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CA2189747A1 - Dye transfer inhibiting compositions with specifically selected metallo catalysts - Google Patents

Dye transfer inhibiting compositions with specifically selected metallo catalysts

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Publication number
CA2189747A1
CA2189747A1 CA 2189747 CA2189747A CA2189747A1 CA 2189747 A1 CA2189747 A1 CA 2189747A1 CA 2189747 CA2189747 CA 2189747 CA 2189747 A CA2189747 A CA 2189747A CA 2189747 A1 CA2189747 A1 CA 2189747A1
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Canada
Prior art keywords
formula
chloro
independently
dye transfer
group
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
Application number
CA 2189747
Other languages
French (fr)
Inventor
Regine Labeque
James Pyott Johnston
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CA2189747A1 publication Critical patent/CA2189747A1/en
Abandoned legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators or bleach catalysts
    • C11D3/3932Inorganic compounds or complexes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0021Dye-stain or dye-transfer inhibiting compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/168Organometallic compounds or orgometallic complexes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

The present invention relates to inhibiting dye transfer compositions comprising (i) one or more of a specific metallo catalyst selected from the group of porphyrins and/or phthalocyanines, (D) an efficient amount of bleaching agent.

Description

wo 95/31526 2 1 8 ~ 7 ~ 7 A ~
DYE TRANSFER INHIBITING COMPOSITIONS

METALLO CATALYSTS
Field of the Invention The present invention relates to a composition and a process for inhibiting dye transfer between fabrics durlng washing.
More in particular, the present invention relates to a composition and a process for inhibiting dye transfer between fabrics during washing comprising specifically selected metallo catalysts.
Background of the Invention One of the most persistent and troublesome 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 attached to other articles in the wash.

WO 95~315Z6 2 1 8 9 7 ~ 7 ~ u~ --suspended or solubilized dyes can to some degree be oxidized in solution by employing known bleaching agents.
However it is important at the s2me time not to bleach the dyes actually rP-n~inin~ 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 oxldlzing bleaching agent together with a catalytic compound such as iron porphins.
Copending EP Patent Application 91202655. 6 filed October 9, l99l, relates to dye transfer inhibiting compositions comprising an enzymatic system capable of generating hydrogen peroxide and porphin catalysts.
It has now been found that specifically selected metallo catalysts in the presence of an efficient amount of a quick releasing bleaching agent are very efficient in preventing dye trans f er .
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 f abrics .
Summary of the Invention The present invention relates to inhibiting dye transfer compositions comprising i) one or more of a specific metallo catalyst selected from the group of porphyrins and/or phthalocyanines, ii) an efficient amount o~ bleaching agent.
-W095131526 218~7 Detailed description of the Invention The term "specific metallo catalysts" herein encompassesone or more of a specific metallo catalyst selected from the groups of porphyrins and/or phthalocyanines as defined below.
A) porphyrins having the following formula I:
Yo C==C~ C R
N~
DY
C ~yO R
FORMULA I
wherein M is a transition metal capable of sustaining oxidation, and if desired may also be joined to one or more axial ligands in addition to the four nitrogen groups, each Y
and Y is independently H, fluoro or chloro, each R ring is X~X
Xl ~ X3 Wo 95/31526 2 1 8 9 7 ~ 7 ~,lIL _. --X and X are independently H OL an electronegative group which is not a water solubilizing group, eg. X and X are independently, fluoro, chloro, bromo, ~ or N02, Xl, X2 and X3 are independently H or an electronegative group, including water solubilizing electronegative groups, including without limitation fluoro, chIoro, bromo, 503H, COCH or N02, subject to the provisions that l) when none of Xl, X2 and X3 is not a water solubilizing group, then at least one Y and Y on each porphyrin ring is other than H,
2) when Y and Y are both H, at least one but not more than two of Xl, X2 and X3 is a water solubilizing group, eg.
S03H or COOH, and at least two of X and X and the Xl, X2 and X3 which are not a water solubilizing group are independently an electronegative group which is not a water solubilizing group, e.g. fluoro, chloro, bromo or N02, and
3) no more than two of Xl, X2 and X3 are water solubilizing groups, or the water soluble salts thereof in which said water solubilizing groups are in corresponding water soluble salt form.
Particular subgroups of the compounds of the foLmula I
are the compounds of the formulae Ia and Ib.
The compounds of ~he formula Ia are those with reference to the structural formula I in which:
a) at least one of Y and Y on each porphyrin ring is fluoro or chloro and the other is H, fluoro or chloro, b) X and X are independently H, fluoro, chloro, bromo or N02 ~
c) Xl, X2 and X3 are independently H, fluoro, chloro, bromo, S03H, COOH or N02, provided that no more than two of Xl, X2 and X3 are S03H or COOH, and d) M is as above defined.

