JP2004277996A - Use of oxidizing system for removing surplus unfixed dye from colored textile material and comprising macrocyclic complex and oxidizing agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oxidizing system for removing surplus unfixed dye from a colored textile material. <P>SOLUTION: Use of the oxidizing system containing a macrocyclic complex and an oxidizer removes the surplus unfixed dye from the colored textile material without effecting on practical coloring of the textile material. The oxidizing system is preferably applied in at least one step of after-color rinsing steps. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to the use of an oxidizing system comprising a macrocyclic metal complex and an oxidizing agent to remove excess unfixed dye from dyed textile materials.

  U.S. Patents Nos. 5,059,086 and 5,069,064 disclose specific macrocyclic metal complexes useful as bleach activators. In combination with a peroxide source, preferably hydrogen peroxide, these bleach activators make it possible to carry out the oxidation reaction. Such oxidation reactions are carried out, for example, for decolorizing colored wastewater in paper bleaching or in the desulfurization of motor fuels. The use in household laundry detergents for removing stains and decoloring at the laundry and in the washing liquor, respectively, is also described. In all these applications, the use of a particular macrocyclic metal complex results in an improvement in results compared to a single treatment using only the peroxide source.

  There is a fundamental problem in the textile industry regarding the removal of excess unfixed dye from textiles after dyeing or printing. The coloring of textile materials, ie printing or dyeing, will hereinafter be distinguished using the term "dyeing".

In order to remove the unfixed dye, the dyer must carry out a very time-consuming and expensive washing operation after the actual dyeing. This is the only way to achieve consumer quality in terms of cleaning, rubbing and stain fastness. One approach to shortening the post dyeing washing operation of textile materials has been shown in US Pat.
U.S. Pat. No. 6,099,586 International Publication 02/16330 pamphlet WO 92/18687 pamphlet European Patent Publication No. 01054934

  Surprisingly, it has now been found that the use of an oxidizing system comprising a macrocyclic metal complex and an oxidizing agent gives the best decolorization of excess unfixed dye from dyed textile material.

  This method provides a highly selective removal of excess unfixed dye from the dyed textile, without the dyed textile itself being decolorized.

The present invention therefore provides a method for removing excess unfixed dye from dyed textile materials,
1) General formula (1)

[Where,
Y ₁ , Y ₃ and Y ₄ are each independently a single bond or a bridge member containing 1, 2 or 3 carbon atoms in the bridge;
Y ₂ is a bridge member having at least one carbon atom in the bridge,
R is independently hydrogen, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy, phenoxy, CH ₂ CF ₃ or CF ₃ at each occurrence, or the same carbon atom Are bonded together to form a substituted or unsubstituted benzene, cycloalkyl or cycloalkenyl ring, and the carbon atom to which the two R groups are attached is benzene, cycloalkyl or cycloalkenyl. Part of a ring,
M is a transition metal in oxidation state I, II, III, IV, V or VI or is selected from groups 6, 7, 8, 9, 10, and 11 of the periodic table;
Q is a counter ion that balances the charge of the macrocyclic metal complex on a stoichiometric basis, and L is another ligand.]
A macrocyclic metal complex of
And 2) providing the use of an oxidizing system comprising two components of an oxidizing agent.

Preferably, in the macrocyclic metal complex of the general formula (1),
Y ₁ , Y ₃ and Y ₄ are each independently a (—CH ₂ —) _x group, wherein x is 1, 2 or 3 and one or more of the (—CH ₂ —) _x groups. more hydrogen atoms may be substituted by R ⁱ groups, R ⁱ is alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy, or (-CH ₂ - ) Two R ⁱ groups which are bonded to two adjacent carbon atoms of the _x group together are benzene, which may contain one or more heteroatoms, preferably N, O or S; Forms a cycloalkyl or cycloalkenyl ring.

Preferably, in the macrocyclic metal complex of the general formula (1),
Y ₂ is a bridge member having 1, 2 or 3 carbon atoms in the bridge, preferably a (—CH ₂ —) _y group, where y is 1 or 2 and (—CH ₂ —) _y One or more hydrogen atoms in the group may be substituted by a R ⁱⁱ group, wherein R ⁱⁱ is alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy. Alternatively, the two R ⁱⁱ groups attached to two adjacent carbon atoms of the (—CH ₂ —) _y group together form one or more heteroatoms, preferably N, O or S, An optionally substituted benzene, cycloalkyl or cycloalkenyl ring, preferably an electron-donating or electron-withdrawing group; To form a more substituted benzene ring.

