CA2127095A1 - Detergent compositions inhibiting dye transfer containing a catalyst, a polymer and a peroxide generating enzyme - Google Patents

Abstract

A dye transfer inhibiting composition comprising: (A) a metallo catalyst selected from (a) metallo porphin and water-soluble or water-dispersible derivatives thereof; (b) metallo porphyrin and water-soluble or water-dispersible derivatives thereof; (c) metallo phthalocyanine and water-soluble or water-dispersible derivatives thereof; (B) a polymer selected from (a) alkoxy containing polymers, (b) hydroxy containing polymers, (c) thiol containing polymers, (d) amide containing polymers, (e) heterocyclic amines containing polymers, (f) polyamines, (g) polyurethanes, (h) polyacrylonitriles; (C) an enzymatic system capable of generating hydrogen peroxide.

Description

W093/15174 PCr/US93/~6~
.~.

2 ~ 3 ~

CONTAINING A CATALYST, A POLYMER AND A PEROXIDE GENERATING ENZYME
, :-;~ ~

Field of the Invention The present invention relates to a composition and a processfor inhibiting dye transfer between fabrics during washing.

..~- ~ ..~
Backqround of the Invention One of the most persistent and trcublesome problems arising during modern fabric laundering operations is the tendency of some colored fabrics to release dye into the laundering solutions. The dye is then transferred onto 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 ttach-d to other articles in the wash.

Suspended or solubilized dyes can to some degree be oxidized `~
in solution by employing known kleaching agents. -. . .

, W093/15174 2l~as~ PCr/USg3/00624 GB 2 101 167 describes a stable liquid bleaching composition containing a hydrogen peroxide precursor which is activated to yield hydrogen peroxide on dilution.
However it is important at the same time not to bleach the dyes actually remaining on the 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 porphins.

Copending EP Patent Application 91202655.6 filed October 9, 1991, r~lates to dye transfer inhibiting compositions comprising an enzymatic system capable of generating hydrogen ~-peroxide and porphin catalysts.

Now it has bèen found that certain specific polymers when added to said enzymatic dye transfer inhibiting compositions ~ ~
enhances the overall performance of said compositions. ~ -The addition of said polymers eliminates or reduces the -~
deposition of the porphin catalyst onto t~e fabrics resulting in improved whiteness benefits. ~;~
' Accordingly, a dye transfer inhibiting composition is provided which exhibits optimum dye transfer inhibiting properties~

According to another embodiment, the invention provides an efficient process for laundering operations involving colored fabrics.

Summarv of the Invention The present invention relates to inhibiting dye transfer compositions comprising :

A. a metallo catalyst selected from WO~3/15174 ~ ~ 2 7 ~ ~ ~ PCT/US93/~624 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. a polymer selected from a) alkoxy containing polymers b) hydroxy containing polymers c) thiol containing polymers d) amide containing polymers ~e) heterocyclic amines containing polymers :
f) polyamines g) polyurethanes h) polyacrylonitriles C. an enzymatic system capable of generating hydrogen ~ :
peroxide ~.:
. According to another embodiment of this invention a process `
is also provided for laundering operations involving colored fabrics. -;

Detailed descri~tion 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 water dispersable derivatives thereof~
b~ metallo porphyrin and water-soluble water- :~-dispersable derivatives thereof c) metallo phtalocyanine and water-soluble or water-dispersable derivatives thereof;

i ~

WO93/15174 PCT/US93/~6~
~ :~ ~ 7 ~ 3 ~
B. a polymer selected from a) alkoxy containing polymers b) hydroxy containing polymers c) thiol containing polymers d) amide containing polymers e) heterocyclic amines containing polymers f) polyamines g) polyurethanes h) polyacrylonitriles ;