W095/31526 ~ ~ r~

The compounds of the formula Ib are those with reference to the structural formula I in which a) Y and Y are independently H, fluoro or chloro, b) X and X are independently H, fluoro, chloro, bromo or N02 ~
c) Xl, X2 and X3 are independently H, fluoro, chloro, bromo, SO3H, COOH and NO2 with the provisions that i) at least one but not more than two of Xl, X2 and X3 are SO3H or COOH, and ii) at least two of X, X, Xl, X2 and X3 is fluoro, chloro, bromo or NO2, and d) M is as above defined.
The preferred compounds of the formula Ia have one or more of the following features:
a) both Y and Y on each porphyrin ring is fluoro or chloroi b) at least two of X, X, Xl, X2 and X3 are fluoro or chloro, more particularly with X and X being fluoro or chloro, and c) N is Fe, Cr, Mn, Co, Ru, Rh, Mo, V.
More preferred compounds of the formula Ia have one or more of the following features:
a) both Y and Y on each porphyrin ring is chloro;
b) at least two of X, X, Xl, X2 and X3 are chloro, more particularly with X and X being chloro, and c) M is Fe, Mn.
The preferred compounds of the formula Ib have one or more of the following features:
a) Y and Y on each porphyrin ring is independently H or chloro;
b) one of Xl, X2 and X3 is SO3H, c) at least two of X, X, Xl, X2 and X3 are fluoro or chloro, and d) M is Fe, Cr, Mn, Co, Ru, Rh, Mo, V.

Wo 95/31S26 ~ t 6 ~ 2 1 ~ q ~
More preferred compounds of the formula Ib have one or more of the following features:
a) Y and Y on each porphyrin ring are independently H or chloro, b) one of X1, X2 and X3 is 503~, c) at least two of X, X, X1, X2 and X3 are chloro, more particularly with X and X being chloro, and d) ~ is ~n, Fe.
Another preferred subclass of the compounds of the formula Ib are those in which one of Y and yG on each porphyrin is other than H, more particularly those in which both Y and Y are fluoro or chloro.
With regard to each R ring as described above, each R
ring will contain the minimum substitution provided for above, but the positioning and number of substitutions above the minimum on each R ring may vary. Preferably, each R ring is the same.
In general, it is preferred that only one of X1, X2 and X3 is a water solllhili7;n~ group. It is also more particularly preferred that when one of Y or Y is to be other than H, that both be other than H.
A subclass of the compounds of the formula Ib described in application SeriaL No . 039, 566 of April 17, 1987, in which Y and Y are H, X and X are each chloro, Xl and X2 are H and R3 is an electronegative group including a water solubili7ing group is in free acid form and those with and without ligands such as the chloride ligand form.
The compounds of the invention having SO3H or COOH
groups are water soLuble and the invention also includes such water soluble compounds in which such groups are in water soluble salt form with a cation of a base such as an alkali IlLetal (sodium, potassium or lithium), and ~lk~line earth metal, or an ammonium cation, preferably an alkali metal or - =
w0 gsl3ls26 ~ 4 7 F~
ammonium cation Such salt forms may be prepared by reacting a compound of the formula I with a base by conventional procedures .
M may be any transition metal which is capable of sustaining oxidation. Examples of preferred metals include Fe, Cr, Mn, V, Rh, Ru and Co. Particularly preferred metals are Fe and Mn. Additionally the metal may be joined to a ligand, The axial ligands, usually one or two but occasionally more, may be virtually any group which is capable of forming a single hydrolysable bond with the M, as known in the art. Examples of axial ligands by way of illustration only include -OCH3, -OH, amines, halide ions, particularly chloride, and water.
B) Substituted phthalocyanines in which at least one of the peripheral carbon atoms in the 1-16 positions of the phthalocyanine nucleus ~M Pc), as shown in Formula (1) 14~
~N~ 6 Formula ( 1 ) wherein M is selected from Fe, Cr, Mn, Co, Ru, Rh, Mo, V
are unsubstituted or substituted by any combination of atoms or groups and sulphonated derivatives thereof provide that the phthalocyanine absorbs electromagnetic radiation at a wavelength from 650nm to 800nm.
In the present phthalocyanines the phthalocyanine nucleus is complexed with a metal represented by M. Preferred metals represented by M are Fe, Mn, Co, Rh, Cr, Ru, Mo or V.

