 4 - 100% Cotton Interlock T-shirt Condition 8 grains per gallon water hardness 35C wash water temperature 5 7C rinse water temperature Miniwasher of 2 U.S. gallon capacity Results The f~l'ow;ng bble shows that when the PVP level is cut by approximately 25% in conjunction with the PEG level being increased by nine times, subslantialo dye t(ar,s~er inhibition is acl-:eved. Lower delta E (dE) readings represent less color change from the original fabric color.
Cl,an e ir dE on Terry Fabric T-e ~.. ent PEG 8000 PVP K-15 PEG-PVP dE
Ratio CYcle 1 CYCI~ 4 Cycle 8 A 5.1ppm 11.75ppm 1:2.3 1.63 7.06 11.52 B 46ppm 8.82ppm 5.2:1 0.81 1.51 3.14 As a result, it app;~a,~ that PEG:PVP ratios dominated by higher PEG amounts deliver more dye t,ansrer inhibition.
Fxa.-,-~le 3 The granular laundry detergent cG-"position of the present invenUon is made as described in Example 1, except that 3.9% sodium carboxymethylcellulose is used instead of 3.9% polyell ,ylene glycol as the poly..,eric agent.
Claims (10)
1. A dye transfer inhibiting composition comprising: (a) dye binding polymers selected from polyvinylpyrrolidone polyamine N-oxide containing polymer, N-vinylimidazole N-vinylpyrrolidone copolymer and mixtures thereof; and (b) polymeric agents selected from alkoxy containing polymers, cellulosic derivatives and mixtures thereof; wherein the ratio of polymeric agent to dye binding polymer on a ppm basis delivered in the wash solution is from 2:1 to 250:1.
2. A dye transfer inhibiting composition according to Claim 1 wherein the polymeric agent is selected from the group consisting of polyethylene glycol carboxymethylcellulose and mixtures thereof.
3. A dye transfer inhibiting composition according to Claim 1 wherein the dye binding polymer is polyvinylpyrrolidone and wherein the ratio of polymeric agent to dye binding polymer on a ppm basis delivered in the wash solution is from 2:1 to 50:1.
4. A dye transfer inhibiting composition according to Claim 1 wherein the dye binding polymer is selected from the group consisting of polyamine N-oxide containing polymers N-vinylimidazole N-vinylpyrrolidone copolymers, and mixtures thereof and wherein the ratio of polymeric agent to dye binding polymer on a ppm basis delivered in the wash solution is from 3:1 to 150:1.
5. A detergent composition which comprises a dye transfer inhibiting composition according to Claim 1 and which further comprises surfactants, builders and other conventional detergent ingredients; wherein the amount of dye binding polymer in the detergent composition is from 0.01% to 10% by weight and the amount of polymeric agent in the detergent composition is from 0.1% to 15% by weight; and wherein the amount of dye binding polymer delivered in the wash solution is from 0.01 ppm to 120 ppm and the amount of polymeric agent delivered in the wash solution is from 1 ppm to 100 ppm.
6. A detergent composition according to Claim 5 wherein the amount of polymeric agent in the detergent composition is from 0.2% to 8% by weight and the amount of polymeric agent delivered in the wash solution is from 3 ppm to 90 ppm.
7. A detergent composition according to Claim 5 wherein the dye binding polymer is polyvinylpyrrolidone the amount of dye binding polymer in the detergent composition is from 0.001% to 5% by weight and the amount of dye binding polymer delivered in the wash solution is from 0.1 ppm to 75 ppm.
8. A detergent composition according to Claim 5 wherein the dye binding polymer is selected from the group consisting of polyamine N-oxide containing polymers, N-vinylimidazole N-vinylpyrrolidone copolymers, and mixtures thereof, the amount of dye binding polymer in the detergent composition is from 0.005% to 5% by weight, and the amount of dye binding polymer delivered in the wash solution is from 0.01 ppm to 30 ppm.
