CA2127096C

CA2127096C - Detergent compositions inhibiting dye transfer containing a catalyst, amine stabilizer and peroxide generating enzyme

Info

Publication number: CA2127096C
Application number: CA 2127096
Authority: CA
Inventors: Christiaan Arthur J. K. Thoen; Adbennaceur Fredj; Regine Labeque
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1992-01-31
Filing date: 1993-01-22
Publication date: 1998-04-14
Anticipated expiration: 2013-01-22
Also published as: CA2127096A1; MX9300514A; EP0553608A1; JPH07503278A; EP0553608B1; CN1075502A; AU4862693A; PH30907A; TR26405A

Abstract

Dye transfer inhibiting compositions are disclosed, comprising: A) a metallo catalyst selected from a) metallo porphin and water-soluble or water-dispersable derivatives thereof; b) metallo porphyrin and water-soluble or water-dispersable derivatives thereof; c) metallo phthalocyanine and water-soluble or water-dispersable derivatives thereof; B) an amine base catalyst stabilizer capable of binding to the 5th ligand of the metallo catalyst; C) an enzymatic system capable of generating hydrogen peroxide.

Description

~i~93~15176 PCT/US93/~626 ~clt~GtNT COMPOSITIONS INHIBITIN6 DYE TRANSFER CONTAININ6 A CATALYST, AMINE STABILIZER AND PF~O~I~F 6ENERATIN6 ENZYME

.

.

F;~ld~of the Tnvention .
Ti~e ~ ent il-~e~.Lion relates to a composition and a process -~
for ir~hibiting dye transfer between fabrics during wa~ki~
: ~ , ,~ ' .
Bac~Loul-d of the Invention One of the most persistent and troublesome problems arising during modern fabric laundering operations is the ten~ency of ~ome colored fabrics to release dye into the laundering solutions. The dye is then transferred on~o other fabrics being washed therewith.

one way of overcoming this problem would be to bleach the fugitive dyes'washed out of dyed fabrics before they have the opportunity to become at~ch~ to other articles in the wash.

S~ r-nA~d or solubilized dyes can to some degree be ~ i 7 ~; in solution by employing known bleaching agents.

og3/15176 ~ 12~ 09 6 PCT/US93/~626-~

GB 2 101 167 describes a stable liquid bleaching compositioncontaining a hydrogen peroxide precursor which is activated to yield hydrogen peroxide on dil:tion.

However it is important at ~hè same time not to bleach the dyes actually remaining on thè fabrics, that is, not to cause color damage.

U.S. Patent 4,077,768 describes a process for inhibiting dye transfer by the use of an oxidizing bleaching agent together with a catalytic compound such as iron porphinc.

Cop~ndi~g EP Patent Application 91202655.6 filed October 9, 991, relates to dye transfer i~hihiting compositions ~-comprising an enzymatic system c~p~hle of generating hydrogen peroYi~ and ~GL~hin catalysts.

It has now been found that certain amine base catalys stabilizers when added to said enzymatic dye transfer i ~ i h~ting compositions enhances the overall performance of said compositions.~
The addition of said catalyst stabilizers re~ the rate of s-If-de_L ction of the porphin catalyst ~ ting in im~rovel through-th~ St ~h, stability of the porphin catalyst.
Also, imp.~ved whiteness benefits are obt~inP~ in the presence of catalyst stabilizers, due to a substantial reduction in the amount of porphin catalyst deposited onto the fabrics.
Furthermore, it has been found that said catalyst stabilizers -~
accelerate the oxidation reactivity of the ~oL~hin catalyst thereby încreasing the rate of the dye bleaching. ' '' Accor~in11y, a dye transfer i nh ~ hiting composition is provided which exhibits optimum dye transfer inhibiting properties.
~ , -R~ot~ing to another embodiment, the invention provides an efficient p~o~e for laundering operations involving colored fabrics.

: . .

'~ ~ g3/lsl76 2 1 2 7 0 9 6 PCT/USg3/~K26 Summarv of the Invention The present invention relates to inhibiting dye transfer compositions comprising :
A. a metallo catalyst selected from a) metallo porphin and water-soluble or water-~i~r~rsable derivatives thereof;
b) metallo ~oL~hy~in and water-soluble or water-Ai~r~rsable derivatives thereof;
c) metallo phthalocyanine and water-soluble or water-~isrersable derivativas thereof;

~, 8~. an amine base catalyst stabilizer capable of bin~in~ to the 5th ligand of the metallo catàlyst.