Wo 95131526 2 ~ 8 ~ ~ 4 7 ' i P~
In the phthalocyanines used in the present invention each of the pendant organic radlcals lir~ked via oxygen to the phthalocyanine nucleus is independently selected from aromatic, heteroaromatic, aliphatic and alicyclic radicals, such that any one phthalocyanine nucleus may carry two or more different organic radicals.
It is preferred that each pendant organic radical is independently selected from mono- and bi-cyclic aromatic and heteroaromatic radicals.
Examples of suitable mono- and bi-cyclic aromatic and heteroaromatic radicals are phenyl, naphthyl, especially naphth-2-yl, pyridyl, thiophenyl, furanyl, quinolinyl, thiazolyl, benzothiazolyl and pyrimidyl each of which may be substituted.
Where the pendant organic radical is an aliphatic or alicyclic radical it is preferred that it is selected from Cl_20-alkyl especially Cl_lo alkyl; C2_20 alkenyl especially C3_10 alkenyl and Cq-8 cycloalkyl especially cyclohexyl, each of which may be substituted.
Optional substituents for the pendant organic radicals are preferably selected from Cl_20 alkyl, especially C1_4 alkyl; C1_20 alkoxy, especially Cl_q alkoxy, C1_20 alkenyl, especially C2-g alkenyl; Cl_20 alkylthio, especially C1_4 alkylthio; C1_20 alkoxycarbonyl, especially C1_4 alkoxycarbonyl; hydroxyC1_4 alkoxy, aryl, especially phenyl;
Cl_4 alkylaryl, especially benzyl; arylthio, especially phenylthio; halogen, especially fluoro, chloro and bromo; -CN;-NO2;-CF3;-COR2;-COOR2;-CoNR2R3, -S02R2,-So2NR2R3 and -OR2 in which R2 and R3 are independently selected from -H; alkyl, especially C1_4 alkyl; aryl, especially phenyl; C1_4 alkylaryl, especially benzyl and -SO3A in which A is H, or a metal or ammonium ion or substituted ammonium ion.
In the phthalocyanines used in the present invention it is preferred that from 4 to 16 of the peripheral carbon atoms are linked via an oxygen atom to a pendant organic radical and it is especially preferred that all 16 peripheral carbon atoms are linked via an oxygen atom to a pendant organic radical .

