WO2007128745A1 - Use of metal complex oxidation catalysts together with magnesium compounds in laundry compositions - Google Patents

Abstract

Textile washing/bleaching compositions are provided that comprise metal complex catalysts and magnesium 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 magnesium compounds in laundry compositions

The present invention relates to the use of metal complex oxidation catalysts together with a magnesium 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 90°C 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-I ^J-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 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. The main object of the present invention is, therefore, the use of metal complex catalysts together with magnesium compounds in laundry compositions (bleach containing detergents/bleach additves) for improving the bleaching action of peroxides while retaining a low fiber damage. These damages to fabrics, result, e.g. in loss of tensile strength of the fibers.

Another object of the present invention is the corresponding method of washing/bleaching 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 magnesium 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.

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: 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 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 a more or less severe fiber damage. This effect is most pronounced on cotton (cellulose), the most frequently used fiber for textile garments. In the textile and pulp&paper industry cellulose bleaching is one of the major production steps. A couple of technologies for the reduction of bleach induced cellulose damage are established in these industries like acidic washes in order to reduce transition metal content, addition of reducing agents in a separate step, addition of sequestrants, waterglass and magnesium sulfate.

Sequestrants like phosphonates, phosphates or polyacrylic acids are used frequently in detergents or bleach additives. To the man skilled in the art, the other measures for cellulose damage reduction seem to be not practicable for domestic laundering. Especially the use of magnesium 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 not to be expected that the magnesium species in the wash liquor act in the same way like in the bleach processes of the textile and pulp&paper industry.

Magnesium compounds to be used in the present invention include e.g. magnesium salts and magnesium complexes formed from said magnesium salts and carboxylic, aminocarboxylic, phosphonic and phosphoric acids.

Magnesium salts are for example MgCI₂, MgCl₂x6H₂O, MgCθ3, Mg(HCOs)₂, MgNH₄PO₄x6H₂O, MgO, Mg(OH)₂, MgSO₄, MgSO₄x7H₂O, MgSiO₃, MgSiO₄, Mg(NO₃)₂, Mg(NO₃)₂x6H₂O, Mg(CH₃COO)₂, Mg(CH₃COO)₂x4H₂O, MgHPO₄x3H₂O, Mg-Complexes may be complexes formed from magnesium salts and carboxylic acids like citric acid, salicylic acid, malonic acid, glycine, gluconic 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(methylenephosphonic acid) DTPMP, DTPA, Hexamethylenediaminetetra(methylenephosphonic acid) HDTMPA, hydroxyethylidene(1 ,1diphosphonic acid) HEDP, aminotri(methylenephosphonic acid) ATMP, Indosol-hexaphosphoric acid. These magnesium complexes may also be formed "in situ" in the wash or bleach liquor by adding a soluble magnesium salt and the carboxylic, aminocarboxylic, phosphoric or phosphonic acid separately.

Preferred use may be made of the following magnesium compounds.

MgCI₂x6H₂O, MgSO₄x7H₂O, Mg(HCO₃)₂, MgCO₃, Mg(OH)₂, Mg(CH₃COO)₂, the complexes formed from Mg salts and salicylic, citric and gluconic acid, HEDP, ATMP and DTPMP.