.: -; C. an enzymatic system capable of generating hydrogen ;
peroxide -. . . ~ . .
The Hydroaen Peroxide precursor The oxidizing agent,~hydrogen peroxide is generated in situ -~
by~ùsing an enzymatic hydrogen peroxide generation system. ~ ~
-'`~' ': , `' m e use of an enzymatic hydrogen peroxide generating system allows the continuous generation of low-levels of hydrogen peroxide and provides a practical way of controlling a low ~
ste ~ -state level of Xydrogen peroxide. Maximum effectiveness ~ -occurs~when the component levels are such that the hydrogen peroxide is replenished at a rate similar to its removal due to the oxidation of dyes in the wash water.
The enzyme used in the present invention is an oxidase.
The oxidase is present 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 ~mole of substrate per minute. -Suitable oxidases are urate oxidase, galactose oxidase, alcohol oxidases, amine oxidases, amino acid oxidases, cholesterol oxidàse and glucose oxidase, malate oxidase, glycollàte oxidase, hexose oxidase, aryl alcohol oxidase, L-gulonolactose oxidase, pyranose oxidase, L-sorbose oxidase~, pyridoxine 4-oxidase, 2-2-hydroxyacid oxidase, choline oxidase, ecdysone oxidase.
~ .

WO93~15174 2 1 2 7 ~ ~ ~ PCT/US93/~624 The preferred enzymatic systems are alcohol and aldehyde oxidases, glucose oxidase.
The more preferred systems for granular detergent application would have solid alcohols, e.g. glucose whose oxidation is catalysed by glucose oxidase to glucoronic acid with the formation of hydrogen 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 invention should be at least sufficient to provide in the wash a constant generation of 0.005 to lO ppm AvO per-minute in the wash process~ For example, with the ~ -~
,glucose oxidase , this can be achieved at room temperature and at pH 6 to ll, preferentially 7.5 to lO.5 with 1-20000 U/l glucose oxidase, 0.005 to 0.5 % glucose under constant aeration in the washing process. - ;

M~t~l~l,o ~lY~

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 essential 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 drawings, but are actually present as in I.

Preferred metallo porphin structures are those substituted at one or more of the S, lO, lS and 20 carbon positions of Formula I (Meso positions), with a phenyl or pyridyl substituent selected from the group consisting of:

~( ~) n~ ( A~ m ~ ( B) n- ( A) m :
- .

~D~3/l5l74 9~ S PCT/USg3/~K~

wherein n and m may be o or l; A may be sulfate, sulfonate, phosphate or carboxylate groups; and B is Cl-Cl0 alkyl, polyethoxy alkyl or hydroxy alkyl.

Preferred molecules are those in which the substituents on the phenyl or pyridyl groups are selected from the ~roup consisting of ~ :
CH3, -C2H5~ -CH2CH2CH2SO3-, -CH2--, and -CH2CH(OH)CH2SO3-, - :~
SO3 .
.
A particularly preferred metallo phorphin is one in which the ~ :
lecule is substituted at the 5, 10, 15, and 20 carbon `~
pos:itio~s with the substituent ~1 ~ So3 This preferred compound is known as metallo tetrasulfonated ~.
tetraphenylporphin. The s~mbol 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 c.ompound of Formula I may be substituted at one or more of the remaining carbon positions with Cl-C10 alkyl, hydroxyalkyl or oxyalkyl groups.

l~ ~ 3 `
~ X2/

l5 ~ Fe ~ 5 l3 ~ ~ (I) Porphin derivatives also include chlorophyls, chlorines, i.~.
isobacterio chlorines and bacteriochlorines.
Metallo porphyrin and water-soluble or water-dispersable derivatives. thereof have a structure given in formula II. .
,, W093/15174 ~ 2 7 ~ 9 ~ PCT/US93/ ~ ~

' .~"
X x X ~ .X ~;

x ~ ~ x ~-' y ~~_~ Y (II) where X can be alkyl, alkyl carboxy, alkyl hydroxyl, vinyl, ;~
alkenyl, alkyl sulfate, alkylsulfonate, sulfate, sulfonate.
.
' The symbol x2 of Formula II represents an anion, preferably -~
OH- or CL~
The symboliX can be alkyl, alkylcarboxy, alkylhydroxyl, -vinyl,~alkenyl, alkylsulfate, alkylsu}fonate, sulfate, sulfonate, aryl.
.
:
Metallo phthalocyanin- and derivatives have the structure indicæted in ~ormula III, wherein the atom positions of the p~thalocyanine structure are numbered conventionally. The anionic groups in the above structures contain cations selected from the group consisting of sodium and potassium cations or other non-interfering cations which leave the structures water-soluble. Preferred phthalocyanine derivatives are metallo phthalocyanine trisulfonate and metallo phthalocyanine - `
tetrasulfonate.