In the macrocyclic metal complex of the general formula (1),
The R groups are each independently hydrogen, C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl, C ₄ -C ₁₂ -cycloalkenyl, C ₂ -C ₈ -alkenyl, C ₆ -C ₁₄ -aryl , C ₂ -C ₁₂ -alkynyl, C ₁ -C ₁₂ -alkylaryl, halogen, alkoxy, phenoxy, CH ₂ CF ₃ or CF ₃ , or two R groups bonded to the same carbon atom together is to a substituted or unsubstituted benzene, C 3 _-C 8 _- cycloalkyl or C ₄ -C 12 _- to form a cycloalkenyl ring, the carbon atom to which the two R groups are attached are benzene, cycloalkyl or Part of a cycloalkenyl ring.

  In the macrocyclic metal complex of the general formula (1), M is a transition metal in the oxidation state I, II, III, IV, V or VI, or 6, 7, 8, 9, 10 and It is a transition metal from Group 11. Preferably, the metal M represents Cr, Mo, W, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and / or Pt. Mixtures of the abovementioned metals in the oxidation state or of the abovementioned groups of the periodic table are likewise possible.

  In the macrocyclic metal complex represented by the general formula (1), Q is a counter ion that balances the charge of the macrocyclic metal complex on a stoichiometric basis. The metal-ligand complex is usually negative, preferably -1. Thus, the counterion generally has a positive charge, and thus a preferred negative charge of -1 is therefore +1.

Suitably, Q alkali metal counterions, are preferably the potassium, lithium or ^{sodium, NR} _iii ^{4 +} or ^PR _iii ^{4 +,} where each ^{R iii} are independently hydrogen, alkyl, aryl, alkylaryl, alkenyl Or together form a cycloalkyl, cycloalkenyl or aryl ring optionally containing one or more heteroatoms, preferably oxygen, sulfur or nitrogen.

L is another ligand that can be attached to M. Preferably, L is a reactive ligand, especially H ₂ O, Cl or CN.

The above preferred and particularly preferred meanings for Y _{1 to} Y ₄ , R, R ⁱ , R ⁱⁱ , R ⁱⁱⁱ , Q and L can be combined in any desired way.

  The use according to the invention is preferably carried out according to the general formula (1A)

[Where,
X and Z are each independently hydrogen, an electron-donating or electron-withdrawing group,
R ^iv and R ^v are each independently hydrogen, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy, or together form one or more heteroatoms; Can form a cycloalkyl or cycloalkenyl ring which may contain atoms, preferably oxygen, sulfur or nitrogen,
M is a transition metal in oxidation state I, II, III, IV, V or VI or is selected from groups 6, 7, 8, 9, 10, and 11 of the periodic table;
Q is a counter ion that balances the charge of the macrocyclic metal complex on a stoichiometric basis, and L is another ligand.]
An oxidation system comprising a macrocyclic metal complex having the formula:

  In the macrocyclic metal complex of formula (1A), X and Z may each independently be hydrogen or an electron-donating or electron-withdrawing group. Electron-donating or electron-withdrawing groups alter the electron density of the metal-ligand and consequently affect its reactivity.

Suitable electron-withdrawing groups are, for example, halogen, preferably chlorine, bromine or iodine, more preferably chlorine, SO ₃ ⁻ , OSO ₃ ⁻ , OSO ₃ R ^vi, where R ^vi is hydrogen, alkyl, aryl or alkyl. Aryl) and NO ₂ ^— .

Suitable electron-donating groups are, for example, C ₁ -C ₈ -alkoxy, preferably methoxy, ethoxy, propoxy and butoxy, C ₁ -C ₈ -alkyl, preferably methyl, ethyl, propyl, n-butyl and tert. -Butyl, as well as hydrogen.

In the macrocyclic complex of formula (1A), R ^iv and R ^v are each independently hydrogen, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, halogen, alkoxy or phenoxy group. R ^iv and R ^v are preferably each independently alkyl, particularly preferably C ₁ -C ₅ -alkyl. More preferably, R ^iv and R ^v are both methyl or ethyl. Even more preferably, R ^iv and R ^v together form a cycloalkyl ring, especially a cyclopentyl or cyclohexyl ring, or a cycloalkenyl ring. The cycloalkyl or cycloalkenyl ring may contain one or more heteroatoms, preferably oxygen, sulfur or nitrogen.

