WO1994009104A1

WO1994009104A1 - Detergent composition

Info

Publication number: WO1994009104A1
Application number: PCT/EP1993/002876
Authority: WO
Inventors: Jiri Hora; Rudolf Johan Martens; Ton Swarthoff
Original assignee: Unilever Plc; Unilever Nv
Priority date: 1992-10-21
Filing date: 1993-10-18
Publication date: 1994-04-28
Also published as: ZA937816B; GB9222129D0; AU5334694A

Abstract

A detergent composition comprises a surface-active material, a peroxy compound, hydroxylamine or a precursor thereof and a catalyst capable of destroying said hydroxylamine or precursor thereof. Hydroxylamine inhibits the action of catalase and thereby reduces the loss of available hydrogen peroxide. After the hydroxylamine has performed this action in the wash liquor it is destroyed by the catalyst.

Description

DETERGENT COMPOSITION

This invention relates to a detergent composition and, in particular, it relates to a detergent composition comprising hydroxylamine.

Generally when washing fabrics and, in particular dirty fabrics, there is a build up in the concentration of catalase in the wash liquor. Catalase is known to attack hydrogen peroxide generated from dissolution of perborate, percarbonate, and other hydrogen peroxide adducts commonly used in detergent compositions thereby reducing the amount of hydrogen peroxide available for the bleaching process.

It is known to incorporate hydroxylamine in detergent compositions comprising perborate, percarbonate or any other hydrogen peroxide adduc . It is believed hydroxylamine inhibits the action of catalase and thereby reduces the loss of available hydrogen peroxide. The ability to formulate a composition comprising hydroxylamine therefore has particular advantages.

However, a disadvantage with such compositions is the suspected toxic nature of hydroxylamine. Hydroxylamine may, for example, bind with haem proteins.

It is an object of the present invention to formulate a detergent composition comprising hydroxylamine which inhibits catalase action during the wash process but in which the level of hydroxylamine is reduced during use of the composition in a wash or bleaching process.

It has now been found that at least some of the hydroxylamine in a composition may be destroyed during the wash process if the composition when in use comprises a catalyst capable of destroying the hydroxylamine. The catalyst must be such that it does not interfere the ability of hydroxylamine to inhibit the action of catalase. Preferably, therefore, the reaction between hydroxylamine and catalase is faster than that between hydroxylamine and catalyst. '

Accordingly, the invention provides a detergent composition comprising:- i) a surface-active agent selected from anionic, nonionic, cationic zwitteronic and amphoteric surfactants and mixtures thereof; ii) a peroxy compound; iii) hydroxylamine or a precursor thereof; and iv) a catalyst capable of destroying said hydroxylamine or precursor thereof.

Preferred catalysts include a ligand L which is a macrocyclic organic compound of formula (I):-

riN NRR³³ -- (⁽CCRR RR²²)⁾ _uu ⁾⁾ _e} _-n_] (I)

wherein t is an integer from 2 to 3; s is an integer from 3 to 4, u is zero or one; each R¹, R² and R³ are independently selected from H, alkyl, aryl, substituted alkyl, and substituted aryl.

Examples of preferred ligands of this type are 1,4,7- triazacyclononane (TACN) ; 1,4,7-trimethyl-l,4,7- ι triazacyclononane (1,4,7-Me₃TACN) ; 2-methyl-1,4,7- triazacyclononane (2-MeTACN) ; 1,2,4,7-tetramethyl-l,4,7- triazacyclononane (1,2,4,7-Me₄TACN) ; 1,2,2,4,7-pentamethyl- 1,4,7-triazacyclononane (1,2,2, ,7-Me₅TACN) ; and 1,4,7- tri ethyl, 2-benzyl-l,4,7-triazacyclononane; and 1,4,7- trimethyl-2-decyl-l,4,7-triazacyclononane. Especially preferred is 1,4,7-trimethyl-l,4,7-triazacyclononane. The aforementioned ligands may be synthesised by the methods described in K Wieghardt et al. , Inorganic Chemistry 1982, .2J page 3086 et seq, incorporated herein by reference.

Another preferred ligand L comprises two species of formula (II) [NR⁴ - ⁽CR¹(R²⁾ _u ⁾ -η (ID

wherein t is an integer from 2 to 3; s is an integer from

3 to 4; u is zero or one; each R¹ and R² are independently selected from H, alkyl, aryl, substituted alkyl and substituted aryl; and each R⁴ is independently selected from hydrogen, alkyl, aryl, substituted alkyl and substituted aryl, with the proviso that at least one bridging unit R⁵ is formed by one R⁴ unit from each ligand where R⁵ is the group (CR⁶R₇)_n- (D)_p-(CR⁶R⁷)_m where p is zero or one;

D is selected from a heteroatom such as oxygen and MR⁸ or is part of an optionally substituted; aromatic or saturated homonuclear or heteronuclear ring, n is an integer from 1 to 4; m is an integer from 1 to 4; with the proviso that n + m < 4; each R⁶ and R⁷ are independently selected from H, R⁹ and

OR¹⁰, alkyl, aryl, substituted alkyl and substituted aryl; and each R⁸, R⁹, R¹⁰ are independently selected from H, alkyl, aryl, substituted alkyl and substituted aryl.

An example of a preferred ligand of this type is 1,2- bis(4,7-dimethyl-l,4,7-triaza-l-cyclononyl)ethane, ( [EB-

(Me₂TACN)₂] ) .

The aforementioned ligands may be synthesised as described by K. Wieghardt et al in Inorganic Chemistry, 1985, 24, page 1230 et seq, and J. Chem. , Soc, Che . Co m. , 1987, page 886, or by simple modifications of the synthesises.

The ligand may be incorporated in the compositions of the invention in the form of an acid salt, such as the HCl or H₂S0₄ salt, for example 1,4,7-Me₃TACN hydrochloride. In such a case, the composition of the invention will preferably also contain a source of iron and/or manganese ions.

The source of iron and manganese ions may be a water- soluble salt, such as iron (III) nitrate, manganese nitrate, manganese chloride, manganese sulphate or manganese acetate, or a coordination complex such as manganese acetylacetonate. The source of iron and/or manganese ions should be such that the ions are not too tightly bound therefore allowing interaction between said ions and the ligands of formulae (I) or (II) as hereinbefore defined.

When the composition according to the invention is used in for example, a detergent formulation or textile treatment formulation it is not always necessary that the source of iron and/or manganese ions is included in the formulation. Without being bound by theory, it is believed that in such cases iron and/or manganese ions are picked up from the articles being treated. However, the formulation is more effective if a source iron and/or of manganese ions is included.

Alternatively, the ligand may be incorporated in the compositions of the invention in the form of a mono-, di- or tetranuclear manganese or iron complex.

Alternatively, the catalyst may be in the form of a mono-, di- or tetranuclear manganese or iron complex. Preferred mononuclear complexes have the general formula (III) :

[L Mn X_p]²Y_q (III)

wherein Mn is manganese in the II, III or IV oxidation state, each X represents a coordinating species independently selected from OR", where R" is a C_J-C_JO radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl and radical combinations thereof or at least two R" radicals may be connected to one another so as to form a bridging unit between two oxygens that coordinate with the manganese,

Cl^", Br^", I^", F^', NCS\ N₃ ^~, I₃ ^", NH₃, OH^", 0₂ ^2", HOC, H₂0, SH, CN^", OCN^', S₄ ²\ R^aC00\ R^aS0₄\ R^aS0₃ ^~ where R^a is selected from H, alkyl, aryl, substituted alkyl and substituted aryl and R^DCOO^" where R^b is selected from alkyl, aryl, substituted alkyl and substituted aryl and mixtures thereof; p is an integer from 1-3; z denotes the charge of the complex and is an integer which can be positive, zero or negative;

Y is a monovalent or multivalent counter-ion, leading to charge neutrality, the type of which is dependent upon the charge z of the complex; q = z/ [charge Y] ; and L is a ligand of formula (I) as hereinbefore defined.

These mononuclear complexes are further described in Applicants copending European Patent Specification 549272 and US Patent 5194416.

Preferred dinuclear complexes have the formula (IV) or formula (V) , see below

In complexes of formula (IV) each Mn is manganese independently in the III or IV oxidation state; each X represents a coordinating or bridging species independently selected from the group consisting of H₂0,

0₂ ^2', 0²-,OH-, HCV, SIT, S²\ >SO, Cl, N^3", SCN^", NH₂ ^", NR,

R^aS0₄ ^~, R^aS0₃ ^"and R^aCOO^" where R^a is selected from H, alkyl, aryl, substituted alkyl, substituted aryl and R^bCOO^" where

R^b is selected from alkyl, aryl, substituted alkyl and substituted aryl;

L is a ligand of formula (I) as hereinbefore defined, containing at least three nitrogen atoms which coordinate to the manganese centres; z denotes the charge of the complex and is an integer which can be positive or negative;

Y is a monovalent or multivalent counter-ion, leading to charge neutrality, which is dependent upon the charge z of the complex; and q = z/ [charge Y] .

In dinuclear complexes of formula (V)

each Mn is manganese independently in the III or IV oxidation state; each X represents a coordinating or bridging species independently selected from the group consisting of H₂0,

0₂ ²\ 0²-,OH^", H0₂ ^", SH\ S^2", >SO, Cl, N^3", SCN^", NH₂ ^", NR,

R^aS0₄ ^", R^aS0₃ ^"and R^aCOO^" where R^a is selected from H, alkyl, aryl, substituted alkyl, substituted a*ryl and R^bCOO^" where

R is selected from alkyl, aryl, substituted alkyl and substituted aryl;

L is a ligand comprising two species of formula (II) as hereinbefore defined, and in which at least three nitrogen atoms of the ligand L are coordinated to each manganese centre; z denotes the charge of the complex and is an integer which can be positive or negative;

Y is a monovalent or multivalent counter-ion, leading to charge neutrality, which is dependent upon the charge z of the complex; and q = z/.[charge Y] .

Particularly preferred dinuclear manganese-complexes are those wherein each X is independently selected from CH₃COO^"

, 0₂ ^2", and O^2", and, most preferably, wherein the manganese is in the IV oxidation state and each X is O^2". They include those having the formula

i) [Mn^IV ₂ (μ-0)₃ (1, 4, 7-Me₃TACN) ₂] (PF₆) ₂ ii) [Mn^IV ₂ (μ-0)₃ (1, 2 , 4, 7-Me₄TACN) ₂] (PF₆) ₂ iii) [Mn^ι ₂ (μ-OAc)₂ (1, 4, 7-Me₃TACN) ₂] (PF₆) ₂ iv) [Mn^IU ₂ (μ-O) (μ-OAc) ₂ ^' (1, 2 , 4, 7-Me₄TACN) ₂] (PF₆) ₂ v) [Mn^IV ₂ (μ-0)₂(μ-0₂) (1, 4, 7-Me₃TACN) ₂] (PF₆)₂ vi) [Mn^IVMn^III(μ-0)₂(μ-OAc) (EB- (Me₂TACN) ₂) ] (PF₆) ₂

and any of these complexes but with other counterions such as S0₄ ^2", C10₄ ^" etc.

Other dinuclear complexes of this type are further described in EP-A-458 397 and EP-A-458 398. An example of a tetra-nuclear manganese complex is:

[Mn^IV ₄(μ-0)₆(TACN)₄] (C10₄)₄.

As stated hereinbefore, the advantage of the compositions of the invention is that the concentration of hydroxylamine is reduced during the washing or bleach process.

Without being bound by theory, it is believed hydroxylamine is oxidised by molecular oxygen in the presence of the ligand, which may be part of a mono-, di- or tetranuclear complex, and source of manganese and/or iron ions.

The bleach detergent compositions of the invention will contain at least one surface-active compound, which may be anionic, cationic, nonionic or amphoteric in character, present in an amount from about 3 to about 40%, preferably from 5 to 35% by weight.

Generally, mixtures of the above surface-active compounds are used. In particular, mixtures of anionic and nonionic surface-active compounds are commonly used.

The surface-active material may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof. Many suitable actives are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.

Synthetic anionic surfactants are well known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C₈-C₁₅; primary (C₁₂.₁₅) and secondary alkyl sulphates (C₁₄_₁₈) , particularly sodium C₁₂-i₅ primary alcohol sulphates; olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.

It may also be desirable to include one or more soaps of fatty acids. These are preferably sodium soaps derived from naturally occurring fatty acids, for example, the fatty acids from coconut oil, beef tallow, sunflower or hardened rapeseed oil. Soaps may be incorporated in the compositions of the invention, preferably at a level of less than 25% by weight. They are particularly useful at low levels in binary (soap/anionic) or ternary mixtures together with nonionic or mixed synthetic anionic and nonionic compounds. Soaps which may be used are preferably the sodium, or, less desirably, potassium salts of saturated or unsaturated C₁₀-C₂₄ fatty acids or mixtures thereof. Typically such soaps may be present at levels between about 0.5% and about 25% by weight, with lower levels of between about 0.5% to about 5% being generally sufficient for lather control. If the soap is present at a level between about 2% and about 20%, particularly between about 5% and about 10%, this can give beneficial detergency effects. The inclusion of soap is particularly valuable in detergent compositions to be used in hard water since the soap acts as a supplementary builder.

Suitable nonionic detergent compounds which may be used include the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.

Specific nonionic detergent compounds are alkyl (C₆-₂₂) phenol-ethylene oxide condensates, the condensation products of linear or branched aliphatic C₈-₂₀ primary or secondary alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other so-called nonionic detergent compounds include long-chain tertiary amine oxides and tertiary phosphine oxides.

Further suitable nonionic surfactants are alkyl polyglycosides of general formula

O

II R₄0(R₅0)_c(G)_y or R₄CO(R₅0)_t (G)_y

in which R₄ is an organic hydrophobic residue containing 10 to 20 carbon atoms, R₅ contains 2 to 4 carbon atoms, G is a saccharide residue containing 5 to 6 carbon atoms, t is in the range 0 to 25 and y is in the range from 1 to 10.

Alkyl polyglycosides of formula R₄0(G)_y, ie. a formula as given above in which t is zero, are available from Horizon Chemical Co.

O-alkanoyl glucosides are described in International Patent Application WO 88/10147 (Novo Industri A/S) . In particular the surfactants described therein are glucose esters with the acyl group attached in the 3- or 6- position such as 3-0-acyl-D-glucose.

Further possible hydrophobic nonionic surfactants are monoglyceryl ethers or esters of the respective formulae 0

II

R₈OCH₂CHCH₂OH and R₈COCH₂CHCH₂OH

I I

OH OH

R₈ is preferably a saturated or unsaturated aliphatic residue. In particular, R₈ may be linear or branched alkyl or alkenyl.

The monoglyceryl ethers of alkanols are known materials and can be prepared, for example by the condensation of a higher alkanol and glycidol. Glycerol monoesters are of course well known and available from various suppliers including Alkyril Chemicals Inc.

Other nonionic materials are the alkyl methyl sulphoxides and alkyl hydroxyethylsulphoxides wherein the alkyl chain

The peroxy bleach compounds which can be utilized in the bleaching composition and detergent bleach composition of the present invention include hydrogen peroxide, hydrogen peroxide-liberating compounds, hydrogen peroxide- generating systems and mixtures thereof.

Hydrogen peroxide sources are well known in the art. They include the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. Mixtures of two or more of such compounds may also be used. Particularly preferred are sodium percarbonate and sodium perborate and, especially, sodium perborate monohydrate. Sodium perborate monohydrate is preferred to sodium perborate tetrahydrate because of its excellent storage stability combined with its ability to dissolve very quickly in aqueous bleaching solutions. Sodium percarbonate may be preferred for environmental reasons. The amount thereof in the compositions of the invention usually will be within the range from 1 to 30% by weight, preferably 5 to 25% by weight.

Alkylhydroxy peroxides are another class of peroxy bleach compound. Examples of these materials include cumene hydroperoxide and t-butyl hydroperoxide.

Organic peroxyacids may also be suitable as the peroxide bleaching agent. Such materials normally have the general formula: 0

HOO - C R - Y

wherein R is an alkylene or substituted alkylene group containing from 1 to about 20 carbon atoms, optionally having an internal amide linkage; or a phenylene or substituted phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an imido-aromatic or non-aromatic group, a 0

II COOH or C-OOH group or a quaternary ammonium group. Typical monoperoxy acids useful herein include, for example: i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g. peroxy-α-naphthoic acid; ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids, e.g. peroxylauric acid, peroxystearic acid and N,N-phthaloylaminoperoxy caproic acid (PAP) ; iii) 6-octylamino-6-oxo-peroxyhexanoic acid. Typical diperoxyacids useful herein include, for example: iv) 1,12-diperoxydodecanedioic acid (DPDA) ; v) 1, 9-diperoxyazelaic acid; vi) diperoxybrassilic acid; diperoxysebasic acid and diperoxyisophthalic acid; vii) 2-decylperoxybutane-l,4-dioic acid; viii) 4,4'-sulphonylbisperoxybenzoic acid.

Also inorganic peroxyacid compounds are suitable, 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 2-10% by weight, preferably from 4-8% by weight.

All these peroxide compounds may be utilized alone or in conjunction with a peroxyacid bleach precursor and/or an organic bleach catalyst.

Peroxyacid bleach precursors are known and amply described in literature, such as in the GB Patents 836,988; 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 US Patents 1,246,339; 3,332,882; 4,128,494, 4,412,934 and 4, 675,393.

Another useful class of peroxyacid bleach precursors is that of the cationic i.e. quaternary ammonium substituted peroxyacid precursors as disclosed in US Patents 4,751,015 and 4,397,757, in EP-A-284292 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-dimethyl-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 cationic peroxyacid bleach precursors is formed by the cationic nitriles as disclos in EP-A-0303520 and in Applicant's co-pending European Patent Specification No's 464 880 and 458 396.

Any one of these peroxyacid bleach precursors can be use in the present invention, though some may be more preferred than others.

Of the above classes of bleach precursors, the preferred classes are the esters, including acyl phenol sulphonate and acyl alkyl phenol sulphonates; the acyl-amides; the quaternary ammonium substituted peroxyacid precursors including the cationic nitriles and sulphonimides.

Examples of said preferred peroxyacid bleach precursors activators are sodium-4-benzoloxy benzene sulphonate

(SBOBS) ; N,N,N' ,N'-tetraacetyl ethylene diamine (TAED) ; sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate; sodiu 4-methyl-3-benzoloxy benzoate; SPCC; trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3,5, 5-trimethyl hexanoyloxybenzene sulphonate (STHOBS) ; substituted cationic nitriles, and sulphonimides as disclosed in EP-A-0,453,003 and EP-A-0,446, 982.

The precursors may be used in an amount of about 1-8%, preferably from 2-5% by weight, of the composition.

The detergent composition of the invention will generally contain one or more detergency builders, suitably in an amount of from 5 to 80 wt%, preferably fr 20 to 80 wt%. This may be any material capable of reducing the level of free calcium and/or magnesium ions in the wash liquor and will preferably provide the compositions with other beneficial properties such as the generation of an alkaline pH and the suspension of soil removed from the fabric.

Preferred builders include alkali metal (preferably sodium) aluminosilicates, which may suitably be incorporated in amounts of from 5 to 60% by weight (anhydrous basis) of the composition, and may be either crystalline or amorphous or mixtures thereof, having the general formula:

0.8-1.5 Na,0.Al,0,.0.8-6 SiO

These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5-3.5 Si0₂ units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.

Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter & Gamble) . The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof. Also of interest is the novel zeolite P described and claimed in EP 384070 (Unilever) .

Other builders may also be included in the detergent composition of the invention if necessary or desired: suitable organic or inorganic water-soluble or water-insoluble builders will readily suggest themselves to the skilled detergent formulator. Inorganic builders that may be present include alkali metal (generally sodium) carbonate; while organic builders include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates; and organic precipitant builders such as alkyl- and alkenylmalonates and succinates, and sulphonated fatty acid salts.

Especially preferred supplementary builders are polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, especially from 1 to 10 wt%; and monomeric polycarboxylates, more especially citric acid and its salts, suitably used in amounts of from 3 to 20 wt%, more preferably from 5 to 15 wt%.

Preferably the detergent composition comprises a surface- active material, a peroxy bleach compound, hydroxylamine, a ligand of formula (I) or (II) , as hereinbefore defined, and optionally a source of iron and/or manganese ions wherein the surface active material comprises 0 to 25% by weight of nonionic surfactant, the weight ratio of nonionic surfactant to anionic surfactant being at least 0.75 if the composition contains 0-75% by weight of a carbonate builder expressed as sodium carbonate and at least 2.2 if the composition contains more than 7.5% by weight of carbonate builder.

In the detergent compositions according to the invention the ligand is preferably in the form of a mononuclear or dinuclear complex of formulae (III) , (IV) or (V) as hereinbefore defined. Preferably the composition according to the invention will comprise 0-15% by weight of anionic surfactant and from 10-40% by weight of nonionic surfactant.

In a further preferred embodiment the surface active system is free from C₁₆-C₂₂ fatty acid soaps.

In another preferred embodiment the composition is an all nonionic based formulation exempt from any anionic surfactant.

Hydroxylamine is preferably incorporated in the compositions of the invention in the form of a salt such as hydroxylamine sulphate. It is preferably present at a level of 0.01 to 10% by weight, most preferably 0.1 to 2.5% by weight based on the composition.

The ligand and, optionally, the source of iron and/or manganese ions will be present in the bleach and detergent bleach compositions in amounts so as to provide the required level of ligand and metal ions in the wash liquor. Normally, an amount of ligand is incorporated in the composition from 0.0015% to about 1.5% by weight, preferably 0.003% to 0.75% by weight, and the amount of iron and/or manganese ion source incorporated is from 0.0005% to about 0.5% by weight, preferably 0.001% to 0.25%. y weight.

When used in a detergent bleach composition to be dosed at low levels, for example by Japanese and US consumers at dosages of about 1 and 2 g/1 respectively the ligand content is 0.0075 to 1.5% by weight preferably 0.015 to 0.75% by weight, and the iron and/or manganese is present at 0.0025 to 0.5% by weight, preferably 0.005 to 0.25%. At higher product dosages as used, for example, by

European consumers, the ligand content in the composition is 0.0015 to 0.3% by weight, preferably from 0.003 to 0.15% and the iron and/or manganese present at 0.0005 to 0.1% by weight, preferably from 0.001 to 0.05%.

When the ligand is incorporated in the compositions of the invention in the form of a mono-, di- or tetranuclear complex, the amount added will be such that the effective level of the Mn-complex catalyst, expressed in terms of parts per million (ppm) of manganese in the aqueous washing or bleach solution, will normally range from 0.001 ppm to 100 ppm, preferably from 0.01 ppm to 10 ppm, most preferably from 0.05 ppm to 5 ppm.

When the dosage of the detergent bleach composition is relatively low, e.g. about 1 and 2 g/1 by consumers in Japan and USA, respectively, the Mn content in the formulation is 0.001 to 1.0%, preferably 0.005 to 0.50%. At higher product dosage as used e.g. by European consumers, the Mn content in the formulation is 0.0005 to 0.25%, preferably from 0.001 to 0.1%.

It is desirable that the compositions according to the invention be approximately neutral or at least slightly alkaline, that is when the composition is dissolved in an amount to give surfactant concentration of 1 g/1 in distilled water at 25°C the pH should desirably be at least 7.5. For solid compositions the pH will usually be greater, such as at least 9. To achieve the required pH, the compositions may include a water-soluble alkaline salt. This salt may be a detergency builder (as described above) or a non-building alkaline material.

The detergent composition of the invention may also contain one of the detergency enzymes well-known in the art for their ability to degrade and aid in the removal of various soils and stains. Suitable enzymes include proteases, for example Savinase (Trade Mark) ; lipases, for example Lipolase (Trade Mark) ; amylases, for example Termamyl (Trade Mark) and cellulases, for example celluzyme (Trade Mark) all supplied by Novo/Nordisk. Detergency enzymes are commonly employed in the form of granules liquids, slurries, optionally with a protective coating, in amounts of from about 0.1% to about 3.0% by weight of the composition.

The detergent composition of the invention may also contain a fluorescer (optical brightener) , for example, Tinopal (Trade Mark) DMS or Tinopal DBS available from Ciba-Geigy AG, Basel, Switzerland. Tinopal DMS is disodium 4,4'bis-(2-morpholino-4-anilino-s-triazin-6- ylamino) stilbene disulphonate; and Tinopal DBS is disodium 2,2'bis-(phenyl-styryl) disulphonate.

An antifoam material is advantageously included in the detergent composition of the invention, especially if the powder is primarily intended for use in front-loading drum-type automatic washing machines. Suitable antifoam materials are usually in granular form, such as those described in EP 266 863A (Unilever) . Such antifoam granules typically comprise a mixture of silicone oil, petroleum jelly, hydrophobic silica and alkyl phosphate as antifoam active material, sorbed onto a porous absorbent water-soluble carbonate-based inorganic carrier material.

Antifoam granules may be present in any amount up to 5% by weight of the composition.

Further ingredients which can optionally be employed in the detergent composition of the invention include polymers containing carboxylic or sulphonic acid groups in acid form or wholly or partially neutralised to sodium or potassium salts, the sodium salts being preferred. Preferred polymers are homopolymers and copolymers of acrylic acid and/or maleic acid or maleic anhydride. Of especial interest are polyacrylates, polyalphahydroxy acrylates, acrylic/maleic acid copolymers, and acrylic phosphinates. Other polymers which are especially preferred for use in liquid detergent compositions are deflocculating polymers such as for example disclosed in EP 346995.

The molecular weights of homopolymers and copolymers are generally 1000 to 150,000, preferably 1500 to 100,000. The amount of any polymer may lie in the range from 0.5 to 5% by weight of the composition. Other suitable polymeric materials are cellulose ethers such as carboxy methyl cellulose, methyl cellulose, hydroxy alkyl celluloses, and mixed ethers, such as methyl hydroxy ethyl cellulose, methyl hydroxy propyl cellulose, and methyl carboxy methyl cellulose. Mixtures of different cellulose ethers, particularly mixtures of carboxy methyl cellulose and methyl cellulose, are suitable. Polyethylene glycol of molecular weight from 400 to 50,000, preferably from 1000 to 10,000, and copolymers of polyethylene oxide with polypropylene oxide are suitable as also are copolymers of polyacrylate with polyethylene glycol. Polyvinyl pyrrolidone of molecular weight of 10,000 to 60,000, preferably of 30,000 to 50,000 and copolymers of polyvinyl pyrrolidone with other poly pyrrolidones are suitable. Polyacrylic phosphinates and related copolymers of molecular weight 1000 to 100,000, in particular 3,000 to 30,000 are also suitable.

It may also be desirable to include in the detergent composition of the invention an amount of an alkali metal silicate, particularly sodium ortho-, meta- or preferably neutral or alkaline silicate. The presence of such alkali metal silicates at levels, for example, of 0.1 to 10 wt%, may be advantageous in providing protection against the corrosion of metal parts in washing machines, besides providing some measure of building and giving processing benefits.

Further examples of other ingredients which may be present in the composition include fabric softening agents such as fatty amines, fabric softening clay materials, lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids; heavy metal sequestrants such as EDTA and the phosphonic acid derivatives (i.e. Dequest (Trade Mark) type materials) ; perfumes including deodorant perfumes; germicides; pigments, colorants or coloured speckles; and inorganic salts such as sodium and magnesium sulphate. Sodium sulphate may if desired be present as a filler material in amounts up to 40% by weight of the composition; however as little as 10% or less by weight of the composition of sodium sulphate, or even none at all, may be present.

Of these additives, transition metal sequestrants, such as EDTA and the phosphonic acid derivatives, e.g. ethylene diamine tetra- (methylene phosphonate) - EDTMP - are of special importance, as not only do they improve the stability of the catalyst/H₂0₂ system and sensitive ingredients, such as enzymes, fluorescent agents, perfumes and the like, but also improve the bleach performance, especially at the higher pH region of above 10, particularly at pH 10.5 and above.

Detergent compositions of the invention formulated as free-flowing particles, e.g. in powdered or granulated form, can be produced by any of the conventional techniques employed in the manufacture of detergent compositions, for instance by slurry-making, followed by spray-drying to form a detergent base powder to which the heat-sensitive ingredients including the peroxy compound bleach and optionally some other ingredients as desired, and the ligand, source of iron and/or manganese ions and mono-, or di- or tetranuclear manganese complex, as appropriate, may be added as dry substances.

It will be appreciated, however, that the detergent base powder compositions, to which the ligand, source of iron and/or manganese ions and mono-, di- or tetranuclear manganese complex, as appropriate, is added, can itself be made in a variety of other ways, such as the so-called part-part processing, non-tower route processing, dry- mixing, agglomeration, granulation, extrusion, compacting and densifying processes etc., such ways being well known to those skilled in the art and not forming the essential part of the present invention.

Alternatively, the ligand, source of iron and/or manganese ions and mono-, di- or tetranuclear manganese complex, as appropriate, can be added separately to a wash/bleach water containing the peroxy compound.

In that case, the ligand, source of iron and/or manganese ions and mono-, di- or tetranuclear manganese complex, as appropriate is presented as a detergent additive product. Such additive products are intended to supplement or boost the performance of conventional detergent compositions and may contain any of the components of such compositions, although they will not comprise all of the components as present in a fully formulated detergent composition. Additive products in accordance with this aspect of the invention will normally be added to an aqueous liquor containing a source of (alkaline) hydrogen peroxide, although in certain circumstances the additive product may be used as separate treatment in a pre-wash or in the rinse .

Additive products in accordance with this aspect of the invention may comprise the compound alone or preferably, in combination with a carrier, such as a compatible aqueous or non-aqueous liquid medium or a particulate substrate or a flexible non-particulate substrate.

Examples of compatible particular substrates include inert materials, such as clays and other aluminosilicates, including zeolites, both natural and synthetic of origin. Other compatible particulate carrier materials include hydratable inorganic salts, such as carbonates and sulphates.

The detergent composition of the invention may also be formulated in other product forms, such as flakes, tablets, bars and liquids, particularly non-aqueous liquid detergent compositions.

Such non-aqueous liquid detergent compositions are known in the art and various formulations have been proposed, e.g. in US Patents 2,864,7701; 3,368,977; 4,772,412; GB Patents 1,205,711; 1,370,377; 2,194,536; DE-A-2,233,771 and EP-A-0, 028, 849.

These are compositions which normally comprises a non- aqueous liquid medium, with or without a solid phase dispersed therein. The non-aqueous liquid medium may be a liquid surfactant, preferably a liquid nonionic surfactant; a polar solvent, e.g. polyols, such as glycerol, sorbitol, ethylene glycol, optionally combined with low-molecular monohydric alcohols, e.g. ethanol or isopropanol; or mixtures thereof.

The solid phase can be builders, alkalis, abrasives, polymers, clays, other solid ionic surfactants, bleaches, fluorescent agents and other usual solid detergent ingredients.

The invention will now be illustrated by the following non-limiting examples.

EXAMPLES

Examples I - IX

Experiments were carried out with sodium perborate monohydrate on standard tea-stained test cloths.

The experiments were all carried out in a temperature- controlled glass beaker equipped with a magnetic stirrer, thermocouple and a pH electrode and at a constant temperature of 30 or 40°C. When the experiments were carried out, air (100 ml/min) was bubbled through the solutions in the beakers, in order to mimic the aeration of a wash solution in a washing machine. In the experiments tap water (16°FH) was used.

Two test cloths were immersed for 30 minutes in each of the compositions of the examples. After rinsing with tap water, the cloths were dried in a tumble drier. The reflectance (R₄₆₀.) was measured on a Macbeth 1500/Plus colour measurement system, ex Macbeth, before and after treatment. The difference (Δ R₄₆₀.) in the value gives a measure of the effectiveness of the treatment. The (Δ R₄₆₀.) results presented below are an average value for two test cloths. Deter ent Formulation

In the examples, hydroxylamine inhibition of catalase formation was examined in a detergent powder formulation, the composition of which is given below. The formulation was dosed at a level of 5g/l. The amount of sodium perborate monohydrate used was 17.2%, yielding a hydrogen peroxide concentration of 8.6 xlO^"3 mol/1.

Air was bubbled through 2 litres of water at 30°C. About 10 ml of the water was removed and used to dissolve the hydroxylamine sulphate (0.8 mmol), when present. Small amounts of water were also required to dissolve the ligand, in the form of a dinuclear manganese complex, and catalase, when present. To the remaining water all the remaining components except the ligand were added with stirring. Stirring was continued for 1 minute to dissolve all components. Thereafter, the hydroxylamine solution was added.

Within 30 seconds, samples were extracted from the resulting solution and thereafter separate solutions of the ligand and catalase were added, as necessary, together with the test cloths.

Catalase (ex Aspergillus Niger) was added to mimic the build up of catalase formed when dirty cloths are washed. The amount used is expressed in "units"/C, where one unit will decompase 1.0 x 10^"6 mol/{ H₂0₂ per minute at pH 7.0 at 25°C, while the H₂0₂ concentration falls from 10.3 to 9.2 x 10^"3 mol/1.

Thereafter, samples of the wash liquor were analysed for hydrogen peroxide and hydroxylamine. Hydrogen peroxide was analysed according to the procedure described by C Allain et al in Clin. Chem., vol 20, 470 (1974). The procedure is based on the specific catalysed reaction of hydrogen peroxide with 4-aminoantipyrine/phenol to form a quinoneimine dye, the concentration of which is determined spectrophotometrically at 500 nm. Hydroxylamine was analysed by a procedure described by P.Pietta et al in Analyst, vol 107, 341 (1982). In the procedure hydroxylamine is reacted with 2,4, 6-trinitrobenzene sulphonic acid (TNBS) and the concentration of the reaction product determined spectrophotometrically at 494nm.

The results obtained are given in Table I.

10

15

dinuclear manganese complex of formula (IV) prepared in accordance with the method described in E-A-458 397.

A comparison of Example III (no hydroxylamine) with Example VII clearly demonstrates the benefit, in terms of bleaching performance, of the presence of hydroxylamine.

A comparison of Examples V with Example VIII (no complex) clearly demonstrates the advantage of including of the dinuclear complex in the detergent composition in terms of the reduction of the level of hydroxylamine remaining after the wash process is completed.

Similar results would be expected if the dinuclear manganese complex is replaced by a mononuclear manganese complex or ligand and source of iron and/or manganese added separately, as hereinbefore described.

Example X-XIII

In the following examples the procedure used in Examples I-IX was repeated except (i) the solution containing the detergent formulation, catalase, ligand etc was at a temperature of 20°C. After the test cloths were added, the solution was heated up to 40°C over a period of 12 minutes and maintained at that temperature for a further 38 minutes.

The results obtained are given in Table II

10

15

Claims

1. A detergent composition comprising

i) a surface-active material selected from anionic, nonionic, catinic, zwitteronic, amphoteric surfactants and mixtures thereof; ii) a peroxy compound; iii) hydroxylamine or a precursor thereof; and iv) a catalyst capable of destroying said hydroxylamine or precursor thereof .

2. A detergent composition according to claim 1 in which the catalyst comprises i) a ligand L which is a macrocyclic organic compound of formula (I)

[NR³ - ⁽CR¹⁽R ⁾ _u ⁾ _tl "] ⁽I⁾

wherein t is an integer from 2 to 3; s is an integer from 3 to 4, u is zero or one; each R¹, R² and R³ are independently selected from H, alkyl, aryl, substituted alkyl, and substituted aryl;

or ii) a ligand comprising two species of formula (II)

[NR⁴ (CR^X(R² 'u⁾ T| (ID

wherein t is an integer from 2 to 3; s is an integer from 3 to 4; u is zero or one; each R¹ and R² are independently selected from H, alkyl, aryl, substituted alkyl and substituted aryl; and each R⁴ is independently selected from hydrogen, alkyl, aryl, substituted alkyl and substituted aryl, with the proviso that at least one bridging unit R⁵ is formed by one R⁴ unit from each ligand where R⁵ is the group (CR⁶R₇)_n- (D)_p-(CR⁶R )_m where p is zero or one; D is selected from a heteroatom such as oxygen and NR⁸ or is part of an optionally substituted; aromatic or saturated homonuclear or heteronuclear ring, n is an integer from 1 to 4; m is an integer from 1 to 4; with the proviso that n + m < 4; each R⁶ and R⁷ are independently selected from H, NR⁹ and OR¹⁰, alkyl, aryl, substituted alkyl and substituted aryl; and each R⁸, R⁹, R¹⁰ are independently selected from H, alkyl, aryl, substituted alkyl and substituted aryl.

3. A detergent composition according to claim 1 wherein the catalyst is selected from:- (i) mononuclear manganese complexes of formula

(III) :-

[L Mn X_p]^zY_q (III)

wherein Mn is manganese in the II, III or IV oxidation state, each X represents a coordinating species independently selected from OR¹¹, where R¹¹ is a Cj-C₂₀ radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl and radical combinations thereof or at least two R¹¹ radicals may be connected to one another so as to form a bridging unit between two oxygens that coordinate with the manganese, Cl^", Br^", I^", F^", NCS^", N₃ ^", I₃ ^", NH₃, OH^",0₂ ^2", HOO^", H₂0, SH, CN^'OCN^",

S₄ ^2", R^aCOO^", R^βS0₃ ^", R^aS0₄ ^" where R^a is selected from H, alkyl, aryl, substituted alkyl and substituted aryl and R^bCOO where R^b is selected from alkyl or aryl, substituted alkyl, substituted aryl and mixtures thereof; p is an integer from 1-3; z denotes the charge of the complex and is an integer which can be positive or negative;

Y is a monovalent or multivalent counter-ion, leading to charge neutrality, which is dependent upon the charge z of the complex; q = 7.1 [charge Y] ; and is a ligand which is a macrocyclic organic compound of formula (I):-

_Γ [NR³ - (CR R²)_u)_t] (I)

(ii) dinuclear manganese complexes of formula (IV):-

wherein each Mn is manganese which may independently be in the III or IV oxidation state; each X independently represents a coordinating or bridging species selected from the group consisting of H₂0, 0₂ ^2", O^2", OH^", H0₂ ^", SH^", S^2",

>SO, Cl^", N^3", SCN^", NH₂ ^", NR, R^a ₃S0₄ ^", R^aS0₃ ^" and

R^aCOO^" where R^a is selected from H, alkyl, aryl, substituted alkyl and substituted aryl and

R^bCOO^", where R^b is selected from alkyl, aryl, substituted alkyl and substituted aryl; z denotes the charge of the complex and is an integer which can be positive or negative;

Y is a monovalent or multivalent counter-ion, leading to charge neutrality, which is dependent upon the charge z of the complex; q = z/ [charge Y] ; and

L is a ligand of formula (I) as hereinbefore defined; and

(iii)dinuclear manganese complexes of formula (V):-

>S0, Cl^", N^3", SCN^", NH₂ ^", NR, R^a ₃S0₄ ^", R^aS0₃ ^" and R^aCOO^" where R^a is selected from H, alkyl, aryl, substituted alkyl and substituted aryl and R^bCOO^", where R^b is selected from alkyl, aryl, substituted alkyl and substituted aryl; 5 z denotes the charge of the^s complex and is an integer which can be positive or negative; Y is a monovalent or multivalent counter-ion, leading to charge neutrality, which is dependent upon the charge z of the complex; 10 q = z/ [charge Y] ; and

L is a ligand which comprises two species of formula (II) :-

[ LNINRK⁴' - ( (CLRK- (Rκ²-)_{u tt}]j_s -i (II)

L 1

15 wherein t is an integer from 2 to 3 ; s is an integer from 3 to 4, u is zero or one; each R¹, R² and R⁴ are independently selected from hydrogen, alkyl, aryl, substituted alkyl and

20 substituted aryl, with the proviso that a bridging unit R⁵ is formed by one R⁴ unit from each ligand where R⁵ is the group

^' (CR⁶R⁷)_n-(D)_p- (CR⁶R⁷)_m where p is zero or one; D is selected from a heteroatom such as oxygen and NR⁸

25 or is part of an aromatic or saturated homonuclear or heteronuclear ring, n is an integer from 1 to 4; m is an integer from 1 to 4; with the proviso that n + m < 4;

30 R⁶ and R⁷ are each independently selected from H,

NR⁹ and OR¹⁰, alkyl, aryl, substituted alkyl and substituted aryl; and

R⁸, R⁹, R¹⁰, are each independently selected from H, alkyl, aryl, substituted alkyl and

35 substituted aryl; and

4. A detergency composition according to claim 3 wherein in the complexes of formulae (III) , (IV) and (V) each X is independently selected from CH₃COO^", 0₂ ^2" and O^2".

5. A detergent composition according to claim 3 wherein each X is 0^2" and Mn is manganese in the IV oxidation state.

6. A detergent composition according to claim 1 comprising

i) 3 to 40% by weight of a surface-active material; ii) 1 to 30% by weight of a peroxy compound; iii) 0.01 to 10% by weight of hydroxylamine or a precursor thereof; and iv) 0.0015 to 1.5% by weight of catalyst.

7. A detergent composition according to claim 4 further comprising 5 to 80% by weight of a detergency builder.

8. A detergent composition according to claim 1 wherein the peroxy compound is selected from hydrogen peroxide; hydrogen-peroxide liberating compounds; hydrogen-peroxide generating systems; alkyl hydroxy peroxides; organic peroxyacids; and inorganic peroxyacid compounds .

9. Use of detergent composition according to any one of claims 1 to 8 to treat stained fabrics comprises contacting the stained fabrics in an aqueous medium with said detergent composition.