wo 95/31526 2 ~ 8 9 7 ~ 7 Examples of suitable atoms or groups which can be attached to any of the remaining peripheral carbon atoms of the phthalocyanine nucleus are hydrogen, halogen, sulphonate groups -S03A in which A is H, or a metal or ammonium ion or a substituted ammonium ion, and any of the pendant organic radicals described above and hereinafter represented by R. It is preferred that the atoms or groups attached to the remaining peripheral carbon atoms are selected from -H, -F, -CI, -Br, -I, -S03H, -S03Na, -S03K, -So3Li and -S03NH4 or any combination thereof. It is especially preferred that these atoms or goups are -H, -CI, -Br, -S03H, -S03Na or -S03NH4.
The sulphonated derivatives of the phthalocyanines used in the present invention carrying up to 50 S03A groups, preferably up to 40 S03A groups and more preferably up to 30 S03A groups, which are attached directly to the phthalocyanine nucleus and/or to the pendant organic radicals are a preferred group of compounds for the present invention.
In the preferred group the average number of S03A groups is preferably from 2 to 40 and more preferably from 2 to 30 and especially, preferably 16 to 30. It is also preferred that for each pendant organic radical there is at least one S03A group, although each organic radical may carry none, one or more than one S03A group.
Where A is a metal ion it is preferably an alkali or ;1l k~l inP earth metal ion, especially an alkali metal ion such as a sodium, potassium or lithium ion. Where A is an ammonium ion it is preferably +NH4 or a substituted ammonium ion which Pnh~nrPS the water-solubility of the compound. Examples of suitable substituted ammonium ions which enhance the water solubility of the compound are mono, di, tri and tetra alkyl and hydroxylalkyl ammonium ions in which the alkyl groups preferably contain from 1 to 4 carbon atoms such as +N~CH3)4;
+N(C2Hs)4; +N(C2H40H)4; +NH3CH3; +NH2(CH3)2 and NH(cH3)3-The substituted ammonium ion represented by A preferablyhas one fatty alkyl group as described above, the r~ ~inin~
groups being preferably H or Cl_4 alkyl, especially H or methyl. Suitable ammonium ions include 2-W09~31526 21~97~7 lo ethylhexylammonium, 1,1, 3, 3-tetramethylbutylammonium and 3, 5, 5-trimethylhexylammonium.
In compounds of the Formula (l) each of the peripheral carbon atoms in the 1 to 16 positions of the phthalocyanine nucleus are attached to a group Y and each Y is independently selected from -H, halogen, -503A in which A is as hereinbefore defined, and OR in which R is a pendant organic radical as hereinbefore defined.
According to a further feature of the present invention there are provided phthalocyanine compounds of the Formula (2):
M Pc ~O-R) aXb ~S03A~ d Formula (2) wherein:
M Pc is a phthalocyanine nucleus as defined in Formula (l);
each R independently is an organic radical;
each X independently is a halogen or hydrogen; the O-R and X
groups being attached to one or more or the 16 peripheral carbon atoms of the phthaloxyanine nucleus;
A is selected from H, a metal, ammonium or substituted ammonium as described above;
a is from 1 to 16;
b is from O to 15;
d is an average value from O.1 to 50;
a+b is from 1 to 16;
In phthalocyanines of Formula (2) ~ is any of the metals descIibed above for M.
In phthalocyanines for Formula ~2) it is especially preferred that M is Fe, Mn.
In a phthalocyanine of Formula (2) each of the radicals denoted by R may be c~l e~teri from any of the pendant organic radicals hereinbefore defined in relation to Formula ~1) above .
In a phthalocyanine of formula (2) it is preferred that a is ~rom 4 to 16 and more preferably from 5 to 16. It is especially preferred that a is 16.
In a phthalocyanine of Formula ~2~ each halogen denoted by X is preferably ~n~F~r~n~ tly selected from -F, -CI, -Br 7'~7 W095/31526 ,- ~; r~_ and -I and it is especially preferred that each halogen denoted by X is independently -CI or -Br.
In a phthalocyanine of Formula (2 ) it is preferred that b is from O to 12, and more preferably from O to 11.
When a+b is <16 the rr-~in~l~r of the 16 peripheral carbon atoms, not carrying a group O-R or X, may carry a sulphonate group, -S03A or a group represented by R. It is however preferred that the sum of a+b is 16. It is also preferred that a is 4, 8, 12 or 16, and especially 8, 12 or 16. -In phthalocyanines of Formula t2) the metal ion denoted by A is preferably an alkali or alkaline earth metal ion and more preferably is selected from lithium, sodium and potassium ion. It is especially preferred that a is a sodium, an ammonium ion or hydrogen.
In phthalocyanines of Formula (2) it is preferred that d is an average value from 2 to 40. It is more preferred that d is an average value from 2 to 30, especially preferred that d is an average value from 16 to 30.
According to a further feature of the present invention there are provided phthalocyanine compounds of the Formula (3):
M Pc ( ~R1 ) aXb Formula ( 3 ) wherein:
M Pc is as defined in Formula (1) R1 is selected from opt~.~nally substituted aryl and optionall ~ substituted heteroaryl;
X is halogen or H;
a is an integer from 1 to 16;
b is an integer from O to 15; and a+b is e~ual to 16.
Preferred phthalocyanine compounds of formulae (3) are those ( 1 ) wherein M is selected from Mn, Fe, Co;
X is halogen;
a is 4, 8 or 12; and b is 12, 8 or 4.