9. A dye transfer inhibiting composition according to Claim 1 wherein the polyamine N-oxide containing polymer contains units having the following structural formula:
wherein P is a polymerisable unit, whereto the R-N-O group can be attached or wherein the R-N-O group forms part of the polymerisable unit or a combination of both;
wherein A is NC, CO, C, -O-, -S-, or-N-; x is 0 or 1; and wherein R are aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups or any combination 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.
wherein P is a polymerisable unit, whereto the R-N-O group can be attached or wherein the R-N-O group forms part of the polymerisable unit or a combination of both;
wherein A is NC, CO, C, -O-, -S-, or-N-; x is 0 or 1; and wherein R are aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups or any combination 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.
10. A dye transfer inhibiting composition according to Claim 1 wherein the N-vinylimidazole N-vinylpyrrolidone copolymer has an average molecular weight from 5,000 to1,000,000.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US9441893A | 1993-07-19 | 1993-07-19 | |
| US094,418 | 1993-07-19 | ||
| US25012894A | 1994-06-03 | 1994-06-03 | |
| US250,128 | 1994-06-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2167372A1 true CA2167372A1 (en) | 1995-02-02 |
Family
ID=26788848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2167372 Abandoned CA2167372A1 (en) | 1993-07-19 | 1994-06-16 | Detergent compositions inhibiting dye transfer in washing |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0710275A1 (en) |
| JP (1) | JPH09500673A (en) |
| AU (1) | AU7247294A (en) |
| BR (1) | BR9407130A (en) |
| CA (1) | CA2167372A1 (en) |
| WO (1) | WO1995003390A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69706715T2 (en) | 1996-01-25 | 2002-05-29 | Unilever Nv | detergent composition |
| DE69710749T2 (en) * | 1996-10-18 | 2002-11-14 | Procter & Gamble | DETERGENT COMPOSITIONS |
| US5880081A (en) * | 1997-04-07 | 1999-03-09 | Gopalkrishnan; Sridhar | Concentrated built liquid detergents containing a dye-transfer inhibiting additive |
| US6794355B1 (en) * | 1998-11-02 | 2004-09-21 | The Procter & Gamble Company | Fabric care composition having reduced fabric abrasion |
| US6191098B1 (en) | 1999-04-28 | 2001-02-20 | National Starch And Chemical Investment Holding Corporation | Polyvinylpyridinium derivatives as anti-dye transfer agents |
| USRE39450E1 (en) * | 1999-04-28 | 2006-12-26 | National Starch And Chemical Investment Holding Co | Polyvinylpyrridinium derivatives as anti-dye transfer agents |
| US6306815B1 (en) | 1999-09-10 | 2001-10-23 | National Starch And Chemical Investment Holding Corporation | Quaternary polyvinylpyrridinium derivatives as anti-dye transfer agents |
| US6887524B2 (en) * | 2000-10-13 | 2005-05-03 | The Procter & Gamble Company | Method for manufacturing laundry additive article |
| US7256166B2 (en) | 2002-01-18 | 2007-08-14 | The Procter & Gamble Company | Laundry articles |
| GB0229147D0 (en) | 2002-12-13 | 2003-01-15 | Unilever Plc | Polymers and laundry detergent compositions containing them |
| GB0229146D0 (en) | 2002-12-13 | 2003-01-15 | Unilever Plc | Polymers and laundry detergent compositions containing them |
| DE102012212727A1 (en) * | 2012-07-19 | 2014-01-23 | Henkel Ag & Co. Kgaa | Liquid detergent with improved color transfer inhibition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3318816A (en) * | 1964-11-12 | 1967-05-09 | Colgate Palmolive Co | Detergent composition in solid form containing a synergistic mixture of cmc and pvp |
| SE459972B (en) * | 1983-03-29 | 1989-08-28 | Colgate Palmolive Co | DIRTY REFERENCE PARTICULAR DETERGENT COMPOSITION CONTAINING A DIRT-REFERENCE POLYMER, PROCEDURE FOR ITS PREPARATION AND ITS USE OF WASHING OF SYNTHETIC ORGANIC POLYMER FIBERIAL |