  In the macrocyclic metal complex of the general formula (1a), M is a transition metal having an oxidation state I, II, III, IV, V or VI, or 6, 7, 8, 9, 10 and It is a transition metal from Group 11. Preferably, the metal M represents Cr, Mo, W, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and / or Pt. Mixtures of the above-mentioned metals in the oxidation state or of the above-mentioned groups of the periodic table are likewise possible.

  In the macrocyclic metal complex of the general formula (1a), Q is a counter ion that balances the charge of the macrocyclic metal complex on a stoichiometric basis. The metal-ligand complex is usually negative, preferably -1. Thus, the counterion generally has a positive charge, and thus a preferred negative charge of -1 is therefore +1.

Suitably, Q is an alkali metal counterion, potassium preferably lithium or ^{sodium, NR} _iii ^{4 +} or ^PR _iii ⁴ is ^+, wherein each ^{R iii} are independently hydrogen, alkyl, aryl, alkylaryl, alkenyl Together or together, they form a cycloalkyl, cycloalkenyl or aryl ring which may optionally contain at least one further atom as carbon.

In the macrocyclic metal complex of the general formula (1a), L is another ligand that can be bonded to M. Preferably, L is a labile ligand, especially H ₂ O, Cl or CN.

  The preparation of the macrocyclic metal complexes used in the use of the present invention is described in EP-A-918840, U.S. Pat. No. 6,099,586 and each of which is expressly incorporated herein by reference. It is described in WO 02/16330 pamphlet.

  The oxidizing agent can be any organic or inorganic oxidizing agent. Peroxy compounds are typically used. Suitable peroxy compounds are hydrogen peroxide, hydrogen peroxide adducts, compounds capable of releasing or generating hydrogen peroxide in aqueous solution, organic peroxides, persulfates, perphosphates and persilicates.

  Hydrogen peroxide adducts include alkali metals, preferably sodium, lithium or potassium, carbonate peroxyhydrate and urea peroxide.

  Compounds capable of generating hydrogen peroxide in aqueous solution include alkali metals, especially sodium, potassium or lithium, perborate (mono- or tetrahydrate). Such perborates are commercially available.

  Alternatively, alcohol oxidase and its appropriate alcohol substrate can be used as a peroxide source.

  Organic peroxides include benzoyl and cumene hydroperoxide.

  Persulfates include peroxymonosulfate or caroic acid.

  Particularly preferred oxidizing agents are hydrogen peroxide and sodium perborate.

  The macrocyclic metal complex is used in the oxidation system used in the present invention in an amount within the range of 0.01 μmol to 1000 μmol. An amount in the range from 0.1 μmol to 100 μmol is preferred.

  The oxidizing agent is used in the oxidizing system used in the present invention in an amount ranging from 0.01 to 1000 mmol. An amount in the range of 0.1 to 100 ppm is preferred.

  The use according to the invention is preferably carried out by contacting the dyed textile material with an oxidizing system in at least one of the post-dye rinsing stages.

  The dyeing can be a dyeing using any commercially available dye. Reactive dyes, direct dyes, direct dyes, acid dyes, metal complex dyes, disperse dyes, vat dyes and sulfur dyes may be mentioned.

  Dyeing is preferably carried out with water-soluble dyes and more preferably with reactive dyes.

  Preferably, the dyed textile material is oxidized in at least one of the post-dye rinsing stages by at least one of the rinsing solutions having the two components of the oxidizing system, which are added separately in any order or otherwise separately and simultaneously. Contact with system.

  More preferably, the dyed textile material is contacted with the oxidizing system in one of the post-dye rinsing steps.

  The macrocyclic metal complex is typically in the form of an aqueous solution optionally with 0.5 to 40% by weight, based on the total solution, of a pH stabilizer and a water-soluble or at least partially water-soluble solvent. Added. Suitable water-soluble solvents include ethanol, methanol, isopropanol, ethylene glycol, diethylene glycol, polyethylene glycols, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, acetone, acetonitrile, acetamide, tetrahydrofuran, dioxane, dimethyl sulfoxide, dimethyl Formamide, sulfolane or mixtures thereof may be mentioned. Suitable pH stabilizers are phosphate, citrate buffers, carbonate buffers or borate buffers, or mixtures thereof.