WO 95/31526 2 1 8 ~ ~ ~1 7 ( 2 ) where i n:
M is selected from Mn, Fe, Co, V;
X is halogen;
a is 4, 8 or 12 and b is 12, 8, 4.
( 3 ) where in:
M is selected from Mn, Fe;
X is hydrogen;
a is 8 or 12; and b is 8 or 4.
( 4 ) wherein M is selected from Fe, Mn, Ni;
a is from 5 to 16; and b is from 11 to 0.
( 5 ) wherein M is selected from Fe, Mn, Ni;
a is from 1 to 3, and b is from 15 to 3.
( 6 ) wherein M is selected from Fe, Mn, Co, Ni and V;
X is halogen;
a is from l to 16; and b i5 from 15 to 0.
( 7 ) wherein:
M is selected from Fe, Mn, Co, Ni and V;
a is from 1 to 14; and b is from 15 to 2, provided that at least one X is H and one X is halogen.
In a phthalocyanine of Formula (3) it is preferred that each of the radicals denoted by Rl is independently selected from mono- or bi-cyclic aromatic or heteroaromatic radicals.
Examples of suible aromatic and heteroaromatic radicals are those described above for R. The radicals denoted by Rl are more preferably phenyl or naphthyl, especially 2-naphthyl.
Preferred substituents for the Rl group are as described for R.
In a phthalocyanine of Formula (3) it is preferred that a is an integer from 4 to 16 and that b is an integer from 12 to 0. It is also preferred that a is 4, 8, 12 or 16, more especially 8, 12 or 16, and that b is 12, 8, 4 or 0.
In a phthalocyanine of Formula ~3) it is preferred that the metal denoted by M is Fe, Mn, Co, Cr, Ru, Rh, Mo, V.

7~7 WO 95/31526 . P~ L _.

The phthalocyanines can be sulphonated directly on the Pc nucleus, particularly when any of the 1-16 positions is unsubstituted (i.e. the 1-16 peripheral carbon atoms carry a hydrogen atom) or on any of the pendant organic groups R or Rl, or on both the Pc nucleus and the pendant organic groups.
The preferred molar range of the specifically selected metallo catalyst of the present invention in the wash is 10-8 molar to 10-3 molar, more preferably 10-6 to 10-4 molar.
An efficient amount of bleaching agent The dye transfer inhibiting compositions according to the present invention comprise an efficient amount of bleaching agent .
According to the present invention, an efficient amount of bleach is by definition the necessary amount of bleach which ined with a bleach catalyst leads to a level of dye oxidation which is between 40% to 100%, preferably 40% to 60%, more preferred 60% to 80~, most preferred 80%-100% of the maximu~ (Z) per cent of dye oxidation that can be achieved under the most optimal conditions det~rmin~-l by those skilled in the art.
The bleaches suitable for the present invention can be activated or non-activated bleaches.
Preferably, the bleaches suitable for the present invention include peroxygen bleaches. Examples of suitable water-soluble solid peroxygen bleaches include hydrogen peroxide releasing agents such as hydrogen peroxide, perborates, e.g. perborate monohydrate, perborate tetrahydrate, persulfates, percarbonates, peroxydisulfates, perphosphates and peroxyhydrates. Preferred bleaches are percarbonates and perborates .