C. an enzymatic system c~pAhle of generating hyd~o~en peroxide. ' ~ -c~ing to another embodiment of this invention a ~c ~r-is also provided for laundering operations involving colored fabrics. ~;

Detail~ de~cription of the invention The present invention provides a dye transfer inhibiting composition comprising :
A. a metallo catalyst selected from a) metallo porphin and water-soluble or watex~
Ai ~r rsable derivatives thereof;
b) metallo porphyrin and water-soluble or water-~isr~rsable derivatives thereof;
c) metallo phthalocyanine and water-soluble or water-dispersable derivatives thereof;
.
B. an amin- base catalyst stabilizer rAp~hle of binAin~ to the Sth ligand of the metallo catalyst.

C. an enzymatic system cAp~hle of qenerating hydrogen peroxide.

wo 93/lsli6 o 9 6 pcr/us93~oo62~r The Hvdroqen Peroxide Precursor The oxidizing agent, hydrogen peroxide is generated in situ by usinq an enzymatic hydrogen peroxide generation system.

The use of an enzymatic hydrogen peroxide generating system allows the continuous generation of low levels of hyd~Gyen peroxide and provides a practical way of controlling a low steady-state level of hyd~o~en peroxide. Maximum effectiveness occurs when the component levels are such that the hydrogen peroxide is repl~ni~ at a rate similar to its removal due to the oxidation of dyes in the wash water. ~;
The enzyme used~in the ~ ent invention is an ox~ e.
The oxidase is y~-?nt by 0.1 - 20000 units, preferably 0.5 to 5000 units per gram of the composition. One unit is the amount of enzyme needed to convert 1 mol of substrate per minute.
Suitable QYi ~ are urate oxidase, galactose oxidase, alcohol QXi ~ 5 ~ amine oYi~es, amino acid oxi~A~e.c, cholesterol oY~ e and glucose oxidase, malate oxidase, glycollate QYi A-~? ~ hexose oxidase, aryl alcohol oxidase, L~
gulonolactose oxi~a~o~ pyranose oxidase, L ~or~o~e ~x~ e, pyri~oYine 4-oxidase, 2-2 hydlo~acid c oYi~rq, choline nxi~a~e, ecdysone oxi~e.

The preferred enzymatic systems are alcohol and aldehyde QYi ~ses, gl~cQc~ oxidase.
The more preferred systems for granular detergent application would have solid alcohols, e.g. glucose whose oxidation is catalysed by glu-:-? oxidase to glucoronic acid with the formation of hydLG~ peroxide.
The more preferred systems for liquid detergent application would involve liquid alcohols which could for example, also act as solvents. An example is ethanol/ethanol oxidase.
The quantity of oxidase to be employed in compositions according to the ill~e--~ion should be at least sufficient to provide in the wash a constant generation of 0.005 to 10 ppm AvO per minute. For example, with the glucose oxidase , this can be achieved at room temperature and at pH 6 to 11, preferentially 7 to 9 with 1-20000 U/l gl~co~e oxidase, 0.00s wo g3/lsl76 2 1 2 7 0 9 6 PCT/USg~/ ~ 26 s to o.s % giucose under constant aeration in the washing process.

Metallo catalvst The preferred usage range of the .catalyst in the wash is 10-8 molar to 10-3 molar, more preferred 10-6 - 10-4 molar.
The e~?ntial metallo porphin structure may be visualized as indicated in Formula I in the accompanying drawings. In Formula I the atom positions of the porphin structure are numbered conventionally and the double bonds are put in conventionally. In other formula, the double bonds have been ~ :
omitted in the dr~wings, but are actu~lly ~ nt a8 in I.
' Prefersed metallo porphin stru~u~e_ are ~o~e substituted at one or more of the 5, 10, 15 and 20 carbon positions of Formula I (Meso posîtions), with a ~he..~l or pyridyl substituent .selected from the group consisting of .
_0)~-O~

wh-rein n and m may be O or l; A may be sulfate, sulfonate, phosphate or c~rh~ylate groups; and B is Cl-C10 alkyl, polyethoxy alkyl or hydroxy alkyl.