..

W093/15174 PCT/US93/~K24 2 :~ 2 . V .~ ~
8 ~0 Another form of substitution possible for the present invention is substitution of the central metal by Fe, Mn, Co, Rh, Cr, Ru, Mo or other transition metals.

Still a number of considerations are significant in selectinq variants of or substituents in the basic porphin or azaporphin structure. In the first place, one would choose compounds `-~
which are available or can be readily synthesized.

Beyond 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 ~ --repell-d by nega~ively 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 attracted to, or at least not repelled by such stained surfaces.
~ .:
` Polymeric aaents The dye transfer inhibiting benefits can be optimized by adding small amounts of polymers.

These polymers of the present invention reduce the deposition of the porphin catalyst onto the fabric, resulting in better whiteness maintenance of the white fabric.
The compounds suitable for the present invention having reduced deposition effect of the porphin catalyst are polymers having alkoxy moieties.
These polymer$ include copolymeric blocks of ethylene terephthalate and polyethylene oxide or polypropylene oxide terephthalate and the like. These polymers are often used as ~soil release agents.

:
:

WO93/15174 PCT/US93/~624 2 ;L ~ 7 ~
g More preferred alkoxy containing polymers include polyethylene glycol or polypropylene glycol and derivatives thereof.
Particulary preferred are the copolymers of said polymers e.g Pluriol(R).
Another preferred soil release agent is a copolymer having ~-random blocks of ethylene terephthalate and polyethylene oxide ~ -(PE0) terephtalate. More specifically, these polymers are . ~
comprised of repeating units of ethylene terephthalate and PE0 ~-:
terephthalate in a mole ratio of ethylene terephtalate units to PE0 terephthalate units of from 2S:75 to 35:65, said PE0 ~:~
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 SS,000. ~ r ` ' ~.' Another preferred polymeric soil release agent is a polyester with repeating units of ethylene terephthalate containing 10- :
15~ by weight of ethylene terephthalate units together with 90- :
80% by weight of polyoxyethylene terephthalate units, derived ~ :
from a polyoxyethylene glycol of average molecular weight 300-5,000, and the mole ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the polymeric compound is between 2:1 and 6:1.
.~ .
Highly preferred polymers are compounds of formula :

X-(OCH2CH2)n [ (OC- R1 -Co-R2)u(-oc-R3 - 80-R2)V ]

oc-R4-co-(CH2CH20)n~X

wherein the Rl moieties are all 1,4-phenylene moieties: the R2 moieties are essentially ethylene moieties, 1,2-propylene moieties or mixtures thereof; the R3 moieties are substituted 1,3-phenylene moieties having the substituent 0 [ (R2-oc-R4-co ] w (CH2CH20)n-X

WO93/15174 PCT/USs3/~K24 212~9~j - . 10 at the 5 position; the R4 moieties are Rl or R3 moieties, or mixtures thereof; each X is ethyl or preferably methyl; each n is from 12 to 43; when w is o, u + v is from 3 to 10; when w is ~
at least 1, u + v + w is from 3 to 10. -Particularly preferred block polyesters are those where v is o, i.e. the linear block polyesters. For these most preferred linear block polyesters, u typically ranges from 3 to 8, especially for those made from dimethyl terephthalate, ethylene glycol (or 1,2-propylene glycol) and methyl capped polyethylene glycol. The most water soluble of these linear block polyesters are those where u is from 3 to 5.
. .
Other polymers suitable for the present invention having ~olyalkoxymoiety are al~oxylated polyamines. Such materials can conveniently be represented as molecules of the empirical structures with repeating units : -.
[N R] n Amine form (alkoxy)y and - Rl rN+ R] n nX~ Quaternized form (alkoxy)y Wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms;
Rl may be a Cl-C20 hydrocarbon; the alkoxy groups are ethoxy, propoxy, and the like, and y is 2-30, most preferably from 10-20; n is an integer of at least 2, preferably from 2-20, most preferably 3-5; and X~ is an anion such as halide or methylsulfate, resulting from the quaternization reaction.

