WO1995024267A1

WO1995024267A1 - Metallomacrocycle catalyst composition

Info

Publication number: WO1995024267A1
Application number: PCT/US1995/001880
Authority: WO
Inventors: Robert A. Walker Johnstone; Paul Anthony Stocks; Frederick Edward Hardy; Johan Gerwin L. Pluyter; Anthony Joseph Simpson
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1994-03-08
Filing date: 1995-02-16
Publication date: 1995-09-14
Anticipated expiration: 1996-09-08
Also published as: MX9603972A; JPH09509886A; CN1146165A

Abstract

A metallomacrocycle catalyst composition comprising a complex of: (i) a transition metal catalyst selected from: (a) a transition metal porphin and mixtures thereof; (b) a transition metal phthalocyanine and mixtures thereof; (c) mixtures of transition metal porphin and transition metal phthalocyanine; and (ii) an amphiphilic polymer and mixtures thereof; the complex increasing the half life of the catalyst by a factor of at least 1.1.

Description

METALLOMACROCYCLE CATALYST COMPOSITION

Field of the invention

The present invention relates to a composition which is capable of enhancing the half life in aqueous media, containing a source of hydrogen peroxide, of a metallomacrocycle catalyst composition; to a Dye Transfer Inhibiting (DTI) composition and its process for inhibiting dye transfer between fabrics during washing.

Background of the invention

One of the most persistent and troublesome problems arising during modern fabric laundering operations is the tendency of some coloured fabrics to release dye into the laundering solutions. The dye is then transferred onto other fabrics being washed therewith.

One way of overcoming this problem would be to bleach the fugitive dyes washed out of dyed fabrics before they have the opportunity to become attached to other articles in the wash.

Suspended or solubilised dyes can to some degree be oxidised in solution by employing known bleaching agents. European Patent 538228 describes a DTI composition comprising a metallo catalyst, a polymer and an enzymic system capable of generating hydrogen peroxide wherein said polymer reduces the deposition of the metallo catalyst onto fabrics.

European Patent 553608 describes a DTI composition comprising a metallo catalyst, an amine base catalyst stabiliser, and an enzymic system capable of generating hydrogen peroxide wherein said amine base is capable of binding the 5th ligand of the metallo catalyst.

Both teach a preferred DTI composition with a sulphonated group on the metallo catalyst to provide solubility which is expensive.

It has now been found that certain specific polymers can form a complex with the transition metal catalyst which solubilises it in aqueous solution. This avoids the expensive step of sulphonating the transition metal catalyst.

The addition of said polymer reduces the rate of self destruction of the transition metal catalyst, resulting in improved through-the-wash stability of the transition metal catalyst and enables the use of a wider range of transition metal catalyst compounds.

Accordingly, a dye transfer inhibiting composition is provided which exhibits optimum dye transfer inhibiting properties.

According to another aspect, the invention provides an efficient process for laundering operations involving coloured fabrics.

Summary of the invention

The present invention relates to a metallomacrocycle catalyst composition

comprising a complex of:

(i)-a transition metal catalyst selected from: a-a transition metal porphin and mixtures thereof; b-a transition metal phthalocyanine and mixtures thereof; c-mixtures of transition metal porphin and transition metal phthalocyanine; and (ii)-an amphiphilic polymer and mixtures thereof; the complex increasing the half life of the catalyst by a factor of at least 1.1.

The half life of the catalyst is defined as the half life of the oxidative stability of the catalyst in aqueous media, containing a source of peroxide.

According to another aspect of this invention a dye transfer inhibiting composition, its process and also an epoxidation process is provided.

Chemical formulas of porphin and phthalocyanine in accordance with the invention will refer to Figure land/or 2 and Figure 3 and/or 4.

Figure 1 shows the general formula for porphin compounds wherein the transition metal is in the oxidation state (II).

Figure 2 shows the general formula for porphin compounds wherein the transition metal is in the oxidation state (III).

Figure 3 shows the corresponding formula of phthalocyanine compounds wherein the transition metal is in the oxidation state (II).

Figure 4 shows the corresponding formula of phthalocyanine compounds wherein the transition metal is in the oxidation state (III).

Detailed description of the invention

It is well known in the art that metallo catalysts e.g. metallo porphins are susceptible to self-destruction . As a result of said self destruction, the level of added catalyst should be such that sufficient active catalyst is present to bleach the dyes throughout the total wash cycle.

It has now been found that the life time of the metallo catalyst in aqueous media is enhanced by adding a polymer which forms a complex with the catalyst and also solubilises it. This is provided by a micellar polymer or polymeric pseudomicelle which are capable of self-organisation due to hydrophobic interactions. The hydrophobic 'microdomain' created by this class of amphiphilic polymer solubilises the hydrophobic catalyst. In its broadest aspect, the present invention provides a complex comprising two elements :

(i)-a transition metal catalyst selected from: a-a transition metal porphin and mixtures thereof, b-a transition metal phthalocyanine and mixtures thereof, c-mixtures of transition metal porphin and transition metal phthalocyanine, and (ii)-an amphiphilic polymer and mixtures thereof; the complex increasing the half life of the catalyst by a factor of at least

1.1.

Transition metal catalyst

The essential transition metal porphin structure may be visualised as indicated in Figure 1 and/or Figure 2 in the separate sheet. In Figure land 2 the atom positions are numbered conventionally and the double bonds are put in conventionally.

Porphin and porphyrin, in the literature, are used as synonyms, but conventionally porphin stands for the simplest porphyrin without any substituents; wherein porphyrin is a sub-class of porphin. The references to porphin in this application will include porphyrin.

Transition metal porphin structures are those substituted at one or more of the 5, 10, 15 and 20 carbon positions of formula 1 (Meso positions) with substituents selected from hydrogen, alkyl groups such as methyl, ethyl, propyl, t-butyl group, and aromatic ring systems selected from substituted or unsubstituted pyridyl, pyridyl-N-oxide, phenyl, naphthyl and anthracyl moieties.

Preferred transition metal porphin structures are those substituted at one or more of the 5, 10, 15 and 20 carbon positions of formula 1 (Meso positions), with an aromatic ring system selected from substituted or unsubstituted phenyl, pyridyl, pyridyl-N-oxide, naphthyl and anthracyl substituent. A more preferred metallo porphin is one in which the molecule is substituted at the 5,10,15 and 20 carbon positions with a pyridyl substituent selected from:

where each X\ , independently, is selected from H, F, CI, Br, NO2, alkyl, alkoxy, cycloalkyl, aralkyl, aryl, alkaryl and heteroaryl; preferably H, CI or F; and X2 is selected from O", OH, H, alkyl, alkoxy, cycloalkyl, aralkyl, aryl, alkaryl and heteroaryl, preferably O".

Another highly preferred metallo porphin is one in which the molecule is substituted at the 5,10,15 and 20 carbon positions with a phenyl substituent selected from:

where each X, independently, is selected from H, F, CI, Br, -SO3H, SO2NR2 where R is selected from H, alkyl, and hydroxyalkyl,-Cθ2H, alkyl, alkoxy, cycloalkyl, aralkyl, aryl, alkaryl and heteroaryl, preferably H, CI or F;

Substitution by an NO2 group is also suitable but in only one of the X positions.

A particularly preferred transition metal porphin is one in which the molecule is substituted at the 5, 10, 15 and 20 carbon positions with a phenyl substituent, wherein said phenyl is substituted with X=H. This preferred compound is known as transition metal tetraphenylporphin. The compound of Figure 1 and/or Figure 2 may be substituted at one or more of the remaining carbon positions by substituents selected from F, CI, Br and Ci-C ιo alkyl.

Furthermore, the compound of Figure 1 and/or Figure 2 may be substituted at one or more of the 2,3,7,8, 12,13, 17, 18 carbon positions by a substituent selected from F, CI, Br, alkyl, alkylcarboxy, alkylhydroxyl, vinyl, alkenyl and aryl.

The transition metals which can be used are selected from Cu, Fe, Mn, Co, Cr, Ti, V or other transition metals, preferably Mn.

For oxidation state of the transition metal porphin greater than (II), the symbol X^ of Figure 2 represents an anion, preferably OH- or CI- when the oxidation state is (III).

More preferably, the transition metal of the porphin is in the oxidation state (III).

Porphin derivatives also include chlorophylls, chlorins and bacteriochlorins.

Transition metal phthalocyanines and their derivatives have the structure indicated in Figure 3 and/or Figure 4, wherein the atom positions of the phthalocyanine structure are numbered conventionally.

Transition metal phthalocyanine structures are those substituted at one or more of the 1-4, 6, 8-11 , 13, 15-18, 20, 22-25, 27 atom positions of Figure 3 and/or Figure 4 with substituents selected from hydrogen, alkyl groups such as methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as pyridyl, phenyl, naphthalene and anthracene groups.

A preferred transition metal phthalocyanine is non-substituted phthalocyanine. The transition metals which can be used are selected from Cu, Fe, Mn, Co, Cr, Ti, V or other transition metals, preferably Mn.

For oxidation state of the transition metal phthalocyanine greater than (II), the symbol X^ of Figure 4 represents an anion, preferably OH- or Cl- when the oxidation state is (III).

More preferably, the transition metal of the phthalocyanine is in the oxidation state (II).

Polymer

The second element of the invention is a polymer comprising at least one hydrophilic group and at least one hydrophobic group, such that the ratio of hydrophilic group and hydrophobic groups lies in the range from 1:10 to 10:1 ; preferably from 1:3 to 3: 1.

The, at least partially, hydrophobic moieties interact with the insoluble catalyst through hydrophobic interactions such as 11-11 interactions, and/or charge transfer interactions, and/or Van der Waals interactions which stabilise the composition in a polymeric pseudo micelle while the hydrophilic group(s) of the polymer solubilise the composition. When acting by charge transfer interactions, an electron donor-acceptor complex is formed.

Preferred polymeric structures for solubilisation of oxidative catalysis are structures of the formula :

R R R R

[(-(CH)_n-(C)_m-(CH)_p-)_v-A-] _q [«CH)_r-(C)_s-(CH)_t-)_w-B- u

Rl R2

where A and B can be selected from : -CH2-, NH ,0 , ketone, an ester linkage, an amide linkage, an imine linkage; where n,m,p,r,s,t can independently be any entire number as long as (n + m+p)v- (r-r-s-ι^Lt)w range from 1-1000 , preferably from 1-500 and such that the ratio v/w varies between 0.1 and 1 ; where the values of q and u, independently lie in the range from 1-10.

Each R, independently, can be selected from H, alkyl, haloalkyl, alkenyl, alkynyl; preferably H or CH3.

Rl is selected from (partially) hydrophobic moieties containing aromatic hydrocarbon rings derived from compounds such as toluene, methyl styrene, stilbene, pyridine, naphthalene, anthracene, phenanthrene, phenyl, histidine, tryptophan, phenyl alanine, tyrosine, alkyl benzene, xylenes, carbazoles, xanthenes, acridines, purines, pyridazines and indoles.

R2 is selected to provide water-solubility and these substituents are therefore hydrophilic in nature such as -OH, hydroxyalkyl such as hydroxy methyl and hydroxyethyl; polyoxyethylene, hydroxyphenyl and derivatives thereof, moieties derived from pyrrolidone, pyridine-N-oxide, N-oxide derivatives of histidine, tryptophan, phenyl alanine, tyrosine; phenyl sulphonate, naphthalene sulphonate, imidazole, water-soluble salt derivatives of naphthalene, anthracene, phenanthrene, phenyl, carbazoles, xanthenes, acridines, purines, pyridazines, indoles, -COOH, -COOM, -SO3M where M is an alkali metal ion ; -NR2, -NR3 ^"*^" X ^~ where X is a halide ion and R is, independently selected from H, alkyl, and hydroxyalkyl.

Rl and R2, independently, can be substituents on the moieties A and B in the event that A and/or B are not an ether, ketone, amide, imine, or ester linkage.

Another class of polymer suitable for the present invention are the substituted polysaccharides of the unit structure:

Rl R2 where C and D are oligosaccharide units and where oligosaccharide units comprise the product of polycondensation of monosaccharides by O- glycosidic linkage containing up to 10 such residues selected from hexose, pentose and deoxyhexose residues; where the values of q and u, independently, lie in the range from 1 to 10; and where the substituents Rl and R2 remain the same as mentioned before.

A third class of polymers that has been identified as suitable for this invention has the unit structure:

[ ^L-E I -] q — [ ^L-F j -] ^J u

Rl R2

where E and F are di-substituted aromatic moieties such as phenylene, naphthalene, phenanthroline, anthracene, thiophene; where the values of q and u, independently, lie in the range from 1 to 10; where the substituents Rl and R2 remain the same as mentioned before.

The molecular weight of the polymer is in the range of from 500 to 1000000 and preferably from 1000 to 500000.

The polymeric systems described can be random, graft, or block polymers.

The polymeric system can also contain more than two different monomers as long as the ratio of hydrophilic and hydrophobic groups lies in the range from 1 :10 to 10: 1; preferably from 1 :3 to 3:1.

Preferred polymers are aromatic amphiphilic polymers selected from: polystyrene sodium sulphonate-co-vinyl naphthalene, poly vinyl pyrrolidone-co- vinyl imidazol, polynaphthalene sulphonate (TAMOL®).

A more preferred copolymer is polystyrene sodium sulphonate-co-vinyl naphthalene.

Furthermore, the polymeric system can be a homopolymer which exhibits amphiphilic character such as partially neutralised polymethacrylic acid.

There is also another special group of saccharides that are suitable for the solubilisation of oxidative catalysts which are the cyclic polysaccharides such as natural cyclodextrins and modified cyclodextrins. Where the polymer is a cyclodextrin, an inclusion complex is formed with the transition metal catalyst.

Preparation and Isolation of complex comprising

i)-porphin catalyst and derivatives thereof

The process for making a metallomacrocycle catalyst composition which is a transition metal porphin catalyst composition in solid form comprises the following steps: a-dissolving said metallomacrocycle catalyst in a water miscible organic material; b-dissolving said polymer in H2O; c-adding said predissolved polymer to the predissolved catalyst; d-adding at least 25 % of distilled water slowly with stirring; and e-removing the water miscible organic material by evaporation and the water by freeze drying.

The water miscible organic material may be any material in which the organo metallic catalyst is soluble.

A suitable material is a water-miscible organic solvent selected from methanol, ethanol, isopropanol, n-propanol, acetone, N- Methylpyrrolidone and Dimethylformamide, preferably methanol, ethanol, isopropanol, n-propanol or acetone.

A particularly preferred water miscible material for the production of the catalyst complex in liquid form is a nonionic surfactant of formula

R-(0-CH₂-CH₂)_n-OH

where R is a C8-C22 alkyl; where n lies in the range from 2 to 24, preferably 7.

ii)-phthalocyanine catalyst and derivatives thereof The process for making a metallomacrocycle catalyst composition which is a transition metal phthalocyanine catalyst composition in solid form comprises two steps: a)-Synthesis of the complex from solution or from a polymer melt. b)-Isolation of the complex as a pure solid or as a silica supported granulate form of the complex.

aVSynthesis of the complex .

l)-From solution, the synthesis comprises the following steps: i)-Transition metal phthalocyanine catalyst is dissolved in a water- miscible organic solvent, preferably Dimethylsulfoxide (DMSO). ii)- Addition of solid polymer to this solution, and iii)- Addition of a small amount of water while the mixture is stirred continuously.

2)-From a polymer melt the synthesis comprises the following steps: Transition metal phthalocyanine catalyst is dissolved in melted polymer and stirred for half an hour.

b-Isolation of the complex

l)-Isolation of the complex as a pure solid

The solution is mixed with an excess of acetone. During 2-4 hours a coloured precipitate is formed which is isolated using suction filtration followed by vacuum drying.

2)-Isolation of the complex as a silica supported granulate form of the complex

The complex in the aqueous solution is extracted with underivatized silica gel (containing hydroxyl groups) until the solution is colourless. The silica is collected after suction filtration and dried under vacuum.

The principal use of the invention relates to a DTI composition and also to an epoxidation process.

1)-DTI composition The complex can be used in two forms: a)-as an additive b)-in a complete formulation

a)-as an additive

This first form relates to a detergent additive composition adapted to provide Dye Transfer Inhibition, when added to an aqueous wash liquor containing a surfactant and a source of active oxygen, further comprising enzymes, builders and other conventional detergent ingredients.

In this instance, the addition of the complex can be by itself or with other additives.

A process is also provided for inhibiting dye transfer between fabrics during laundering operations involving coloured fabrics, said process comprising contacting said fabrics with a laundering solution containing a detergent additive composition together with a source of available oxygen.

The source of available oxygen will be more fully described hereinafter.

b)-in a complete formulation

The second form relates to a Dye Transfer Inhibiting composition comprising an organometallic composition, described hereinbefore, together with a source of available oxygen.

A process is also provided for inhibiting dye transfer between fabrics during laundering operations involving coloured fabrics, said process comprising contacting said fabrics with a laundering solution containing a dye transfer inhibiting composition together with a source of available oxygen.

The source of available oxygen will be more fully described hereinafter.

In both a) and b), the complex is normally at a level from 0.0001 % to 0.1 % by weight of the detergent composition, preferably from 0.0005% to 0.01 % , more preferably 0.002% .

This is designed to provide a complex at a level, in the wash, from 1*10" 8 molar to 1*10^~3 molar, preferably from 1*10"^ molar to 1*10^~4 molar.

Detergent compositions in accordance with the invention also comprise in general items those ingredients commonly found in detergent products which may include organic surfactants, additional detergent builders, oxygen bleach systems and ancillary materials such as anti-redeposition and soil suspension agents, suds suppressors, additional heavy metal ion chelating agents, enzymes, optical brighteners, photoactivated bleaches, perfumes and colours. Some products also include fabric softening and antistatic agents.

Oxygen bleach system can be selected from:

©-conventional bleaches which can comprise:

Hydrogen peroxide itself, organic peroxy carboxylic acids, inorganic peroxy bleaches selected from persulphate, inorganic perhydrate such as perborate, percarbonate, perpolyphosphates, and combination of said inorganic peroxy bleaches with organic peroxyacid precursors where the bleach activator is selected from N-acyl compounds such as tetraacetylethylenediamine (TAED), O-acyl compounds such as Nonanoyl Oxy Benzene Sulphonate (NOBS, described in US 4,412,934), 3,5,- trimethylhexanoyl Oxy Benzene Sulphonate ( ISONOBS, described in EP 120,591 ), Benzoyl caprolactam, Phenol sulphonate ester of acylaminocaproic acid.

The bleach level in the wash lies in the range from 100 to 10000 ppm, preferably from 100 to 1000 ppm.

In the case of using the combination of said inorganic peroxy bleaches with organic peroxyacid precursors, the precursor-to-bleach ratio lies in the range from 0.05 to 0.8, preferably from 0.1 to 0.6.

(ii)-an enzymatic hydrogen peroxide generation system which allows the continuous generation of low levels of hydrogen peroxide and provides a practical way of controlling a low steady-state level of hydrogen peroxide. Maximum effectiveness occurs when the component levels are such that the hydrogen peroxide is replenished at a rate similar to its removal due to the oxidation of dyes in the wash water.

Such enzymatic systems are disclosed in EP 91202655.6 filed October 9, 1991.

A suitable enzyme is an oxidase such as urate oxidase, galactose oxidase, alcohol oxidase, amine oxidase, amino acid oxidase, cholesterol oxidase and glucose oxidase, malate oxidase, glycollate oxidase, hexose oxidase, aryl alcohol oxidase, L-gulonolactose oxidase, pyranose oxidase, L- sorbose oxidase, pyridoxine 4-oxidase, 2-2-hydroxyacid oxidase, choline oxidase, ecdysone oxidase.

The preferred enzymatic systems are alcohol oxidase, aldehyde oxidase and glucose oxidase.

The more preferred systems for granular detergent application would have solid alcohols, e.g. glucose whose oxidation is catalysed by glucose oxidase to glucuronic acid with the formation of hydrogen peroxide.

The more preferred systems for liquid detergent application would involve liquid alcohols which could for example, also act as solvents. An example is ethanol/ethanol oxidase.

Commercially available enzymes are glucose oxidase sold by

FINNSUGAR under the tradenames Fermcozyme®, Ovazyme®, and urate oxidase sold by NOVO under the tradename Uricase S.

The present compositions are conveniently used as detergent additive products to conventional detergent compositions.

Such additive products are intended to implement or boost the performance of conventional detergent compositions.

The present invention also encompasses dye transfer inhibiting compositions which will contain other detergent ingredients and thus serve as detergent compositions.

Other detergent ingredients

A wide range of surfactants can be used in the detergent compositions. A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in U.S. P. 3,929,678 issued to Laughlin and Heuring on December, 30, 1975. A list of suitable cationic surfactants is given in U.S. P. 4,259,217 issued to Murphy on March 31, 1981.

Mixtures of anionic surfactants are suitable herein, particularly blends of sulphate, sulphonate and/or carboxy late surfactants. Mixtures of sulphonate and sulphate surfactants are normally employed in a sulphonate to sulphate weight ratio of from 5: 1 to 1 :2, preferably from 3: 1 to 2:3, more preferably from 3: 1 to 1 : 1. Preferred sulphonates include alkyl benzene sulphonates having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a Ci2^_Cl8 fatty source, preferably from a C16-C18 f^attv source. In each instance the cation is an alkali metal, preferably sodium. Preferred sulphate surfactants in such sulphonate sulphate mixtures are alkyl sulphates having from 12 to 22, preferably 16 to 18 carbon atoms in the alkyl radical.

Another useful surfactant system comprises a mixture of two alkyl sulphate materials whose respective mean chain lengths differ from each other. One such system comprises a mixture of C1 -C15 alkyl sulphate and C16-C18 alkyl sulphate in a weight ratio of C14-C15: Ci6-Cιg of from 3: 1 to 1 : 1. The alkyl sulphates may also be combined with alkyl ethoxy sulphates having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6. The cation in each instance is again an alkali metal, preferably sodium.

Another highly preferred anionic surfactant system comprises a mixture of a C12-C2O alkyl sulfate salt with a water soluble Cn_Ci8 alkyl ethoxysulfate salt containing an average of from 1 to 7 ethoxy groups per mole wherein the weight ratio of alkyl sulfate to alkyl ethoxysulfate salt lies in the range from 2 : 1 to 19 : 1 , more preferably from 3 : 1 to 12 : 1 and most preferably from 3.5 : 1 to 10 : 1.

The alkyl sulfate salts may be derived from natural or synthetic hydrocarbon sources. Preferred examples of such salts include the substantially branched C14-C15 alkyl sulfate salts, that is where the degree of branching of the C14-C15 alkyl chain is greater than about 20% . Such substantially branched C14-C15 alkyl sulfate salts are usually derived from synthetic sources. Also preferred are C16-C20 alkyl sulfate salts which are usually derived from natural sources such as tallow fat and marine oils.

The C11-C18 alkyl ethoxysulfate salt comprises a primary alkyl ethoxysulfate which is derived from the condensation product of a C\\- Ci8 alcohol condensed with an average of from one to seven ethylene oxide groups, per mole. Preferred are the Ci2^_Cl5 alkyl ethoxysulfate salts with an average of from one to five ethoxy groups per mole, and most preferably with an average of from one to three ethoxy groups per mole. Thus C11-C18 alcohol itself can be obtained from natural or synthetic sources. Thus, C H-CJ S alcohols, derived from natural fats, or Ziegler olefin build-up, or OXO synthesis can form suitable sources for the alkyl group. Examples of synthetically derived materials include Dobanol 25 (RTM) sold by Shell Chemicals (UK) Ltd which is a blend of C12-C15 alcohols, Ethyl 24 sold by the Ethyl Corporation, a blend of C13.C15 alcohols in the ratio 67% C13, 33% C15 sold under the trade name Lutensol by BASF GmbH and Synperonic (RTM) by ICI Ltd. , and Lial 125 sold by Liquichimica Italiana. Examples of naturally occurring materials from which the alcohols can be derived are coconut oil and palm kernel oil and the corresponding fatty acids. The level of CJ I-CJS alkyl ethoxysulfate is preferably from 0.5% to 10% more preferably from 0.5% to 5 % and most preferably from 1 % to 3 % by weight of the composition.

Other anionic surfactants suitable for the purposes of the invention are the alkali metal sarcosinates of formula

R-CON (R¹) CH2 COOM wherin R is a C5-C17 linear or branched alkyl or alkenyl group, R is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the lauroyl, Cocoyl (C12-C14), myristyl and oleyl methyl sarcosinates in the form of their sodium salts.

One class of nonionic surfactants useful in the present invention comprises condensates of ethylene oxide with a hydrophobic moiety, providing surfactants having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

Especially preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing an average of from 3-8 moles of ethylene oxide per mole of alcohol, particularly the C14-C15 primary alcohols containing an average of from 6-8 moles of ethylene oxide per mole of alcohol and the C12-C15 primary alcohols containing an average of from 3-5 moles of ethylene oxide per mole of alcohol. Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula

RO (C_nH_2nO)_tZ_x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 6 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and

0094118.

Another preferred nonionic surfactant is a polyhydroxy fatty acid amide surfactant compound having the structural formula:

O R¹

R^ N

(I)

wherein: Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably Cj or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R^ is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C17 alkyl or alkenyl, or mixture thereof: and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxlylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials. Z preferably will be selected from the group consisting of -CH2-(CHOH)_n-CH2θH, -CH(CH2θH)-(CHOH)_n._r CH2OH, -CH2-(CHOH)2(CHOR')(CHOH)-CH2θH, where n is an integer from 3 to 5, inclusive, and R¹ is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2θH.

In Formula (I), R can be, for example, N-methyl, N-ethyl, N-propyl, N- isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.

R2-CO-N < can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.

Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymalto- triotityl, etc. Preferred compound are N-methyl N-ldeoxyglucityl C14- Ci8 fatty acid amides. A further class of surfactants suitable for the purposes of the invention are the gemini polyhydroxyfatty acid amide more fully disclosed in US Patent Application No 08/187251.

A further class of surfactants are the semi-polar surfactants such as amine oxides. Suitable amine oxides are selected from mono C6-C20_> preferably C10-C14 N-alkyl or alkenyl amine oxides and propylene-1 ,3- diamine dioxides wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxpropyl groups.

Cationic surfactants can also be used in the detergent compositions herein and suitable quaternary ammonium surfactants are selected from mono C8-C16, preferably C10-C14 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Laundry detergent compositions of the present invention comprise from 3% to 30% of surfactant but more usually comprise from 5% to 20%, more preferably from 7% to 15 % surfactant by weight of the compositions.

Machine dishwashing detergent compositions of the present invention comprise from 0% to 10% by weight, preferably from 0.5% to 10% by weight, most preferably from 1 % to 5 % of surfactant by weight of the compositions.

Another highly preferred component of the detergent compositions of the invention is a detergent builder system comprising one or more other non- phosphate detergent builders. These can include, but are not restricted to, alkali metal aluminosilicates zeolites, amorphous and crystalline layered sodium silicates, ethylenediamine-N,N'-disuccinic acid (EDDS), carbonates borates, monomeric polycarboxylates, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms and mixtures of any of the foregoing. Whilst a range of aluminosilicate ion exchange materials can be used, preferred sodium aluminosilicate zeolites as disclosed in British Patent 1429143 have the unit cell formula

Na_z [(A102 ) z (Si0₂ )_y ] xH ₂0 wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate materials are in hydrated form and are preferably crystalline, containing from 10% to 28% , more preferably from 18% to 22% water in bound form.

Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available and can be naturally occurring materials, but are preferably synthetically derived. A method for producing aluminosilicate ion exchange materials is discussed in US Patent No. 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS, Zeolite MAP, Zeolite MAB and mixtures thereof. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material is Zeolite A and has the formula

Na 12 [(A10₂ ) 12 (Si0₂)l2 ]. H₂ O

wherein x is from 20 to 30, especially 27. Zeolite X of formula Na86 [(Alθ2)86(Siθ2)l06]- 276 H2O is also suitable, as well as Zeolite HS of formula Na6 [(Alθ2)6(Siθ2)6] 7.5 H2 O).

Preferred non-phosphate builder salts are the crystalline layered sodium silicates of the general formula

NaMSi_xθ2χ+ i .yH2θ

wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. For the purposes of the present invention, x in the general formula above has a value of 2, 3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred examples of this formula comprise the -, β -, γ - and δ - forms of Na2S_2θ5. These materials are available from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is δ -Na2Si2θ5, NaSKS-6.

The laundry detergent compositions of the present invention preferably comprise crystalline layered sodium silicate at a level of from 1 % to 80% by weight of the composition, more preferably from 5% to 40% and most preferably from 7% to 20% by weight.

The crystalline layered sodium silicate material is preferably present in granular detergent compositions in accord with the invention as a particulate in intimate admixture with a solid, water-soluble ionisable material. The solid, water-soluble ionisable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof.

Suitable organic acids include ascorbic, citric, glutaric, gluconic, glycolic, malic, maleic, malonic, oxalic, succinic and tartaric acids, 1 hydroxy ethane 1 , 1-diphosphonic acid (EHDP), amino poly methylene phosphonic acids such as NTMP, EDTMP & DETPMP, and mixtures of any of the foregoing. Suitable acid salts include sodium hydrogen carbonate, sodium hydrogen oxalate, sodium hydrogen sulphate, sodium acid pyrophosphate, sodium acid orthophosphate, sodium hydrogen tartrate or mixtures of any of the foregoing.

The particulate mixture of crystalline layered silicate and solid water soluble ionisable material will have a pH of at least 10 (as measured on a 1 % solution in 20 °C distilled water) and more usually will have a pH of at least 11 , normally at least 11.5.

The incorporation of other ingredients additional to the crystalline layered silicate and ionisable water soluble compound can be advantageous particularly in the processing of the particulate and also in enhancing the stability of detergent compositions in which the particulates are included. In particular, certain types of agglomerates may require the addition of one or more binder agents in order to assist in binding the silicate and ionisable water soluble material so as to produce particulates with acceptable physical characteristics. The binder agents may be present at a level of from 0% to 20% by weight of the composition. Preferably, the binder agents will be in intimate admixture with the silicate and ionisable water soluble material. Preferred binder agents have a melting point between 30°C-70°C. The binder agents are preferably present in amounts from 1-10% by weight of the composition and most preferably from 2-5 % by weight of the composition.

Preferred binder agents include the C10-C20 alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole of alcohol and more preferably the C 5-C2O primary alcohol ethoxylates containing from 20-100 moles of ethylene oxide per mole of alcohol.

Other preferred binder agents include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols with an average weight of from 600 to 10,000 are examples of such polymeric materials. Copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the polymer are further examples of polymeric materials useful as binder agents. These polymeric materials may be used as such or in combination with solvents such as water, propylene glycol and the above mentioned Cιo~ C20 alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole. Further examples of binder agents in accord with the invention include the C10 -C20 mono- and diglycerol ethers and also the C10-C20 fatty acids. Solutions of certain inorganic salts including sodium silicate are also of use for this purpose.

Cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acid or their salts are other examples of binder agents in accord with the invention.

The particulate can also include other components that are conventional in detergent compositions, provided that these are not incompatible per se and do not interfere with the building function of the crystalline layered silicate.

Suitable polycarboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831 ,368, 821 ,369 and 821 ,370. Polycarboxylates containing two carboxy groups include the water- soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxy lates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1 ,379,241 , lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2- oxa-l ,l ,3-propanetricarboxylates described in British Patent No.1 ,387,447.

Polycarboxylates containing four carboxy group include oxodisuccinates disclosed in British Patent No.1 ,261 , 829, 1 ,1 ,2,2-ethane tetracarboxy lates, 1 ,1 ,3,3-propane tetracarboxylates and 1 ,1 ,2,3-propane tetracarboxy lates.

Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 ,398,421 and 1 ,398,422 and in U.S. Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane- cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxy lates, 2,3,4,5-tetrahydrofuran-cis,cis,cis-tetracarboxylates, 2,5-tetrahydrofuran- cis-dicarboxy lates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1 ,2,3,4,5,6- hexane-hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phtalic acid derivatives disclosed in British Patent No.1 ,425, 343.

Of the above, the preferred polycarboxylates are hydro xycarboxy lates containing up to three carboxy groups per molecule, more particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as components of builder systems of detergent compositions in accordance with the present invention.

Other suitable water soluble organic salts are the homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1 ,596,756. Examples of such salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000. These materials are normally used at levels of from 0.5% to 10% by weight more preferably from 0.75 % to 8 % , most preferably from 1 % to 6% by weight of the composition.

The detergent compositions of the present invention will comprise non- phosphate detergent builder compounds at a level of from 1 % to 80% by weight of the compositions, more preferably from 10% to 60% by weight and most preferably from 20% to 50% by weight.

Within the preferred laundry detergent compositions, sodium aluminosilicate such as Zeolite A will comprise from 20% to 60% by weight of the total amount of builder, a monomeric or oligomeric carboxylate will comprise from 5 % to 30% by weight of the total amount of builder and the crystalline layered silicate will comprise from 10% to 65% by weight of the total amount of builder. In such compositions the builder system preferably also incorporates a combination of auxiliary inorganic and organic builders such as sodium carbonate and maleic anhydride/acrylic acid copolymers in amounts of up to 35 % by weight of the total builder.

A suitable chelant for inclusion in the detergent composition in accordance with the invention is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na2EDDS and Na4EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg2EDDS. The magnesium salts are the most preferred for inclusion in compositions in accordance with the invention.

The detergent compositions may contain optional chelant ingredients. Such optional chelants may include the organic phosphonates, including amino alkylene poly (alkylene phosphonate), alkali metal ethane 1- hydroxy diphosphonates, nitrilo tremethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates. The phosphonate compounds may be present either in their acid form or as a complex of either an alkali or alkaline metal ion, the molar ratio of said metal ion to said phosphonate compound being at least 1 : 1. Such complexes are described in US-A-4,259,200. Preferably, the organic phosphonate compounds where present are in the form of their magnesium salt. The level of phosphorus containing chelants in the compositions of the invention is preferably minimised, with their complete exclusion from the compositions being most preferred.

Amorphous silicates are useful components of detergent compositions. Silicates are present in the machine detergent compositions at a level of less than 10% by weight of the composition, more preferably less than 5% by weight. Whilst soluble silicates serve a variety of purposes in conventional laundry detergent formulations, their presence may be unnecessary in detergent compositions incorporating crystalline layered silicate material. However as the crystalline layered silicate, which forms part of the builder system of the detergent composition, must be added as a dry mix ingredient, soluble silicates may still be useful as structurants in the spray dried granules that normally form part of a laundry detergent composition. This is particularly desirable if the spray dried granule does not incorporate an aluminosilicate builder and would otherwise comprise only organic materials. Suitable silicates are those having an Siθ2:Na2θ ratio in the range from 1.6 to 3.4, ratios from 2.0 to 2.8 being preferred.

Anti-redeposition and soil-suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, homo-or co-polymeric polycarboxylic acids or their salts and ployamino compounds. Polymers of this type include the polyacrylates and copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer disclosed in detail in EP-A- 137669. Polyamino compounds such as those derived from aspartic acid are disclosed in EP-A-305282, EP-A-305283 and EP-A-351629. These materials are normally used at levels of from 0.5 % to 10% by weight, more preferably from 0.75 % to 8 % , most preferably from 1 % to 6% by weight of the composition.

Other useful polymeric materials are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 0.20% to 5% more preferably from 0.25% to 2.5% by weight. These polymers and the previously mentioned homo- or co-polymeric polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.

Preferred optical brighteners are anionic in character, examples of which are disodium 4,4l-bis-(2-diethanolamino-4-anilino -s- triazin-6- ylamino)stilbene-2:2l disulphonate, disodium 4,4l-bis-(2-morpholino -4- anilino-2-triazin-6-ylaminostilbene-2:2l-disulphonate, disodium 4, 4l-bis- (2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2l - disulphonate, monosodium 4 >4 l-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2- sulphonate, disodium 4,4l-bis-(2-anilino-4-(N-methyl-N-2- hydroxy ethylamino)-2-triazin-6-y lamino)stilbene-2 ,21 - disulphonate , disodium 4,4l-bis-(4-phenyl-2, 1 ,3-triazol-2-yl)stilbene-2,2l disulphonate, disodium 4,4lbis(2-anilino-4-(l-methyl-2-hydroxyethylamino)-s-triazin-6- ylamino)stilbene-2, 21 disulphonate and sodium 2(stilbyl-4H-(naphtho- 11 ,2l :4,5)-l ,2,3 - triazole-2^- sulphonate, disodium 4,4'-bis-(2- sulphosty ry l)-bipheny 1.

Soil-release agents useful in detergent compositions are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0272033. A particular preferred polymer has the formula:

Polyvinyl pyrrolidones, typically of MWt 5000-20000, preferably 10000- 15000, also form useful agents in preventing the transfer of labile dyestuffs between fabrics during the washing process. Also, other useful agents are polyvinylimadazoline, polyvinylpyrrolidone, polyvinyl alcohol which are more fully described in EP-538,228.

Another optional detergent composition ingredient is a suds suppressor, exemplified by silicones, and silica-silicone mixtures. Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms, exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water- dispersible, substantially non-surface-active detergent-impermeable carrier. Alternatively the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.

As mentioned above, useful silicone suds controlling agents can comprise a mixture of an alkylated siloxane, of the type referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica. A preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethyl- silanated) silica having a particle size in the range from 10 nanometers to 20 nanometers and a specific surface area above 50 m^/g, intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 1 : 1 to about 1 :2. A preferred silicone suds controlling agent is disclosed in Bartollota et al. US Patent 3,933,672. Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent Application DTOS 2,646, 126 published April 28, 1977. An example of such a compound is DC0544, commercially available from Dow Corning, which is a siloxane/glycol copolymer.

The suds suppressors described above are normally employed at levels of from 0.001 % to 5% by weight of the composition, preferably from 0.1 % to 3 % by weight.

The preferred methods of incorporation comprise either application of the suds suppressors in liquid form by spray-on to one or more of the major components of the composition or alternatively the formation of the suds suppressors into separate particulates that can then be mixed with the other solid components of the composition. The incorporation of the suds modifiers as separate particulates also permits the inclusion therein of other suds controlling materials such as C20-C24 fatty acids, microcrystalline waxes and high MWt copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the dispersibility of the matrix. Techniques for forming such suds modifying particulates are disclosed in the previously mentioned Bartolotta et al US Patent No. 3,933,672.

Another optional ingredient useful in detergent compositions is one or more enzymes. These may be incorporated at a level of from 0.1 % to 10% , more preferably 0.5% to 5% by weight of the detergent composition.

Preferred enzymatic materials include the commercially available amylases, neutral and alkaline proteases, Upases, esterases and cellulases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include those sold under the tradenames Alcalase and Savinase by Novo Industries A/S (Denmark) and Maxatase by International Bio-Synthetics, Inc. (The Netherlands). Preferred amylases include, for example, α-amylases obtained from a special strain of B licheniforms, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, Rapidase, sold by International Bio-Synthetics Inc, and Termamyl, sold by Novo Industries A/S.

An especially preferred lipase enzyme is manufactured and sold by Novo Industries A/S (Denmark) under the trade name Lipolase (Biotechnology Newswatch, 7 March 1988, page 6) and mentioned along with other suitable lipases in EP-A-0258068 (Novo).

A further optional ingredient useful in detergent compostions is a corrosion inhibitor. C14-C20 fatty acids are preferred examples of such corrosion inhibitors.

Fabric softening agents can also be incorporated into laundry detergent compositions. These agents may be inorganic or organic in type. Inorganic softening agents are examplified by the smectite clays disclosed in GB-A-1 ,400,898. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A-1514276 and EP-B- 0011340.

Their combination with mono C12-C14 quaternary ammonium salts is disclosed in EP-B-0026527 & 528. Other useful organic fabric softening agents are the dilong chain amides as disclosed in EP-B-0242919. Additional organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A- 0299575 and 0313146, cellulase as disclosed in US Patent Application No 08/105422.

Levels of smectite clay are normally in the range from 5% to 15% , more preferably from 8% to 12% by weight, with the material being added as a dry mixed component to the remainder of the formulation. Organic fabric softening agents such as the water-insoluble tertiary amines or dilong chain amide materials are incorporated at levels of from 0.5% to 5% by weight, normally from 1 % to 3 % by weight, whilst the high molecular weight polyethylene oxide materials and the water soluble cationic materials are added at levels of from 0.1 % to 2% , normally from 0.15 % to 1.5 % by weight. Where a portion of the composition is spray dried, these materials can be added to the aqueous slurry fed to the spray drying tower, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as a molten liquid on to other solid components of the composition.

The detergent composition according to the invention can be in liquid, paste, or granular forms. Granular compositions according to the present invention can also be in "compact form" , i.e. they may have a relatively higher density than conventional granular detergents, i.e. from 550 to 950 g/1; in such case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt" , compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; "compact" detergents typically comprise not more than 10% filler salt.

The present invention also relates to a process for inhibiting dye transfer from one fabric to another of solubilised and suspended dyes encountered during fabric washing process.

The process comprises contacting fabrics with a laundering solution as hereinbefore described.

The process of the invention is conveniently carried out in the course of the washing process. The washing process is preferably carried out at

5°C to 90°C, especially 20°C to 60°C, but the catalysts are effective at up to 95 °C. The pH of the treatment solution is preferably from 7 to 11 , especially from 7.5 to 10.5.

The detergent compositions according to the present invention include compositions which are to be used for cleaning substrates, such as fabrics, fibers, hard surfaces, skin , etc., for example hard surface cleaning composition compositions (with or without abrasives), laundry detergent compositions and automatic and non automatic dishwashing compositions.

2)-Epoxidation process

The second use of the invention relates to an epoxidation process. Therefore, an epoxidation process carried with the presence of imidazole is provided wherein the metallomacrocycle catalyst composition comprises a complex of

1.1.

The invention is illustrated in the following non limiting examples.

Example 1

Isolation of complex comprising porphin

The method below outlines the procedure in isolating the MnTPP complex, where MnTPP is Tetraphenylporphyrin Manganese (III) Chloride available as Aldrich no 25,4754 and the polymer PSSSVN is polystyrene sodium sulphonate vinylnaphthalene copolymer with MW 310,000 :

1 -preparation of PSSSVN

To a 150 ml conical flask fitted with thermometer, magnetic stirrer, air condenser and argon blanket via a Normag bubbler is charged:

13.36g of 2-vinylnaphthalene available in Aldrich lot 0252956 (0.087 mole)

20. Og of 4-styrenesulphonic acid, sodium salt available in Aldrich lot

06014 KW (0.097 mole)

90 ml of dimethyl sulphoxide available in Aldrich, argon sparged.

The mix is stirred at room temperature to dissolve the solid before adding

1.06g of α,α' azoisobutyronitrile available in Fluka lot 278989988

(6.45mmole, i.e. 3.5 mole% of monomers). The dark red solution obtained is then heated to 60°C and held for 21 hours.

Then, this solution is added, with Sprutor agitation, by means of an automatic 10ml pipette (in 'burette' mode) to 700 ml of n-butanol.

The cream-coloured solid which formed is vacuum filtered, washed with ether and dried in vacuo over CaCb.The dry weight at this step is 42.81g

Then lg of the retained solid sample is dissolved in 1.2 liter of distilled water and filtered through a sintered glass filter funnel (porosity no 4).

The solution is thereafter freeze-dried using the Edwards EF-6 dryer.

The dry weight of PSSSVN obtained is 38.2g

2-Preparation of the complex

To a 250 ml round bottom flask is added:

0.3g of MnTPP

60 ml Ethanol

3.0g PSSSVN

Then to this solution is added slowly with stirring 100ml of distilled water. The mix is charged to a 500 ml flask and placed on a rotary evaporator under reduced pressure. The system is azeotroped with 400 ml of distilled water to a final volume of 200 ml.

The solution is then freeze-dried.

The dry weight of the green complex obtained is 3.16 g and contains 8% by weight of MnTPP.

Example 2

Test method for oxidative stability of MnTPP determination

The following solutions were prepared:

1-A catalyst solution comprising 10 mg MnTPP in a mixture of lg ethanol/lg water (0.5% solution)

2-A catalyst/polymer solution comprising 8 mg MnTPP + 92 mg

PSSSVN in a mixture of 5g ethanol / 5g water (1 % MnTPP/PSSSVN solution); this solution is then lyophilised and a 0.5% solution in EtOH and water(50:50) is made.

3-A buffer solution comprising 0.1M sodium carbonate at pH 10.

MnTPP oxidative stability method: 50ml of the buffer solution is taken to which is added lOOμl of the 0.5%

MnTPP solution (10 ppm).

The wavelength spectrum is scanned between 350 and 800nm wherein the major peak of MnTPP is around 472nm and is used as a reference (100%

MnTPP)

0.025g of sodium perborate monohydrate is added and the wavelength is scanned again.

MnTPP/PSSSVN oxidative stability method:

50ml of the buffer solution is taken to which is added 1250μl of the 0.5%

MnTPP/PSSSVN solution (10 ppm MnTPP/ 115 ppm PSSSVN).

The wavelength spectrum is scanned between 350 and 800nm and is used as a reference (100% MnTPP/PSSSVN)

0.025g of sodium perborate monohydrate is added and the wavelength is scanned at several times.

The peak height is proportionate to the amount of active catalyst.

A comparison of the stability of the two catalyst samples is shown below:

half-life of the catalyst MnTPP < 30 seconds

MnTPP/PSSSVN 50 minutes

Conclusion:

The oxidative stability of MnTPP is significantly improved by complexing with PSSSVN

Example 3

aVTest method for DTI

The following solutions were prepared

2- A catalyst/polymer solution comprising 8 mg MnTPP + 92 mg

PSSSVN in a mixture of 5g ethanol / 5g water (1 % MnTPP/PSSSVN solution) 3-Detergent solution: 0.7% of a commercial detergent solution in city water at pH 10.5.

For measurement of the DTI performance of the catalyst alone, the following method is used.

Firstly, 200 ml of the Detergent solution per jar is taken, then 5 steel balls are added for agitation. To this jar is added 500μl of the catalyst solution and then a piece of bleeding fabric (Direct blue 90).

Secondly, one jar without bleeding fabric and without catalyst ('target' multifiber) and one jar with bleeding fabric and without catalyst

('reference¹ multifiber) are prepared.

To each jar is added a multifiber, and then the jars are rotated in the

Launder-o-meter at 30 °C for 30 minutes.

The reflectance values (L, a, b-values) of the dry multifibers are measured by using a colorimeter (Spectraflash manufactured by ICS) in order to calculate the Delta E and then the percentage dye oxidation versus the reference multifiber (maximum Delta E).

% dye oxidation = 100* (1- delta E / delta E of the reference)

For measurement of the DTI performance of the catalyst/polymer, the same procedure is used but in this instance, the catalyst/polymer solution takes the place of the catalyst solution. The % dye oxidation relates to the % DTI.

b)-DTI performance in a commercial detergent solution of MnTPP- PSSSVN versus MnTPP.

Catalyst Level (ppm) % DTI

MnTPP

0.5 19

2 59

MnTPP/PSSSVN

0.5 76

2 91

cVDTI Performance of various MnTPP-Polymer Complexes in a commercial detergent solution

The DTI performance of MnTPP-Polymer Complexes was determined with different polymers such as PSSSVN described in Example 1 , Sodium polynaphthalene sulphonate sold by BASF AG under the trade names TAMOL® NH, TAMOL® NNOK, TAMOL® NOC and also with poly vinyl (pyrrolidone-co-imidazol) (PVPVI) where the MW lies in the range from 100-1000000, said polymer being more fully described in EP-0 372 291.

All polymers contained 8 % in weight of MnTPP and the level of MnTPP in the wash was 2 ppm. The temperature was 30°C.

Results were as follows:

Polymer Net % DTI*

None 59

PSSSVN 88

TAMOL NH 77

TAMOL NNOC 78

TAMOL NOC 83

PVPVI 48 * Net % DTI means: % DTI of the complex - % DTI of the polymer. Except for PVPVI, none of the polymers alone provided DTI benefits.

Conclusion:

The MnTPP-polymer complex versus the MnTPP alone provides better

DTI performance, the biggest benefit being obtained with PSSSVN.

dVDye selectivity of MnTPP-PSSSVN (at 2 ppm MnTPP^{^}) in a commercial detergent solution.

Removed of selective dyes were as follows:

Dye % DTI

Acid Blue 260 30

Direct Blue 90 86

Direct Blue 218 57

Blue Satin 85

Red Satin 45

Acid Red 151 69

Direct Brown 3 0

Direct Red 80 4

Conclusion: The MnTPP-PSSSVN provides DTI on a variety of dyes with good performance.

Example 4

Isolation of complex comprising phthalocyanine

The method below outlines the procedure in isolating the MnPc complex, where MnPc was Phthalocyanine Manganese(II) available in Aldrich no 37955-7 and the polymer PVPVI was polyvinyl (pyrrolidone-co-imidazol) where the MWt lies in the range from 100-1000000, said polymer being more fully described in EP-0 372 291.

0.0361 g of MnPc is dissolved in 10 ml of dimethylsulfoxide (DMSO). To the MnPc solution is dissolved 0.0509 g of PVPVI. The mixture is then poured into an excess (200 ml) of distilled water. A bright blue colour appears and the solution is filtered to remove the excess of MnPc. The blue product in the filtrate is then collected by extraction with 0.4892 g of hydrophilic silica underivatized sold by DEGUSSA under the tradename Sipernat® D22LS. The silica becomes blue while the solution becomes colourless and the silica is then collected and dried.

Atomic absorption is used to confirm the presence of the complex on the support and the silica has been found to contain 0.11 % by weight of the complex.

Example 5

Epoxidation reactions utilising the Manganese tetra(para- methoxypheny porphyrin /PSSSVN system.

aVEpoxidation of Cyclooctene

Tetra(para-methoxyphenyl)porphyrin is available in Aldrich No 25-288-3 Manganese tetra(p-methoxyphenyl)porphyrin (7.4.10^~3mmol) incorporated into the PSSSVN polymer is dissolved in distilled water (4ml). Dichloromethane (3 ml) is added to form a biphasic system, and to this mixture is added cyclooctene (lmmol), imidazole (4.4.10~2mmol) and finally H2O2 (3mmol). The reaction is carried out in stoppered round bottom flask which is occasionally opened to release any pressure build up. The formation of the cyclooctene epoxide is observed by following the reaction by gas chromatography using an authentic sample of the epoxide as an external standard. The gas chromatograms are obtained on a Dani 3800 machine incorporating an FFAP 30m column. After 24 hours, the analysis of the reaction by gas chromatography shows that 48% of cyclooctene epoxide has been produced relative to the starting material. % cyclooctene epoxide Blank (no complex) 8

Manganese tetra(p-methoxy- 48 phenyOporphyrin /PSSSVN

bVEpoxidation of 1 -methyl cyclohexene

The reaction is carried out using the procedure described for cyclooctene but substituting 1-methyl cyclohexene in place of cyclooctene. After 48 hours, the analysis of the reaction by gas chromatography shows that 19% of 1-methyl cyclohexene epoxide has been produced relative to the starting material.

% 1-methyl cyclohexene epoxide Blank (no complex) 2

Manganese tetra(p-methoxy- 19 phenyOporphyrin /PSSSVN

cVEpoxidation of tetramethyl ethene

The reaction is carried out using the procedure described for cyclooctene but substituting tetramethyl ethene in place of cyclooctene. After 48 hours, the analysis of the reaction by gas chromatography shows that 7% of tetramethyl ethene epoxide has been produced relative to the starting material.

% tetramethyl ethene epoxide Blank (no complex) 3

Manganese tetra(p-methoxy- 7 phenyOporphyrin /PSSSVN

Conclusion:

The Manganese tetra(para-methoxyphenyl)porphyrin /PSSSVN system versus hydrogen peroxide alone (Blank) in epoxidation reactions increases the yield of epoxide. Example 6

In the detergent compositions, the abbreviated component identifications have the following meanings:

LAS Sodium linear C12 alkyl benzene sulphonate

TAS Sodium tallow alkyl sulphate

C25EY A C 12- 15 predominantly linear primary alcohol condensed with an average of Y moles of ethylene oxide

C45EY A C 14-15 predominantly linear primary alcohol condensed with an average of Y moles of ethylene oxide

polyhydroxy N-Lauroyl N-Methyl Glucamine fatty acid amide

Zeolite A Hydrated Sodium Aluminosilicate of formula

Nai2(A10₂Si0₂)l2- 27H₂0 having a primary particle size in the range from

1 to 10 micrometers

Citrate Tri-sodium citrate dihydrate

MA/AA Maleic Acid/Acrylic Acid copolymer, sodium salt sold by BASF under the trade name Sokalan ® CP 5 with a molecular weight of 90,000.

Carbonate Anhydrous sodium carbonate Perborate Anhydrous sodium perborate monohydrate and tetrahydrate bleach, empirical formula NaBθ2-H2θ2

TAED Tetraacetyl ethylene diamine

DETPMP Diethylene triamine penta (methylene phosphonic) acid

EDDS Ethylenediamine-N,N'-disuccinic acid (S,S isomer)

CMC Sodium carboxymethyl cellulose

Enzyme Mixed proteolytic and lipolytic enzyme sold by Novo Industries AS.

Lipase Lipolytic enzyme sold by Novo Industries A/S under the tradename Lipolase.

Protease Proteolytic enzyme sold by Novo Industries A/S under the tradename Savinase.

Cellulase Enzyme sold by Novo Industries A/S under the tradename Endo A

Silicate : Amorphous Sodium Silicate 2 ratio (Siθ2:Na2θ)

Sulphate Anhydrous magnesium sulphate.

Complex catalyst: Manganese Tetraphenylporphyrin/polystyrene sodium sulphonate vinylnaphthalene copolymer(MnTPP/PSSSVN) The following detergent compositions were prepared (parts by weight). Compositions A, B, C, D are in accordance with the present invention.

A B C D

LAS - - 6.54 6.92

TAS - - 2.94 2.05

45AS 6.86 6.86 - -

C25E3S 1.71 1.71 0.16 0.16

C45E7 - - 4.0 4.0

C25E5 2.21 2.21 - -

C25E3 1.16 1.16 - - polyhydroxy 1.45 1.45 - - fatty acid amide

Zeolite 10.2 10.2 18.0 20.2

Citrate - - - 5.5

Citric 2.5 2.3 2.35 -

SKS-6 9.2 8.5 8.64 -

Carbonate 5.8 9.8 16.0 15.4

Silicate - - 0.56 3.0

Bicarbonate - - 4.6 -

Sulphate - 8.0 - -

MA/AA 3.85 3.0 3.92 4.0

CMC 0.30 0.30 0.30 0.31

SRP 0.20 0.15 0.20 0.30

PVP - - - -

PVNO 0.02 - - -

Savinase 0.41 0.25 0.37 1.4

Lipolase 0.11 0.07 0.22 0.36

Endo A 0.20 0.12 0.13 0.13

PB4 - - - 11.64

PB1 - - - 8.7

TAED 4.7 1.6 - 5.0

DETPMP - - 4.8 0.38

MgS04 0.38 0.38 0.4 0.40

Percarbonat 16.9 10.0 17.5 ^— e EDDS 0.21 0.21 0.21 -

Brightener 0.22 0.18 0.19 0.19

Complex 0.002 0.002 0.002 0.002 catalyst

Suds 2.75 2.75 0.85 0.85 suppressor perfumes 0.35 0.4 0.35 0.43

Water minors and miscellaneous to balance

Example 7

A detergent aditive formulation (parts by weight) in accordance with the present invention is also provided:

Zeolite 26.0

Citrate 10.4

Carbonate 11.9

Silicate 2.0

Bicarbonate 6.0

Sulphate 4.8

MA/AA 4.6

CMC 0.31

Complex 0.002 catalyst

Water minors ; and miscellaneous to balance

Claims

1-A metallomacrocycle catalyst composition comprising a complex of (i)-a transition metal catalyst selected from: a-a transition metal porphin and mixtures thereof, b-a transition metal phthalocyanine and mixtures thereof, c-mixtures of transition metal porphin and transition metal phthalocyanine; and (ii)-an amphiphilic polymer and mixtures thereof; the complex increasing the half life of the catalyst by a factor of at least 1.1.

2-A metallomacrocycle catalyst composition according to claim 1 wherein said polymer comprises at least one hydrophilic group and at least one hydrophobic group, such that the ratio of hydrophilic group and hydrophobic group lie in the range from 1 :10 to 10: 1; preferably from 1:3 to 3: 1.

3-A metallomacrocycle catalyst composition according to either one of claims 1 & 2 wherein said polymer is an aromatic amphiphilic polymer.

4-A metallomacrocycle catalyst composition according to either one of claims 1-3 wherein said polymer has a polymeric system selected from random, graft, block polymers.

5-A metallomacrocycle catalyst composition according to any one of claims 1-4 wherein said polymer has the general structure:

R R R R R R

^" (-(CH)_n-(C)_m-(CH)_p-)_v-A-] _q [(-(CH)_r-(C)_s-(CH)_t-)_w-B-]_u

Rl R2

where A and B can be selected from : -CH2-, NH, O, ketone, an ester linkage, an amide linkage, an imine linkage; where n,m,p,r,s,t can independently be any integer as long as (n+m+p)v + (r + s+t)w range from 1-1000, preferably from 1-500; where the values of q and u, independently, lie in the range from 1 to 10; where each R, independently, can be selected from H, alkyl, alkylhalide, alkylyl; preferably H, CH3; where Rl is selected from hydrophobic moieties containing conjugated aromatic hydrocarbon rings and R2 is selected from hydrophilic moieties.

6-A metallomacrocycle catalyst composition according to anyone of claims 1-4 wherein said polymer has the unit structure:

Rl R2

where C and D are oligosaccharide units; where the values of q and u, independently, lie in the range from 1 to 10; where Rl is selected from hydrophobic moieties containing conjugated aromatic hydrocarbon rings and R2 is selected from hydrophilic moieties.

7-A metallomacrocycle catalyst composition according to anyone of claims 1-4 wherein said polymer has the unit structure:

[-E 1 -] q — [ ^L-F I -] ^J u

Rl R2

where E and F are di-substituted aromatic moieties such as phenylene, naphthalene, phenanthroline, anthracene, thiophene; where the values of q and u, independently, lie in the range from 1 to 10; where Rl is selected from hydrophobic moieties containing conjugated aromatic hydrocarbon rings and R2 is selected from hydrophilic moieties.

8-A metallomacrocycle catalyst composition according to anyone of claims 5-7, where Rl is selected from toluene, methyl styrene, stilbene, pyridine, naphthalene, anthracene, phenanthrene, phenyl, histidine, tryptophan, phenyl alanine, tyrosine, alkyl benzene, xylenes, carbazoles, xanthenes, acridines, purines, pyridazines and indoles.

9-A metallomacrocycle catalyst composition according to anyone of claims 5-8, where R2 is selected from hydrophilic moieties such as -OH, hydroxyalkyl such as hydroxymethyl and hydroxyethyl; polyoxyethylene, hydroxyphenyl and derivatives thereof, moieties derived from pyrrolidone, pyridine-N-oxide, N-oxide derivatives of histidine, tryptophan, phenyl alanine and tyrosine; phenyl sulphonate, naphthalene sulphonate, imidazole, water-soluble salt derivatives of naphthalene, anthracene, phenanthrene, phenyl, carbazoles, xanthenes, acridines, purines, pyridazines and indoles, -COOH, -COOM, -SO3M where M is an alkali metal ion ; -NR2, -NR3 + X ^~ where X is a halide ion and R is, independently, selected from H, alkyl, and hydroxyalkyl.

10-A metallomacrocycle catalyst composition according to anyone of claims 1-9 wherein said polymer has a molecular weight between 5*10^ and 1 *1 θ6» preferably between 1 *10^ and 5*10^.

11-A metallomacrocycle catalyst composition according to anyone of claims 8-10 when dependent on claim 5 wherein said polymer is a copolymer such as polystyrene sodium sulphonate-co-vinyl naphthalene.

12- A metallomacrocycle catalyst composition according to claim 1 wherein said polymer is a cyclodextrin and an inclusion complex is formed with the transition metal catalyst.

13-A metallomacrocycle catalyst composition according to anyone of claims 1-12 wherein said porphin comprises a simple porphyrin such as tetrapheny lporphy rin .

14- A metallomacrocycle catalyst composition according to anyone of claims 1-12 wherein said transition metal porphin is substituted on at least one of its meso positions with a pyridyl group of formula :

where each Xi , independently, is selected from H, F, CI, Br, NO2, alkyl, alkoxy, cycloalkyl, aralkyl, aryl, alkaryl, and heteroaryl, preferably H, CI or F; and X2 is selected from O", OH, H, alkyl, alkoxy, cycloalkyl, aralkyl, aryl, alkaryl, and heteroaryl, preferably O^".

15-A metallomacrocycle catalyst composition according to anyone of claims 1-12 wherein said transition metal porphin is substituted on at least one of its meso positions with a phenyl group of formula :

where each X, independently, is selected from H, F, CI, Br, alkyl, alkoxy, cycloalkyl, aralkyl, aryl, alkaryl, and heteroaryl, preferably H, CI or F.

16-A metallomacrocycle catalyst composition according to anyone of claims 1-15 wherein said porphin contains a transition metal selected from Cu, Fe, Mn, Co, Cr, Ti and V, preferably Mn.

17-A metallomacrocycle catalyst composition according to anyone of claims 1-12 wherein said phthalocyanine contains a transition metal selected from Cu, Fe, Mn, Co, Cr, Ti and V, preferably Mn. 18-A Dye Transfer Inhibiting composition comprising a metallomacrocycle catalyst composition according to anyone of claims 1- 17 together with a peroxide source.

19- A Dye Transfer Inhibiting composition comprising a metallomacrocycle catalyst composition according to claim 18 wherein said peroxide source is selected from H2O2, organic peroxy carboxylic acids, inorganic peroxy bleaches and combination of said inorganic peroxy bleaches with organic peroxyacid precursors.

20-A Dye Transfer Inhibiting composition comprising a metallomacrocycle catalyst composition according to claim 1-18 wherein said peroxide source is an oxidoreductase selected from glucose oxidase enzyme and alcohol oxidase enzyme.

21 -A detergent composition which comprises a metallomacrocycle catalyst composition according to any one of claims 1-17 together with a peroxide source and further comprising enzymes, surfactants, builders and other conventional detergent ingredients.

22-A detergent composition according to claim 21 where the peroxide source is selected from H2O2, organic peroxy carboxylic acids, inorganic peroxy bleaches, combination of said inorganic peroxy bleaches with organic peroxyacid precursors, glucose oxidase enzyme and alcohol oxidase enzymes.

23- A detergent additive composition adapted to provide Dye Transfer Inhibition when added to an aqueous wash liquor containing a surfactant and a source of active oxygen, said composition comprising a metallomacrocycle catalyst composition according to anyone of claims 1-17.

24-A process for inhibiting dye transfer between fabrics during laundering operations involving coloured fabrics, said process comprising contacting said fabrics with a laundering solution containing a detergent additive composition according to claim 23.

25-A process for inhibiting dye transfer between fabrics during laundering operations involving coloured fabrics, said process comprising contacting said fabrics with a laundering solution containing a Dye Transfer Inhibiting composition according to any one of claims 18-20, or a detergent composition according to either one of claims 21&22.

26-An epoxidation process carried with the presence of imidazole, wherein the metallomacrocycle catalyst composition comprises a complex of

1.1.

27-An epoxidation process according to claim 26 wherein the epoxidised material is selected from: cyclooctene, 1-methyl cyclohexene and tetramethyl ethene.