| DE3519012A1 (en) * | 1985-05-25 | 1986-11-27 | Henkel KGaA, 4000 Düsseldorf | DETERGENT WITH ADDITIVES TO PREVENT DYE AND BRIGHTENER TRANSFER |
| GB8618635D0 (en) * | 1986-07-30 | 1986-09-10 | Unilever Plc | Detergent composition |
| EP0508034B1 (en) * | 1991-04-12 | 1996-02-28 | The Procter & Gamble Company | Compact detergent composition containing polyvinylpyrrolidone |
| EP0537381B1 (en) * | 1991-10-14 | 1998-03-25 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer in washing |
| EP0581753B1 (en) * | 1992-07-15 | 1998-12-09 | The Procter & Gamble Company | Dye transfer inhibiting compositions comprising polymeric dispersing agents |
-
1994
- 1994-06-16 CA CA 2167372 patent/CA2167372A1/en not_active Abandoned
- 1994-06-16 WO PCT/US1994/006849 patent/WO1995003390A1/en not_active Application Discontinuation
- 1994-06-16 AU AU72472/94A patent/AU7247294A/en not_active Abandoned
- 1994-06-16 EP EP94921967A patent/EP0710275A1/en not_active Withdrawn
- 1994-06-16 BR BR9407130A patent/BR9407130A/en not_active Application Discontinuation
- 1994-06-16 JP JP7505137A patent/JPH09500673A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0710275A1 (en) | 1996-05-08 |
| AU7247294A (en) | 1995-02-20 |
| WO1995003390A1 (en) | 1995-02-02 |
| JPH09500673A (en) | 1997-01-21 |
| BR9407130A (en) | 1996-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5466802A (en) | Detergent compositions which provide dye transfer inhibition benefits | |
| CA1102202A (en) | Granular detergent compositions for improved greasy soil removal | |
| CA1239602A (en) | Detergent composition | |
| AU661672B2 (en) | Detergent compositions containing lipase and water-soluble quaternary ammonium compounds | |
| AU663084B2 (en) | Compact detergent composition containing polyvinylpyrrolidone | |
| CA1231206A (en) | Fabric cleaning/conditioning compositions | |
| CA1152263A (en) | Detergent-compatible fabric softening and antistatic compositions | |
| EP1735418B1 (en) | Softening laundry detergent | |
| CA2167372A1 (en) | Detergent compositions inhibiting dye transfer in washing | |
| WO1992018597A1 (en) | Compact detergent composition containing polyvinylpyrrolidone | |
| US3876563A (en) | Liquid detergent compositions | |
| CZ20496A3 (en) | Detergents inhibiting transfer of dyestuff | |
| WO1995002673A1 (en) | LOW pH GRANULAR DETERGENT COMPOSITION HAVING IMPROVED BIODEGRADABILITY | |
| US5843192A (en) | Washing composition and use of polymer to clean and provide soil resistance to an article | |
| AU9379498A (en) | Water soluble dye complexing polymers as dye transfer inhibitors in laundry detergent and fabric softener compositions | |
| US6207633B1 (en) | Granular detergent composition containing an optimum surfactant system for cold temperature laundering | |
| CA2164821A1 (en) | Granular detergent compositions containing selected builders in optimum ratios | |
| CA1223105A (en) | Fabric softeners | |
| JPH07505670A (en) | Applications of modified polyester for cleaning cotton-containing fabrics | |
| NZ243130A (en) | Preparation of free-flowing spray-dried particulate detergent by | |
| EP0594893B1 (en) | Detergent compositions inhibiting dye transfer | |
| US6194374B1 (en) | Biodegradable fabric softening compositions based on a combination of pentaerythritol esters, bentonite and a polyphosphonate compound | |
| US5597795A (en) | Detergent compositions inhibiting dye transfer | |
| JP2003522284A (en) | Laundry detergent composition having a combination of a cyclic amine polymer and a dye adhesion inhibitor | |
| EP1115823B1 (en) | Fabric softening compositions containing pentaerythritol esters, bentonite and polyphosphonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Dead |