The most highly preferred polyamines for use herein are the so-called ethoxylated polyethylene imines, i.e., the ~ :
polymerized reaction product of ethylene oxide with ethylene-imine, having the general formula ~
-' .

Other polymers suitable for use in the present invention are alkoxylated nonionic surfactants.
.
~The condensation products of aliphatic alcohols with from ~a~out l~ to~about 25 moles of ethylene oxide. The alkyl chain of~the~al~iphatic alcohol can either be straight or branched, ~pr~imary~-or~s-condary, and genera}ly contains from about~8 to ~"about~;22~carbon~atoms. Pr-ferred nonionic surfactants for use in the present i m ention are nonionic surfactants having at least~3,~ preferably at l-ast 5 ethoxy groups and a C10-C20 ~;alkyl`~chain. ~ ~
~Suitable~nonionic surfactants include polyethyleneoxide ~co ~ nsat-s of alkyl phenols, condensation products of ethylene ~oxide~with a hydrophobic base formed by the condensation of ~propyl-n- Qxide with prQpylene`glycol~or ethylenediamine.
~Semi-p`olar nonionic detergent surfactants which include water-solubl- amine oxides, water-soluble phosphine oxides and water-soluble su}foxides are suitable for the present invention.
Hydroxy containing polymers, e.g. polyvinyl alcohol and polyaminoacids containing hydroxyl groups such as polyserine, polythreonine and polytyrosine as well as thiol containing ~polymers such as polycysteine are suitable for the present invention.

Amide containing polymers are also suitable for the present invention.
These include compounds of formula :

H - (NH-R-(CO))n~~OH
.

- (NH - Rl~- NH - CO - R2 ~- C)n - OH

WO93/15174 PCT/US93/~K24 ~ t~j 12 wherein Rl is amino acid side chain, or alkyl (Cl - cl2) or aryl groups Most preferred amide containing polymer is polyvinyl pyrolidone or alkoxylated derivatives thereof.

Other polymers suitable for the present invention are polyurethanes, polyacrylonitrile and polyamines including polyaminoacids containing basic amino acids such as diamino monocarboxylic aminoacids e.g. lysine, arginine, histidine ...), polyethylenimine and ethoxylated amine containing , polymers (e.g. tetraethylene pentamine etc.).

Polymers containing heterocyclic amines such as polyvinyl pyridine~and derivatives thereof are suitable for the present invention. Particulary preferred heterocyclic amine is polyvinylimidazoline.

The polymers suitable for the present invention have an average -molecular weight within the range of about l000 to 50,000, preferably from 2000 to 25,000 and most preferred from 2000 to 15,000.

The level of polymer in the detergent composition is from 0.0l to 5% by weight, preferably from 0.l to 2% and most preferred from 0.2 to 1%

DETERGENT INGREDIENTS

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

WOg3/l5174 ~ i ~ 7 i~ ~ ~, PCr/US93/~K24 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 l:l. Preferred sulphonates include alkyl benzene suiphonates having from 9 to 15, especially ll to 13 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a Cl2-Cl8 fatty source preferably from a Cl6-Cl8 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 l0 to 20, preferably l0 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, coconut alkyl sulphate, and Cl4_l5 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-lipophilic balance (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 ~liphatic or aromatic in nature and the length of the polyoxyethylene 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 hydrophobic elements. ;~

Especially preferred nonionic surfactants of this type are `
the Cg-Cl5 primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the Cl4-C15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol and the C12-C14 primary alcohols ~
containing 3-5 moles of ethylene oxide per mole of alcohol. ;

.