Preferred molecules are those in which the substituents on -the phenyl or pyridyl ~LGu~s are selected from the ~ou~ :
consisting of -CH3, -C2Hs, -CH2CH2CH2S03-, -CH2--, and -CH2CH(OH)CH2S03-, -so3 A particularly preferred metallo phorphin is one in which the molecule is substituted at the 5, 10 15, and 20 carbon ':
positions with the substituent ~\S03~ ' ":

W093/15176 PCT/US93/~626 2~2~ o 9 6 6 - This preferred compound is known as metallo tetrasulfonated tetraphenylporphin. The symbol xl is (=cY-) wherein each Y, independently, is hydrogen, chlorine, bromine or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl. .

The symbol x2 of Formula I represents an anion, preferably OH- or Cl-. The com~oul.d of Formula I may be substituted at one or more of the remaining carbon positions with Cl-ClO
alkyl, hy~loxyalkyl or oxyalkyl ~lOU~

l7 lS~ / S
13 ~ (I) Porphin derivatives also include chlorophyls, chlorines, i.e. '~-~
isobacterio chlorines and bacteriochlorines.
Metallo ~o.~hylin and water-soluble or water-dispersable derivatives thereof have a structure given in formula II.

X~X
~2 ~ ~

x X ~ (II) where X can be alkyl, alkyl carboxy, alkyl hydroxyl, vinyl, alkenyl, alkyl sulfate, alkylsulfonate, sulfate, sulfonate, aryl.

The symbol x2 of Formula II represents an anion, preferably OH- or Cl-.
The symbol X can be alkyl, alkylcarboxy, alkylhydroxyl, vinyl, Alkenyl, alkylsulfate, alkylsulfonate, sulfate, sulfonate.

WO g3/15176 2 1 2 7 0 9 6 PCT/US93/~K26 Metallo phthalocyanine and derivatives have the structure indicated in Formula III, wherein the atom positions of the phthalocyanine structure are numbered conventionally. The anionic groups in the above structures contain cations selected from the ~LoU~ consisting of sodium and potassium cations or other non-interfering cations which leave the structures water-soluble. Preferred phthalocyAni r.e derivatives are metallo phthalocyAnine trisulfonate and metallo phthalocyanine tetrasulfonate.

p~5 ~15 ~ (III) Another form of substitution possible for the present h.~e..~ion is sukstitution of the central metal by Fe, Mn, Co Rh, Cr, Ru, Mo or other transition metals.

Still a number of considerations are significant in selecting variants of or substituents in the basic porphin or azaporphin structure. In the first place, one would choo~e com~ou,.ds which are available or can be readily synthesized.
' ~ y~..d this, the choice of the substituent groups can be used to control the solubility of the catalyst in water or in detergent solutions. Yet again, especially where it is desired to avoid attacking dyes attached to solid surfaces, the substituents can control the affinity of the catalyst compound for the surface. Thus, strongly negatively charged substituted compounds, for instance the tetrasulfonated porphin, may be -repelled by nçgatively charged stains or stained surfaces and are therefore most likely not to cause attack on fixed dyes, whereas the cationic or zwitterionic compounds may be -WO g3/15176 PCr/US93/00626 2l2 7og6 attracted to, or at least not repelled by such stained surfaces.

Amine base catalYst stabilizer The dye transfer inhibiting benefits can be optimized by adding small amounts of catalyst stabilizers.
It is well known in art that catalyst e.g. metallo porphins are ~;
~ certible to self-destruction. As a result of said selfdestruction, the level of catalyst sh4~lld be such that sufficient active catalyst is present to bleach the dyes ~~ ~
throughout the total wash cycle. ~' It has now been found that the stability of metallo catalyst used in the pL~ -ent invention is i~ ved by A~Ain~ amine base catalyst stabilizers carAhle of bin~in~ the 5th ligand of the central atom in the metallo porphin structure. Preferred hete~G~lic compounds suitable for the present invention are imidazole compounds of the formula :

RiC - CH-X-R2 -.

N N-Y

Rl wherein Y is hydrogen or oxygen or a Cl-C12 alkyl, Ri, Rl and R2 are selected inA~penAently hydrogen or Cl-C30 alkyl or alkenyl ~LOu~_~ and X is selected from the group of :

~ I ~I ,.