  If hydrogen peroxide is used as the oxidizing agent, it is used, for example, in the form of a commercially available aqueous solution having an analytical result of 3-50%.

  In the use of the present invention, not only the oxidizing system but also other additives such as detergents, preferably surfactants, sequestering agents, antifoams, enzymes such as amylases, pectinases, proteases, peroxidases, laccases. Or lipases, water treatment agents such as water softeners, pH stabilizers such as phosphate, citrate, carbonate or borate buffers or mixtures thereof, or soluble or partially soluble in water It may be advantageous to also use a solvent that is Suitable water-soluble solvents are ethanol, methanol, isopropanol, ethylene glycol, diethylene glycol, polyethylene glycols, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, acetone, acetonitrile, acetamide, tetrahydrofuran, dioxane, dimethyl sulfoxide, dimethyl Formamide, sulfolane or a mixture thereof.

  Such additives are used at 0 to 50% by weight and preferably at 0.01 to 30% by weight, based on the rinsing liquid.

  The processing time of the dyed textile material during the rinsing step depends on the type and amount of excess dye to be decolorized. Generally, 2 to 60 minutes is sufficient. If appropriate, further addition of either or both of the components of the oxidizing system during the treatment may be advantageous.

  The dyed textile material can be cotton, filament viscose, staple viscose, lyocell, wool, silk, polyester, polyamide, polyacrylonitrile and elastane or blends thereof. The dyed textile material can more preferably be cotton, filament viscose and lyocell or a blend thereof with polyester, polyamide or elastane.

  The process for removing excess unfixed dye is generally carried out at a temperature of from 25 to 95C and preferably from 40 to 80C. The pH of the rinsing liquid is in the range of 4-13, preferably 5-12 and more preferably 7-11.

  The following examples describe macrocyclic metal complexes produced by the methods described in Examples 1-6 of WO 02/16330.

Use This compound is referred to below as 1b .

The starting point is a loop formed of refined and bleached cotton that is dyed in a laboratory dyeing machine (eg, Mathis Spectraday) at a 10: 1 liquor ratio using the following formula: Is a knit:
Resupumitto of 10g of cotton ^{0.4g / l (RESPUMIT) (R} ) NF,
0.5 g / l pretreated over Perusofutaru ^{(PERSOFTAL) (R)} 10 minutes at 25 ° C. Among consisting of sodium chloride solution of L and 80 g / l of. The temperature was raised to 50 ° C., 8% of Remazoru the fiber weight at that time ^{(Remazol) (R)} Deep Black (Deep Black) N
Is added in three portions at 10 minute intervals. Then, after another 10 minutes,
2.0 g / l thorium carbonate is added in three portions at 10 minute intervals. Then, after another 10 minutes,
3.0 g / l of a 50% aqueous sodium peroxide solution are added in three portions at 10 minute intervals. Subsequently, it is finally heated to 60 ° C. at 1 ° C./min and then treated at 60 ° C. for 60 minutes.

Immediately after staining, the stained samples are rinsed in a 10: 1 liquid ratio as follows:
-Drainage of the staining solution,
-(First rinsing stage) addition of fresh water, rinsing at 60 ° C for 10 minutes, drainage,
-(Second rinsing stage) addition of fresh water at 95 ° C over 10 minutes, drainage,
-(Third rinsing step) addition of fresh water with 1 μmol of compound 1b , treatment at 60 ° C. for 5 minutes, addition of 4.4 mmol of hydrogen peroxide, treatment at 60 ° C. for 10 minutes, drainage,
-(Fourth rinsing step) Addition of fresh water, rinsing at 40 ° C for 10 minutes, and drainage.

  Finally, the sample is centrifuged and dried.

A comparative test is performed in which a third rinsing step is performed without adding compound 1b and without hydrogen peroxide. Otherwise, all steps are performed in the same way.

  The table below shows the degree of color of the individual rinses (measured as absorbance at 598 nm; the lower the absorbance, the lower the degree of color):

The results clearly show a significantly better decolorization of the rinse in bath 3 in the presence of compound 1b and hydrogen peroxide for the process according to the invention and a consequent lower coloration of the final rinse.

  The washing-off effect is evaluated by measuring the water resistance of the dyed product in accordance with German Standard Specification DIN 54006 (water resistance of the dyeing, severe exposure). Use cotton as the adjacent cloth. The rating scale is from 1 to 5, where 5 indicates the best robustness.

  The method of the present invention thus provides a substantial improvement in water resistance by a score of 0.5.