-Wo95131526 2~8~7 ` P.~ 5 The hydrogen peroxide releasing agents can be used in combination with bleach activatorS such as tetraacetylethylenediamine ~TAED), nonanoyloxybenzenesulfonate (NOBS, described in US q, 412, 934), 3, 5, 5-trimethylhexanoloxybenzenesulfonate ~ISONOBS, described in EP
lZO, 591), or pentaacetylglucose (PAG), which are perhydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect.
The hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process. Such enzymatic systems are disclosed in EP Patent Application 91202655. 6 filed October 9, I991.
Other peroxygen bleaches suitable for the present invention include organic peroxyacids such as percarboxylic acids.
TQst Method~:
For a given catalyst concentration, temperature and pH, the following two test methods can be used to estimate the optimum bleach level that gives the maximum level of dye oxidation, i.e. Z.
(a) In solution dye bleaching:
In a detergent solution, fix the initial concentration of dye (e.g. 40 ppm) and catalyst. Record the absorbance spectrum of this solution using a W-Vis spectrophotometer according to procedures known to those skilled in the art.
Add a given concentration of bleach (H202, oxone, percarbonate, perborate, activated bleach, etc. . ) and stir the solution containing the dye and catalyst. After stirring for 30 min, record again the absorbance spectrum of the solution.
The amount of dye oxidation can then be determined from the change in the absorbance maximum for the dye. Keeping the experimental conditions the same, vary the amount of bleach so as to achieve the maximum dye oxidation.

W095/31526 ~ 7~ 7 - y~

(b) Reduction of dye transfer from fabric to another fabric In either a washing machine or launderometer, add a known bleeding fabric and a known uncolored pick-up tracer (e.g.
cotton) to the wash load. After simulating a wash cycle, determine the amount of dye that has been picked up by the 'cracer according to methods known to those skilled in the art.
Now to separate washing machines, add the same amount of bleeding fabric and pick-up tracer, a fixed amount of catalyst and vary the bleach level. Determine the level of dye transfer onto the pick-up tracers and vary the amount of bleach as to minimize dye transfer. In this way the most optimal bleach concentration can be determined.
DETERGENT ADJUNCTS
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.
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, especially 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-C18 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 c2rbon 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 C14_15 alkyl sulphates. The cation in each instance is again an alkali metal cation, preferably sodium.

:s WO95/31526 ~ ~9 ~ 47 r~

One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having 2n average hydrophilic-lipophilic balance ~HL~3) 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 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-Cls primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C14-C15 primary alcohols containing 6-a 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.
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 disclosed in EP-B
0 070 077, 0 075 996 and 0 094 118.
Also suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula R2 - C - N - z O Rl wo 95/31526 21 ~ g 7 4 7 r~
wherein Rl is H, or Rl is Cl_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is Cs_3l 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 ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene 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 (Na2Si25)-Suitable polycarboxylates builders for use herein includecitric 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-dodecenylsuccinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.

WO95/31526 218g't~7 18 r~l"
Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4, 663, 071 ~ sper; ~1 l y for the liquid execution herein, suitable fatty acid builders for use herein are saturated or unsaturated C10-18 fatty acids, as well 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.
Preferred builder systems for use in granular compositions include a mixture o~ a water-insoluble aluminosilicate builder such as zeolite A, and a watersoluble carboxylate chelating agent such as citric a~id.
Other builder materlals that can form part of the builder system for use in granular compositions the purposes of the invention include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amiono 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 G3-A-1, 596, 756.
Examples of such salts are polyacrylates of ~W 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 ~ nrl~ Pci in amounts of from 10% to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight.
Other c~ on~nts used in detergent compositions may be employed, such as bleaches, suds boosting or depressing agents, enzymes and stabilizers or activators therefor, soil-suspending agents soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and perfumes.