R4 ~

R3 ~ C

O

, .:

- WO g3/15176 2 1 2 7 0 9 6 PCT/US931~K26 ~3 R3 ~ ~
wherein R3 is a Cl-C5 alkanediyl group, or is ~ ;

(CH CH2 ~)n (CH2 CH2)~
"' ~ '- . ' ' ~with n~being an integer from O to 10, and m is an integer from -.
O~to 2~ n+m>1, and R4 being a Cl_4 alkyl group or hy~ en. ;
Xost~preferred are im~ ole derivatives incl~in~ histidine, purines,~ hiroYanthine, i-idazolidica-Lo~lic acid, histamine, polyhistidine~, alkylated imidazole.

Other hete-o~lic compounds suitable for the p-~-ent invention are pyridine and alkylated pyri~in~~ and derivatives thereof, pyrole and derivatives thereof.

~ Non hete~o~y~lic com~o~ s capable of binAing the 5th ligand of the central atom in the porphin structure are suitable for the present invention.

These non heterocyclic comro~n~C include non heteLG~olic amines, having the formula (C2Hs)3N, C3H7NH2, (C6Hll)2NH, 1,5 -diazabicyclot4.3.0]non-5-ene.
' ~eoon~, the catalyst stabilizers of the present invention r~ e the deposition of the porphin catalyst onto the fabric, resulting ' better whi~enQr~ main~nAnc~ of white fabrics.
Also, it has been found that the addition of the catalyst stabilizers mentioned hereinabove not only ~ ts in less '~
self-deJtruction of the structure but also L~-ults in less ---~
~d-position of oxi~i7ed or non oxidized ~o~hin. ~ '-': ' WOg3/15176 PCT/US93/~626~
2~ og6 10 ~ Furthermore, it has been found that the rate of dye oxidation by the porphin catalyst is greatly enhanced by the presence of the said catalyst stabilizers. This results in an increased dye bleaching.
The amine base catalyst stabili~er is present in a molar ratio of iron porphin to amine base catalyst from 1:1 to 1:5000, preferably from 1:1 to 1:2500.

The p~.-ent compositions are conveniently used as additives to conventional detergent compositions for use in laundry operations.
The present invention also encompA~er dye transfer inhibiting compositions which will contain detergent i..~Lelients and thus serve as detergent compositions.
~ . .
;K~;r. ~ ING~ TF~JTS

A wide range of surfactants can be used in the detergent compositions. A typical listinq of anionic, nonionic, ampholytic and zwitterionic cl~c~~c, and species of these surfactants, is given in US Patent 3,664,961 i~ to Norris on May 23, 1972.

Mixtures of anionic surfactants are particularly suitable herein, especially mixtures of sulphonate and sulphate surfactants in a weight ratio of from 5:1 to 1:2, preferably from 3:1 to 2:3, more preferably from 3:1 to 1:1. Preferred sulphonates include alkyl benzene sulphonates having from 9 to 15, e~p~cially 11 to 13 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a C12-C18 fatty source preferably from a C16-Clg fatty source. In each instance the cation is an alkali metal, preferably sodium. Preferred sulphate surfactants 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, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6. Examples of -preferred alkyl sulphates herein are tallow alkyl sulphate, ~

WO93/15176 2 1 2 7 0 9 6 PCT/US93/~626 coconut alkyl sulphate, and cl4_15 alkyl sulphates. The cation in each instance is again an alkali metal cation, preferably sodium.
One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lirorhilic h~l~nce (HLB) in the range from 8 to 17, preferably 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 the polyoxyethylene ~c~p which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired d~.ee of balance between hydrophilic and hy~o~ ~ic elements.
'~cr~cially preferred nonionic surfactants of this type are the Cg-Cls primary alcohol ethoxylates cont~ining 3-8 moles of ethylene oxide per mole of alcohol, particularly the C14-C15 primary alcohols contAining 6-8 moles of ethylene oxide per mole of alcohol and the C12-C14 primary alcohols con~inin~ 3-5 moles of ethylene oxide per mole of alcohol.

