WO2009000685A1

WO2009000685A1 - Use of metal complex oxidation catalysts together with zinc compounds in laundry compositions

Info

Publication number: WO2009000685A1
Application number: PCT/EP2008/057529
Authority: WO
Inventors: Hauke Rohwer; Menno Hazenkamp; Marie-José DUBS
Original assignee: Basf Se
Priority date: 2007-06-25
Filing date: 2008-06-16
Publication date: 2008-12-31

Abstract

Textile washing/bleaching compositions are provided that comprise metal complex catalysts and zinc compounds for improving the bleaching action of peroxides and reducing catalyst-induced fabric damage resulting in loss of tensile strength of the fibers and/or colour damage (fading).

Description

Use of Metal Complex Oxidation Catalysts Together with Zinc Compounds in Laundry Compositions.

The present invention relates to the use of metal complex oxidation catalysts together with a zinc compound in laundry compositions, such as laundry washing or bleaching compositions for textile materials.

These compositions improve the bleaching action of peroxides, without at the same time causing any appreciable damages to the textile fibres and dyeings.

Peroxide-containing bleaching agents have been used in washing and cleaning processes for some time. They have an excellent action at a liquor temperature of 90⁰C and above, but their performance noticeably decreases with lower temperatures. It is known that various transition metal ions, added in the form of suitable salts, or coordination compounds containing such cations catalyse the bleaching action of H₂O₂, or of precursors that release H₂O₂, or of other peroxo compounds, the bleaching action of which is unsatisfactory at lower temperatures. Particularly significant for practical purposes are those combinations of transition metal ions and ligands the peroxide activation of which is manifested in an increased tendency towards oxidation in respect of substrates and not only in a catalase-like disproportionation. The latter activation, which tends rather to be undesirable in the present case, could impair the bleaching effects of H₂O₂ and its derivatives which are insufficient at low temperatures.

With respect to H₂O₂ activation having effective bleaching action, mononuclear and polynuclear variants of manganese complexes with various ligands, especially with 1 ,4,7- trimethyl-1 ,4,7-triazacyclononane and optionally oxygen-containing bridge ligands, are currently regarded as being especially effective. Such catalysts have adequate stability under practical conditions and, with Mnⁿ⁺, contain an ecologically acceptable metal cation, but their use sometimes is unfortunately associated with considerable damage to dyes and fibres.

It has now been surprisingly found that the improved metal complex bleaching technology for oxidation processes according to the present invention overcomes the disadvantages mentioned above, i.e, it especially reduces the damages to textile fabrics induced by said catalysts in the laundry process without impairing the bleach activity. One object of the present invention is, therefore, the use of a metal complex catalyst together with 1 ppm to 95 ppm of zinc in a textile laundry composition, based on the weight of the total laundry composition for improving the bleaching action of peroxides while retaining a low color change and reduced fabric damage.

A similar solution has already been disclosed in EP 0 718 398 where a variety of metal salts, such as for example Mg salts, have been suggested. However, a significantly higher amount of metal ions in the detergent seems to be necessary according to the disclosure of EP 0 718 398, namely 0.01 to 2% by weight.

Under textile laundry composition within the instant invention there is understood a composition comprising

0 to 50%, preferably 0 to 30 %, of an anionic surfactant and/or of a non-ionic surfactant, 0 to 70%, preferably 0 to 50 %, of a builder substance,

0 to 70% of a salt;

1 to 99%, preferably 1 to 50 %, of a peroxide or a peroxide-forming substance where the sum of components adds to 100%.

In other words textile laundry compositions comprise laundry detergents and bleaching compositions.

Low color change and reduced fiber damage means, for example, low or no loss of tensile strength of the fibers and low or no color fading of the dyes.

Preferably fabric damage, which results in loss of tensile strength of the fibers is reduced or even prevented and/or a reduced color fading is achieved.

Another object of the present invention is the corresponding method of washing/bleaching a textile material with said laundry compositions.

Other objects of the present invention are washing/bleaching agents (detergents/bleach additives) comprising said metal oxidation catalysts and zinc compounds and being in the form of a powder, granular or liquid composition; included are complete washing/bleaching agents or premixtures containing single components (suitable to form the agent).

These and other objects of the present invention are described in detailed manner hereinbelow.

For example the laundry composition is a bleach-containing detergent composition.

The use of zinc salts in a detergent is not straight forward since the major part of the detergent ingredients serves as water softening compound while immobilizing earth alkali cations like calcium, magnesium, strontium and barium in order to prevent lime soap formation and scaling. Consequently it is to be expected that a zinc species in the wash liquor will be deactivated by the other detergent ingredients.

For instance zinc is added in the form of zinc compounds, such as zinc salts or zinc complexes formed from zinc salts and carboxylic, aminocarboxylic or phosphonic/phosphoric acids.

Zinc salts are for example ZnCI₂, ZnCI₂x6H₂O, ZnCO₃, Zn(HCO₃)₂, ZnNH₄PO₄x6H₂O, ZnO, Zn(OH)₂, ZnSO₄, ZnSO₄x7H₂O, ZnSiO₃, ZnSiO₄, Zn(NO₃)₂, Zn(NO₃)₂x6H₂O, Zn(CH₃COO)₂, Zn(CH₃COO)₂x4H₂O, ZnHPO₄x3H₂O, Zn-sulfonates, Zn acetate dihydrate; Zn acetylacetonate hydrate; ZnBr₂, Zn citrate tribasic dihydrate, Zn sulphate monohydrate, Zn SO₄ heptahydrate.

Zn-Complexes may be complexes formed from zinc salts and carboxylic acids like oxalic acid, citric acid, salicylic acid, malonic acid, glycine, gluconic acid, phthalic acid, tartaric acid, ethylendiaminetetraacetic acid EDTA, ethylenediaminedisuccinate EDDS, nitrilotriacetic acid NTA, diethylenetraiminepentaacetate DTPA, propylenediaminetetraacetate PDTA, methylglycinediacetic acid MGDA, Asparticacid diacetat ASDA, Glutamicacid diacetat GLDA, Hydroxyethyliminodiacetate HEIDA, lminodisuccinat IDS, polyacrylates, co- polymerisates of acrylic acid and maleic acid or organic phosphates and phosphonates like ethylendiaminetetra(methylenephosphonic acid) EDTMP, diethylentriaminepenta(methylene- phosphonic acid) DTPMP, DTPA, Hexamethylenediaminetetra(methylenephosphonic acid) HDTMPA, hydroxyethylidene(1 ,1diphosphonic acid) HEDP, aminotri(methylenephosphonic - A -

acid) ATMP, Indosol-hexaphosphoric acid, Aspartic- and Polyaspartic acid, pyrithione, o- hydroxy-aniline derivatives, brenzcatechine derivatives e. g. Trion = brenzcatechine-2,4-di- sulfonicacid.

These zinc complexes may also be formed "in situ" in the wash or bleach liquor by adding a soluble zinc salt and the carboxylic, aminocarboxylic, phosphoric or phosphonic acid separately. Compounds formed from zinc ions with cellulose/cellulose derivatives, starch/starch derivatives or sugar/sugar derivatives are also part of this invention. For example use may be made of the following zinc compounds:

ZnCI₂x6H₂O, ZnSO₄x7H₂O, Zn(HCOs)₂, ZnCO₃, Zn(OH)₂, Zn(CH₃COO)₂, the complexes formed from Zn salts and salicylic, citric and gluconic acid, EDTMP, EDTA, HEDP, ATMP and DTPMP.

Preferably the zinc compounds are selected from the group consisting of ZnCI₂x6H₂O, ZnSO₄x7H₂O, Zn(HCO₃)₂, ZnCO₃, Zn(OH)₂, Zn(CH₃COO)₂, the complexes formed from Zn and salicylic, citric and gluconic acid, HEDP (hydroxyethylidene(1 ,1 diphosphonic acid)), EDTMP (ethylenediamine-tetramethylene-phosphonic acid), ATMP (aminotri(methylene phosphonic acid)) and DTPMP (diethylenetriamine-penta(methylenephosphonic acid)).

Most preferred is the complex of a Zn salt with ethylenediamine-tetramethylene-phosphonic acid.

For example the Zn compounds may be used together with similar compounds that contain Fe, Cu, Co, Cr, Al, Sr or Ba -ions instead of Zn.

The metal complex catalyst may be selected from a wide range of organic molecules (ligands) and complexes thereof. Suitable complexes or ligands can be found, for example in: DE102004003710, EP 549271 , EP 549272, EP 458397, EP 458398, EP 0909809, EP 0765381 , EP 1001009, EP 977828, EP 1557457, EP 1083173, EP 1445305, EP 1225215, EP 0877078, EP 0783035, EP 0761809, EP 1520910, US 5244594, US 5246621 , US 5194416, US 51 1461 1 , US 2005187126, US 6828293, US 6365562, US 20020028753, US 6602441 , US 61 19705, WO2002/088289, WO2003/104234, WO2004/007657, WO1997/48787, WO 2005/068074, WO 2005/068075, WO 2005/105303, WO 97/16521 , WO 00/42150, WO 96/06154, WO 02/48301 , WO 05/042532 and WO 03/072688; the complexes and ligands which are herein incorporated by reference.

These catalysts are described as being active for catalyzing the bleaching action of peroxy compounds on various stains. Beside the desired effects like the bleaching of stains and soil on textiles in domestic laundering this kind of products tend to exhibit sometimes more or less severe color and fiber damage. This effect is most pronounced on cotton (cellulose), the most frequently used fiber for textile garments.