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; Ci-Ci₂alkyl unsubstituted or substituted by halogen, d-C₄alkoxy, phenyl, carboxyl, Ci-C₄alkoxycarbonyl or mono- or di- Ci-C₄alkylated amino groups; C₄-Cβcycloalkyl unsubstituted or substituted by CrC₄alkyl or by Ci-C₄alkoxy; phenyl unsubstituted or substituted by Ci-C₄alkyl, Ci-C₄alkoxy, C₂-C₅- alkanoylamino, nitro, sulfo or mono- or di-CrC₄alkylated amino groups; or naphthyl unsubstituted or substituted by Ci-C₄alkyl, Ci-C₄alkoxy, C₂-C₅alkanoylamino, nitro, sulfo or mono- or di-CrC₄alkylated amino groups; each R₂, independently of the other(s), is hydrogen; hydroxy; CrCi₂alkyl unsubstituted or substituted by halogen, Ci-C₄alkoxy, phenyl, carboxyl, Ci-C₄alkoxycarbonyl or by a mono- or di-CrC₄alkylated amino group; C-i-Cβalkoxy unsubstituted or substituted by halogen, Ci-C₄alkoxy, phenyl, carboxyl, Ci-C₄alkoxycarbonyl or by a mono- or di-Ci-C₄- alkylated amino group; halogen; N(Ci-C₄alkyl)₂ or NH(Ci-C₄alkyl) in which at least one alkyl group may be substituted by halogen, Ci-C₄alkoxy, phenyl, carboxyl, Ci-C₄alkoxy- carbonyl 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, CrC₄alkoxy, phenyl, carboxyl, Ci-C₄alkoxycarbonyl or by a mono- or di-CrC₄alkylated 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 CrC₈alkyl or di(linear or branched CrC₈alkyl)amino; -(CH₂)_r-N R₁-(CH₂),--, 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, R3', R₄', Rs', Re', R3", 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 CrC₈alkyl; linear or branched partially fluorinated or perfluorinated CrC₈alkyl; -NHR₈; -NR₈Rg; -N⁰R₈RgR₁₂ 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, R₉ and Ri₂ are the same or different and each is linear or branched Ci-Ci₂alkyl; 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; R₁₁, R₁₁' and R₁₁" are each independently of the others hydrogen; linear or branched C₁-C₈- alkyl or aryl, and Me is a transition metal; bleach catalysts of formula (3)

(3), wherein

R₁₃, R₁₄, Ri5, Ri6, Ri7, Ri8, Ri₉, R20, R21, R22 and R₂₃ are each independently of the others hydrogen; unsubstituted or substituted CrC₁₈alkyl; unsubstituted or substituted aryl; cyano; halogen; nitro; -COOR₂₄; -SO₃R₂₄, wherein R₂₄ is in each case hydrogen; a cation; unsubstituted or substituted C₁-C₁₈- alkyl or unsubstituted or substituted aryl;

wherein R₂₅ is in each case hydrogen; or unsubstituted or substituted C-ι-C₁₈alkyl; -NR₂₆R₂₇; -(C_rC₆alkylene)-N R₂₆R₂₇; -N⁰R₂₆R₂₇R₂₈; -(C_rC₆alkylene)-N⁰R₂₆R₂₇R₂₈; -N(R₂₅)-(C₁-C₆alkylene)-NR₂₆R₂₇; -N[(C₁-C₆alkylene)-NR₂₆R₂₇]₂; -N(R₂₅)-(C₁-C₆alkylene)-N⁰R₂₆R₂₇R₂₈; -N[(C_rC₆alkylene)-N⁰R₂₆R₂₇R₂₈]₂;

-N(R₂₅)-NR₂₆R₂₇; or -N(R₂₅)-N⁰R₂₆R₂₇R₂₈, wherein R₂₆, R₂₇ and R₂₈ are each independently of the others hydrogen; unsubstituted or substituted C-ι-C₁₈alkyl; 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-C"i₈alkyl 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^ΘR₄₁ R₄₂R₄₃; -N[(Ci-C₆alkylene)-N^ΘR₄₁R₄₂R₄₃]₂; -N(R₄₀)-NR₄₁R₄₂; or -N(R₄₀)-N^ΘR₄₁R₄₂R₄₃, wherein R₄₀ is as defined hereinbefore; and wherein R₄₁, R₄₂ and R₄₃ are each independently of the others hydrogen; unsubstituted or substituted C-ι-C₁₈alkyl 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):

terpyιϊdin-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 CrC₄alkyl; Ci-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, CrC₄alkoxy, 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 CrC₄alkyl, Ci-C₄alkoxy, 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 CrC₄alkyl, d-C₄alkoxy, phenyl or hydroxy. Special preference is given to the corresponding phenyl radicals.

The CrC₆alkylene 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 CrC₄alkylene 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 M-IV, cobalt M-III, nickel M-Ml and copper M-Ml, 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 CrCi₈alkyl or aryl. For R' as CrCi₈alkyl or aryl, the definitions and preferred meanings given hereinbefore and hereinafter apply. Especially preferably, R' is hydrogen; d-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 (1')

wherein each R₂, independently of the other(s), is hydroxy; CrC₄alkyl unsubstituted or substituted by halogen, d-C₄alkoxy, phenyl, carboxyl, CrC₄alkoxycarbonyl or by a mono- or di- CrC₄alkylated amino group; CrC₄alkoxy unsubstituted or substituted by halogen, CrC₄alkoxy, phenyl, carboxyl, CrC₄alkoxycarbonyl or by a mono- or di-CrC₄alkylated amino group; halogen; N(Ci-C₄alkyl)₂ or NH(Ci-C₄alkyl) in which at least one alkyl group may be substituted by halogen, CrC₄alkoxy, phenyl, carboxyl, CrC₄alkoxycarbonyl or by a mono- or di-CrC₄alkylated 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;

-(CH₂)_r-NR₁-(CH₂)r 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 CrC₄alkyl; linear or branched partially fluorinated or perfluorinated CrC₄alkyl; -NHR₈; -NR₈Rg; -N⁰R₈RgR₁₂; or linear or branched Ci-C₄alkyl-Rio, wherein R₁₀ is -OR₇; -COOR₇; -NH₂; -NHR₈; -NR₈R₉; Or -N⁰R₈R₉R₁₂; and wherein R₈, R₉ and R₁₂, 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; CrC₄alkoxy; hydroxy; nitro; NHR₆; NR₆R₇ Or -N⁰R₅R₆R₇, wherein R₅, R₆ and R₇ are each independently of the others Ci-C₄alkyl.

Preference is given likewise to bleach catalysts of formula (3) wherein R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, 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

Ci-C₄alkyl 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; -(C_rC₄alkylene)-N R₂₆R₂₇; -N⁰R₂₆R₂₇R₂₈; -(C_rC₄alkylene)-N⁰R₂₆R₂₇R₂₈; -N(R₂₅)-(C₁-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^ΘR₂₆R₂₇R₂₈, 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(III) complexes of formula (3')

wherein

Ri8 is unsubstituted or substituted CrC₄alkyl; 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 CrC₄alkyl or unsubstituted or substituted aryl;

-NR₂₆R₂₇; -(CrC₄alkylene)-N R₂₆R₂₇; -N⁰R₂₆R₂₇R₂₈; -(Ci-C₄alkylene)-N^ΘR₂₆R₂₇R₂₈; -N(R₂₅)-(Ci-C₄alkylene)-NR₂₆R₂₇; -N[(Ci-C₄alkylene)-NR₂₆R₂₇]₂; -N(R₂₅)-( Ci-C₄alkylene)-N^ΘR₂₆R₂₇R₂₈; -N[(Ci-C₄alkylene)-N^ΘR₂₆R₂₇R₂₈]₂; -N(R₂₅)-NR₂₆R₂₇; or -N(R₂₅)-N^ΘR₂₆R₂₇R₂₈, 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

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

Bleach catalysts of formula (3') to which special preference is given are those wherein R₁₈ is CrC₄alkoxy; hydroxy; N-mono- or N,N-di-Ci-C₄alkylamino substituted by hydroxy in the alkyl moiety; or an unsubstituted or Ci-C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring, and

R-_I5 and R₂₁ 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 CrC₄alkyl-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, R31, 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; -(C_rC₄alkylene)-NR₄₁R₄₂; -N⁰R₄₁R₄₂R₄₃; -(C_rC₄alkylene)-N^ΘR₄₁ R₄₂R₄₃;

-N(R₄₀)-(C₁-C₄alkylene)-NR₄₁R₄₂; -N[(C_rC₄alkylene)-NR₄₁R₄₂]₂;

-N(R₄₀)-(C₁-C₄alkylene)-N^ΘR₄₁R₄₂R₄₃; -N[(C_rC₄alkylene)-N^ΘR₄₁R₄₂R₄₃]₂; -N(R₄₀)-NR₄₁R₄₂; or -N(R₄₀)-N^ΘR₄₁R₄₂R₄₃, 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(III) complexes of formula (4' )

wherein

+^CH₂CH₂OH / \ CH₉CH₉OH + — N N . __N' ^XN ; -NCH₂CH₂N(CH₃)₃ ; -NCH₂CH₂N(CH₃)₂ ;

' on, ' '\ / CH₉CH₉OH ' '

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

R'₃₁ and R'₃₅ each independently of the other has the meanings given for R'₃₃ or is hydrogen, and

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

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

wherein R'₃₃ is -OH,

— N N ■ — N N-CH₉CH₉OH ■ — N. N-CH, ■

_V1+^CH₂CH₂OH OH OH OH +

— N N. — N Yj' ^{2 2} ■ -NCH₂CH₂N(CH₃), ; — NCH₂CH₂N(CH₃)₂ ;

CH, ^{^}CH₂CH₂OH

CH₀ CH,

-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'₃₁ and R'₃₅ each independently of the other has the meanings given for R'₃₃ or is hydrogen, and

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

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 -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 magnesium 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 magnesium 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 magnesium compound is added in an amount which in the liquor gives a concentration of 0.5 to 100 mg Mg/litre of liquor, preferably 1 to 75mg Mg/litre of liquor, and mostly preferred 1.0 to 50 mg//litre

Another object of present invention relates to a washing/bleaching agent or a premixture of single components to be used for forming said washing/bleaching agent containing 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) 0.1 to 10%, preferably 0.25 to 7% of the magnesium compound (F).

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

These agents are used in the washing/bleaching liquors. 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.

The amount of the magnesium compound (F) gives a concentration of 0.5 to 50 mg Mg/litre in the liquor, preferably 1 to 40mg 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 considered as bleaching agents; they can be added separately to washing liquors (wich may contain 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 0.5 to 50 mg Mg per litre of liquor. The liquor preferably contains from 1 to 30 mg of the metal complex and 1 to 40 mg Mg 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 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. Preferred sulfates are those having from 12 to 22 carbon atoms in the alkyl radical, optionally in combination with alkyl ethoxysulfates in which the alkyl radical has from 10 to 20 carbon atoms.

Preferred sulfonates are e.g. alkylbenzenesulfonat.es having from 9 to 15 carbon atoms in the alkyl radical. The cation in the case of anionic surfactants is preferably an alkali metal cation, especially sodium.

Preferred carboxylates are alkali metal sarcosinates of formula R-CO-N(R'¹)-CH₂COOM'¹ wherein R is alkyl or alkenyl having from 8 to 18 carbon atoms in the alkyl or alkenyl radical, R'¹ is Ci-C₄alkyl and M'¹ is an alkali metal.

The non-ionic surfactant (B) can be, for example, a condensation product of from 3 to 8 mol of ethylene oxide with 1 mol of a primary alcohol having from 9 to 15 carbon atoms.

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

Especially suitable silicates are sodium salts of crystalline layered silicates of the formula NaHSi_tO_2t+i.pH₂O or Na₂Si_tθ_2t+i.pH₂O wherein t is a number from 1.9 to 4 and p is a number from 0 to 20.

Among the aluminosilicates, preference is given to those commercially available under the nnaammeess ZZeeoolliittee^R A, B, X and HS, and also to mixtures comprising two or more of these components.

Among the polycarboxylates, preference is given to polyhydroxycarboxylat.es, especially citrates, and acrylates and also 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 (S₁S) form.

Phosphonates or aminoalkylene-poly(alkylenephosphonates) that are especially suitable are alkali metal salts of 1-hydroxyethane-1 ,1-diphosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid.

As the peroxide component (D) there come into consideration, 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.

The organic peroxides are, for example, mono- or poly-peroxides, especially organic peracids or salts thereof, such as phthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanedioic acid, diperoxynonanedioic acid, diperoxydecanedioic acid, diperoxyphthalic acid or salts thereof.

Preferably, however, inorganic peroxides are used, for example persulfates, perborates, percarbonates and/or persilicates. It will be understood that mixtures of inorganic and/or organic peroxides can also be used. 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.

The peroxides are added to the agent preferably by mixing the components, for example using a screw metering system and/or a fluidised bed mixer.

The agents may comprise, in addition to the combination of components according to the invention, one or more optical brighteners, for example from the class bis-triazinylamino- stilbenedisulfonic acid, bis-triazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl or bis- benzofuranylbiphenyl, a bis-benzoxalyl derivative, bis-benzimidazolyl derivative or coumarin derivative or a pyrazoline derivative.

The agent may also comprise suspending agents for dirt, e.g. sodium carboxymethylcellulose, pH regulators, e.g. alkali metal or alkaline earth metal silicates, foam regulators, e.g. soap, salts for regulating the spray-drying and the granulating properties, e.g. sodium sulfate, perfumes and, optionally, antistatic agents and softeners, enzymes, such as amylase, bleaches, pigments and/or toning agents. Such constituents must especially be stable towards the bleaching agent used.

In addition to the bleach catalyst it is also possible to use further transition metal salts or complexes known as bleach-activating active ingredients and/or conventional bleach activators, that is to say compounds that, under perhydrolysis conditions, yield unsubstituted or substituted perbenzo- and/or peroxo-carboxylic acids having from 1 to 10 carbon atoms, especially from 2 to 4 carbon atoms. Suitable bleach activators include the customary bleach activators, mentioned at the beginning, that carry O- and/or N-acyl groups having the indicated number of carbon atoms and/or unsubstituted or substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N,N-diacetyl-N,N- dimethylurea (DDU), acylated triazine derivatives, especially 1 ,5-diacetyl-2,4- dioxohexahydro-1 ,3,5-triazine (DADHT), compounds of formula (4"):

wherein R'-i is a sulfonate group, a carboxylic acid group or a carboxylate group, and wherein R'₂ 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.

Further preferred additives to the agents according to the invention are 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 or polyvinylpyridine-N-oxides whch 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 preferably used in an amount of from 0.05 to 5 % by weight, especially from 0.2 to 1.7 % by weight, based on the total weight of the washing agent.

The invention relates also to granules that comprise the catalysts and a magnesium 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) from 1 to 99% by weight, preferably from 1 to 40% by weight, especially from 1 to 30% by weight, of a metal complex compound (bleach catalyst), especially of formulae (1 ) to (4), b) from 1 to 99% by weight, preferably from 10 to 99% by weight, especially from 20 to 80 % by weight, of a binder, c) from 0 to 20 % by weight, especially from 1 to 20 % by weight, of an encapsulating material, d) from 0.1 to 80% by weight, especially from 0.1 to 50% by weight of a magnesium compound e) from 0 to 20 % by weight of a further additive and f) from 0 to 20 % by weight of water. The addition of the magnesium 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

wherein

R'n is C₈-C₂₂alkyl or C₈-Ci₈alkenyl;

R'i₂ is hydrogen; Ci-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'i₂ 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 (9-11 ), 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 CHo CHo

-(CH₂-CH₂-O)-, __(CH__CH₂_₀₎_ and -(CH₂-CH-O)- ■

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

Preferred non-ionic dispersants may be surfactants of formula

^γi Y₂ Y, Y ¹.4 (6) R

14

wherein

R₁₃ is C₈-C₂₂alkyl;

R-_I4 is hydrogen or Ci-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-C^ R₁₆

wherein

R₁₅ is C₉-Ci₄alkyl; Ri6 is Ci-C₄alkyl;

Y5, Yβ, Y7 and Ye are each independently of the others hydrogen, methyl or ethyl, one of the radicals Y₅, Y₆ and one of the radicals Y₇, Y₈ 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 Ci3θxo-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 Ci₃fatty 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 -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, carboxymethylcellulose, 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 poly- methacrylates.

Further additives (d) 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. Tiθ₂) 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.

Magnesium 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. Example 1

Washing Conditions:

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

Fabrics: White cotton 100% bleached ex Ciba and WfK11 A WfK Testgewebe

Germany

Detergent: 6.4g/l AATCC 1993 containing 15.6% sodium percarbonate

Liquor Ratio: 5:1 Temperature: 60°C

Washing Cycles: 20

Fabric damage was evaluated by measuring tensile strength loss (TSL) of the WfK11 A standard textile. TSL were quantified according to standard procedure according to DIN-ISO 13934-1. The weight loss percent of the tensile strength is calculated vs. an original unwashed swatch. Initial tensile strength: 924 N.

The following metal complex catalysts were applied in an amount (10 μmol/l) that is known to cause damage:

(1 ) Penta-amminechlorocobalt(lll)-chloride, (2) Mn (II) complex according to formula (3) with R₁₈ = -OH, R₁₅, R₂₁ = piperazine,

(3) Mn (II) complex according to formula (3) with R₁₈ = -OH, R₁₅, R₂₁ = -N-methyl-N- hydroxyethyl (other substituents: hydrogen).

The addition of 0.25 mmol/l, 0.50 mmol/l and 1.0 mmol/l MgCI₂x6H₂O resulted in a significant decrease in TSL compared to the experiment without MgCI₂x6H₂O addition.

Claims

Claims:

1. Use of a metal complex catalyst together with magnesium compounds in a textile laundry composition for improving the bleaching action of peroxides while retaining a low fiber damage

2. The use according to claim 1 , wherein fabric damage results in loss of tensile strength of the fibers .

3. The use according to any one claims 1 and 2, wherein the laundry composition is a bleach-containing detergent composition.

4. The use according to any one of claims 1 to 3, wherein the metal complex catalysts are selected from the compounds of chemical formulae (1 ) to (4).

5. The use according to any one of claims 1 to 4, wherein the magnesium compounds are magnesium salts or magnesium complexes formed from magnesium salts and carboxylic, aminocarboxylic or phosphonic/phosphoric acids.

6. The use according to claim 5, wherein the magnesium compounds are selected from the group consisting of MgCI₂x6H₂O, MgSO₄x7H₂O, Mg(HCO₃)₂, MgCO₃, Mg(OH)₂, Mg(CH₃COO)₂, the complexes formed from Mg and salicylic, citric and gluconic acid, HEDP (hydroxyethylidene(1 ,1 diphosphonic acid)), ATMP (aminotri(methylene phosphonic acid)) and DTPMP (diethylenetriamine-penta(methylenephosphonic acid)).

7. The use according to any one of claims 1 to 6 wherein the laundry composition contains 0.1 to 200 mg of a metal complex catalyst per litre and 0.5 to 100 mg Mg/litre.

8. 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 contains

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) 0.1 to 10%, preferably 0.25 to 7% of a magnesium compound (F).

9. The washing/bleaching agent according to claim 8, which comprises components (A) and/or (B), and (C) to (F).

10. The premixture for a washing/bleaching agent according to claim 8, which comprises components (D) to (F) to be preferably incorporated into liquid detergents.

1 1. The washing/bleaching agent or premixture of single components according to any one of claims 8 to 10 being in the form of a powder, granular or liquid composition.

12. Method of preparing a textile laundry composition (washing liquor) for improving the bleaching action of peroxides and reducing catalyst-induced fabric damage, which comprises adding 0.5 to 20 g/litre of the washing/bleaching agent or a premixture for such an agent according to any one of claims 8 to 11 to the liquor.

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

14. Granules for incorporation into a powder- or granule-form washing or bleaching agent according to claim 1 1 , which comprise

(a) 1 to 99% by weight, preferably from 1 to 40% by weight, of the metal complex catalyst, especially of formulae (1 ) to (4),

(b) 1 to 99% by weight, preferably from 10 to 99% by weight, of a binder,

(c) 0 to 20 % by weight, preferably from 1 to 20 % by weight, of an encapsulating material,

(d) 0.1 to 80% by weight, preferably from 0.1 to 50% by weight of the magnesium compound,

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

(f) 0 to 20 % by weight of water.