Another cl A~C of nonionic surfactants comprises alkyl polyglucoside compounds of general formula RO (CnH2nO)tzx wherein Z is a moiety derived from glucose, R is a saturated hydrophobic alkyl group that contains fr~m 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the com~o~ C including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
Also suitable as nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula R2 _ C - N - Z, ~: ' O Rl ' WO93/15176 PCT/US93/~626 2127 Og6 12 wherein Rl is H, or R1 is Cl_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5_31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a - linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, Rl is methyl, R2 is a straight Cll_l5 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as gl~o~e, fructose, maltose, lactose, in a reductive amination reaction.

The compositions accordinq to the p~~ent invention may further comprise a builder system. Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethyle,~ amine tetraacetate, metal ion sequestrants such as aminopolyphocrhonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethyleneph~ OI~ic acid. Tho~h less preferred for obvious environmental reasons, phQ~r~te builders can also be used herein.
Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.
Another suitable inorganic builder material is layered silicate, e.g. SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si205).
Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R-CH(COOH)CH2(COOH) wherein R is C10-20 alkyl or alkenyl, preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents. Specific examples include lauryl succinate , myristyl succinate, palmityl succinate2-~o~ecenylsuccinate, 2-tetradecenyl succinate. Succinate - -builders are preferably used in the form of their water-soluble ~

~ .

WO93/15176 2 1 2 7 0 9 ~ PCT/US93/~K26 salts, including sodium, potassium, ammonium and alkanolammonium salts.
Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
Especially for the liquid execution herein, suitable fatty acid builders for use herein are saturated or unsaturated C10-18 fatty acids, as well as the COL~_POnA; ng soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid.
Another preferred builder system for liquid compositions is - h~ on ~o~cçnyl s~ccinic acid.
- Preferred builder systems for use in granular compositions include a mix~e of a water-insoluble aluminosilicate builder such as zeolite A, and a watersoluble carboxylate chelating agent such as citric acid.
Other buildèr materials that can form part of the builder -~
system for use in grannl~r compositions for the pu~ ee of this invention include inorganic materials such as ~ i metal carbonates, birarbo~-tes, silicates, and organic materials such ~-~
as the organic ph-sr~onates, amino polyalkylene phosphonates and amino polyca~Loxylates.
Other suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polyca~o~ylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756.
Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
Detergency builder salts are normally included in amounts of from 10% to 80% by weight of the composition preferably from 20% to 70% and most ~ lly from 30% to 60% by weight.
The compositions of the pL~ -ent i--v~ ion ~ho~ld be free from ~G.Ivention~l bleaching agents. Other components used in detergent compositions may be employed, such as suds ~OG_ Ling or depressing agents, enzymes and .
:

WO93/15176 PCT/US93/~626~
2~ o96 14 stabilizers or activators therefore, soil-suspending aqents soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and perfumes. Especially preferred are combinations with enzyme technologies which also provide a type of color care benefit. Examples are cellulase for color maintenance/ rejuvenation.
These components, particularly the enzymes, optical brighteners, coloring agents, and perfumes, should preferably be cho~~n such that they are compatible with the bleach component of the composition.

The detergent compositions according to the invention can be in liquid, paste or granular forms. Granular compositions according to the present invention can also be in "compact form", i.e. they may have a relatively higher density than cG..ventional granular detergents, i.e. from 550 to 950 g/l; in such case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt", compared to conventional granula~r detergents; typical filler salts are A~ ine earth metal salts of sulphates and chlorides, typically sodium sulphate; "compact"
detergents typically comprise not more than 10% filler salt.
The present invention also ralates to a process for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics.
The process comprises contacting fabrics with a laundering solution as hereinbefore described.
The process of the invention is conveniently carried out in the course of the washing process. The washing process is preferably carried out at 5-C to 90-C, especially 20 to 60, but the catalysts are effective at up to 95-C. The pH of the treatment solution is preferably from 7 to 11, especially from ~"
7.0 to g.o. ~

~og3/lsl76 2 1 2 7 0 9 ~ PCT/US93/~K26 The process and compositions of the invention can also be used as additive during laundry operations.

The following examples are meant to exemplify compositions of the present invention, but are not n~cecQ~rily meant to limit or otherwise define the scope of the invention, said scope being determined according to claims which follow.