WO93/15174 PCT/US93/~624 ~ 1 ~? 7 J~

Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula :

RO (cnH2no)tzx wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds 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 di~sclosed 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, ~ ~
. I I . . :
o R~
:
.
wherein Rl is H, or Rl is Cl_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is Cs_31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a ~-linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. 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 glucose, fructose, maltose, lactose, in a reductive amination reaction.

The compositions according to the present 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 ethylenedia-ine tetraacetate, metal ion ;~
sequèstrants such as aminopolyphosphonates! particularly ~ethylenediamine tetramethylene phosphonic acid and diethylene ~ -.

~ ' G J ~
WO93~15174 PCT/US93/~624 triamine pentamethylenephosphonic acid. Though less preferred for obvious environmental reasons, phosphate 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)CH2tCOOH) 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-dodecenylsuccinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanola D onium 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 corresponding 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 based on dodecenyl succinic acid.
Preferred builder systems for use in granular compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, and a watersoluble carboxylate chelating agent such as citrîc acid. -Other builder materials that can form part of the builder system for use in granular compositions for the purposes of this invention include inorganic materials such as alkali metal wo g3/lsl74 2 1 2 7 ~ 9 S 16 PCT/USY3/~6~

carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amino polyalkylene phosphonates and amino polycarboxylates.
Other suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756.
Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
. . ~
. Detergency builder salts are normally included in amounts of from 10% to 8Q% by weight-of the composition preferably fr~om 20~ to ?0% and most usually from 30% to 60S by weight.

The compositions of the present invention should be free from conventional bleaching agents. Other components used in detergent campositions may be employed, such as suds boosting or depressing agents, enzymes and stabi}izers or activators therefore, soil-suspending agents 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 chosen 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 relati~ely .

WO93/15174 2 1 2 ~ r~ PCT/US93/~624 higher density than conventional granular detergents, i.e. from 550 to g5o 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 granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate: "compact"
detergents typically comprise not more than 10% filler ~;
salt.
The present invention also relates 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 ~, 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 7.5 to 10.5. ~ ;

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 necessarily meant to limit or otherwise define the scope of the invention, said scope being determined according to claims which follow.

SpectxoDhotometric characterization The following technique can be used to characterize polymers spectrophotometrically to check if they have the potential to reduce porphin deposition.

First, a O.lM phosphate buffer solution, whose pH has been adjusted to desired pH, is prepared in which the metal porphin concentration is about 10-5 molar. Second, put a 1 WO93/15174 PCT/US93/~K24 21~7~09~ `

ml sample of the solution in a 1 ml cuvette. Third, scan the sample under the spectrophotometer. The absorbance spectrum has a peak which is characteristic of the soret band. In the same cuvette, add increasing amounts of the polymer starting with 10 ppm and up to lO00 ppm. Gently shake the sample after each addition of polymer and wait for a few minutes before measuring the spectrum again. Compare the spectrum to the original spectrum of the porphin solution.
Look for the following differences :

(i) a shift in the wavelength of the absorbance peak (i.e. a shift in the Soret band). Typical changes are in the order of 3 nm and higher. ~-.(ii) OR a net broadening in the absorbance spectrum.

Changes in the absolute amount of absorbance alone are not `
significant.

As an example Fe(III)TPPS was scanned between 350 and 500 nm.
The absorbance peak occurs at about 414 nm. Upon binding with PVP the maximum shifts to 419 nm. -Example I
A 50 mM borate buffer solution was prepared in which the concentration of Fe(III)TPPS was 10-5 molar (10 ppm by weight).
The pH of the solution was either adjusted to 8.0 or 10.5. In a beaker containing 100 ml of the solution, a piece of knitted cotton weighting approximately 14 g was added and was left to soak for 30 min. The cotton fabric was occasionally stirred in the solution. This experiment was repeated in solutions containing the following polymers in weight concentrations of 50 or lO0 ppm:

Wo93/15174 ~ ~ 27 S ~ i PCT/US93/~6~

; . .
Polymer average Molecular weight coneentrationby weight (ppm) Polyvinyl alcohol (PVA) 10000 100 :
Polyvinylpyrolidone (PVP) 12000 50 Pluriol 6100* 2000 100 Polyethylene glyeol (PEG) 15000 . 100 The degree of Fe(III)TPPS deposition onto the knitted eotton fabrie after it was extensively rinsed under running tap water and tumble dried was quantified by measuring the Hunter L, a, b ~ ~ r~.
,values using a Colorimeter (Speetraflash manufaetured by ICS).
The ehange in the eolor of the fabrie ean be eharaeterized by a ~ ~-parameter e defined as e= (a + b)l/2 where b represents the intensity of refleeted yellow light (positive b value) or the intensity of refleeted blue light (negative b value), and a is a measure~of the intensity of the refleeted red light (positive a value) or the refleeted green light (negative a value). The L :
- :value is a measure of whiteness with higher L value representing greater whiteness.

System I: p~ = 8.0 .
solution L value e value no FeTPPS 95.74 1.17 FeTPPS only 93.55 8.35 FeTPPS+PEG 94.34 3.57 FeTPPS+PVA -95.32 2.62 FeTPPS+PVP 95.91 1.38 FeTPPS+Pluriol 96.02 1.78 WO93/15174 PCT/US93/~624 - 2 l ~rl09r3 20 syste~ II: pH = 10.5 solution L value c value no FeTPPS 95.22 1.05 FeTPPS only 93.94 8.22 FeTPPS~PYA 94.91 3.51 -FeTPPS+PEG 95.53 2.04 FeTPPS+PVP 95.48 1.44 FeTPPS+Pluriol 95.45 1.37 . . , Example II
'~ ;A~50~mM borate buffer solution at pH 8.0, was prepared in ~;``
which~tne concentration of Fe~ITI)TPPS was 10-5 molar (10 ppm by weight). The Fe(III)TPPS deposition was studied on knitted -~ ~
; ~ cotton~fabric weighting approximately 150g in a beaker -~- conta~ining one liter of said solution. The procedure consisted of soaking the knitted cotton fabric in the solution for 15 min ~and then~replacing it by a`new fabric of the same dimensions ;after squeezing all the water out from the first. ~ A 2 ml sample of~t~e solution was taken out each time before and after putt~ng a new fabric in the solution. This procedurè was repeated three times.`~The concentration of Fe~III)TPPS in the solution was determined spectrophotometrically from the 2 ml sample by observing the absorbance peak at 414 nm (characteristic of the Fe(III)TPPS Soret band).
- This experimental procedure was repeated in the same buffered solution (pH=8.0) solutions 1000 ppm of C12_15 alkyl alcohol ethoxylated 7~times (III), and 0.01% polyvinylimidazolidone K60 (PVI) by weight,;respectively. The per cent of Fe(III)TPPS left in solution after the first, second and third cycles are tabulated below.

solution 1st 2nd 3rd --.~.
.. .
- :: ..
FeTPPS only 76 ~ 52 33 FeTPPS+(II~I) 96 93 84 `~; "
FeTPPS+PVI 100 89 79 .

WO 93/lS174 2 :1 2 7 ~ i PCr/USg3/00624 Example III
A liquid dye transfer inhibiting composition according to the present invention is prepared, having the following `
compositions: :

% ~ .
Linear alkylbenzene sulfonate 10 ~`- M
Alkyl sulphate 4 Fatty alcohol (C12-C15) ethoxylate 12 Tatty acid 10 Ol-ic acid 4 Citric acid NaOH~ 3.4-Propanediol 1.5 Ethanol 5 ";
Ethanol~oxidase 5 u/ml ~ .
Ferric tetrasulfonated tetraphenylporphin 0.1 polymer o.5 ~Minors up to 100 : .
ExamDle IV
A compact granular dye transfer inhibiting composition according to the present invention is prepared, having the following formulation:

Linear alkyl benzene sulphonate 11.40 Tallow alkyl sulphate 1.80 C45 alkyl sulphate 3.00 C45 alcohol 7 times ethoxylated 4.00 Tallow alcohol 11 times ethoxylated 1.80 Dispersant 0.07 Silicone fluid 0.80 ~:
Trisodium citrate 14.00 Citric acid 3,00 ~ -~

Zeolite 32.50 Maleic acid actylic acid copolymer 5.00 ~ - , , -....~

WO93/15174 PCT/US93/~K24 21~7~ 22 DETMPA l.oo Cellulase (active protein) 0.03 ~. ;
Alkalase/BAN 0.60 Lipase 0.36 Sodium silicate 2.00 .
Sodium sulphate 3.50 ~: ~
Ferric tetrasulfonated tetraphenylporphin 0.025 ~ -:
Glucose 10.00 Glucose oxidase 100 u/ml polymer 0.3 Minors up to 100 ~' . . ~
:.``.'.. ;;

Claims (25)

WHAT IS CLAIMED IS:

1. A dye transfer inhibiting composition 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. a polymer selected from a) alkoxy containing polymers b) hydroxy containing polymers c) thiol containing polymers d) amide containing polymers e) heterocyclic amines containing polymers f) polyamines g) polyurethanes h) polyacrylonitrile C. an enzymatic system capable of generating hydrogen peroxide.

2. A dye transfer inhibiting composition according to claim 1 wherein the polymer is selected from a) alkoxy containing polymers b) amide containing polymers c) heterocyclic amines containing polymers d) hydroxy containing polymers

3. A dye transfer inhibiting composition according to claim 1-2 wherein the alkoxy containing polymer is polyethylene glycol or a copolymer of ethylene-propylene glycol or polyethylene terephthalate and derivatives thereof.

4. A dye transfer inhibiting composition according to claim 1-2 wherein the amide containing polymer is polyvinylpyrrolidone and derivatives thereof.

5. A dye transfer inhibiting composition according to claim 1-2, wherein the heterocyclic amines containing polymer is polyvinylimidazoline and derivatives thereof

6. A dye transfer inhibiting composition according to claim 1-2, wherein the hydroxy containing polymer is polyvinylalcohol and derivatives thereof

7. A dye transfer inhibiting composition according to claim 1-6 wherein said enzymatic system comprises an oxidase and as a substrate an alcohol, an aldehyde or a combination of both.

8. A dye transfer inhibiting composition according to claim 1-7, 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.

9. A dye transfer inhibiting composition according to claim 8 wherein the substituents on the phenyl or pyridyl groups are selected from the group consisitng of -CH3, -C2H5, -CH2CH2CH2SO3-, -CH2COO-, -CH2C-H(OH)CH2SO3-, and -SO3.

10. A dye transfer inhibiting composition according to claim 1-7, 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.

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

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

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

14. A dye transfer inhibiting composition according to claim 7 wherein the oxidase is present by 0.1 -20000 units per gram of the composition, most preferred 0.5 to 5000 units per gram of the composition.

15. A dye transfer inhibiting composition according to claim 7 wherein said substrate is glucose.

16. A dye transfer inhibiting composition according to claim 7 wherein said substrate consists of a C1-C6 alcohol.

17. A dye transfer inhibiting composition according to claim 7 wherein said substrate is ethanol.

18. A dye transfer inhibiting composition according to claim 7 in which the substrate is present from 0.1 to 50% by weight of the composition.

19. A dye transfer inhibiting composition according to claim 1 which yields hydrogen peroxide at a concentration from 0.005 to 10 ppm/min.

20. A dye transfer inhibiting composition according to claim 1 wherein said polymer is present in an amount from 0.01 to 10%, preferably from 0.1 to 5% by weight of the composition.

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

22. A detergent composition which comprises a dye transfer inhibiting composition according to any of the preceding claims further comprising enzymes, surfactants,builders and other conventional detergent ingredients.

23. 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 claims 1-22.

24. A process for inhibiting dye transfer according to claim 23 which is carried out at a temperature in the range of from 5°C
to 90°C.

25. A process for inhibiting dye transfer according to claim 23-24 wherein the pH of the bleaching bath is from 7 to 11.