Treatment with the oxidation system of the present invention did not affect dyeing on cotton.

The main features and aspects of the present invention are summarized as follows.

1. To remove excess unfixed dye from dyed textile material,
1) General formula (1)

[Where,
Y ₁ , Y ₃ and Y ₄ are each independently a single bond or a bridge member containing 1, 2 or 3 carbon atoms in the bridge;
Y ₂ is a bridge member having at least one carbon atom in the bridge,
R is independently hydrogen, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy, phenoxy, CH ₂ CF ₃ or CF ₃ at each occurrence, or the same carbon atom Are bonded together to form a substituted or unsubstituted benzene, cycloalkyl or cycloalkenyl ring, and the carbon atom to which the two R groups are attached is benzene, cycloalkyl or cycloalkenyl. Part of a ring,
M is a transition metal in oxidation state I, II, III, IV, V or VI or is selected from groups 6, 7, 8, 9, 10, and 11 of the periodic table;
Q is a counter ion that balances the charge of the macrocyclic metal complex on a stoichiometric basis, and L is another ligand.]
A macrocyclic metal complex of
And 2) the use of an oxidizing system comprising two components of an oxidizing agent.

  2. Use according to claim 1, characterized in that the dyed textile material is contacted with the oxidizing system in at least one of the post-dye rinsing steps.

3. In the macrocyclic metal complex of the general formula (1),
Y ₁ , Y ₃ and Y ₄ are each independently a (—CH ₂ —) _x group, wherein x is 1, 2 or 3 and one or more of the (—CH ₂ —) _x groups. more hydrogen atoms may be substituted by R ⁱ groups, R ⁱ is alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy, or (-CH ₂ - ) Two R ⁱ groups which are bonded to two adjacent carbon atoms of the _x group together are benzene, which may contain one or more heteroatoms, preferably N, O or S; Use according to 1 or 2, characterized in that it forms a cycloalkyl or cycloalkenyl ring.

4. In the macrocyclic metal complex of the general formula (1),
Y ₂ is a bridge member having 1, 2 or 3 carbon atoms in the bridge, preferably - a _y group, wherein y is 1 or 2 and _{(-CH 2) (-CH 2 -} ) y One or more hydrogen atoms in the group may be substituted by a R ⁱⁱ group, wherein R ⁱⁱ is alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy. Or two R ⁱⁱ groups bonded to two adjacent carbon atoms of the (—CH ₂ —) _y group together contain one or more heteroatoms, preferably N, O or S An optionally substituted benzene, cycloalkyl or cycloalkenyl ring, preferably an electron-donating or electron-withdrawing group. Use according to one or more of the above 1 to 3, characterized in that the benzene ring forms an optionally substituted benzene ring.

5. In the macrocyclic metal complex of the general formula (1),
R groups are each independently hydrogen, C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl, C ₄ -C ₁₂ -cycloalkenyl, C ₂ -C ₈ -alkenyl, C ₆ -C ₁₄ -aryl , C ₂ -C ₁₂ -alkynyl, C ₁ -C ₁₂ -alkylaryl, halogen, alkoxy, phenoxy, CH ₂ CF ₃ or CF ₃ , or two R groups bonded to the same carbon atom together is to a substituted or unsubstituted benzene, C 3 _-C 8 _- cycloalkyl or C ₄ -C 12 _- to form a cycloalkenyl ring, carbon atom of benzene in which two R groups are attached, cycloalkyl or Use according to one or more of the above items 1 to 4, characterized in that it is part of an alkenyl ring.

  6. In the macrocyclic metal complex of the general formula (1), M is Cr, Mo, W, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and / or Pt, or a metal in the above oxidation state or Use according to one or more of the above items 1 to 5, characterized in that they represent a mixture of the groups of the periodic table of the above.

7. In the macrocyclic metal complex of general formula (1), Q is an alkali metal counterion, preferably potassium, lithium or sodium, NR ⁱⁱⁱ ₄ ⁺ or PR ⁱⁱⁱ ₄ ⁺ , wherein each R ⁱⁱⁱ is independently hydrogen, alkyl , Aryl, alkylaryl, alkenyl, or together form a cycloalkyl, cycloalkenyl or aryl ring optionally containing one or more heteroatoms, preferably oxygen, sulfur or nitrogen Use according to one or more of the above items 1 to 6, characterized in that:

8. In the macrocyclic metal complex of the general formula (1), L is a reactive ligand, preferably H ₂ O, Cl or CN, wherein one or more of the above items 1 to 7 Use according to.