EXUIID1~ 1 ~omc~c~-~us ~ye bloaching The extent of dye oxidation was compared between a composition containing imidazole as amine base catalyst and a system without amine base catalyst. -~
~ '~
Composition A: A detergent solution tlOOmL) cont~inin~ dyes (40 ppm final ~c~centration), gl~o-e (0.}% by weight) and a ferric tetrasulfonated tetrAp~nylporphin catalyst (l x lO-5 M) was ~erAred and its pH value adjusted to 8Ø
Composition B: A detergent solution (lOOmL) containin~ dyes (40 ~
ppm final concentrat.ion), gl~Q~? (0.1% by weight), and ferric -~;
tetrasulfonated tetraphenylporphin catalyst (2.5 x 10-6 M) and imidazole (lO mM) was prepared and its pH value adjusted to pH
8Ø

Test method :
The absorbance spectrum was recorded (350-750 nm). This region encomr~e~ the wavelength maximum of the dyes (as noted in the table below) and the Soret band of the catalyst (414 nm).
Glucose oxidase (final concentration O.lU/mL) was then added to the stirred solution to initiate the reaction. After 30 min the absorbance a~e_~rum was recorded and the decrease in the absorbance maximum of the dyes noted.

Blank experiments indicated that n~ oxidation of the dyes occurred over the same period in the absence of catalyst or '' gl~rQ~ oxidase.

W093/15176 PCT/US93/~626 -.
, % destruction of dye Dy~s CI # l~x COMP A COMP B

Acid Blue 9 42000 630 nm 13 53 Direct blue 98 23155 570 nm 62 90 Direct blue 120 34090 570 nm 50 83 Acid blue 113 26360 595 nm 39 95 FD&C Red 40 16035 500 nm 0 30 Acid Yellow 40 18950 440 nm 0 30 Conclusion : Even though a lower level of iron porphin catalyst iS ~L -?nt in composition B, dyes are ,oxidized to a much bigger extent compared to composition A containing 4 times the iron porphin catalyst level.
~m~l~ 2 8t~b~lity of the ~etallo catalysts The -tabllity of different po~yh~Lins and phthalocya~ine~ was ;~"'~
dete~rmined in the ~L~ Ce of imidazole as amine base catalyst. ;'~

A,d'etergent solution (lOOmL) of glucose (0.1% by weight) and di~ferent metallo catalysts (10 x 10-5 M) was prepared and the pH adjusted to 8Ø To initiate ~he reaction, different levels of glucose oxidase were~ . The destruction of the catalyst was measured in each case by quantifying the decrease in absorption of the Soret band (414 nm). '-' The catalyst destruction was compared with and without imidazole at different time intervals.

93/15176 2I27096 PCr/US93/00626 % calalyst destrucUon U Glox/ mL No ~With 10 mM imid~zole 10 min 20 min 30 min 10 min 20 min 30 min Iron Tetra~ultonat~d ~etr~phenylporphin 0.1 53 7 0 92 87 82 H~min chl~lde 0.05 67 42 29 100 93 0.25 33 21 13 92 68 49 ~ ' Iron ph~ nin~ unon~t~d 0.05 69 31 18 88 85 ~2 ~
o.l 47 16 0 88 83 80 : -nophth~locy~nin-t~ulhn-t~d -O1 30 0 ~ 77 EX~D1e 3 D-position of F~.r~
' A 50 mM borate buffer solution tPH 8.0) of ferric tetrasulfonated tetraphenylporphin catalyst (FeTPPS) (10-5 M, 10 ppm by weight) was prepared. The FeTPPS ~rocition was studied as follows: a knitted cotton fabric (~14g) wa8 6~k~ in the FeTPPS solution (100 mL) for 15 min. At the end the fabric wa8 removed and the water squeezed out of it. A solution sample (2 mL) was ~en before and after soaking. The ~oncentration of FeTPPS in the solution was determined spectrophotometrically from the 2 ml sample by observing the absorbance peak at 414 nm (characteristic of the FeTPPS Soret band).
This experimental procedure was repeated with and without imidazole (10 mM).

solution % Porphyrin left in solution FeTPPS only 50 FeTPPS+Imidazole 8~

Conclusion : The pr~-ence of imidazole strongly re~-lc~s the ~on~oncy of FeTPPS to deposit onto fabrics.