~ WO 95/31526 P~
19 2'189747 Especially preferred are combinations with technologies which also provide a type of color care benefit. Examples of these technologies are polyvinylpyrrolidone polymers and other polymers which have dye transfer inhibit~ng properties.
Another example of said technologies are cellulase for color maintenance/ re j uvenation .
Other examples are polymers disclosed in EP 92870017 . 8 filed January 31, 1992 and enzyme oxidation scavengers disclosed in EP 92870018 . 6 filed January 31, 1992. also particularly suitable are amine base catalyst stabilizers disclosed in EP
92870019.4 filed January 31, 1992.
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 conventional 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 amQunt of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are ~l k~l inP earth metal salts of sulphates and chlorides, typically sodium sulphate;
"compact" detergents typically comprise not more than 10%
filler salt. The liquid compositions according to the present invention can also be in "concentrated form", in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents.
~ he 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 75 C, ~per;~l ly 20 to 60, WO95131526 ~ 7~7 - 20 P~
but the polymers 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 us ed ~ ~ddi ~ ive du~inq l~undry ope ra t i ons .

Claims (9)

WHAT IS CLAIMED IS:
1. A dye transfer inhibiting composition comprising i) one or more of a specific metallo catalyst selected from the group of porphyrins and/or phthalocyanines, said porphyrins having the formula I

FORMULA I
wherein M is a transition metal capable of sustaining oxidation, and if desired may also be joined to one or more axial ligands in addition to the four nitrogen groups, each Y
and Y° is independently H, fluoro or chloro, each R ring is X and X° are independently H or an electronegative group which is not a water solubilizing group, eg. X and X° are independently, fluoro,= chloro, bromo, or NO2, X1, X2 and X3 are independently H or an electronegative group, including water solubilizing electronegative groups, including without limitation fluoro, chloro, bromo, SO3H, COCH or NO2, subject to the provisions that 1) when none of X1, X2 and X3 is not a water solubilizing group, then at least one Y and Y° on each porphyrin ring is other than H, 2) when Y and Y° are both H, at least one but not more than two of X1, X2 and X3 is a water solubilizing group, eg.
SO3H or COOH, and at least two of X and X° and the X1, X2 and X3 which are not a water solubilizing group are independently an electronegative group which is not a water solubilizing group, e.g. fluoro, chloro, bromo or NO2, and 3) no more than two of X1, X2 and X3 are water solubilizing groups, or the water soluble salts thereof in which said water solubilizing groups are in corresponding water soluble salt form, said phthalocyanines having the formula (1) Formula (1) wherein M is selected from Fe, Cr, Mn, Co, Ru, Rh, Mo,V, in which at least one of the peripheral carbon atoms in the 1-16 positions of the phthalocyanine nucleus (M Pc) are unsubstituted or substituted by any combination of atoms or groups and sulphonated derivatives thereof provide that the phthalocyanine absorbs electromagnetic radiation at a wavelength from 650nm to 800nm, ii) an efficient amount of bleaching agent.
2. A detergent inhibiting composition according to claim 1 wherein the porphyrins have one or more of the following features:
a) Y and Y° on each porphyrin ring are independently H or chloro, b) one of X1, X2 and X3 is SO3H, c) at least two of X, X°, X1, X2 and X3 are chloro, more particularly with X and X° being chloro, and d) M is Mn, Fe.
3. A detergent inhibiting composition according to claim 1 where the phthalocyanine have the formula (2) M Pc (O-R)aXb(SO3A)d Formula (2) wherein:
M Pc is a phthalocyanine nucleus as defined in Formula (1);
each R independently is an organic radical;
each X independently is a halogen or hydrogen; the O-R and X
groups being attached to one or more or the 16 peripheral carbon atoms of the phthaloxyanine nucleus;
A is selected from H, a metal, ammonium or substituted ammonium as described above;
a is from 1 to 16;
b is from 0 to 15;
d is an average value from 0.1 to 50;
a+b is from 1 to 16.
4. A detergent inhibiting composition according to claim 1 where the phthalocyanine have the formula (3) M Pc (O-R1)aXb Formula (3) wherein:
M Pc is as defined in Formula (1) R1 is selected from optionally substituted aryl and optionally substituted heteroaryl:
X is halogen or H;
a is an integer from 1 to 16;
b is an integer from 0 to 15; and a+b is equal to 16.
5. A dye transfer inhibiting composition according to claims 1-4 wherein the wash concentration of the metallo catalyst is from 10-8 to 10-3 molar, preferably from 10-6 to 10-4 molar.
6. A dye transfer inhibiting composition according to claims 1-5 wherein the bleaching agent is selected from an activated or a non-activated bleach.
7. A dye transfer inhibiting composition according to claims 1-6 which is a detergent additive, in the form of a non-dusting granule or a liquid.
8. 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.
9. A detergent composition which comprises a dye transfer inhibiting composition according to any of the preceding claims further comprising a cellulase.
CA 2189747 1994-05-11 1995-04-25 Dye transfer inhibiting compositions with specifically selected metallo catalysts Abandoned CA2189747A1 (en)