  9. The macrocyclic metal complex used is represented by the general formula (1A)

[Where,
X and Z are each independently hydrogen, an electron-donating or electron-withdrawing group,
R ^iv and R ^v are each independently hydrogen, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy, or together form one or more heteroatoms; Forming a cycloalkyl or cycloalkenyl ring which may contain atoms,
M is a transition metal in oxidation state I, II, III, IV, V or VI or is selected from groups 6, 7, 8, 9, 10, and 11 of the periodic table;
Q is a counter ion that balances the charge of the macrocyclic metal complex on a stoichiometric basis, and L is another ligand.]
Use according to claim 1, characterized by having:

10. X and Z in the general formula (1A) are each independently halogen, preferably chlorine, bromine or iodine, SO ₃ ⁻ , OSO ₃ ⁻ , OSO ₃ R ^vi (where R ^vi is hydrogen, alkyl, aryl or alkyl) Aryl), NO ₂ ⁻ , C ₁ -C ₈ -alkoxy, preferably methoxy, ethoxy, propoxy and butoxy, C ₁ -C ₈ -alkyl, preferably methyl, ethyl, propyl, n-butyl and tert-butyl , Or hydrogen.

11. In the macrocyclic complex of formula (1A), R ^iv and R ^v are each independently hydrogen, alkyl, preferably C ₁ -C ₅ -alkyl, more preferably both are also methyl or ethyl, cycloalkyl, cycloalkenyl, An alkenyl, aryl, alkynyl, halogen, alkoxy or phenoxy group or together form a cycloalkyl ring, in particular a cyclopentyl or cyclohexyl ring, or a cycloalkenyl ring, optionally with one or more cycloalkyl or cycloalkenyl rings; Use according to 9 or 10 above, characterized in that it may contain further heteroatoms, preferably oxygen, sulfur or nitrogen.

  12. The oxidizing agent is hydrogen peroxide, a hydrogen peroxide adduct, preferably an alkali metal, especially sodium, lithium or potassium, carbonate peroxyhydrate, urea peroxide or a compound capable of releasing or generating hydrogen peroxide in an aqueous solution, preferably an alkali Metals, especially sodium, potassium or lithium, perborate (mono- or tetrahydrate), organic peroxides, preferably benzoyl or cumene hydroperoxide, persulfates, preferably peroxymonosulfate or caroic acid, Use according to one or more of the above items 1 to 11, characterized in that it comprises a phosphate or a persilicate.

  13. The dyed textile material is contacted with the oxidizing system in at least one of the post-dyeing rinsing steps by at least one of the rinsing solutions having the two components of the oxidizing system added separately in either order or otherwise separately and simultaneously. Use according to one or more of the above items 1 to 12, characterized in that:

  14． Use according to one or more of claims 1 to 13, characterized in that the dyed textile material is contacted with the oxidizing system in at least one of the post-dye rinsing steps.

  15. Use according to one or more of the above items 1 to 14, characterized in that the dyed textile material is dyed with a water-soluble dye, preferably a reactive dye.

  16. A dyed textile material obtainable by use of an oxidizing system according to one or more of the above items 1 to 15.

Claims (2)

To remove excess unfixed dye from dyed textile material,
1) General formula (1)

[Where,
Y ₁ , Y ₃ and Y ₄ are each independently a single bond or a bridge member containing 1, 2 or 3 carbon atoms in the bridge;
Y ₂ is a bridge member having at least one carbon atom in the bridge,
R is independently hydrogen, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy, phenoxy, CH ₂ CF ₃ or CF ₃ at each occurrence, or the same carbon atom Are bonded together to form a substituted or unsubstituted benzene, cycloalkyl or cycloalkenyl ring, and the carbon atom to which the two R groups are attached is benzene, cycloalkyl or cycloalkenyl. Part of a ring,
M is a transition metal in oxidation state I, II, III, IV, V or VI or is selected from groups 6, 7, 8, 9, 10, and 11 of the periodic table;
Q is a counter ion that balances the charge of the macrocyclic metal complex on a stoichiometric basis, and L is another ligand.]
A macrocyclic metal complex of
And 2) the use of an oxidizing system comprising two components of an oxidizing agent.   Dyed textile material obtainable by use of an oxidizing system according to claim 1.