WO93/15176 PCT/US93/~62~

- Exam~le IV

A liquid dye transfer inhibiting composition according to the present invention is prepared, having the following compositions :
% .
Linear alkylbenzene sulfonate lO
Alkyl sulphate 4 Fatty alcohol (Cl2-Cl5) ethoxylate 12 Fatty acid l0 Oleic acid 4 Cit~ic acid l :~
NaOH 3.4 Propanediol l.5 Ethano} 5 Ethanoloxidase 5 u/ml Ferric tetrasulfonated tetraphenylporphin O.l imidazole 3 ::
Minors up to lO0 ~-:

ExamDlè V
':.
A compact granular dye transfer inhibiting composition a~G-ding to the present invention is prepared, having the following formulation:

Linear alkyl benzene sulphonate ll.40 Tallow alkyl sulphate l.80 C45 alkyl sulphate 3.00 C45 alcohol 7 times ethoxylated 4.00 Tallow alcohol ll times ethoxylated l.80 Dispersant 0.07 Silicone fluid 0.80 Tri~oAium citrate 14.00 Citric acid 3.00 Zeolite 32.50 Maleic acid actylic acid copolymer 5.00 .

'~093/15176 2 I 2 7 0 9 6 PCT/US93/~626 19 ,:
DETMPA 1.00 Cellulase ~active protein) 0.03 ~1kA lase/BAN 0.60 Lipase 0.36 Sodium silicate 2.00 :
Sodium sulphate 3.S0 Ferric tetrasulfonated tetraphenylporphin 0.025 Glucose 10.00 Glucose oxidase 100 u/ml imidazole 3 Minors up to 100 , .

:: .

Claims

CLAIMS:

1. A dye transfer inhibiting composition comprising:
A. A metallo bleach catalyst selected from a) metallo porphin and water-soluble or water-dispersable derivatives thereof, b) metallo porphyrin and water-soluble or water-dispersable derivatives thereof, c) metallo phthalocyanine and water-soluble or water-dispersable derivatives thereof; wherein said metallo bleach catalyst is present in an amount sufficient to provide a wash solution at a concentration of from 10-8 to 10-3 molar;
B. an amine base catalyst stabilizer capable of binding the 5th ligand of the metallo bleach catalyst and capable of reducing the rate of self-destruction of said metallo bleach catalyst; said catalyst stabilizer is selected from the group consisting of imidazole compounds, pyridine compounds, alkylated pyridine compounds, pyrole compounds, (C2H5)3N,C3H7NH2,(C6H11)2NH,1,5-diazabicyclo(4,3,0)non-5-ene and mixtures thereof, and is present in said composition in a molar ratio of metallo bleach catalyst to catalyst stabilizer of from 1:1 to 1:5,000; and C. an enzymatic system capable of generating hydrogen peroxide present in an amount capable of yielding hydrogen peroxide at a concentration of from 0.005 to 10 ppm/min in said wash solution.

2. A dye transfer inhibiting compositions according to claim 1 wherein said amine base catalyst stabilizer is selected from imidazole and derivates thereof.

3. A dye transfer inhibiting composition according to claim 1 wherein said amine base catalyst stabilizer is selected from pyridine and its derivatives thereof.

4. A dye transfer inhibiting composition according to claim 1-3 wherein said enzymatic system comprises an oxidase and as a substrate an alcohol, an aldehyde or a combination of both.

5. A dye transfer inhibiting composition according to any one of claims 1-3, containing a metallo porphin derivative, wherein said iron porphin is substituted on at least one of its meso positions with a phenyl or pyridyl substituent selected from the group consisting of and wherein n and m may be 0 or 1, A is selected from the group consisting of sulfate, sulfonate, phosphate, and carboxylate groups, and B is selected from the group consisting of C1-C10 alkyl, C1-C10 polyethoxyalkyl and C1-C10 hydroxyalkyl.

6. A dye transfer inhibiting composition according to claim 5 wherein the substituents on the phenyl or pyridyl groups are selected from the group consisting of -CH3, -C2H5, -CH2CH2CH2SO3-, -CH2COO-, -CH2C-H(OH)CH2SO3-, and -SO3.

7. A dye transfer inhibiting composition according to any one of claims 1-3, containing a metallo porphin derivative, wherein said metallo porphin is substituted on at least one of its meso positions with a phenyl substituent selected from the group consisting of wherein X1 is (=CY-) wherein each Y, independently, is hydrogen, chlorine, bromine or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl.