Applications Claiming Priority (2)

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US5876625A (en) * 1996-07-22 1999-03-02 Carnegie Mellon University Metal ligand containing bleaching compositions
JP2001509192A (en) * 1997-01-24 2001-07-10 ザ、プロクター、エンド、ギャンブル、カンパニー Low hue photo bleach
DE19710370A1 (en) * 1997-03-13 1998-09-17 Henkel Kgaa Use of cage metal-enclosed transition metal complexes to enhance coverage
GB0020846D0 (en) 2000-08-23 2000-10-11 Unilever Plc Ligands for bleaching compositions and synthesis thereof
GB0118934D0 (en) * 2001-08-02 2001-09-26 Unilever Plc Improvements relating to bleaching compositions
GB0118936D0 (en) * 2001-08-02 2001-09-26 Unilever Plc Improvements relating to colour-safe fabric treatment compositions
US7060818B2 (en) 2003-02-21 2006-06-13 Carnegie Mellon University Synthesis of macrocyclic tetraamido compounds and new metal insertion process
CN101922110B (en) * 2010-09-14 2012-10-31 东华大学 A method of low-temperature activated bleaching using water-soluble metal phthalocyanine
CN101922111B (en) * 2010-09-14 2012-05-09 东华大学 A method of low temperature activation bleaching using water-soluble metalloporphyrins
CN102408745B (en) * 2011-11-25 2014-06-18 北京科技大学 Asymmetrical dye molecule adopting tetraphenylporphin as core, and preparation method thereof

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GB1541576A (en) * 1975-06-20 1979-03-07 Procter & Gamble Ltd Inhibiting dye ltransfer in washing
US4672047A (en) * 1984-03-08 1987-06-09 Travis Chandler Mercaptan oxidation catalyst
US4892941A (en) * 1987-04-17 1990-01-09 Dolphin David H Porphyrins
GB8720863D0 (en) * 1987-09-04 1987-10-14 Unilever Plc Metalloporphyrins
DE69129150T2 (en) * 1991-10-14 1998-10-08 The Procter & Gamble Co., Cincinnati, Ohio Detergent compositions with additives to prevent dye transfer
EP0596184B1 (en) * 1992-11-06 1998-04-15 The Procter & Gamble Company Detergent compositions inhibiting dye transfer
WO1994024250A1 (en) * 1993-04-08 1994-10-27 The Procter & Gamble Company Composition and process for inhibiting dye transfer
DE4313529A1 (en) * 1993-04-24 1994-10-27 Hoechst Ag laundry detergent
EP0622447A1 (en) * 1993-04-26 1994-11-02 The Procter & Gamble Company Enzymatic detergent compositions inhibiting dye transfer

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CN1151756A (en) 1997-06-11
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EP0759968A4 (en) 1998-05-20
WO1995031526A1 (en) 1995-11-23

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