As to the bleach catalysts, those of the following formulae (1 ) to (4) are of special interest:

wherein each R₁, independently of the other, is hydrogen; d-d₂alkyl unsubstituted or substituted by halogen, d-C₄alkoxy, phenyl, carboxyl, d-C₄alkoxycarbonyl or mono- or di-Ci-C₄alkylated amino groups; C₄-C₈cycloalkyl unsubstituted or substituted by Ci-C₄alkyl or by Ci-C₄alkoxy; phenyl unsubstituted or substituted by Ci-C₄alkyl, Ci-C₄alkoxy, C₂-C₅alkanoylamino, nitro, sulfo or mono- or di-Ci-C₄alkylated amino groups; or naphthyl unsubstituted or substituted by CrC₄alkyl, Ci-C₄alkoxy, C₂-C₅alkanoylamino, nitro, sulfo or mono- or di-CrC₄alkylated amino groups; each R₂, independently of the other(s), is hydrogen; hydroxy; d-d₂alkyl unsubstituted or substituted by halogen, d-dalkoxy, phenyl, carboxyl, d-dalkoxycarbonyl or by a mono- or di-d-dalkylated amino group; d-C₈alkoxy unsubstituted or substituted by halogen, d- dalkoxy, phenyl, carboxyl, d-dalkoxycarbonyl or by a mono- or di-d-dalkylated amino group; halogen; N(d-C₄alkyl)₂ or NH(d-dalkyl) in which at least one alkyl group may be substituted by halogen, d-dalkoxy, phenyl, carboxyl, d-dalkoxycarbonyl or by a mono- or di-d-C₄alkylated amino group; N^Θ(d-dalkyl)₃ or NH^Θ(d-dalkyl)₂ in which at least one alkyl group may be substituted by halogen, d-dalkoxy, phenyl, carboxyl, d-dalkoxycarbonyl or by a mono- or di-d-dalkylated amino group; or a water-soluble group; Y is linear or branched alkylene of formula -[C(Ri)₂]_m, wherein m is a number from 1 to 8 and each R₁ independently of the other(s), is as defined hereinbefore; -CX=CX-, wherein X is cyano, linear or branched Ci-C₈alkyl or di(linear or branched Ci-C₈alkyl)amino; -(CH₂X-NR₁-(CH₂X-, wherein R₁ is as defined hereinbefore and r is 1 , 2, 3 or 4; or a 1 ,2-cyclohexylene or phenylene group of formula:

wherein R is hydrogen, CH₂OH, CH₂NH₂ or SO₃M, wherein M is hydrogen, an alkali metal ion, ammonium or a cation that is formed from an amine, each q, independently of the other, is 0, 1 , 2 or 3; and

A is an anion; bleach catalysts of formula (2)

wherein

R₃, R₄, R₅, Re, Rβ', R₄', FR₅ ¹, R₆', R₃", R₄", R₅" and R₆" are each independently of the others hydrogen; cyano; halogen; -SO₃M; -SO₂NH₂; -SO₂NHR₇; -SO₂N(R₇)₂; -OR₇; -COOR₇; nitro; linear or branched C-i-Csalkyl; linear or branched partially fluorinated or perfluorinated C₁-

C₈alkyl; -NHR₈; -NR₈R₉; -N⁰R₈R₉R₁₂ or linear or branched C_rC₈alkyl-R₁₀;

M is hydrogen; an alkali metal cation; an alkaline earth metal cation; ammonium or an organic ammonium cation;

R₇ is hydrogen; or linear or branched CrC₄alkyl;

R₁₀ is OR₇; -COOR₇; -NH₂; -NHR₈; -NR₈R₉ or -N⁰R₈R₉R₁₂; R₈, Rg and Ri₂ are the same or different and each is linear or branched d-C^alkyl; or R₈ and

R₉ together with the nitrogen atom linking them form a 5-, 6- or 7-membered ring that may contain further hetero atoms;

Rii, R₁₁ ¹ and Rn" are each independently of the others hydrogen; linear or branched CrC₈- alkyl or aryl, and

Me is a transition metal; bleach catalysts of formula (3)

Ri3, Ri4, Ri5, Ri6, Ri7, Ri₈, Rig, R20, R21 , R22 and R₂₃ are each independently of the others hydrogen; unsubstituted or substituted Ci-Ci₈alkyl; unsubstituted or substituted aryl; cyano; halogen; nitro; -COOR₂₄; -SO₃R₂₄, wherein R₂₄ is in each case hydrogen; a cation; unsubstituted or substituted Ci-C-ι₈alkyl or unsubstituted or substituted aryl;

wherein R₂₅ is in each case hydrogen; or unsubstituted or substituted Ci-Ci₈alkyl;

-NR₂₆R₂₇; -(CrC₆alkylene)-N R₂₆R₂₇; -N⁰R₂₆R₂₇R₂₈; -(Ci-C₆alkylene)-N^ΘR₂₆R₂₇R₂₈;

-N(R₂₅)-(Ci-C₆alkylene)-NR₂₆R₂₇; -N[(C_rC₆alkylene)-NR₂₆R₂₇]₂;

-N(R₂₅)-(Ci-C₆alkylene)-N^ΘR₂₆R₂₇R₂₈; -N[(Ci-C₆alkylene)-N^ΘR₂₆R₂₇R₂₈]₂; -N(R₂₅)-NR₂₆R₂₇; or

-N(R₂₅)-N^ΘR₂₆R₂₇R₂₈, wherein R₂₆, R₂₇ and R₂₈ are each independently of the others hydrogen; unsubstituted or substituted Ci-Ci₈alkyl; or unsubstituted or substituted aryl; or wherein R₂₆ and R₂₇, together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7- membered ring that may contain further hetero atoms,

Me is a transition metal and A is an anion; bleach catalysts of formula (4)

wherein

Q is N or -CR₃₈;

R₂₉, R₃o, R31, R32, R33, R34, R35, R36, R37 and R₃₈ are each independently of the others hydrogen; unsubstituted or substituted Ci-Ci₈alkyl; unsubstituted or substituted aryl; cyano; halogen; nitro; -COOR₃₉; -SO₃R₃₉, wherein R₃₉ is in each case hydrogen; a cation; unsubstituted or substituted Ci-Ci₈alkyl or unsubstituted or substituted aryl;

wherein R₄₀ is in each case hydrogen; unsubstituted or substituted CrCi₈alkyl or unsubstituted or substituted aryl;

-NR41R42; -(Ci-C₆alkylene)-NR₄iR₄2; -N⁰R₄₁R₄₂R₄₃; -(Ci-C₆alkylene)-N^ΘR₄₁ R₄₂R₄₃;

-N(R₄₀)-(Ci-C₆alkylene)-NR₄₁R₄₂; -N[(C_rC₆alkylene)-NR₄₁R₄₂]₂;

-N(R₄₀)-(Ci-C₆alkylene)-N^ΘR₄₁R₄₂R₄₃; -N[(Ci-C₆alkylene)-N^ΘR₄₁R₄₂R₄₃]₂; -N(R₄₀)-NR₄₁R₄₂; or -

wherein R₄₀ is as defined hereinbefore; and wherein R₄₁, R₄₂ and R₄₃ are each independently of the others hydrogen; unsubstituted or substituted CrC₁₈alkyl or unsubstituted or substituted aryl; or R₄₁ and R₄₂, together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring that may contain further hetero atoms;

Me is a transition metal and

A is an anion.

The ligands in the metal complexes of formulae (3) and (4) that are substituted by hydroxyl can also be formulated as compounds having a pyridone structure, in accordance with the following scheme (illustrated here by the example of a terpyridine substituted by hydroxy in the 4' position):

terpyridin-4'-one structure terpyridin-4'-ol structure.

The special position of the above hydroxy-substituted terpyridines within the terpyridine family is due to the fact that these ligands can be be deprotonated and are therefore able to function as anionic ligands.

Accordingly, there are generally to be understood by hydroxyl-substituted terpyridines also those having a corresponding pyridone structure.

Suitable substituents for the alkyl groups, aryl groups, alkylene groups or 5-, 6- or 7- membered rings include especially Ci-C₄alkyl; d-C₄alkoxy; hydroxyl; sulfo; sulfato; halogen; cyano; nitro; carboxyl; amino; phenyl unsubstituted or substituted by N-mono- or N,N-di- Ci-C₄alkylamino substituted by hydroxy in the alkyl moiety, N-phenylamino, N-naphthyl- amino, phenyl, phenoxy or by naphthyloxy.

The alkyl radicals mentioned for the compounds of formulae (1 ), (2), (3) and (4) are, for example, straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl or straight-chain or branched pentyl, hexyl, heptyl or octyl. The mentioned alkyl radicals may be unsubstituted or may be substituted, for example, by hydroxyl, Ci-C₄alkoxy, sulfo or sulfato, especially by hydroxyl. Preference is given to the corresponding unsubstituted alkyl radicals. Special preference is given to methyl and ethyl, especially methyl.

As aryl radicals for the compounds of formulae (1 ), (2), (3) and (4) there come into consideration, for example, phenyl or naphthyl unsubstituted or substituted by Ci-C₄alkyl, CrC₄alkoxy, halogen, cyano, nitro, carboxyl, sulfo, hydroxyl, amino, N-mono- or N,N-di- Ci-C₄alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, N-phenylamino, N-naphthylamino, in which the amino groups may be quaternised, phenyl, phenoxy or by naphthyloxy. Preferred substituents are Ci-C₄alkyl, Ci-C₄alkoxy, phenyl or hydroxy. Special preference is given to the corresponding phenyl radicals.

The Ci-C₆alkylene groups mentioned for the compounds of formulae (1 ), (2), (3) and (4) include, for example, straight-chain or branched alkylene radicals, such as methylene, ethylene, n-propylene or n-butylene. Preference is given to Ci-C₄alkylene groups. The mentioned alkylene radicals may be unsubstituted or substituted, for example by hydroxyl or by Ci-C₄alkoxy.

For the compounds of formulae (1 ), (2), (3) and (4), halogen is preferably chlorine, bromine or fluorine, with special preference being given to chlorine.

As cations for the compounds of formulae (1 ), (2), (3) and (4) there come into consideration, for example, alkali metal cations, such as lithium, potassium or, especially, sodium, alkaline earth metal cations, such as magnesium or calcium, and ammonium cations. The corresponding alkali metal cations, especially sodium, are preferred.

Suitable metal ions for Me for the compounds of formulae (2), (3) and (4) include, for example, manganese in oxidation states N-V, titanium in oxidation states III and IV, iron in oxidation states I to IV, cobalt in oxidation states I to III, nickel in oxidation states I to III and copper in oxidation states I to III. Of those, special preference is given to manganese, especially manganese in oxidation states Il to IV, more especially in oxidation state II. Also of interest are titanium IV, iron N-IV, cobalt N-III, nickel N-III and copper N-Nl, especially iron N-IV.

As anion A for the compounds of formulae (1 ), (2), (3) and (4) there come into consideration, for example, R'COO^"; CIO₄ ^"; BF₄ ^"; PF₆ ^"; R¹SO₃ ^"; R¹SO₄ ^"; SO₄ ^2"; NO₃ ^"; F^"; Cl^"; Br^" or I^", wherein R' is hydrogen or unsubstituted or substituted Ci-Ci₈alkyl or aryl. For R' as Ci-Ci₈alkyl or aryl, the definitions and preferred meanings given hereinbefore and hereinafter apply. Especially preferably, R' is hydrogen; Ci-C₄alkyl; phenyl or sulfophenyl, especially hydrogen or 4-sulfophenyl. The charge of the anion A is accordingly especially 1^" or 2^", more especially 1^". A can also be a customary organic counter-ion, for example citrate, oxalate or tartrate.

Preference is given to bleach catalysts of formula (1¹)

wherein each R₂, independently of the other(s), is hydroxy; Ci-C₄alkyl unsubstituted or substituted by halogen, d-C₄alkoxy, phenyl, carboxyl, Ci-C₄alkoxycarbonyl or by a mono- or di-

Ci-C₄alkylated amino group; Ci-C₄alkoxy unsubstituted or substituted by halogen,

Ci-C₄alkoxy, phenyl, carboxyl, Ci-C₄alkoxycarbonyl or by a mono- or di-Ci-C₄alkylated amino group; halogen; N(d-C₄alkyl)₂ or NH(Ci-C₄alkyl) in which at least one alkyl group may be substituted by halogen, Ci-C₄alkoxy, phenyl, carboxyl, Ci-C₄alkoxycarbonyl or by a mono- or di-Ci-C₄alkylated amino group; or a water-soluble group;

Y is linear or branched alkylene of formula -[C(Ri)₂J_m, wherein m is a number from 1 to 4 and each R₁, independently of the other(s), is as defined hereinbefore;

-(CH₂X-NR₁-(CH₂X- wherein R₁ is as defined hereinbefore and r is 1 or 2; or a 1 ,2- cyclohexylene or phenylene group of formula:

wherein R is hydrogen, CH₂OH, CH₂NH₂ or SO₃M, wherein M is hydrogen, an alkali metal ion, ammonium or a cation that is formed from an amine, each q, independently of the other, is 0, 1 or 2; and

A is F^"; Cl^"; Br^"; I^"; perchlorate; sulfate; nitrate; OH^"; BF₄ ^"; PF₆ ^" or carboxylate.

Preference is given likewise to bleach catalysts of formula (2) wherein R₃, R₄, R₅, Re, Rs', R₄', Rs', Re', Rs", R₄", Rs" and R₆" are each independently of the others hydrogen; cyano; Cl; -SO₃M, wherein M is hydrogen; an alkali metal cation; an alkaline earth metal cation; ammonium; an organic ammonium cation; nitro; linear or branched Ci-C₄alkyl; linear or branched partially fluorinated or perfluorinated

Ci-C₄alkyl; -NHR₈; -NR₈R₉; -N⁰R₈R₉Ri₂; or linear or branched Ci-C₄alkyl-R₁₀, wherein R₁₀ is -OR₇; -COOR₇; -NH₂; -NHR₈; -NR₈R₉; Or -N⁰R₈R₉R₁₂; and wherein R₈, R₉ and Ri₂, are identical or different and are each linear or branched

Ci-C₄alkyl.

Bleach catalysts of formula (2) to which special preference is given are 1 :1 Me(III) complexes of formula (2')

wherein Me is Mn or Fe,

R₃, R₃' and R₃" are each independently of the others hydrogen; Ci-C₄alkyl; Ci-C₄alkoxy; hydroxy; nitro; NHR₆; NR₆R₇ Or -N⁰R₅R₆R₇, wherein R₅, R₆ and R₇ are each independently of the others CrC₄alkyl and Rn, R'n and R"n are as defined hereinbefore.

Preference is given likewise to bleach catalysts of formula (3) wherein

Ri₃, Ri₄, Ri₅, Ri₆, Ri₇, Ri₈, Ri₉, R₂₀, R₂i, R₂₂ and R₂₃ are each independently of the others hydrogen; unsubstituted or substituted Ci-C₄alkyl; unsubstituted or substituted aryl; cyano; halogen; nitro; -COOR₂₄; -SO₃R₂₄, wherein R₂₄ is in each case hydrogen; a cation; unsubstituted or substituted CrC₄alkyl or unsubstituted or substituted aryl;

-SR₂₅; -SO₂R₂₅; -OR₂₅, wherein R₂₅ is in each case hydrogen; unsubstituted or substituted Ci-C₄alkyl or unsubstituted or substituted aryl;

-NR₂₆R₂₇; -(Ci-C₄alkylene)-N R₂₆R₂₇; -N⁰R₂₆R₂₇R₂₈; -(C_rC₄alkylene)-N⁰R₂₆R₂₇R₂₈; -N(R₂₅)-(Ci-C₄alkylene)-NR₂₆R₂₇; -N[(C_rC₄alkylene)-NR₂₆R₂₇]₂; -N(R₂₅)-( Ci-C₄alkylene)-N^ΘR₂6R27R28; -N[(Ci-C₄alkylene)-N^ΘR₂6R27R28]2; -N(R₂S)-NR₂₆R₂₇; or -N(R₂₅)-N^ΘR₂₆R₂₇R_28! wherein R₂₅ is as defined hereinbefore; and wherein R₂₆, R₂₇ and R₂₈ are each independently of the others hydrogen; or unsubstituted or substituted CrC₄alkyl or unsubstituted or substituted aryl; or R₂₆ and R₂₇, together with the nitrogen atom linking them, form an unsubstituted or substituted 6-membered ring that may contain further hetero atoms, especially a piperazine ring.

Bleach catalysts of formula (3) to which greater preference is given are 1 :1 Me(II or III) complexes of formula (3')

wherein

Ri₈ is unsubstituted or substituted Ci-C₄alkyl; unsubstituted or substituted aryl; cyano; halogen; nitro; -COOR₂₄; -SO₃R₂₄, wherein R₂₄ is in each case hydrogen; a cation; unsubstituted or substituted CrC₄alkyl or unsubstituted or substituted aryl; or R₁₈ is

wherein R₂₅ is in each case hydrogen; unsubstituted or substituted CrC₄alkyl or unsubstituted or substituted aryl;

-NR₂₆R₂₇; -(Ci-C₄alkylene)-N R₂₆R₂₇; -N⁰R₂₆R₂₇R₂₈; -(C_rC₄alkylene)-N⁰R₂₆R₂₇R₂₈;

-N(R₂₅)-(Ci-C₄alkylene)-NR₂₆R₂₇; -N[(C_rC₄alkylene)-NR₂₆R₂₇]₂;

-N(R₂₅M Ci-C₄alkylene)-N^ΘR₂₆R₂₇R₂₈; -N[(C_rC₄alkylene)-N⁰R₂₆R₂₇R₂₈]₂; -N(R₂₅)-NR₂₆R₂₇; or

-N(R₂₅)-N⁰R₂₆R₂₇R₂₈, wherein R₂₅ is as defined hereinbefore; and wherein R₂₆, R₂₇ and R₂₈ are each independently of the others hydrogen; or unsubstituted or substituted CrC₄alkyl or unsubstituted or substituted aryl; or R₂₆ and R₂₇, together with the nitrogen atom linking them, form an unsubstituted or substituted 6-membered ring that may contain further hetero atoms, especially a piperazine ring; Ri5 and R₂i are each independently of the other hydrogen or have the meanings given for

When in the bleach catalysts of formulae 2, 2', 3, 3' or 4 the radicals R₈ and R₉, R₂6 and R₂7 or R₄₁ and R₄₂ together with the atom to which they are bonded form a 5, 6 or 7-membered ring, such a ring is preferably

; — N N-CH₂CH₂OH _; — N N-CH_{3 ;} — N N'_CH ;

/ \₊_CH₂CH₂OH / \₊ CH₂CH₂OH

-YJ)^NXH₃ : °^r -YJ)^N:CH₂CH₂OH

Other preferred substitution patterns for these substituents are

— NCH₂CH₂N(CH₃)₃ ; — NCH₂CH₂N(CH₃)₂ ; CH₃ CH₃

-NHCH₂CH₂N(CH₃)_{3 ;} -NHCH₂CH₂N(CH₃)₂ ■ -N[CH₂CH₂N(CH₃)₃]₂ ; -N[CH₂CH₂N(CH₃)₂]_{2 ;}

-N[CH₂CH₂CH₂N(CH₃)₂]₂ or -N[CH₂CH₂CH₂N(CH₃)₃]₂ -NC^OH

CH₃

Bleach catalysts of formula (3') to which special preference is given are those wherein R-_I8 is Ci-C₄alkoxy; hydroxy; N-mono- or N,N-di-C-i-C₄alkylamino substituted by hydroxy in the alkyl moiety; or an unsubstituted or Ci-C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring, and Ri5 and R₂i are each independently of the other hydrogen; Ci-C₄alkoxy; hydroxy; N-mono- or N,N-di-Ci-C₄alkylamino substituted by hydroxy in the alkyl moiety; or an unsubstituted or d- C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring.

Preference is given likewise to bleach catalysts of formula (4) wherein Q is N or CR₃₈,

R₂₉, R₃₀, R₃i, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R37 and R₃₈ are each independently of the others hydrogen; unsubstituted or substituted Ci-C₄alkyl; unsubstituted or substituted aryl; cyano; halogen; nitro; -COOR₃₉; -SO₃R₃₉, wherein R₃₉ is in each case hydrogen; a cation; or unsubstituted or substituted Ci-C₄alkyl or unsubstituted or substituted aryl;

wherein R₄₀ is in each case hydrogen; or unsubstituted or substituted CrC₄alkyl or unsubstituted or substituted aryl;

-NR41R42; -(Ci-C₄alkylene)-NR₄iR₄2; -N⁰R₄IR₄₂R₄S! -(C_rC₄alkylene)-N^ΘR₄₁ R₄₂R₄₃;

-N(R₄₀)-(Ci-C₄alkylene)-NR₄₁R₄₂; -N[(C_rC₄alkylene)-NR₄₁R₄₂]₂;

-N(R₄₀)-(Ci-C₄alkylene)-N^ΘR₄₁R₄₂R₄₃; -N[(C_rC₄alkylene)-N^ΘR₄₁R₄₂R₄₃]₂; -N(R₄₀)-NR₄₁R₄₂; or -

wherein R₄₁, R₄₂ and R₄₃ are each independently of the others hydrogen; unsubstituted or substituted CrC₄alkyl or unsubstituted or substituted aryl; or wherein R₄₁ and R₄₂, together with the nitrogen atom linking them, form an unsubstituted or substituted 6-membered ring that may contain further hetero atoms, especially a piperazine ring.

Bleach catalysts of formula (4) to which greater preference is given are 1 :1 Me(II or III) complexes of formula (4'α)

wherein R'₃₃ is -OH;

_V1+^CH₂CH₂OH _S+/CH₂CH₂OH

— N N. — N N. . — NCH₂CH₂N(CH₃)₃ ; — NCH₂CH₂N(CH₃),,

CH, CH₂CH₂OH

CH '3, C ^H¹ '3,

+ +

-NHCH₂CH₂N(CH₃)_{3 ;} — NHCH₂CH₂N(CH₃)₂ ^■ — N[CH₂CH₂N(CH₃)₃]₂ ;

-N[CH₂CH₂CH₂N(CH₃)₂]₂ or -N[CH₂CH₂CH₂N(CH₃)₃]₂ -NC₂H₅OH

CH, R'₃i and R'₃₅ each independently of the other has the meanings given for R'₃₃ or is hydrogen, and

Bleach catalysts of formula (4) to which greater preference is likewise given are 1 :1 Me(II or III) complexes of formula (4'β)

wherein R'₃₃ is -OH,

_,+,CH₃

-N N ^■ — N N-CH₀CH₂OH — N N-CH '3, ■ ; — N N 'CH₃ '

₊_CH₂CH₂OH / \ _V^₊ CCHH₂₉CCHH₂₉OOHH +

— N N . __N' V ^{2 2} _; -NCH₂CH₂N(CH₃)₃ ; -NCH₂CH₂N(CH₃)₂ ;

^^ -^π3 ' ^{^}CH₂CH₂OH U I H₃ U I H₃

-NHCH₂CH₂N(CH₃)_{3 ;} -NHCH₂CH₂N(CH₃)₂ ^■ -N[CH₂CH₂N(CH₃)₃]₂ ; -N[CH₂CH₂N(CH₃)₂]_{2 ;}

+ — N[CH₂CH₂CH₂N(CH₃)₂]₂ or — N[CH₂CH₂CH₂N(CH₃)₃]₂

R'₃i and R'₃₅ each independently of the other has the meanings given for R'₃₃ or is hydrogen, and

The above-mentioned bleach catalysts of formulae (1 ) to (3) are prepared according to generally known processes.

Compounds of the bispyridyl-pyrimidine type (formula (4), wherein Q = CR₃₈) can be prepared in a manner known per se [F. H. Case et al., J. Org. Chem. 1967, 32(5), 1591- 1596]). For that purpose, for example, one part pyridine-2-carboxylic acid ester and one part ethyl acetate can be reacted with sodium hydride, and the intermediate obtained after aqueous work-up, a β-keto ester, can be reacted with 2-amidinopyridine, to yield the corresponding pyrimidine derivatives, which can be converted to the corresponding chlorine compounds by reaction with a chlorinating agent such as, for example, PCI₅/POCI₃. Reactions of those compounds with amines, as desired in the presence of an excess of redox-active transition metal salts, such as manganese, iron or ruthenium, in order to accelerate substitution, yield amine-substituted bispyridyl-pyrimidines. Preparation processes using the last two mentioned metal anions are described, for example, in J. Chem. Soc, Dalton Trans 1990, 1405-1409 (E. C. Constable et al) and New. J. Chem. 1992, 16, 855-867.

Compounds of the bispyridyl-triazine type (formula (4), wherein Q = N) can be prepared analogously to known processes (e.g. EP-A-555 180 and EP-A-556 156 or F. H. Case et al., J. Am. Chem. Soc. 1959, 81 , 905-906) by, for example, reacting two parts 2-cyanopyridine with urea or guanidine and a base.

The metal complex catalysts and zinc compounds are preferably used together with peroxy compounds. Examples that may be mentioned in that regard include the following uses: a) the bleaching of spots or stains on textile material in the context of a washing process; b) the prevention of redeposition of migrating dyes during the washing of textile material

Preference is given to the bleaching of spots or stains on textile material and the prevention of the redeposition of migrating dyes in the context of a washing process. For those purposes it is preferable to use aqueous formulations of the metal complex catalysts and zinc compounds.

Processes for preventing the redeposition of migrating dyes in a washing/bleaching liquor are usually carried out by adding to the washing liquor, which contains a peroxide-containing washing agent, one or more metal complex catalysts in an amount of from 0.1 to 200 mg, preferably from 1 to 75 mg, especially from 3 to 50 mg, per litre of washing liquor. It will be understood that in such an application, as well as in the other applications, the metal complex catalysts can alternatively be formed in situ, the metal salt (e.g. manganese(ll) salt, such as manganese(ll) chloride) and the ligand being added in the desired molar ratios.

The textile laundry composition contains preferably 1 to 80 ppm of Zn, based on the weight of the total composition. The zinc compound is added in an amount which in the liquor gives a concentration of 0.01 to 0.38 mg Zn/litre of liquor, preferably 0.02 to 0.35mg Zn/litre of liquor, and mostly preferred 0.03 to 0.30 mg Zn/litre

A further aspect of the invention is a method for improving the bleaching action of peroxides while retaining a low color and fabric damage, comprising applying a textile laundry composition which contains a metal complex catalyst together with 1 ppm to 95 ppm of zinc, based on the weight of the total laundry composition to a fiber or fabric.

Another object of the present invention relates to a washing/bleaching agent or a premixture of single components to be used for forming said washing/bleaching agent comprising

I) 0 to 50%, preferably 0 to 30 %, of an anionic surfactant (A) and/or of a non-ionic surfactant (B),

II) 0 to 70%, preferably 0 to 50 %, of a builder substance (C), III) 1 to 99%, preferably 1 to 50 %, of a peroxide or a peroxide-forming substance (D),

IV) 0.005 to 2%, preferably 0.01 to 1% or 0.05 to 1 % of the metal complex catalyst (E). and

V) 1 ppm to 95 ppm, of zinc (F).

The sum of components adds to 100%.

The amount of Zn is preferably from 1 ppm to 80 ppm.

The above percentages/ppm are in each case percentages/ppm by weight, based on the total weight of the agent.

These agents are used in the washing/bleaching liquors.

In one embodiment of the invention, the washing/bleaching agent comprises components (A) and/or (B), and (C) to (F).

In another embodiment of the invention the premixture for a washing/bleaching agent comprises components (D) to (F), preferably incorporated into liquid detergents. When the agents according to the invention comprise a component (A) and/or (B), the amount thereof is preferably 1 - 50 %, especially 1 - 30 %.

When the agents according to the invention comprise a component (C), the amount thereof is preferably 1 to 70 %, especially 1 to 50 %. Special preference is given to an amount of from 5 to 50 % and especially an amount of from 10 to 50 %.

The amount of the metal complex catalyst (E) gives a concentration of 0.5 to 50 mg/litre in the liquor, preferably 1 to 30 mg/litre, when from 0.5 to 20 g/litre of the washing (cleaning) or bleaching agent are added to the liquor.

Agents containing components (D) to (F) (premix) can be used e.g. to be incorporated into liquid detergents.

Corresponding washing processes are usually carried out by using an aqueous liquor comprising a peroxide and from 0.1 to 200 mg of one or more metal complexes and 0.01 to 0.38 mg Zn per litre of liquor. The liquor preferably contains from 1 to 30 mg of the metal complex and 0.02 to 0.35 mg Zn per litre of liquor.

The agents according to the invention can be, for example, a peroxide-containing complete washing agent or a separate bleaching additive. A bleaching additive is used for removing coloured stains on textiles in a separate liquor before the clothes are washed with a bleach- free washing agent. A bleaching additive can also be used in a liquor together with a bleach- free washing agent, or even a bleach containing detergent.

The washing/bleaching agent or premixture of single components can be in the form of a powder, granular or liquid composition.

A further aspect of the invention is a method of preparing a textile laundry composition (washing liquor) for improving the bleaching action of peroxides and reducing catalyst- induced color and fabric damage, which comprises adding 0.5 to 20 g/litre of the washing/bleaching agent or a premixture for such an agent to the liquor. For example the method of washing (cleaning)/bleaching textile materials comprises using the laundry composition (washing liquors) as prepared above.

The washing/bleaching agent according to the invention can be in solid or liquid form, for example in the form of a liquid, non-aqueous washing agent, comprising not more than 5 % by weight water, preferably comprising from 0 to 1 % by weight water, and, as base, a suspension of a builder substance in a non-ionic surfactant, e.g. as described in GB-A- 2 158 454.

The washing agent is preferably in the form of a powder or, especially, granules.

The latter can be prepared, for example, by first preparing an initial powder by spray-drying an aqueous suspension containing all the components listed above except for components (D), (E) and (F), and then adding the dry components (D), (E) and F) and mixing everything together. It is also possible to add components (E) and( F) to an aqueous suspension containing components (A), (B) and (C), then to carry out spray-drying and then to mix component (D) with the dry mass.

It is also possible to start with an aqueous suspension that contains components (A) and (C), but none or only some of component (B). The suspension is spray-dried, then component (E) and (F) are mixed with component (B) and added, and then component (D) is mixed in the dry state.

It is also possible to mix all the components together in the dry state.

The anionic surfactant A) can be, for example, a sulfate, sulfonate or carboxylate surfactant or a mixture thereof. Preference is given to alkylbenzenesulfonat.es, alkyl sulfates, alkyl ether sulfates, olefin sulfonates, fatty acid salts, alkyl and alkenyl ether carboxylates or to an α- sulfonic fatty acid salt or an ester thereof.

Preferred sulfonates are, for example, alkylbenzenesulfonat.es having from 10 to 20 carbon atoms in the alkyl radical, alkyl sulfates having from 8 to 18 carbon atoms in the alkyl radical, alkyl ether sulfates having from 8 to 18 carbon atoms in the alkyl radical, and fatty acid salts derived from palm oil or tallow and having from 8 to 18 carbon atoms in the alkyl moiety. The average molar number of ethylene oxide units added to the alkyl ether sulfates is from 1 to 20, preferably from 1 to 10. The cation in the anionic surfactants is preferably an alkaline metal cation, especially sodium or potassium, more especially sodium. Preferred carboxylates are alkali metal sarcosinates of formula R_Ig-CON(R₂O)CH₂COOM₁ wherein R₁₉ is C₉-C₁₇alkyl or C₉-C₁₇alkenyl, R₂₀ is CrC₄alkyl and M₁ is an alkali metal, especially sodium.

The non-ionic surfactant B) may be, for example, a primary or secondary alcohol ethoxylate, especially a C₈-C₂₀ aliphatic alcohol ethoxylated with an average of from 1 to 20 mol of ethylene oxide per alcohol group. Preference is given to primary and secondary C₁₀-C₁₅ aliphatic alcohols ethoxylated with an average of from 1 to 10 mol of ethylene oxide per alcohol group. Non-ethoxylated non-ionic surfactants, for example alkylpolyglycosides, glycerol monoethers and polyhydroxyamides (glucamide), may likewise be used.

The total amount of anionic and non-ionic surfactants is preferably from 5 to 50 wt-%, especially from 5 to 40 wt-% and more especially from 5 to 30 wt-%. The lower limit of those surfactants to which even greater preference is given is 10 wt-%.

In addition to anionic and/or non-ionic surfactants the composition may contain cationic surfactants. Possible cationic surfactants include all common cationic surface-active compounds, especially surfactants having a textile softening effect.

Non-limited examples of cationic surfactants are given in the formulas below:

R

+ I

P— N— (CH₂)_n — CH-CH₂

R

P-N- (CH₂J_n -T-R p ! ! R- 4N-^» (CH₂) -T-R ₁₃ (CH₂)_n -T-R _β p^β and ^δ

wherein each radical R_α is independent of the others C_1-6-alkyl-, -alkenyl- or -hydroxyalkyl; each radical R_β is independent of the others C₈-₂₈-alkyl- or alkenyl;

R_γ is R_α or (CHz)_n-T- R_β;

R₅ is R_α or R_β or (CH₂)_n-T- R_β; T = -CH₂-, -O-CO- or -CO-O- and n is between 0 and 5. Preferred cationic surfactants present in the composition according to the invention include hydroxyalkyl-trialkyl-ammonium-compounds, especially C12-18- alkyl(hydroxyethyl)dimethylammonium compounds, and especially preferred the corresponding chloride salts. Compositions of the present invention can contain between 0.5 wt-% and 15 wt-% of the cationic surfactant, based on the total weight of the compostion.

As builder substance C) there come into consideration, for example, alkali metal phosphates, especially tripolyphosphates, carbonates and hydrogen carbonates, especially their sodium salts, silicates, aluminum silicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylenepoly(alkylenephosphonates) and mixtures of such compounds.

Silicates that are especially suitable are sodium salts of crystalline layered silicates of the formula NaHSi_tθ₂t+i.pH₂O or Na₂Si_tθ₂t+i.pH₂O wherein t is a number from 1.9 to 4 and p is a number from 0 to 20.

Among the aluminum silicates, preference is given to those commercially available under the names zeolite A, B, X and HS, and also to mixtures comprising two or more of such components. Special preference is given to zeolite A.

Among the polycarboxylates, preference is given to polyhydroxycarboxylat.es, especially citrates, and acrylates, and also to copolymers thereof with maleic anhydride. Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylene- diamine disuccinate either in racemic form or in the enantiomerically pure (S, S) form.

Phosphonates or aminoalkylenepoly(alkylenephosphonates) that are especially suitable are alkali metal salts of 1-hydroxyethane-1 ,1-diphosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepenta- methylenephosphonic acid, and also salts thereof. Also preferred polyphosphonates have the following formula

R_1TN- (CH₂CH₂N), -R₁₈ I

^R18 wherein Ri8 is CH₂PO₃H₂ or a water soluble salt thereof and d is an integer of the value 0, 1 , 2 or 3.

Especially preferred are the polyphosphonates wherein b is an integer of the value of 1.

The amount of the peroxide or the peroxide-forming substance is preferably 0.5 - 30 wt-%, more preferably 1 - 20 wt-% and especially preferably 1 - 15 wt-%.

As the peroxide component D) there come into consideration every compound which is capable of yielding hydrogen peroxide in aqueous solutions, for example, the organic and inorganic peroxides known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 10 to 95°C.

Preferably, however, inorganic peroxides are used, for example persulfates, perborates, percarbonates and/or persilicates.

Example of suitable inorganic peroxides are sodium perborate tetrahydrate or sodium perborated monohydrate, sodium percarbonate, inorganic peroxyacid compounds, such as for example potassium monopersulphate (MPS). If organic or inorganic peroxyacids are used as the peroxygen compound, the amount thereof will normally be within the range of about 2-80 wt-%, preferably from 4-30 wt-%.

The organic peroxides are, for example, mono- or poly-peroxides, urea peroxides, a combination of a d-C₄alkanol oxidase and d-C₄alkanol (Such as methanol oxidase and ethanol as described in WO95/07972), alkylhydroxy peroxides, such as cumene hydroperoxide and t-butyl hydroperoxide.

The peroxides may be in a variety of crystalline forms and have different water contents, and they may also be used together with other inorganic or organic compounds in order to improve their storage stability.

All these peroxy compounds may be utilized alone or in conjunction with a peroxyacid bleach precursor and/or an organic bleach catalyst not containing a transition metal. Generally, the bleaching composition of the invention can be suitably formulated to contain from 2 to 80 wt-%, preferably from 4 to 30 wt-%, of the peroxy bleaching agent. As oxidants, peroxo acids can also be used. One example are organic mono peracids of

O

, . R_1TC-O-OM formula ¹⁹ wherein

M signifies hydrogen or a cation, Rig signifies unsubstituted Ci-Ci₈alkyl; substituted Ci-Ci₈alkyl; unsubstituted aryl; substituted aryl; -(CrC6alkylene)-aryl, wherein the alkylene and/or the alkyl group may be substituted; and phthalimidoCi-C₈alkylene, wherein the phthalimido and/or the alkylene group may be substituted.

O

Preferred mono organic peroxy acids and their salts are those of formula ¹⁹ wherein

M signifies hydrogen or an alkali metal, and

R'i₉ signifies unsubstituted Ci-C₄alkyl; phenyl;-CrC₂alkylene-phenyl or phthalimidoC-i-Csalkylene.

Especially preferred is CH₃COOOH and its alkali salts.

Especially preferred is also ε-phthalimido peroxy hexanoic acid and its alkali salts.

Also suitable are diperoxyacids, for example, 1 ,12-diperoxydodecanedioic acid (DPDA), 1 ,9-diperoxyazelaic acid, diperoxybrassilic acid, diperoxysebasic acid, diperoxyisophthalic acid, 2-decyldiperoxybutane-1 ,4-diotic acid and 4,4'- sulphonylbisperoxybenzoic acid.

Instead of the peroxy acid it is also possible to use organic peroxy acid precursors and H₂O₂. Such precursors are the corresponding carboxyacid or the corresponding carboxyanhydrid or the corresponding carbonylchlorid, or amides, or esters, which can form the peroxy acids on perhydrolysis. Such reactions are commonly known.

Peroxyacid bleach precursors are known and amply described in literature, such as in the British Patents 836988; 864,798; 907,356; 1 ,003,310 and 1 ,519,351 ; German Patent

3,337,921 ; EP-A-0185522; EP-A-0174132; EP-A-0120591 ; and U.S. Pat. Nos. 1 ,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393. Peroxy acids precursers are often referred to as bleach activators. Suitable bleach activators include the bleach activators, that carry O- and/or N-acyl groups and/or unsubstituted or substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED); acylated glycolurils, especially tetraacetyl glycol urea (TAGU), N,N-diacetyl-N,N-dimethylurea (DDU); sodium-4-benzoyloxy benzene sulphonate (SBOBS); sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3- benzoloxy benzoate; trimethyl ammonium toluyloxy-benzene sulphonate;acylated triazine derivatives, especially 1 ,5-diacetyl-2,4-dioxohexahydro-1 ,3,5-triazine (DADHT); compounds of formula (6):

wherein R₂₂ is a sulfonate group, a carboxylic acid group or a carboxylate group, and wherein R₂₁ is linear or branched (C₇-Ci₅)alkyl, especially activators known under the names SNOBS, SLOBS and DOBA; acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran; and also acetylated sorbitol and mannitol and acylated sugar derivatives, especially pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone. It is also possible to use the combinations of conventional bleach activators known from German Patent Application DE-A-44 43 177. Nitrile compounds that form perimine acids with peroxides also come into consideration as bleach activators.

Another useful class of peroxyacid bleach precursors is that of the cationic i.e. quaternary ammonium substituted peroxyacid precursors as disclosed in US Pat. Nos. 4,751 ,015 and 4,397,757, in EP-A0284292 and EP-A-331 ,229. Examples of peroxyacid bleach precursors of this class are: 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphonphenyl carbonate chloride - (SPCC), N-octyl,N,N-dimehyl-N10 -carbophenoxy decyl ammonium chloride - (ODC), 3-(N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate and N,N,N-trimethyl ammonium toluyloxy benzene sulphonate. A further special class of bleach precursors is formed by the cationic nitriles as disclosed in EP-A-303,520, WO 96/40661 and in European Patent Specification No.'s 458,396, 790244 and 464,880. These cationic nitriles also known as nitril quats have the formula

R

R '40

38 2X

-N- (CH₂)_n..-N-

N≡C ~C≡N (δ)

R 39 R ^■41 wherein

R_3O is a Ci-C₂₄alkyl; a Ci-C₂₄alkenyl; an alkaryl having a Ci-C₂₄alkyl; a substituted d-

C₂₄alkyl; a substituted Ci-C₂₄alkenyl; a substituted aryl,

R₃₁ and R₃₂ are each independently a Ci-C₃alkyl; hydroxyalkyl having 1 to 3 carbon atoms, -(C₂H₄O)_nH, n being 1 to 6; -CH₂-CN

R₃₃ is is a Ci-C₂₀alkyl; a Ci-C₂₀alkenyl; a substituted Ci-C₂₀alkyl; a substituted

Ci-C₂₀alkenyl; an alkaryl having a Ci-C₂₄alkyl and at least one other substituent, R3₄, R35, R36, R37 and R₃₈ are each independently hydrogen, a Ci-Ci_Oalkyl, a Ci-Ci_Oalkenyl, a substituted Ci-Ci_Oalkyl, a substituted Ci-Ci_Oalkenyl, carboxyl, sulfonyl or cyano R₃₈, R₃9, R₄0 and R₄₁ are each independently a Ci-C₆alkyl, n' is an integer from 1 to 3, n" is an integer from 1 to 16, and X is an anion.

Other nitril quats have the following formula

wherein

R₄₂ and R₄₃ form, together with the nitrogen atom to which they are bonded, a ring comprising 4 to 6 carbon atoms, this ring may also be substituted by Ci-C₅-alkyl, Ci-C₅-alkoxy, Ci-C₅-alkanoyl, phenyl, amino, ammonium, cyano, cyanamino or chloro and 1 or 2 carbon atom(s) of this ring may also be substituted by a nitrogen atom, by a oxygen atom, by a N-R₄₇-group and/or by a R₄₄-N-R₄7-group, wherein R₄₇ is hydrogen, d-C₅-alkyl, C₂-C₅-alkenyl, C₂-C₅-alkinyl, phenyl, C₇-C₉-aralkyl, C₅-C₇-cycloalkyl, d-C₅-alkanoyl, cyanomethyl or cyano,

R₄₄ is CrC₂₄-, preferably Ci-C₄-alkyl; C₂-C₂₄- alkenyl, preferably C₂-C₄-alkenyl, cyanomethyl or Ci-C₄-alkoxy-Ci-C₄-alkyl,

R₄₅ and R₄₆ are independently from each other hydrogen; d-C₄-alkyl; d-C₄-alkenyl; d-C₄-alkoxy-Ci-C₄-alkyl; phenyl or d-C₃-alkylphenyl, preferably hydrogen, methyl or phenyl, whereby preferably the moiety R₄₅ signifies hydrogen, if R₄₆ is not hydrogen, and

X^" is an anion.

Suitable examples of nitril quats of formula (ε) are

, and

Other nitrile quats have the formula

wherein

A is a saturated ring formed by a plurality of atoms in addition to the N₁ atom, the saturated ring atoms to include at least one carbon atom and at least one heteroatom in addition to the N₁ atom, the said one heteroatom selected from the group consisting of O, S and N atoms, the substituent R₄₇ bound to the N₁ atom of the Formula (φ) structure is (a) a C₁-Cs- alkyl or alkoxylated alkyl where the alkoxy is C_2-4, (b) a C₄-C₂₄cycloalkyl, (c) a C₇-C₂₄alkaryl, (d) a repeating or nonrepeating alkoxy or alkoxylated alcohol, where the alkoxy unit is C_2-4, or (e) -CRsoRsrC≡N where R₅₀ and R₅₁ are each H, a CrC₂₄alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit is C₂-C₄, in Formula (φ) at least one of the R₄s and R₄g substituents is H and the other of R₄s and R₄g is H, a C"i-C₂₄alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit is C_2-4, and Y is at least one counterion.

The precursors may be used in an amount of up to 12 wt-%, preferably from 2-10 wt-% based on the total weight of the composition.

It is possible to use H₂O₂, O₂, air, the peroxy-containing compounds, the peroxy-acids as well as their precursors, further bleach catalyst and bleach activists in any combination with the inventive metall complexes.

The compositions may comprise, in addition to the combination according to the invention, one or more optical brighteners, for example from the classes bis-triazinylamino- stilbenedisulfonic acid, bis-triazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl or bis- benzofuranylbiphenyl, α bis-benzoxalyl derivative, bis-benzimidazolyl derivative or coumarin derivative or a pyrazoline derivative. The compositions may furthermore comprise one or more further additives. Such additives are, for example, dirt-suspending agents, for example sodium carboxymethylcellulose; pH regulators, for example alkali metal or alkaline earth metal silicates; foam regulators, for example soap; salts for adjusting the spray drying and the granulating properties, for example sodium sulfate; perfumes; and also, if appropriate, antistatics and softening agents such as, for example, smectite; bleaching agents; pigments; and/or toning agents. These constituents should especially be stable to any bleaching agent employed. If the detergent composition is used in an automatic dishwasher it is also common to use silver-corrosion inhibitors. Such auxiliaries are added in a total amount of from 0.1 - 20 wt-%, preferably from 0.5 - 10 wt-%, especially from 0.5 - 5 wt-%, based on the total weight of the detergent formulation.

Furthermore, the detergent may optionally also comprise enzymes. Enzymes can be added for the purpose of stain removal. The enzymes usually improve the action on stains caused by protein or starch, such as, for example, blood, milk, grass or fruit juices. Preferred enzymes are cellulases and proteases, especially proteases. Cellulases are enzymes that react with cellulose and its derivatives and hydrolyse them to form glucose, cellobiose and cellooligosaccharides. Cellulases remove dirt and, in addition, have the effect of enhancing the soft handle of the fabric. Examples of customary enzymes include, but are by no means limited to, the following: proteases as described in US-B-6 242 405, column 14, lines 21 to 32; lipases as described in US-B-6 242 405, column 14, lines 33 to 46; amylases as described in US-B-6 242 405, column 14, lines 47 to 56; and cellulases as described in US-B-6 242 405, column 14, lines 57 to 64. Commercially available detergent proteases, such as Alcalase^®, Esperase^®, Everlase^®,

Savinase^®, Kannase^® and Durazym^®, are sold e.g. by NOVOZYMES A/S.

Commercially available detergent amylases, such as Termamyl^®, Duramyl^®, Stainzyme^®,

Natalase^®, Ban^® and Fungamyl^®, are sold e.g. by NOVOZYMES A/S.

Commercially available detergent ellulases, such as Celluzyme^®, Carezyme^® and Endolase^®, are sold e.g. by NOVOZYMES A/S.

Commercially available detergent lipases, such as Lipolase^®, Lipolase Ultra^® and Lipoprime^®, are sold e.g. by NOVOZYMES A/S.

Suitable mannanases, such as Mannanaway^®, are sold by NOVOZYMES A/S. The enzymes, when used, may be present in a total amount of from 0.01 to 5 wt-%, especially from 0.05 to 5 wt-% and more especially from 0.1 to 4 wt-%, based on the total weight of the detergent formulation.

Further preferred additives to the compositions according to the invention are dye-fixing agents and/or polymers which, during the washing of textiles, prevent staining caused by dyes in the washing liquor that have been released from the textiles under the washing conditions. Such polymers are preferably polyvinylpyrrolidones, polyvinylimidazoles or polyvinylpyridine-N-oxides, which may have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight in the range of from 5000 to 60 000, more especially from 10 000 to 50 000. Such polymers are usually used in a total amount of from 0.01 to 5 wt-%, especially from 0.05 to 5 wt-%, more especially from 0.1 to 2 wt-%, based on the total weight of the detergent formulation. Preferred polymers are those mentioned in WO-A-02/02865 (see especially page 1 , last paragraph and page 2, first paragraph) and those in WO-A-04/05688.

The invention relates also to granules that comprise the catalysts and a zinc compound according to the invention and are suitable for incorporation into a powder- or granule-form washing or bleaching agent. Such granules preferably comprise: (a) 1 to 99% by weight of the metal complex catalyst,

(b) 1 to 99% by weight of a binder,

(c) 0 to 20 % by weight of an encapsulating material,

(d) 1 to 1900 ppm by weight of zinc,

(e) 0 to 20 % by weight of a further additive and (f) 0 to 20 % by weight of water.

The addition of the zinc compound to the detergent or bleach additive is not limited to its incorporation into the metal complex granules. It can also directly be added to the detergent/bleach additive. The addition via the metal complex granules and direct addition is also possible.

As binder (b) there can be used anionic dispersants, non-ionic dispersants, polymers and waxes that are water-soluble, dispersible or emulsifiable in water. The anionic dispersants used are, for example, commercially available water-soluble anionic dispersants for dyes, pigments etc..

The following products, especially, come into consideration: condensation products of aromatic sulfonic acids and formaldehyde, condensation products of aromatic sulfonic acids with unsubstituted or chlorinated diphenylene or diphenyl oxides and optionally formaldehyde, (mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerised organic sulfonic acids, sodium salts of polymerised alkylnaphthalene-sulfonic acids, sodium salts of polymerised alkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkyl polyglycol ether sulfates, polyalkylated polynuclear arylsulfonates, methylene-linked condensation products of arylsulfonic acids and hydroxyarylsulfonic acids, sodium salts of dialkylsulfosuccinic acids, sodium salts of alkyl diglycol ether sulfates, sodium salts of poly- naphthalene-methanesulfonates, lignosulfonates or oxylignosulfonates or heterocyclic polysulfonic acids.

Especially suitable anionic dispersants are condensation products of naphthalenesulfonic acids with formaldehyde, sodium salts of polymerised organic sulfonic acids, (mono-/di-)alkylnaphthalenesulfonates, polyalkylated polynuclear arylsulfonates, sodium salts of polymerised alkylbenzenesulfonic acids, lignosulfonates, oxylignosulfonates and condensation products of naphthalenesulfonic acid with a polychloromethyldiphenyl.

Suitable non-ionic dispersants are especially compounds having a melting point of, preferably, at least 35°C that are emulsifiable, dispersible or soluble in water, for example the following compounds: 1. fatty alcohols having from 8 to 22 carbon atoms, especially cetyl alcohol; 2. addition products of, preferably, from 2 to 80mol of alkylene oxide, especially ethylene oxide, wherein some of the ethylene oxide units may have been replaced by substituted epoxides, such as styrene oxide and/or propylene oxide, with higher unsaturated or saturated monoalcohols, fatty acids, fatty amines or fatty amides having from 8 to 22 carbon atoms or with benzyl alcohols, phenyl phenols, benzyl phenols or alkyl phenols, the alkyl radicals of which have at least 4 carbon atoms;

3. alkylene oxide, especially propylene oxide, condensation products (block polymers);

4. ethylene oxide/propylene oxide adducts with diamines, especially ethylenediamine; 5. reaction products of a fatty acid having from 8 to 22 carbon atoms and a primary or secondary amine having at least one hydroxy-lower alkyl or lower alkoxy-lower alkyl group, or alkylene oxide addition products of such hydroxyalkyl-group-containing reaction products;

6. sorbitan esters, preferably with long-chain ester groups, or ethoxylated sorbitan esters, such as polyoxyethylene sorbitan monolaurate having from 4 to 10 ethylene oxide units or polyoxyethylene sorbitan trioleate having from 4 to 20 ethylene oxide units;

7. addition products of propylene oxide with a tri- to hexa-hydric aliphatic alcohol having from 3 to 6 carbon atoms, e.g. glycerol or pentaerythritol; and

8. fatty alcohol polyglycol mixed ethers, especially addition products of from 3 to 30 mol of ethylene oxide and from 3 to 30 mol of propylene oxide with aliphatic monoalcohols having from 8 to 22 carbon atoms.

Especially suitable non-ionic dispersants are surfactants of formula

R'ii-O-(alkylene-O)_n-R'i2 (5),

wherein

R'ii is C₈-C₂₂alkyl or C₈-Ci₈alkenyl;

R'i₂ is hydrogen; d-C₄alkyl; a cycloaliphatic radical having at least 6 carbon atoms; or benzyl;

"alkylene" is an alkylene radical having from 2 to 4 carbon atoms and n is a number from 1 to 60.

A substituent R'n or R'₁₂ in formula (5) is advantageously the hydrocarbon radical of an unsaturated or, preferably, saturated aliphatic monoalcohol having from 8 to 22 carbon atoms. The hydrocarbon radical may be straight-chain or branched. R'n and R'₁₂ are preferably each independently of the other an alkyl radical having from 9 to 14 carbon atoms.

Aliphatic saturated monoalcohols that come into consideration include natural alcohols, e.g. lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, and also synthetic alcohols, e.g. 2-ethylhexanol, 1 ,1 ,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethyl- hexanol, trimethylnonyl alcohol, decanol, Cg-CnOxo-alcohol, tridecyl alcohol, isotridecyl alcohol and linear primary alcohols (Alfols) having from 8 to 22 carbon atoms. Some examples of such Alfols are Alfol (8-10), Alfol (9-1 1 ), Alfol (10-14), Alfol (12-13) and Alfol (16- 18). ("Alfol" is a registered trade mark).

Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol, hexadecenyl alcohol and oleyl alcohol.

The alcohol radicals may be present singly or in the form of mixtures of two or more components, e.g. mixtures of alkyl and/or alkenyl groups that are derived from soybean fatty acids, palm kernel fatty acids or tallow oils.

(Alkylene-O) chains are preferably divalent radicals of the formulae

-(CH₂-CH₂-O)-, _₍ )- ■

Examples of a cycloaliphatic radical can be cycloheptyl, cyclooctyl and preferably cyclohexyl.

Preferred non-ionic dispersants may be surfactants of formula

R₁₃-O-( IC¹H- ?CH-O)T-( [C³H- !C⁴H-OT^- R₁₄ ⁽⁶⁾

wherein

Ri3 is C₈-C₂₂alkyl; Ri₄ is hydrogen or d-C₄alkyl; Yi, Y₂, Y₃ and Y₄ are each independently of the others hydrogen, methyl or ethyl; n₂ is a number from O to 8; and n₃ is a number from 2 to 40.

Further important non-ionic dispersants correspond to formula

γ5 Y₆ Y₇ Y₈

I l I l (7),

R₁₅-O-(CH-CH-O^ (CH-CH-O^ R₁₆

wherein Ri5 is C₉-Ci₄alkyl; Ri6 is Ci-C₄alkyl;

Ys, Yβ, Y7 and Y₈ are each independently of the others hydrogen, methyl or ethyl, one of the radicals Y₅, Yβ and one of the radicals Y₇, Ys always being hydrogen; and n₄ and n₅ are each independently of the other an integer from 4 to 8.

The non-ionic dispersants of formulae (5) to (7) can be used in the form of mixtures. For example, as surfactant mixtures there come into consideration non-end-group-terminated fatty alcohol ethoxylates of formula (5), e.g. compounds of formula (5) wherein Rn is C₈-C₂₂alkyl, R₁₂ is hydrogen and the alkylene-0 chain is the radical -(CH₂-CH₂-O)- and also end-group-terminated fatty alcohol ethoxylates of formula (7).

Examples of non-ionic dispersants of formulae (5), (6) and (7) include reaction products of a Cio-Ci₃fatty alcohol, e.g. a Ci₃oxo-alcohol, with from 3 to 10 mol of ethylene oxide, propylene oxide and/or butylene oxide or the reaction product of one mol of a C^fatty alcohol with 6 mol of ethylene oxide and 1 mol of butylene oxide, it being possible for the addition products each to be end-group-terminated with Ci-C₄alkyl, preferably methyl or butyl.

Such dispersants can be used singly or in the form of mixtures of two or more dispersants.

Instead of, or in addition to, the anionic or non-ionic dispersant, the granules according to the invention may comprise a water-soluble organic polymer as binder. Such polymers may be used singly or in the form of mixtures of two or more polymers.

Water-soluble polymers may be, for example, polyethylene glycols, copolymers of ethylene oxide with propylene oxide, gelatin, polyacrylates, polymethacrylates, polyvinylpyrrolidones, vinylpyrrolidones, vinyl acetates, polyvinylimidazoles, polyvinylpyridine-N-oxides, copolymers of vinylpyrrolidone with long-chain α-olefins, copolymers of vinylpyrrolidone with vinylimidazole, poly(vinylpyrrolidone/dimethylaminoethyl methacrylates), copolymers of vinylpyrrolidone/dimethylaminopropyl methacrylamides, copolymers of vinylpyrrolidone/dimethylaminopropyl acrylamides, quaternised copolymers of vinylpyrrolidones and dimethylaminoethyl methacrylates, terpolymers of vinylcaprolactam/ vinylpyrrolidone/dimethylaminoethyl methacrylates, copolymers of vinylpyrrolidone and methacrylamidopropyl-trimethylammonium chloride, terpolymers of caprolactam/vinyl- pyrrolidone/dimethylaminoethyl methacrylates, copolymers of styrene and acrylic acid, polycarboxylic acids, polyacrylamides, carboxymethylcellulose, hydroxymethylcellulose, polyvinyl alcohols, polyvinyl acetate, hydrolysed polyvinyl acetate, copolymers of ethyl acrylate with methacrylate and methacrylic acid, copolymers of maleic acid with unsaturated hydrocarbons, and also mixed polymerisation products of the mentioned polymers.

Of those organic polymers, special preference is given to polyethylene glycols, carboxy- methylcellulose, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates, copolymers of vinylpyrrolidone and vinyl acetate, and also polyacrylates, copolymers of ethyl acrylate with methacrylate and methacrylic acid, and polymethacrylates.

Suitable water-emulsifiable or water-dispersible binders also include paraffin waxes.

Encapsulating materials (c) include especially water-soluble and water-dispersible polymers and waxes. Of those materials, preference is given to polyethylene glycols, polyamides, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates, copolymers of vinylpyrrolidone and vinyl acetate, and also polyacrylates, paraffins, fatty acids, copolymers of ethyl acrylate with methacrylate and methacrylic acid, and polymethacrylates.

Further additives (e) that come into consideration are, for example, wetting agents, dust removers, water-insoluble or water-soluble dyes or pigments, and also dissolution accelerators, optical brighteners and sequestering agents.

The preparation of the granules according to the invention is carried out, for example, starting from: (a) a solution or suspension which is subjected to a subsequent drying/shaping step or

(b) a suspension of the active ingredient in a melt, with subsequent shaping and solidification. (a) First of all the anionic or non-ionic dispersant and/or the polymer and, if appropriate, the further additives are dissolved in water and stirred, if desired with heating, until a homogeneous solution has been obtained. The catalyst according to the invention is then dissolved or suspended in the resulting aqueous solution. The solids content of the solution should preferably be at least 30% by weight, especially 40 to 50 % by weight, based on the total weight of the solution. The viscosity of the solution is preferably less than 200 mPas.

The aqueous solution so prepared, comprising the bleach catalyst according to the invention, is then subjected to a drying step in which all water, with the exception of a residual amount, is removed, solid particles (granules) being formed at the same time. Known methods are suitable for producing the granules from the aqueous solution. In principle, both continuous and discontinuous methods are suitable. Continuous methods are preferred, especially spray-drying and fluidised bed granulation processes.

Especially suitable are spray-drying processes in which the active ingredient solution is sprayed into a chamber with circulating hot air. The atomisation of the solution is effected e.g. using unitary or binary nozzles or is brought about by the spinning effect of a rapidly rotating disc. In order to increase the particle size, the spray-drying process may be combined with an additional agglomeration of the liquid particles with solid nuclei in a fluidised bed that forms an integral part of the chamber (so-called fluid spray). The fine particles (<100 μm) obtained by a conventional spray-drying process may, if necessary after being separated from the exhaust gas flow, be fed as nuclei, without further treatment, directly into the atomizing cone of the atomiser of the spray-dryer for the purpose of agglomeration with the liquid droplets of the active ingredient.

During the granulation step, the water can rapidly be removed from the solutions comprising the catalyst according to the invention, binder and further additives. It is expressly intended that agglomeration of the droplets forming in the atomising cone, or the agglomeration of droplets with solid particles, will take place.

If necessary, the granules formed in the spray-dryer are removed in a continuous process, for example by a sieving operation. The fines and the oversize particles are either recycled directly to the process (without being redissolved) or are dissolved in the liquid active ingredient formulation and subsequently granulated again. A further preparation method according to (a) is a process in which the polymer is mixed with water and then the catalyst is dissolved/suspended in the polymer solution, thus forming an aqueous phase, the catalyst according to the invention being homogeneously distributed in that phase. At the same time or subsequently, the aqueous phase is dispersed in a water- immiscible liquid in the presence of a dispersion stabiliser in order that a stable dispersion is formed. The water is then removed from the dispersion by distillation, forming substantially dry particles. In those particles, the catalyst is homogeneously distributed in the polymer matrix.

The granules according to the invention are wear-resistant, low in dust, pourable and readily meterable. They can be added directly to a formulation, such as a washing agent formulation, in the desired concentration of the catalyst according to the invention.

Where the coloured appearance of the granules in the washing agent is to be suppressed, this can be achieved, for example, by embedding the granules in a droplet of a whitish meltable substance ("water-soluble wax") or by adding a white pigment (e.g. TiC>₂) to the granule formulation or, preferably, by encapsulating the granules in a melt consisting, for example, of a water-soluble wax, as described in EP-A-O 323 407, a white solid being added to the melt in order to reinforce the masking effect of the capsule.

(b) The catalyst according to the invention is dried in a separate step prior to the melt- granulation and, if necessary, dry-ground in a mill so that all the solids particles are < 50 μm in size. The drying is carried out in an apparatus customary for the purpose, for example in a paddle dryer, vacuum cabinet or freeze-dryer.

The finely particulate catalyst is suspended in the molten carrier material and homogenised. The desired granules are produced from the suspension in a shaping step with simultaneous solidification of the melt. The choice of a suitable melt-granulation process is made in accordance with the desired size of granules. In principle, any process which can be used to produce granules in a particle size of from 0.1 to 4 mm is suitable. Such processes are droplet processes (with solidification on a cooling belt or during free fall in cold air), melt- prilling (cooling medium gas/liquid), and flake formation with a subsequent comminution step, the granulation apparatus being operated continuously or discontinuously. Where the coloured appearance of the granules prepared from a melt is to be suppressed in the washing agent, in addition to the catalyst it is also possible to suspend in the melt white or coloured pigments which, after solidification, impart the desired coloured appearance to the granules (e.g. titanium dioxide).

If desired, the granules can be covered or encapsulated in an encapsulating material. Methods suitable for such an encapsulation include the customary methods and also the encapsulation of the granules by a melt consisting e.g. of a water-soluble wax, as described, for example, in EP-A-O 323 407, coacervation, complex coacervation and surface polymerisation.

Encapsulating materials (c) include e.g. water-soluble, water-dispersible or water- emulsifiable polymers and waxes.

Zinc compounds (d) include water soluble and water insoluble compounds as mentioned hereinbefore.

Further additives (e) include e.g. wetting agents, dust-removers, water-insoluble or water- soluble dyes or pigments, and also dissolution accelerators, optical brighteners and sequestering agents.

The following Examples serve to illustrate the invention but do not limit the invention thereto. Parts and percentages are given in weight. Temperatures are indicated in degrees centigrade.

General Description Washing Conditions:

The trials are conducted in an ATLAS LINITEST using the following conditions:

Fabrics: White cotton 100% bleached ex Ciba and Wf K1 1A, WfK Testgewebe

Germany

Detergent: 4.7g/l detergent and 0.95g/l sodium percarbonate

Liquor Ratio: 5:1 Temperature: 60⁰C

Washing Cycles: 20

The detergents used are AATCC 1993, ECE 77 standard detergent or detergents of the following compositions:

The catalysts used are:

Mn-complex, compound 101

Mn-complex, compound 102

Mn-complex , compound 103

The Mn-complexes are prepared according to WO2004/007657.

A complex of a Zn salt with ethylenediamine-tetramethylene-phosphonic acid (Dequest 2041 ) or hydroxyethylidene-diphosphonic acid (Dequest 2016) is used in example 3. This Zn- complex is prepared by mixing aliquot amounts of ZnCI₂ and ethylenediamine- tetramethylene-phosphonic acid at a pH of 10.5, adjusted with Na₂COs in water. In examples 1 and 2 ZnCI₂ is used directly without complexing agent.

Fabric damage is evaluated by measuring tensile strength loss (TSL). TSL is quantified according to DIN-ISO 13934-1. The weight loss percent of the tensile strength is calculated vs. an original unwashed specimen. Initial tensile strength: 827 N.

Example 1

Washing conditions as described above

Detergent: AATCC 1993

Catalyst: compound 101 , compound 102, compound 103

Catalyst Concentration: 7μM Zink Concentration: 5μM

Example 2

Washing conditions are as described above

Catalyst: compound 101

Catalyst Concentration: 7μM

Zink Concentration: 5μM

Detergent: BL2, BL3, ECE77

Example 3 Washing conditions are as described above

Catalyst: A

Catalyst Concentration: 7μM

Zink Concentration: 5μM

Detergent: BL3 Phosphonate addition of 20μM Dequest 2016, 2046 (available at Solutia, St. Louis, USA)

All examples containing the Zn-compound show a significantly higher remaining tensile strength. The results clearly indicate that the addition of Zinc contributes to a significant reduction of loss of tensile strength.

Claims

Claims:

1. Use of a metal complex catalyst together with 1 ppm to 95 ppm of zinc in a textile laundry composition, based on the weight of the total laundry composition for improving the bleaching action of peroxides while retaining a low color change and reduced fabric damage.

2. The use according to claim 1 , wherein the textile laundry composition is a bleach- containing detergent composition.

3. The use according to claim 1 , wherein the zinc compounds are zinc salts or zinc complexes formed from zinc salts and carboxylic, aminocarboxylic or phosphonic/phosphoric acids.

4. The use according to claim 3, wherein the zinc compounds are selected from the group consisting of ZnCI₂x6H₂O, ZnSO₄x7H₂O, Zn(HCOs)₂, ZnCO₃, Zn(OH)₂, Zn(CH₃COO)₂, the complexes formed from Zn and salicylic, citric and gluconic acid, HEDP (hydroxyethylidene(1 ,1 diphosphonic acid)), EDTMP (ethylenediamine-tetramethylene- phosphonic acid), ATMP (aminotri(methylene phosphonic acid)) and DTPMP (diethylenetriamine-penta(methylenephosphonic acid)).

5. The use according to claim 1 , wherein the metal complex catalysts are selected from the compounds of chemical formulae (1 ) to (4)

wherein each R₁, independently of the other, is hydrogen; Ci-Ci₂alkyl unsubstituted or substituted by halogen, d-C₄alkoxy, phenyl, carboxyl, Ci-C₄alkoxycarbonyl or mono- or di-Ci-C₄alkylated amino groups; C₄-C₈cycloalkyl unsubstituted or substituted by Ci-C₄alkyl or by Ci-C₄alkoxy; phenyl unsubstituted or substituted by Ci-C₄alkyl, Ci-C₄alkoxy, C₂-C₅alkanoylamino, nitro, sulfo or mono- or di-Ci-C₄alkylated amino groups; or naphthyl unsubstituted or substituted by CrC₄alkyl, CrC₄alkoxy, C₂-C₅alkanoylamino, nitro, sulfo or mono- or di-Ci-C₄alkylated amino groups; each R₂, independently of the other(s), is hydrogen; hydroxy; CrC₁₂alkyl unsubstituted or substituted by halogen, Ci-C₄alkoxy, phenyl, carboxyl, Ci-C₄alkoxycarbonyl or by a mono- or di-Ci-C₄alkylated amino group; Ci-C₈alkoxy unsubstituted or substituted by halogen, C₁- C₄alkoxy, phenyl, carboxyl, Ci-C₄alkoxycarbonyl or by a mono- or di-Ci-C₄alkylated amino group; halogen; N(d-C₄alkyl)₂ or NH(Ci-C₄alkyl) in which at least one alkyl group may be substituted by halogen, Ci-C₄alkoxy, phenyl, carboxyl, Ci-C₄alkoxycarbonyl or by a mono- or di-Ci-C₄alkylated amino group; N^Θ(Ci-C₄alkyl)₃ or NH^Θ(Ci-C₄alkyl)₂ in which at least one alkyl group may be substituted by halogen, Ci-C₄alkoxy, phenyl, carboxyl, Ci-C₄alkoxycarbonyl or by a mono- or di-Ci-C₄alkylated amino group; or a water-soluble group; Y is linear or branched alkylene of formula -[C(Ri)₂]_m, wherein m is a number from 1 to 8 and each R₁ independently of the other(s), is as defined hereinbefore; -CX=CX-, wherein X is cyano, linear or branched Ci-C₈alkyl or di(linear or branched Ci-C₈alkyl)amino; -(CI-I₂X-NR₁-(CI-I₂X-, wherein R₁ is as defined hereinbefore and r is 1 , 2, 3 or 4; or a 1 ,2-cyclohexylene or phenylene group of formula:

wherein R is hydrogen, CH₂OH, CH₂NH₂ or SO₃M, wherein M is hydrogen, an alkali metal ion, ammonium or a cation that is formed from an amine, each q, independently of the other, is 0, 1 , 2 or 3; and A is an anion; bleach catalysts of formula (2)

wherein

R₃, R₄, R₅, Re, Rs', R₄', Rs', Re', Rs", R₄", Rs" and R₆" are each independently of the others hydrogen; cyano; halogen; -SO₃M; -SO₂NH₂; -SO₂NHR₇; -SO₂N(R₇)₂; -OR₇; -COOR₇; nitro; linear or branched Ci-C₈alkyl; linear or branched partially fluorinated or perfluorinated d-

C₈alkyl; -NHR₈; -NR₈R₉; -N⁰R₈R₉Ri₂ or linear or branched C_rC₈alkyl-R₁₀;

R₇ is hydrogen; or linear or branched CrC₄alkyl;

Rio is OR₇; -COOR₇; -NH₂; -NHR₈; -NR₈R₉ or -N⁰R₈R₉R₁₂;

R₈, R₉ and Ri₂ are the same or different and each is linear or branched CrCi₂alkyl; or R₈ and

Rii, Rn¹ and Rn" are each independently of the others hydrogen; linear or branched CrC₈- alkyl or aryl, and

Me is a transition metal; bleach catalysts of formula (3)

(3), wherein

Ri3, Ri4, Ri5, Ri₆, Ri7, Ris, R19, R20, R21 , R22 and R₂3 are each independently of the others hydrogen; unsubstituted or substituted Ci-Ci₈alkyl; unsubstituted or substituted aryl; cyano; halogen; nitro; -COOR₂₄; -SO₃R₂₄, wherein R₂₄ is in each case hydrogen; a cation; unsubstituted or substituted Ci-C-i₈alkyl or unsubstituted or substituted aryl;

-N(R₂₅)-(Ci-C₆alkylene)-NR₂₆R₂₇; -N[(Ci-C₆alkylene)-NR₂₆R₂₇]₂; -N(R₂₅)-(Ci-C₆alkylene)-N^ΘR₂₆R₂₇R₂₈; -N[(Ci-C₆alkylene)-N^ΘR₂₆R₂₇R₂₈]₂; -N(R₂₅)-NR₂₆R₂₇; or

-N(R₂₅)-N^ΘR₂₆R₂₇R_28! wherein R₂₆, R₂₇ and R₂₈ are each independently of the others hydrogen; unsubstituted or substituted Ci-Ci₈alkyl; or unsubstituted or substituted aryl; or wherein R₂₆ and R₂₇, together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7- membered ring that may contain further hetero atoms,

Me is a transition metal and

wherein

Q is N or -CR₃₈;

R₂₉, R₃₀, R₃i, R₃₂, R₃₃, R₃₄, R₃₅, R36, R37 and R₃₈ are each independently of the others hydrogen; unsubstituted or substituted Ci-Ci₈alkyl; unsubstituted or substituted aryl; cyano; halogen; nitro; -COOR₃₉; -SO₃R₃₉, wherein R₃₉ is in each case hydrogen; a cation; unsubstituted or substituted Ci-Ci₈alkyl or unsubstituted or substituted aryl;

wherein R₄₀ is in each case hydrogen; unsubstituted or substituted Ci-Ci₈alkyl or unsubstituted or substituted aryl; -NR₄I R₄₂; -(Ci-C₆alkylene)-NR₄₁R₄₂; -N⁰R₄₁R₄₂R₄₃; -(C_rC₆alkylene)-N^eR₄₁ R₄₂R₄₃; -N(R₄₀)-(Ci-C₆alkylene)-NR₄₁R₄₂; -N[(C_rC₆alkylene)-NR₄₁R₄₂]₂;

wherein R₄₀ is as defined hereinbefore; and wherein R₄₁, R₄₂ and R₄₃ are each independently of the others hydrogen; unsubstituted or substituted CrC₁₈alkyl or unsubstituted or substituted aryl; or R₄₁ and R₄₂, together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring that may contain further hetero atoms; Me is a transition metal and A is an anion.

6. The use according to claim 1 wherein the textile laundry composition contains 0.1 to 200 ppm of a metal complex catalyst, based on the weight of the total composition.

7. The use according to claim 1 wherein the textile laundry composition contains 1 to 80 ppm of Zn, based on the weight of the total composition.

8. A method for improving the bleaching action of peroxides while retaining a low color and fabric damage, comprising applying a textile laundry composition which contains a metal complex catalyst together with 1 ppm to 95 ppm of zinc, based on the weight of the total laundry composition to a fiber or fabric.

9. A washing/bleaching agent or a premixture of single components for such an agent for use in a textile laundry composition for improving the bleaching action of peroxides and reducing catalyst-induced fabric damage which comprises

I) 0 to 50 %, preferably 0 to 30 %, of an anionic surfactant (A) and/or of a non-ionic surfactant (B),

II) 0 to 70 %, preferably 0 to 50 %, of a builder substance (C), III) 1 to 99 %, preferably 1 to 50 %, of a peroxide or a peroxide-forming substance (D),

IV) 0.005 to 2%, preferably 0.01 to 1 % of a metal complex catalyst (E), and

V) 1 to 95 ppm of zinc (F).

10. A washing/bleaching agent according to claim 9, which comprises the components (A) and/or (B) and (C) to (F).

11. The premixture for a washing/bleaching agent according to claim 9, which comprises components (D) to (F).

12. The washing/bleaching agent or premixture of single components according to claim 9 being in the form of a powder, granular or liquid composition.

13. Method of preparing a textile laundry composition (washing liquor) for improving the bleaching action of peroxides and reducing catalyst-induced color and fabric damage, which comprises adding 0.5 to 20 g/litre of the washing/bleaching agent or a premixture for such an agent according claim 9 to the liquor.

14. Method of washing (cleaning)/bleaching textile materials which comprises using the laundry composition (washing liquors) prepared according to claim 12.

15. Granules for incorporation into a powder- or granule-form washing or bleaching agent according to claim 9, which comprise (a) 1 to 99% by weight of the metal complex catalyst,

(b) 1 to 99% by weight of a binder,

(c) 0 to 20 % by weight of an encapsulating material,

(d) 1 ppm to 95 ppm by weight of zinc,