8. A dye transfer inhibiting composition according to claim 7 wherein the catalyst compound is metallo tetrasulfonated tetraphenylporphin.

9. A dye transfer inhibiting composition according to claim 1 wherein the metallo of said metallo catalyst is substituted by Fe, Mn, Co, or other transition metals.

10. A dye transfer inhibiting composition according to claim 1 wherein the concentration of metallo catalyst is from 10-8 to 10-3 molar, preferably from 10-6 to 10-4 molar.

11. A dye transfer inhibiting composition according to claim 4 wherein the oxidase is present by 0.1 - 20000 units, preferably 0.5 to 5000 units per gram of the composition.

12. A dye transfer inhibiting composition according to claim 4 wherein said substrate is glucose.

13. A dye transfer inhibiting composition according to claim 4 wherein said substrate consists of a C1-C6 alcohol.

14. A dye transfer inhibiting composition according to claim 10 wherein said substrate is ethanol.

15. A dye transfer inhibiting composition according to claim 3 in which the substrate is present from 0.1 to 50%
by weight of the composition.

16. A dye transfer inhibiting composition according to claim 1 which yields hydrogen peroxide at a concentration from 0.005 to 10 ppm/min in the wash process.

17. A dye transfer inhibiting composition according to claim 1 wherein said catalyst stabilizer is present in a molar ratio of iron porphin to amine base catalyst from 1:1 to 1:5000, preferably from 1:1 to 1:2500.

18. A dye transfer inhibiting composition according to any one of claims 1-3, 5-6 or 8-17 which is a detergent additive, in the form of a non-dusting granule or a liquid.

19. A detergent composition which comprises a dye transfer inhibiting composition according to any one of claims 1-3, 5-6 or 8-17 of the preceding claims further comprising enzymes, surfactants, builders, and other conventional detergent ingredients.

20. A process for inhibiting dye transfer between fabrics during laundering operations involving colored fabrics, said process comprising contacting said fabrics with a laundering solution containing a dye transfer inhibition composition according to any one of claims 1-3, 5-6 or 8-17.

21. A process for inhibiting dye transfer according to claim 20 which is carried out at a temperature in the range of from 5°C to 90°C.

22. A process for inhibiting dye transfer according to claim 20 wherein the pH of the bleaching bath is from 7 to 11.

23. A process for inhibiting dye transfer according to claim 22 wherein the pH of the bleaching bath is from 7 to 9.

24. A process for inhibiting dye transfer according to claim 21 wherein the pH of the bleaching bath is from 7 to 11.

25. A dye transfer inhibiting composition according to claim 4 which is a detergent additive, in the form of a non-dusting granule or a liquid.

26. A dye transfer inhibiting composition according to claim 7 which is a detergent additive, in the form of a non-dusting granule or a liquid.

27. A detergent composition which comprises a dye transfer inhibiting composition according to claim 4 further comprising enzymes, surfactants, builders, and other conventional detergent ingredients.

28. A detergent composition which comprises a dye transfer inhibiting composition according to claim 7 further comprising enzymes, surfactants, builders, and other conventional detergent ingredients.

29. A process for inhibiting dye transfer between fabrics during laundering operations involving colored fabrics, said process comprising contacting said fabrics with a laundering solution containing a dye transfer inhibition composition according to claim 4.

30. A process for inhibiting dye transfer between fabrics during laundering operations involving colored fabrics, said process comprising contacting said fabrics with a laundering solution containing a dye transfer inhibition composition according to claim 7.

31. A dye transfer inhibiting composition according to claim 4, containing a metallo porphin derivative, wherein said iron porphin is substituted on at least one of its meso positions with a phenyl or pyridyl substituent selected from the group consisting of <IM> and .

wherein n and m may be 0 or 1, A is selected from the group consisting of sulfate, sulfonate, phosphate, and carboxylate groups, and B is selected from the group consisting of C1-C10 alkyl, C1-C10 polyethoxyalkyl and C1-C10 hydroxyalkyl.

32. A dye transfer inhibiting composition according to claim 4, containing a metallo porphin derivative, wherein said metallo porphin is substituted on at least one of its meso positions with a phenyl substituent selected from the group consisting of wherein X1 is (=CY-) wherein each Y, independently, is hydrogen, chlorine, bromine or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl.