WO2001016268A1 - Pretraitement et blanchiment de textiles taches - Google Patents

Pretraitement et blanchiment de textiles taches Download PDF

Info

Publication number
WO2001016268A1
WO2001016268A1 PCT/EP2000/007561 EP0007561W WO0116268A1 WO 2001016268 A1 WO2001016268 A1 WO 2001016268A1 EP 0007561 W EP0007561 W EP 0007561W WO 0116268 A1 WO0116268 A1 WO 0116268A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
pyridin
ligand
optionally substituted
group
Prior art date
Application number
PCT/EP2000/007561
Other languages
English (en)
Inventor
Michel Gilbert Jose Delroisse
David Andrew Ross Jones
Richard George Smith
John Francis Wells
Original Assignee
Unilever Plc
Unilever N.V.
Hindustan Lever Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BR0013593-3A priority Critical patent/BR0013593A/pt
Priority claimed from PCT/GB1999/002878 external-priority patent/WO2000012808A1/fr
Priority claimed from GBGB0004844.7A external-priority patent/GB0004844D0/en
Application filed by Unilever Plc, Unilever N.V., Hindustan Lever Limited filed Critical Unilever Plc
Priority to AU64400/00A priority patent/AU777434B2/en
Priority to EP00951477A priority patent/EP1208184A1/fr
Priority to CA002382114A priority patent/CA2382114A1/fr
Publication of WO2001016268A1 publication Critical patent/WO2001016268A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/55—Acids; Esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/15—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using organic agents

Definitions

  • This invention relates to a method for bleaching stained fabrics, more particularly by pretreating the stained fabric, before washing, with a pretreatment composition that comprises an organic ligand that forms a transition metal complex as bleach catalyst .
  • the invention further relates to the use of the ligand or complex in a pretreatment composition for applying to stained fabrics prior to washing in an aqueous wash liquor.
  • EP-A-0909809 discloses a class of iron coordination complexes useful as catalysts for the bleach activation of peroxy compounds, including iron complexes comprising the ligand N,N-bis (pyridin-2 -yl-methyl) -1, 1-bis (pyridin-2 -yl) -1- aminoethane, also referred to as MeN4Py.
  • These catalysts are said to be useful in bleaching systems comprising a peroxy compound or a precursor thereof, such as in the washing and bleaching of substrates including laundry, dishwashing and hard surface cleaning, or for bleaching in the textile, paper and woodpulp industries, and in waste water treatment .
  • the present invention provides a method of bleaching fabric stains comprising applying a pretreatment composition to a stained fabric, and subsequently washing the pretreated fabric in an aqueous wash liquor, wherein: the pretreatment composition comprises a ligand which forms a complex with a transition metal, the complex catalysing bleaching of stains by atmospheric oxygen; and one or both of the pretreatment composition and the wash liquor are substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system.
  • the present invention provides the use of a ligand which forms a complex with a transition metal, the complex catalysing bleaching of stains by atmospheric oxygen, in a pretreatment composition for applying to stained fabrics prior to stain bleaching by washing the pretreated fabric in an aqueous wash liquor.
  • the ligand is N,N-bis (pyridin-2 -yl-methyl) -1, 1- bis (pyridin-2-yl) -1-aminoethane, and the complex is an iron complex.
  • a peroxygen bleach such as hydrogen peroxide, or a peroxy- based or -generating bleach system
  • a peroxygen bleach such as hydrogen peroxide, or a peroxy- based or -generating bleach system
  • Bleaching of tea stains may also be improved by the pretreatment.
  • a peroxygen bleach such as hydrogen peroxide, or a peroxy-based or -generating bleach system, should be present in the pretreatment composition.
  • one of the pretreatment composition and the wash liquor comprises a peroxygen bleach such as hydrogen peroxide or a peroxy-based or -generating bleach system.
  • the other of the pretreatment composition and the wash liquor is free of peroxygen bleach or a peroxy-based or -generating bleach system. Since the specificity of catalytic bleaching for particular stain types may be altered according to the presence or absence of peroxygen bleach or a peroxy-based or -generating bleach systems, a broader stain profile may be bleached more effectively by ensuring that either the pretreatment or the wash liquor, but not both, comprise peroxy bleach.
  • catalytic bleaching with atmospheric oxygen will predominate in the wash liquor during the wash cycle when the wash liquor is substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system, so as to favour bleaching of tomato stain types over tea stain types
  • peroxy bleach catalysis will predominate during the pretreatment if the pretreatment composition comprises peroxygen bleach or a peroxy-based or -generating bleach system, so as to favour bleaching of tea stain types over tomato stain types.
  • the peroxygen bleach or peroxy-based or - generating bleach system could absent from the pretreatment composition and present only in the wash liquor so as to favour the bleaching of tomato stain types during the pretreatment and the bleaching of tea stain types during the main wash cycle.
  • the pretreatment composition comprises peroxygen bleach or a peroxy-based or -generating bleach system and the wash liquor is substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system.
  • the stained fabric comprises a tea stain.
  • the pretreatment composition is substantially devoid of peroxygen bleach or a peroxy- based or -generating bleach system and the wash liquor comprises peroxygen bleach or a peroxy-based or -generating bleach system.
  • the stained fabric comprises a tomato, oil or tomato/oil stain.
  • the bleaching effect on certain stain types may be enhanced by the presence of unsaturated fatty acids, such as oleic acid, or esters thereof, preferably unsaturated fatty acid oils, in the pretreatment composition.
  • unsaturated fatty acids such as oleic acid, or esters thereof, preferably unsaturated fatty acid oils
  • the pretreatment composition comprises an unsaturated fatty acid oil in combination with the ligand or complex.
  • the unsaturated fatty oils are relatively inexpensive and it is postulated that similar materials will serve to provide a similar bleach enhancing activity. Enhancement of the bleaching process will likely be found in compounds having a hydrogen that is relatively prone to abstraction by a free radical .
  • any suitable fabric that is susceptible to stain bleaching or one that one might wish to subject to bleaching may be used.
  • the fabric is a laundry fabric or garment.
  • the method according to the present invention is carried out on a laundry fabric using an aqueous pretreatment composition.
  • the treatment may be effected prior to a conventional wash cycle .
  • the pretreatment composition will comprise at least the ligand or complex in combination with a suitable medium, such as an aqueous or nonaqueous solvent, or an inert carrier such as a filler.
  • a suitable medium such as an aqueous or nonaqueous solvent, or an inert carrier such as a filler.
  • the composition may take any suitable form, such as a solid, powder, paste, gel or liquid.
  • the pretreatment composition is in the form of a liquid.
  • the pretreatment composition may be applied to the stained fabric by any suitable delivery method, for example by spraying as a liquid or dry powder, from a liquid, gel or paste applicator, or from a bar.
  • the pretreated fabric is left for at least 5 minutes, preferably at least 15 minutes, more preferably at least 50 minutes, before washing .
  • the pretreatment composition may be contacted to the textile fabric in any suitable manner.
  • it may be applied in dry form, such as in powder form, particularly to wetted fabrics, or in a liquor, for example as an aqueous spray-on fabric treatment fluid, or a non-aqueous dry cleaning fluid or spray-on aerosol fluid, to dry or wet fabrics .
  • Suitable pretreatment means for application of the ligand or complex to the textile material prior to the main wash include sprays, pens, roller-ball devices, bars, soft solid applicator sticks and impregnated cloths or cloths containing microcapsules. Such means are well known in the analogous art of deodorant application and/or in spot treatment of textiles.
  • the present invention also extends to a commercial package comprising a ligand or complex preferably as defined below together with instructions for its use.
  • the catalyst may comprise a preformed complex of a ligand and a transition metal.
  • the catalyst may comprise a free ligand that complexes with a transition metal already present in the water or that complexes with a transition metal present in the substrate.
  • the catalyst may also be included in the form of a composition of a free ligand or a transition metal-substitutable metal-ligand complex, and a source of transition metal, whereby the complex is formed in si tu in the medium.
  • the ligand forms a complex with one or more transition metals, in the latter case for example as a dinuclear complex.
  • Suitable transition metals include for example: manganese in oxidation states II-V, iron II-V, copper I-III, cobalt I-III, titanium II-IV, tungsten IV-VI, vanadium II-V and molybdenum II -VI.
  • the transition metal complex preferably is of the general formula:
  • M represents a metal selected from Mn (II) - (III) - (IV) - (V), Cu(I)-(II)-(III) , Fe (II) - (III) - (IV) - (V) , Co(I)-(II)- (III), Ti(II)-(III)-(IV) , V(II)-(III)-(IV)-(V) , Mo(II)- (III) - (IV) - (V) - (VI) and W(IV) - (V) - (VI) , preferably from Fe(II)-(III)-(IV)-(V) ;
  • L represents the ligand, preferably N,N-bis (pyridin-2- yl-methyl) -1, 1-bis (pyridin-2 -yl) -1-aminoethane, or its protonated or deprotonated analogue;
  • X represents a coordinating species selected from any mono, bi or tri charged anions and any neutral molecules able to coordinate the metal in a mono, bi or tridentate manner;
  • the complex is an iron complex comprising the ligand N,N-bis (pyridin-2 -yl-methyl) -1, 1-bis (pyridin-2 -yl) -1- aminoethane.
  • the pretreatment method of the present invention may instead, or additionally, use other ligands and transition metal complexes, provided that the complex formed is capable of catalysing stain bleaching by atmospheric oxygen. Suitable classes of ligands are described below:
  • Ql and Q3 independently represent a group of the formula:
  • Y independently represents a group selected from -0- , S-, -SO-, -S0 2 -, -C(0)-, arylene, alkylene, heteroarylene, heterocycloalkylene, -(G)P-, -P(0)- and -(G)N- , wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, each except hydrogen being optionally substituted by one or more functional groups E;
  • R5, R6, R7 , R8 independently represent a group selected from hydrogen, hydroxy1 , halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or R5 together with R6 , or R7 together with R8 , or both, represent oxygen, or R5 together with R7 and/or independently R6 together with R8 , or R5 together with R8 and/or independently R6 together with R7 , represent C ⁇ _ 6 -alkylene optionally substituted by C ⁇ _ 4 -alkyl, -F, -Cl, -Br or -I; T represents a non-coordinated group selected from hydrogen, hydroxyl , halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalky
  • U represents either a non-coordinated group T independently defined as above or a coordinating group of the general formula (IIA), (IIIA) or (IVA) :
  • Q2 and Q4 are independently defined as for Ql and Q3 ;
  • Q represents -N(T)- (wherein T is independently defined as above) , or an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole;
  • Z2 is independently defined as for Zl
  • Z3 groups independently represent -N(T)- (wherein T is independently defined as above) ;
  • Zl, Z2 and Z4 independently represent an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole.
  • Zl, Z2 and Z4 independently represent groups selected from optionally substituted pyridin-2-yl, optionally substituted imidazol-2-yl, optionally substituted imidazol-4-yl , optionally substituted pyrazol-1-yl , and optionally substituted quinolin-2 -yl . Most preferred is that Zl, Z2 and Z4 each represent optionally substituted pyridin-2-yl .
  • the groups Zl, Z2 and Z4 if substituted, are preferably substituted by a group selected from C ⁇ _ -alkyl, aryl, arylalkyl, heteroaryl, methoxy, hydroxy, nitro, amino, carboxyl, halo, and carbonyl. Preferred is that Zl, Z2 and Z4 are each substituted by a methyl group. Also, we prefer that the Zl groups represent identical groups.
  • Each Ql preferably represents a covalent bond or C1-C4- alkylene, more preferably a covalent bond, methylene or ethylene, most preferably a covalent bond.
  • Group Q preferably represents a covalent bond or C1-C4- alkylene, more preferably a covalent bond.
  • the groups R5 , R6 , R7 , R8 preferably independently represent a group selected from -H, hydroxy-C 0 -C 20 -alkyl , halo-C 0 -C 20 - alkyl, nitroso, formyl-C 0 -C 20 -alkyl , carboxyl-C 0 -C 20 -alkyl and esters and salts thereof, carbamoyl-C 0 -C 20 -alkyl , sulfo-C 0 - C 20 -alkyl and esters and salts thereof, sulfamoyl-C 0 -C 20 - alkyl, amino-C 0 -C 20 -alkyl , aryl-C 0 -C 2o -alkyl , C 0 -C 20 -alkyl , alkoxy-Co-C 8 -alkyl, carbonyl-C 0 -C 6 -
  • Non-coordinated group T preferably represents hydrogen, hydroxy, methyl, ethyl, benzyl, or methoxy.
  • the group U in formula (IA) represents a coordinating group of the general formula (IIA) :
  • Z2 represents an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole, more preferably optionally substituted pyridin-2 -yl or optionally substituted benzimidazol-2-yl .
  • Z4 represents an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole, more preferably optionally substituted pyridin-2 -yl , or an non-coordinating group selected from hydrogen, hydroxy, alkoxy, alkyl, alkenyl, cycloalkyl, aryl, or benzyl.
  • the ligand is selected from:
  • the group Z4 in formula (IIA) represents a group of the general formula (IIAa) :
  • Q4 preferably represents optionally substituted alkylene, preferably -CH 2 -CHOH-CH 2 - or -CH 2 -CH 2 - CH 2 - .
  • the ligand is :
  • group U in formula (IA) represents a coordinating group of the general formula (IIIA) :
  • j is 1 or 2, preferably 1.
  • the ligand is selected from:
  • the ligand is selected from:
  • Qi, Q 2 , Q 3 , Q 4 and Q independently represent a group of the formula:
  • Y independently represents a group selected from -O- , - S-, -SO-, -S0 2 -, -C(O)-, arylene, alkylene, heteroarylene, heterocycloalkylene, -(G)P-, -P(O)- and -(G)N- , wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, each except hydrogen being optionally substituted by one or more functional groups E;
  • R5, R6, R7, R8 independently represent a group selected from hydrogen, hydroxyl , halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or R5 together with R6, or R7 together with R8 , or both, represent oxygen, or R5 together with R7 and/or independently R6 together with R8, or R5 together with R8 and/or independently R6 together with R7 , represent C ⁇ - 6 -alkylene optionally substituted by C ⁇ _ 4 -alkyl, -F, -Cl, -Br or -I,
  • Ri, R 2 , R 3 , R4 comprise coordinating heteroatoms and no more than six heteroatoms are coordinated to the same transition metal atom.
  • At least two, and preferably at least three, of Ri, R 2 , R 3 , R 4 independently represent a group selected from carboxylate, amido, -NH-C (NH) NH 2 , hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole.
  • substituents for groups R lf R 2 , R 3 , R 4 when representing a heterocyclic or heteroaromatic ring, are selected from C ⁇ _ -alkyl, aryl, arylalkyl, heteroaryl, methoxy, hydroxy, nitro, amino, carboxyl, halo, and carbonyl .
  • the groups Q 1# Q 2 , Q 3 , Q 4 preferably independently represent a group selected from -CH 2 - and -CH 2 CH 2 - .
  • Group Q is preferably a group selected from -(CH 2 ) 2 - -, - CH 2 CH(OH)CH 2 -,
  • R represents -H or C ⁇ _ 4 -alkyl.
  • the groups R5 , R6 , R7 , R8 preferably independently represent a group selected from -H, hydroxy-C 0 -C 2 o-alkyl , halo-C 0 -Co- alkyl, nitroso, formyl -C 0 -C 20 -alkyl , carboxyl -C 0 -C 2 o- lkyl and esters and salts thereof, carbamoyl-C 0 -C 2 o-alkyl , sulfo-C 0 - C 0 -alkyl and esters and salts thereof, sulfamoyl-C 0 -C 20 - alkyl, amino-C 0 -C 2 o-alkyl , aryl-C 0 -C 2 o-alkyl , C 0 -C 2 o-alkyl , alkoxy-Co-C 8 -alkyl, carbonyl-C
  • the ligand is of the general formula (IIB) :
  • Preferred classes of ligands according to this aspect are as follows:
  • Ri, R 2 , R 3 , R 4 each independently represent a coordinating group selected from carboxylate, amido, -NH- C(NH)NH 2 , hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole.
  • a coordinating group selected from carboxylate, amido, -NH- C(NH)NH 2 , hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquino
  • Ri, R 2 , R 3 , R 4 each independently represent a coordinating group selected from optionally substituted pyridin-2-yl, optionally substituted imidazol-2-yl, optionally substituted imidazol-4-yl , optionally substituted pyrazol-1-yl, and optionally substituted quinolin-2-yl .
  • Ri R 2 R 3 each independently represent a coordinating group selected from carboxylate, a ido, -NH-C (NH) NH 2 hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole; and
  • Ri, R 2 , R 3 each independently represent a coordinating group selected from optionally substituted pyridin-2 -yl , optionally substituted imidazol-2-yl , optionally substituted imidazol-4-yl , optionally substituted pyrazol-1-yl , and optionally substituted quinolin-2 -yl ; and R 4 represents a group selected from hydrogen, C 3 .-10 optionally substituted alkyl, C ⁇ - 5 -furanyl , C 1 - 5 optionally substituted benzylalkyl, benzyl, C 1 - 5 optionally substituted alkoxy, and C1-2 0 optionally substituted N + Me 3 .
  • Ri, R 4 each independently represent a coordinating group selected from optionally substituted pyridin-2 -yl , optionally substituted imidazol-2-yl , optionally substituted imidazol-4-yl , optionally substituted pyrazol-1-yl , and optionally substituted quinolin-2 -yl ; and
  • R 2 , R 3 each independently represent a group selected from hydrogen, C ⁇ _ ⁇ 0 optionally substituted alkyl, C 1 - 5 - furanyl , C 1 - 5 optionally substituted benzylalkyl, benzyl, C3.-5 optionally substituted alkoxy, and C 1 - 20 optionally substituted N + Me 3 .
  • Examples of preferred ligands in their simplest forms are:
  • N,N' ,N' -tris (3-methyl-pyridin-2 -ylmethyl) -ethylenediamine; N-trimethylammoniumpropyl-N,N' , N' -tris (pyridin-2 -ylmethyl) • ethylenediamine ;
  • N- (2-hydroxyethylene) -N,N' ,N' -tris (3 -methyl-pyridin-2 - ylmethyl) -ethylenediamine; N-methyl-N,N' ,N' -tris (pyridin-2-ylmethyl) -ethylenediamine;
  • N-methyl-N,N' , N 1 -tris (5-methyl-pyridin-2 -ylmethyl) - ethylenediamine
  • N-methyl-N,N' ,N' -tris (3 -methyl -pyridin-2 -ylmethyl) - ethylenediamine ;
  • N,N,N' -tris (1 -methyl -benzimidazol -2 -yl) -N' -methyl- ethylenediamine ; N- (furan-2-yl) -N,N' ,N' -tris (3 -methyl -pyridin-2 -ylmethyl) - ethylenediamine ; N- (2-hydroxyethylene) -N,N' ,N' -tris (3-ethyl-pyridin-2- ylmethyl) -ethylenediamine;
  • N-benzyl-N,N' ,N' -tris (3 -methyl -pyridin-2 -ylmethyl) ethylene- 1 , 2 -diamine; N- (2 -hydroxyethyl) -N,N' ,N' -tris (3 -methyl -pyridin-2- ylmethyl) ethylene- 1, 2 -diamine;
  • N-methyl-N,N' ,N' -tris (5-methyl -pyridin-2 -ylmethyl) ethylene- 1 , 2 -diamine;
  • N-ethyl-N,N' ,N' -tris (5-methyl -pyridin-2 -ylmethyl) ethylene- 1 , 2 -diamine; N-benzyl-N,N' ,N' -tris (5 -methyl -pyridin-2 -ylmethyl) ethylene- 1, 2 -diamine ;
  • N-ethyl-N,N' ,N' -tris (3 -ethyl -pyridin-2 -ylmethyl) ethylene- 1, 2 -diamine; N-benzyl-N,N' ,N' -tris (3 -ethyl -pyridin-2 -ylmethyl) ethylene-
  • N-ethyl-N,N' ,N' -tris (5-ethyl-pyridin-2-ylmethyl) ethylene- 1, 2 -diamine
  • N-benzyl-N,N' ,N' -tris (5 -ethyl -pyridin-2 -ylmethyl) ethylene- 1, 2 -diamine
  • N-benzyl-N,N' ,N' -tris (5 -ethyl -pyridin-2 -ylmethyl) ethylene- 1, 2 -diamine
  • More preferred ligands are:
  • Z x , Z 2 and Z 3 independently represent a coordinating group selected from carboxylate, amido, -NH-C (NH) NH 2 , hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole;
  • Q ⁇ # Q 2 and Q 3 independently represent a group of the formula:
  • Y independently represents a group selected from -0-, - S-, -SO-, -S0 2 -, -C(O)-, arylene, alkylene, heteroarylene, heterocycloalkylene, -(G)P-, -P(O)- and -(G)N- , wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, each except hydrogen being optionally substituted by one or more functional groups E; and
  • R5, R6 , R7, R8 independently represent a group selected from hydrogen, hydroxyl , halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or R5 together with R6 , or R7 together with R8 , or both, represent oxygen, or R5 together with R7 and/or independently R6 together with R8 , or R5 together with R8 and/or independently R6 together with R7, represent C ⁇ -6 -alkylene optionally substituted by C ⁇ - -alkyl, -F, -Cl, -Br or -I.
  • Z 2 and Z 3 each represent a coordinating group, preferably selected from optionally substituted pyridin-2 -yl, optionally substituted imidazol-2-yl , optionally substituted imidazol-4-yl , optionally substituted pyrazol-1-yl , and optionally substituted quinolin-2 -yl .
  • Z i; Z 2 and Z 3 each represent optionally substituted pyridin-2-yl .
  • each Q x , Q 2 and Q 3 independently represent C ⁇ - - alkylene, more preferably a group selected from -CH 2 - and - CH 2 CH 2 -.
  • the groups R5 , R6 , R7, R8 preferably independently represent a group selected from -H, hydroxy-C 0 -C 20 -alkyl , halo-C 0 -C 20 - alkyl, nitroso, formyl-C 0 -C 20 -alkyl , carboxyl-C 0 -C 2 o-alkyl and esters and salts thereof, carbamoyl -C 0 -C 0 -alkyl , sulfo-C 0 - C 2 o-alkyl and esters and salts thereof, sulfamoyl -C 0 -C 20 - alkyl, amino-C 0 -C 2 o-alkyl , aryl-C 0 -C 20 -alkyl , C 0 -C 2 o-alkyl , alkoxy-Co-C 8 -alkyl, carbonyl -C 0
  • the ligand is selected from tris (pyridin-2- ylmethyl) amine, tris (3 -methyl-pyridin-2 -ylmethyl) amine, tris (5-methyl-pyridin-2-ylmethyl) amine, and tris (6-methyl- pyridin-2 -ylmethyl) amine.
  • Q independently represent a group selected from C 2 - 3 - alkylene optionally substituted by H, benzyl or C ⁇ - 8 -alkyl;
  • Qi, Q 2 and Q 3 independently represent a group of the formula :
  • Y independently represents a group selected from -0- , S-, -SO-, -S0 2 -, -C(0)-, arylene, alkylene, heteroarylene, heterocycloalkylene, -(G)P-, -P(0)- and -(G)N- , wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, each except hydrogen being optionally substituted by one or more functional groups E; and
  • R5, R6, R7, R8 independently represent a group selected from hydrogen, hydroxyl , halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or R5 together with R6 , or R7 together with R8 , or both, represent oxygen, or R5 together with R7 and/or independently R6 together with R8 , or R5 together with R8 and/or independently R6 together with R7, represent C ⁇ -6 -alkylene optionally substituted by C ⁇ - -alkyl, -F, -Cl, -Br or -I,
  • Ri, R 2 and R 3 is a coordinating group.
  • At least two, and preferably at least three, of R 1# R 2 and R 3 independently represent a group selected from carboxylate, amido, -NH-C (NH)NH 2 , hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole.
  • Ri, R 2 , R 3 each independently represent a coordinating group selected from optionally substituted pyridin-2 -yl, optionally substituted imidazol-2-yl , optionally substituted imidazol-4-yl , optionally substituted pyrazol - 1 -yl , and optionally substituted quinolin-2 -yl .
  • substituents for groups Ri, R 2 , R 3 when representing a heterocyclic or heteroaromatic ring, are selected from C ⁇ -4 -alkyl, aryl, arylalkyl, heteroaryl, methoxy, hydroxy, nitro, amino, carboxyl, halo, and carbonyl .
  • the groups Q ⁇ , Q 2 and Q 3 independently represent a group selected from -CH 2 - and - CH 2 CH 2 -.
  • Group Q is preferably a group selected from -CH 2 CH 2 - and - CH 2 CH 2 CH2- •
  • the groups R5, R6 , R7 , R8 preferably independently represent a group selected from -H, hydroxy-C 0 -C 20 -alkyl , halo-C 0 -C 20 - alkyl, nitroso, formyl -C 0 -C 20 -alkyl , carboxyl -C 0 -C 20 -alkyl and esters and salts thereof, carbamoyl-C 0 -C 2 o-alkyl , sulfo-C 0 - C 2 o-alkyl and esters and salts thereof, sulfamoyl-C 0 -C 2 o- alkyl, amino-C 0 -C 2 o-alkyl , aryl-C 0 -C 2 o-alkyl , C 0 -C 2 o-alkyl , alkoxy-C 0 -C 8 -alkyl , carbonyl
  • the ligand is of the general formula (IID) :
  • Preferred classes of ligands according to this preferred aspect are as follows :
  • RI , R2 , R3 each independently represent a coordinating group selected from carboxylate, amido, -NH-C (NH) NH 2 , hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole.
  • RI , R2 , R3 each independently represent a coordinating group selected from optionally substituted pyridin-2 -yl , optionally substituted imidazol-2-yl , optionally substituted imidazol-4-yl , optionally substituted pyrazol-1-yl , and optionally substituted quinolin-2 -yl .
  • two of RI, R2 , R3 each independently represent a coordinating group selected from optionally substituted pyridin-2-yl , optionally substituted imidazol-2-yl , optionally substituted imidazol-4-yl , optionally substituted pyrazol-1-yl , and optionally substituted quinolin-2-yl ; and one of RI , R2 , R3 represents a group selected from hydrogen, C ⁇ - ⁇ 0 optionally substituted alkyl, C 1-5 -furanyl , C ⁇ - optionally substituted benzylalkyl, benzyl, C ⁇ -5 optionally substituted alkoxy, and C ⁇ - 2 o optionally substituted N + Me 3 .
  • the ligand is selected from:
  • IE IE
  • g zero or an integer from 1 to 6
  • r represents an integer from 1 to 6
  • s represents zero or an integer from 1 to 6
  • Ql and Q2 independently represent a group of the formula :
  • each Yl independently represents a group selected from -0-, -S-, -SO-, -S0 2 -, -C(O)-, arylene, alkylene, heteroarylene, heterocycloalkylene, -(G)P-, -P(O)- and - (G)N- , wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, each except hydrogen being optionally substituted by one or more functional groups E;
  • each - [-N(Rl) - (Ql) r -] - group is independently defined;
  • RI, R2 , R6, R7, R8 , R9 independently represent a group selected from hydrogen, hydroxyl , halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or R6 together with R7 , or R8 together with R9 , or both, represent oxygen, or R6 together with R8 and/or independently R7 together with R9, or R6 together with R9 and/or independently R7 together with R8 , represent C ⁇ - 6 -alkylene optionally substituted by C 1-4 -alkyl, -F, -Cl, -Br or -I; or one of R1-R9 is a bridging group bound to another moiety of the same general formula;
  • Tl and T2 may together (-T2-T1-) represent a covalent bond linkage when s>l and g>0;
  • the groups R1-R9 are preferably independently selected from -H, hydroxy-Co-C 20 -alkyl , halo-C 0 -C 20 -alkyl , nitroso, formyl - C 0 -C 2 o-alkyl , carboxyl -C 0 -C 20 -alkyl and esters and salts thereof, carbamoyl -C 0 -C 2 o-alkyl , sulpho-C 0 -C 2 o-alkyl and esters and salts thereof, sulphamoyl -C 0 -C 20 -alkyl , amino-C 0 - C 0 -alkyl, aryl-C 0 -C 2 o-alkyl , heteroaryl-C 0 -C 20 -alkyl , Co-C 20 - alkyl, alkoxy-C 0 -C 8 -alkyl , carbonyl
  • R1-R9 may be a bridging group which links the ligand moiety to a second ligand moiety of preferably the same general structure.
  • the bridging group is independently defined according to the formula for Ql, Q2 , preferably being alkylene or hydroxy-alkylene or a heteroaryl -containing bridge, more preferably C ⁇ - 6 -alkylene optionally substituted by C ⁇ -4 -alkyl, -F, -Cl, -Br or -I.
  • RI , R2 , R3 and R4 are preferably independently selected from -H, alkyl, aryl, heteroaryl, and/or one of R1-R4 represents a bridging group bound to another moiety of the same general formula and/or two or more of R1-R4 together represent a bridging group linking N atoms in the same moiety, with the bridging group being alkylene or hydroxy-alkylene or a heteroaryl - containing bridge, preferably heteroarylene.
  • RI , R2 , R3 and R4 are independently selected from -H, methyl, ethyl, isopropyl, nitrogen-containing heteroaryl, or a bridging group bound to another moiety of the same general formula or linking N atoms in the same moiety with the bridging group being alkylene or hydroxy- alkylene .
  • the ligand has the general formula
  • A represents optionally substituted alkylene optionally interrupted by a heteroatom; and n is zero or an integer from 1 to 5.
  • Tl and T2 independently represent groups R4 , R5 as defined for R1-R9, according to the general formula (HIE) :
  • preferred ligands may for example have a structure selected from:
  • the ligand is selected from:
  • Rland R2 are selected from optionally substituted phenols, heteroaryl-C 0 -C 2 o-alkyls
  • R3 and R4 are selected from -H, alkyl, aryl, optionally substituted phenols, heteroaryl -C 0 -C 2 o-alkyls, alkylaryl, aminoalkyl, alkoxy, more preferably RI and R2 being selected from optionally substituted phenols, heteroaryl-C 0 -C 2 -alkyls
  • R3 and R4 are selected from -H, alkyl, aryl, optionally substituted phenols, nitrogen-heteroaryl-C 0 -C 2 -alkyls .
  • the ligand has the general formula:
  • the ligand has the general formula: This class of ligand is particularly preferred according to the invention.
  • the ligand has the general formula:
  • RI, R2 , R3 are as defined for R2 , R4 , R5
  • the ligand is a pentadentate ligand of the general formula (IVE) :
  • R 3 represents hydrogen, optionally substituted alkyl, aryl or arylalkyl, or -R 4 -R 5 , each R 4 independently represents a single bond or optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene, alkylene ether, carboxylic ester or carboxylic amide, and each R 5 independently represents an optionally N- substituted aminoalkyl group or an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl , pyrimidmyl, triazolyl and thiazolyl .
  • Ligands of the class represented by general formula (IVE) are also particularly preferred according to the invention.
  • the ligand having the general formula (IVE) is a pentadentate ligand.
  • 'pentadentate' herein is meant that five hetero atoms can coordinate to the metal M ion in the metal-complex.
  • one coordinating hetero atom is provided by the nitrogen atom in the methylamine backbone, and preferably one coordinating hetero atom is contained in each of the four R 1 and R 2 side groups. Preferably, all the coordinating hetero atoms are nitrogen atoms.
  • the ligand of formula (IVE) preferably comprises at least two substituted or unsubstituted heteroaryl groups in the four side groups.
  • the heteroaryl group is preferably a pyridin-2 -yl group and, if substituted, preferably a methyl- or ethyl-substituted pyridin-2-yl group. More preferably, the heteroaryl group is an unsubstituted pyridin-2-yl group.
  • the heteroaryl group is linked to methylamine, and preferably to the N atom thereof, via a methylene group.
  • the ligand of formula (IVE) contains at least one optionally substituted amino-alkyl side group, more preferably two amino-ethyl side groups, in particular 2-(N- alkyl) amino-ethyl or 2- (N,N-dialkyl) amino-ethyl .
  • R 1 represents pyridin-2 -yl or R 2 represents pyridin-2 -yl -methyl .
  • R 2 or R 1 represents 2 -amino-ethyl, 2- (N- (m) ethyl) amino-ethyl or 2- (N,N-di (m) ethyl) amino-ethyl .
  • R 5 preferably represents 3 -methyl pyridin-2 -yl .
  • R 3 preferably represents hydrogen, benzyl or methyl.
  • pyridin-2 -yl containing ligands such as: N,N-bis (pyridin-2-yl-methyl) -bis (pyridin-2 -yl) methylamine;
  • ligands such as: N,N-bis (2- (N-alkyl) amino-ethyl) -bis (pyridin-2- yl ) methylamine ; N,N-bis (2- (N-alkyl) amino-ethyl) -bis (pyrazol -1- yl) methylamine;
  • More preferred ligands are: N,N-bis (pyridin-2 -yl-methyl) -bis (pyridin-2 -yl) methylamine, hereafter referred to as N4Py.
  • the ligand represents a pentadentate or hexadentate ligand of general formula (VE) :
  • each R 1 independently represents -R 3 -V, in which R 3 represents optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene or alkylene ether, and V represents an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl ;
  • W represents an optionally substituted alkylene bridging group selected from -CH 2 CH 2 -, -CH2CH2CH2- , -CH2CH2CH2CH2- , -CH2-CgH-CH2- , CH 2 -, and -CH 2 -C ⁇ 0 H 6 -CH 2 - ; and R 2 represents a group selected from R 1 , and alkyl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N + (R 4 ) 3 , wherein R 4 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl , alkanyl ether and alkenyl ether.
  • ⁇ pentadentate' is meant that five hetero atoms can coordinate to the metal M ion in the metal -complex.
  • 'hexadentate' is meant that six hetero atoms can in principle coordinate to the metal M ion.
  • one of the arms will not be bound in the complex, so that the hexadentate ligand will be penta coordinating.
  • two hetero atoms are linked by the bridging group W and one coordinating hetero atom is contained in each of the three R 1 groups.
  • the coordinating hetero atoms are nitrogen atoms.
  • the ligand of formula (VE) comprises at least one optionally substituted heteroaryl group in each of the three R 1 groups.
  • the heteroaryl group is a pyridin-2 -yl group, in particular a methyl- or ethyl -substituted pyridin-2-yl group.
  • the heteroaryl group is linked to an N atom in formula (VE) , preferably via an alkylene group, more preferably a methylene group.
  • the heteroaryl group is a 3 -methyl-pyridin-2 -yl group linked to an N atom via methylene .
  • the group R 2 in formula (VE) is a substituted or unsubstituted alkyl, aryl or arylalkyl group, or a group R 1 .
  • R 2 is different from each of the groups R 1 in the formula above.
  • R 2 is methyl, ethyl, benzyl, 2-hydroxyethyl or 2-methoxyethyl. More preferably, R 2 is methyl or ethyl.
  • the bridging group W may be a substituted or unsubstituted alkylene group selected from -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH- 2 CH 2 -, -CH 2 -C 6 H 4 -CH 2 -, -CH 2 -C 6 H 10 -CH 2 -, and -CH 2 -C 10 H e -CH 2 - (wherein -C 6 H -, -C 6 H ⁇ 0 -, -C ⁇ 0 H 6 - can be ortho- , para- , or .neta-C 6 H 4 - , -C 6 H 10 -, -C ⁇ 0 H 6 -).
  • the bridging group W is an ethylene or 1,4-butylene group, more preferably an ethylene group.
  • V represents substituted pyridin-2 -yl, especially methyl-substituted or ethyl -substituted pyridin- 2-yl, and most preferably V represents 3 -methyl pyridin-2- yi-
  • Y in formula (Al) balance the charge z on the complex formed by the ligand L, metal M and coordinating species X.
  • Y may be an anion such as RCOO “ , BPh 4 " , C10 4 " , BF 4 “ , PF 6 “ , RS0 3 ⁇ , RS0 4 “ , S0 4 2 ⁇ , N0 3 " , F “ , Cl “ , Br “ , or I “ , with R being hydrogen, optionally substituted alkyl or optionally substituted aryl.
  • Y may be a common cation such as an alkali metal, alkaline earth metal or (alkyl) ammonium cation.
  • Suitable counter ions Y include those which give rise to the formation of storage-stable solids.
  • Preferred counter ions for the preferred metal complexes are selected from R 7 COO “ , C10 4 " , BF “ , PF 6 " , RS0 3 “ (in particular CF 3 S0 3 “ ) , RS0 4 “ , S0 4 2” , N0 3 “ , F “ , Cl “ , Br “ , and I “ , wherein R represents hydrogen or optionally substituted phenyl, naphthyl or C ⁇ -C 4 alkyl.
  • the complex (Al) can be formed by any appropriate means, including in si tu formation whereby precursors of the complex are transformed into the active complex of general formula (Al) under conditions of storage or use.
  • the complex is formed as a well-defined complex or in a solvent mixture comprising a salt of the metal M and the ligand L or ligand L-generating species.
  • the catalyst may be formed in si tu from suitable precursors for the complex, for example in a solution or dispersion containing the precursor materials.
  • the active catalyst may be formed in si tu in a mixture comprising a salt of the metal M and the ligand L, or a ligand L-generating species, in a suitable solvent.
  • an iron salt such as FeS0 4 can be mixed in solution with the ligand L, or a ligand L-generating species, to form the active complex.
  • the ligand L, or a ligand L-generating species can be mixed with metal M ions present in the substrate or wash liquor to form the active catalyst in si tu .
  • Suitable ligand L-generating species include metal -free compounds or metal coordination complexes that comprise the ligand L and can be substituted by metal M ions to form the active complex according the formula (Al) .
  • the level of the catalyst is such that the in-use level is from l ⁇ M to 50mM, with preferred in-use levels for domestic laundry operations falling in the range 10 to 100 ⁇ M.
  • the pretreatment medium or wash liquor has a pH in the range from pH 6 to 13 , more preferably from pH 6 to 11, still more preferably from pH 8 to 11, and most preferably from pH 8 to 10, in particular from pH 9 to 10.
  • bleaching should be understood as relating generally to the decolourisation of stains or of other materials attached to or associated with a substrate.
  • the present invention can be applied where a requirement is the removal and/or neutralisation by an oxidative bleaching reaction of malodours or other undesirable components attached to or otherwise associated with a substrate.
  • bleaching is to be understood as being restricted to any bleaching mechanism or process that does not require the presence of light or activation by light.
  • photobleaching compositions and processes relying on the use of photobleach catalysts or photobleach activators and the presence of light are excluded from the present invention.
  • one or both of the pretreatment composition and the wash liquor are substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system, whereby the catalytic bleaching by atmospheric oxygen or air will predominate.
  • peroxygen bleach or a peroxy-based or -generating bleach system whereby the catalytic bleaching by atmospheric oxygen or air will predominate.
  • small amounts of hydrogen peroxide or peroxy-based or -generating systems may be included in the composition, if desired.
  • substantially devoid of peroxygen bleach or peroxy-based or -generating bleach systems is meant that the composition contains from 0 to 50 %, preferably from 0 to 10 %, more preferably from 0 to 5 %, and optimally from 0 to 2 % by molar weight on an oxygen basis, of peroxygen bleach or peroxy-based or -generating bleach systems.
  • the composition will be wholly devoid of peroxygen bleach or peroxy-based or -generating bleach systems.
  • At least 10 %, preferably at least 50 % and optimally at least 90 % of any bleaching of the stain substrate is effected by oxygen sourced from the air.
  • one of the pretreatment composition and the wash liquor contains a peroxygen bleach or a peroxy-based or -generating system.
  • the peroxy bleach may be a compound which is capable of yielding hydrogen peroxide in aqueous solution.
  • Hydrogen peroxide sources are well known in the art. They include the alkali metal peroxides, organic peroxides such as urea peroxide, and inorganic persalts, such as the alkali metal perborates, percarbonates, perphosphates persilicates and persulphates . Mixtures of two or more such compounds may also be suitable.
  • sodium perborate tetrahydrate and, especially, sodium perborate monohydrate.
  • Sodium perborate monohydrate is preferred because of its high active oxygen content.
  • Sodium percarbonate may also be preferred for environmental reasons.
  • the amount thereof in the composition of the invention usually will be within the range of about 5-35 % by weight, preferably from 10-25 % by weight .
  • Another suitable hydrogen peroxide generating system is a combination of a C ⁇ -C alkanol oxidase and a C ⁇ -C 4 alkanol, especially a combination of methanol oxidase (MOX) and ethanol.
  • MOX methanol oxidase
  • Alkylhydroxy peroxides are another class of peroxy bleaching compounds. Examples of these materials include cumene hydroperoxide and t-butyl hydroperoxide .
  • Organic peroxyacids may also be suitable as the peroxy bleaching compound.
  • Such materials normally have the general formula:
  • R is an alkyl- or alkylidene- 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 - COOH or -COOOH 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-a-naphthoic acid;
  • aliphatic, substituted aliphatic and arylalkyl monoperoxyacids e.g. peroxylauric acid, peroxystearic acid and N,N-phthaloylaminoperoxy caproic acid (PAP) ; and (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) diperoxybrassylic acid; diperoxysebacic acid and diperoxyisophthalic acid; (vii) 2-decyldiperoxybutane-l, 4-dioic acid; and (viii) 4 , 4 ' -sulphonylbisperoxybenzoic acid.
  • DPDA 12-diperoxydodecanedioic acid
  • DPDA 12-diperoxydodecanedioic acid
  • DPDA 12-diperoxydodecanedioic acid
  • DPDA 12-diperoxydodecanedioic acid
  • DPDA 12-diperoxydodecanedioic acid
  • DPDA 12-diperoxydodecanedioic acid
  • 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 peroxy compounds may be utilized alone or in conjunction with a peroxyacid bleach precursor and/or an organic bleach catalyst not containing a transition metal.
  • MPS potassium monopersulphate
  • the pretreatment composition can be suitably formulated to contain from 2 to 35%, preferably from 5 to 25% by weight, of the peroxy bleaching agent.
  • Peroxyacid bleach precursors are known and amply described in literature, such as in GB-A-836988 ; GB-A-864 , 798 ; GB-A- 907,356; GB-A-1 , 003 , 310 and GB-A-1 , 519 , 351 ; DE-A-3 , 337 , 921 ; EP-A-0,185,522; EP-A-0 , 174 , 132 ; EP-A-0 , 120 , 591 ; and US-A- 1,246,339; US-A-3 , 332 , 882 ; US-A-4 , 128 , 494 ; US-A-4 , 412 , 934 and US-A-4, 675, 393.
  • peroxyacid bleach precursors are those of the cationic i.e. quaternary ammonium substituted peroxyacid precursors as disclosed in US-A-4 , 751 , 015 and US- A-4, 397, 757, in EP-A-0,284,292 and EP-A-331 , 229.
  • peroxyacid bleach precursors of this class are:
  • a further special class of bleach precursors is formed by the cationic nitriles as disclosed in EP-A-303 , 520 ; EP-A- 458,396 and EP-A-464 , 880. Any one of these peroxyacid bleach precursors can be used in the present invention, although some may be more preferred than others .
  • the preferred classes are the esters, including acyl phenol sulphonates and acyl alkyl phenol sulphonates; the acyl- mides ; and the quaternary ammonium substituted peroxyacid precursors including the cationic nitriles.
  • Examples of said preferred peroxyacid bleach precursors or activators are sodium-4-benzoyloxy benzene sulphonate (SBOBS) ; N,N,N'N' -tetraacetyl ethylene diamine (TAED) ; sodium-1-methyl-2 -benzoyloxy benzene-4-sulphonate; sodium-4- methyl-3 -benzoloxy benzoate; 2- (N,N,N-trimethyl ammonium) ethyl sodium-4-sulphophenyl carbonate chloride (SPCC) ; trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3,5,5- trimethyl hexanoyl-oxybenzene sulphonate (STHOBS) ; and the substituted cationic nitriles.
  • SBOBS sodium-4-benzoyloxy benzene sulphonate
  • the precursors may be used in an amount of up to 12 %, preferably from 2-10 % by weight, of the pretreatment composition.
  • the method of the present invention has particular application as a pretreatment in detergent bleaching, especially for laundry cleaning. Accordingly, the method preferably uses a wash liquor that contains a surface-active material, optionally together with detergency builder.
  • the pretreatment composition may also include a surface-active material, optionally together with detergency builder.
  • the pretreatment composition may contain a surface-active material in an amount, for example, of from 10 to 50% by weight.
  • 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.
  • 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.
  • Typical synthetic anionic surface-actives are usually water- soluble alkali metal salts of organic sulphates and sulphonates having alkyl groups containing from about 8 to about 22 carbon atoms, the term "alkyl” being used to include the alkyl portion of higher aryl groups.
  • suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulphates, especially those obtained by sulphating higher (C 8 -C 18 ) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (C 9 - C 2 o) benzene sulphonates, particularly sodium linear secondary alkyl (C ⁇ 0 -C ⁇ 5 ) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and ammonium salts of sulphuric acid esters of higher (C 9 -C ⁇ 8 ) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and ammonium salts of fatty acid amides
  • nonionic surface-active compounds which may be used, preferably together with the anionic surface- active compounds, include, in particular, the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C 6 -C 22 ) phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule; and the condensation products of aliphatic (C 8 -C ⁇ 8 ) primary or secondary linear or branched alcohols with ethylene oxide, generally 2-30 EO .
  • alkylene oxides usually ethylene oxide
  • alkyl (C 6 -C 22 ) phenols generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule
  • condensation products of aliphatic (C 8 -C ⁇ 8 ) primary or secondary linear or branched alcohols with ethylene oxide generally 2-30 EO .
  • nonionic surface-actives include alkyl polyglycosides, sugar esters, long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulphoxides .
  • Amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic actives .
  • the pretreatment composition will preferably comprise from 1 to 15 % wt of anionic surfactant and from 10 to 40 % by weight of nonionic surfactant .
  • the detergent active system is free from C ⁇ S -C ⁇ 2 fatty acid soaps.
  • the pretreatment composition may also contain a detergency builder, for example in an amount of from about 5 to 80 % by weight, preferably from about 10 to 60 % by weight.
  • Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
  • Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid and its water- soluble salts; the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid; and polyacetal carboxylates as disclosed in US-A-4, 144,226 and US-A-4 , 146 , 495.
  • alkali metal polyphosphates such as sodium tripolyphosphate
  • nitrilotriacetic acid and its water- soluble salts the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid
  • polyacetal carboxylates as disclosed in US-A-4,
  • Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate.
  • Examples of calcium ion-exchange builder materials include the various types of water- insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P) , zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0 , 384 , 070.
  • the pretreatment composition or wash liquor may contain any one of the organic and inorganic builder materials, though, for environmental reasons, phosphate builders are preferably omitted or only used in very small amounts.
  • Typical builders usable in the present invention are, for example, sodium carbonate, calcite/carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyloxy malonate, carboxymethyloxy succinate and water- insoluble crystalline or amorphous aluminosilicate builder materials, each of which can be used as the main builder, either alone or in admixture with minor amounts of other builders or polymers as co-builder.
  • the pretreatment composition contains not more than 5% by weight of a carbonate builder, expressed as sodium carbonate, more preferably not more than 2.5 % by weight to substantially nil, if the composition pH lies in the lower alkaline region of up to 10.
  • the pretreatment composition or wash liquor can contain any of the conventional additives in amounts of which such materials are normally employed in fabric washing detergent compositions.
  • these additives include buffers such as carbonates, lather boosters, such as alkanolamides, particularly the monoethanol amides derived from palmkernel fatty acids and coconut fatty acids; lather depressants, such as alkyl phosphates and silicones; anti-redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers; stabilisers, such as phosphonic acid derivatives (i.e.
  • Dequest ® types fabric softening agents; inorganic salts and alkaline buffering agents, such as sodium sulphate and sodium silicate; and, usually in very small amounts, fluorescent agents; perfumes; enzymes, such as proteases, cellulases, lipases, amylases and oxidases; germicides and colourants.
  • Transition metal sequestrants such as EDTA, and phosphonic acid derivatives such as EDTMP (ethylene diamine tetra (methylene phosphonate) ) may also be included, in addition to the catalyst ligand specified, for example to improve the stability sensitive ingredients such as enzymes, fluorescent agents and perfumes, but provided the composition remains bleaching effective.
  • the pretreatment composition containing the catalyst is preferably substantially, and more preferably completely, devoid of transition metal sequestrants (other than the catalyst ligand) .
  • alkyl linear and branched Cl-C8-alkyl
  • alkenyl C2 -C6 -alkenyl
  • cycloalkyl C3-C8-cycloalkyl
  • alkoxy C1-C6-alkoxy
  • alkylene selected from the group consisting of: methylene; 1, 1-ethylene; 1, 2-ethylene; 1 , 1-propylidene; 1 , 2-propylene; 1, 3-propylene; 2 , 2 -propylidene; butan-2-ol-l , 4-diyl ; propan- 2-ol-l, 3-diyl ; 1 , 4-butylene; cyclohexane-1 , 1-diyl ; cyclohexan-1 , 2-diyl ; cyclohexan-1 , 3 -diyl ; cyclohexan-1 , 4- diyl ; cyclopentane-1, 1-diyl ; cyclopentan-1 , 2 -diyl ; and cyclopentan-1 , 3-diyl,
  • aryl selected from homoaromatic compounds having a molecular weight under 300,
  • arylene selected from the group consisting of: 1,2- phenylene; 1 , 3 -phenylene ; 1 , 4-phenylene; 1, 2-naphtalenylene; 1, 3 -naphtalenylene; 1 , 4 -naphtalenylene ; 2 , 3 -naphtalenylene , • l-hydroxy-2 , 3 -phenylene; l-hydroxy-2 , 4-phenylene; 1-hydroxy- 2 , 5 -phenylene ; and l-hydroxy-2 , 6-phenylene,
  • heteroaryl selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazmyl; 1, 3 , 5-triazinyl ; quinolinyl; isoquinolinyl ; quinoxalinyl ; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl ; oxazolidinyl; pyrrolyl; carbazolyl; indolyl ; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl,
  • heteroarylene selected from the group consisting of: pyridindiyl ; quinolindiyl ; pyrazodiyl ; pyrazoldiyl; triazolediyl; pyrazindiyl; and imidazolediyl, wherein the heteroarylene acts as a bridge in the compound via any atom in the ring of the selected heteroarylene, more specifically preferred are: pyridin-2 , 3-diyl ; pyridin-2 , 4-diyl ; pyridin- 2,5-diyl; pyridin-2 , 6-diyl ; pyridin-3 , 4-diyl ; pyridin-3, 5- diyl; quinolin-2 , 3-diyl ; quinolin-2 , 4-diyl ; quinolin-2 , 8- diyl ; isoquinolin-1, 3-diyl ; isoquinolin-1 , 4-diyl ; pyrazol
  • heterocycloalkyl selected from the group consisting of: pyrrolinyl; pyrrolidinyl ; morpholinyl; piperidinyl ; piperazinyl; hexamethylene imine; 1, 4 -piperazinyl ; tetrahydrothiophenyl ; tetrahydrofuranyl ; 1,4,7- triazacyclononanyl ; 1, 4 , 8 , 11-tetraazacyclotetradecanyl ;
  • heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl,
  • heterocycloalkylene selected from the group consisting of: piperidin-1 , 2 -ylene; piperidin-2 , 6-ylene ; piperidin-4 , 4- ylidene; 1 , 4-piperazin-l , 4-ylene ; 1 , 4-piperazin-2 , 3-ylene;
  • each R is independently selected from: hydrogen; Cl-C6-alkyl ; Cl-C6-alkyl-C6H5 ; and phenyl, wherein when both R are C1-C6-alkyl both R together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring,
  • halogen selected from the group consisting of: F; Cl ; Br and I,
  • R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5 ; Li; Na; K; Cs; Mg; and Ca,
  • sulfate the group -OS (0) 2 0R, wherein R is selected from: hydrogen; Cl-C6-alkyl ; phenyl; Cl-C6-alkyl-C6H5 ; Li; Na; K; Cs ; Mg ; and Ca ,
  • sulfone the group -S(0) 2 R, wherein R is selected from: hydrogen; Cl-C6-alkyl ; phenyl; Cl-C6-alkyl-C6H5 and amine (to give sulfonamide) selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; Cl-C6-alkyl; Cl-C6-alkyl-C6H5 ; and phenyl, wherein when both R' are Cl-C6-alkyl both R 1 together may form an -NC3 to an - NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring, carboxylate derivative: the group -C(0)OR, wherein R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl- C6H5; Li; Na; K; Cs; Mg,- and Ca,
  • carbonyl derivative the group -C(0)R, wherein R is selected from: hydrogen; C1-C6-alkyl; phenyl; C1-C6-alkyl- C6H5 and amine (to give amide) selected from the group: - NR'2, wherein each R' is independently selected from: hydrogen; Cl-C6-alkyl; Cl-C6-alkyl-C6H5 ; and phenyl, wherein when both R' are C1-C6-alkyl both R' together may form an - NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring,
  • each R is independently selected from: hydrogen; Cl -C6-alkyl ; phenyl; Cl -C6 -alkyl -C6H5; Li; Na; K; Cs; Mg; and Ca,
  • phosphate the group -OP (O) (0R) 2/ wherein each R is independently selected from: hydrogen; Cl -C6-alkyl ; phenyl;
  • phosphine the group -P(R) 2 , wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; and Cl-C6-alkyl-C6H5 ,
  • phosphine oxide the group -P(0)R 2 , wherein R is independently selected from: hydrogen; Cl-C6-alkyl ; phenyl; and Cl-C6-alkyl-C6H5 ; and amine (to give phosphonamidate) selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; C1-C6 -alkyl; C1-C6- alkyl -C6H5; and phenyl, wherein when both R 1 are C1-C6 -alkyl both R' together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring.
  • alkyl linear and branched Cl-C6-alkyl
  • alkenyl C3 -C6-alkenyl
  • cycloalkyl C6-C8-cycloalkyl
  • alkoxy C1-C4 -alkoxy
  • alkylene selected from the group consisting of: methylene; 1 , 2-ethylene; 1 , 3-propylene; butan-2-ol-l, 4-diyl ; 1,4- butylene; cyclohexane-1, 1-diyl ; cyclohexan-1 , 2 -diyl , ⁇ cyclohexan-1 , 4-diyl ; cyclopentane-1, 1-diyl ; and cyclopentan- 1,2 -diyl,
  • aryl selected from group consisting of: phenyl; biphenyl ; naphthalenyl ; anthracenyl ; and phenanthrenyl ,
  • arylene selected from the group consisting of: 1,2- phenylene; 1 , 3-phenylene ; 1, 4-phenylene; 1, 2-naphtalenylene; 1, 4-naphtalenylene ; 2 , 3 -naphtalenylene and l-hydroxy-2 , 6- phenylene
  • heteroaryl selected from the group consisting of: pyridinyl; pyrimidinyl; quinolinyl; pyrazolyl ; triazolyl; isoquinolinyl ; imidazolyl; and oxazolidinyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl,
  • heteroarylene selected from the group consisting of: pyridin-2, 3-diyl; pyridin-2 , 4-diyl ; pyridin-2 , 6-diyl ; pyridin-3 , 5-diyl; quinolin-2 , 3-diyl ; quinolin-2 , 4-diyl ; isoquinolin-1, 3-diyl ; isoquinolin-1 , 4-diyl ; pyrazol-3,5- diyl; and imidazole-2 , 4-diyl ,
  • heterocycloalkyl selected from the group consisting of: pyrrolidinyl; morpholinyl; piperidinyl ; piperidinyl; 1,4- piperazinyl; tetrahydrofuranyl ; 1 , 4 , 7-triazacyclononanyl ; 1,4,8, 11-tetraazacyclotetradecanyl; 1, 4, 7, 10, 13- pentaazacyclopentadecanyl ; 1,4,7, 10-tetraazacyclododecanyl ; and piperazinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl,
  • heterocycloalkylene selected from the group consisting of: piperidin-2 , 6-ylene; piperidin-4 , 4 -ylidene; 1,4- piperazin-1 , 4-ylene ; 1 , 4-piperazin-2 , 3 -ylene; 1 , 4-piperazin- 2, 6-ylene; tetrahydrothiophen-2 , 5-ylene; tetrahydrothiophen- 3, 4-ylene; tetrahydrofuran-2 , 5-ylene; tetrahydrofuran-3 , 4- ylene; pyrrolidin-2 , 5-ylene; pyrrolidin-2 , 2-ylidene; 1,4,7- triazacyclonon-1, 4-ylene; 1,4, 7 -triazacyclonon-2 , 3-ylene; 1,4, 7-triazacyclonon-2 , 2-ylidene; 1, 4 , 8 , 11- tetraazacyclotetradec-1, 4-ylene; 1,4,8,11- tetra
  • each R is independently selected from: hydrogen; Cl-C6-alkyl ; and benzyl,
  • halogen selected from the group consisting of: F and Cl ,
  • R is selected from: hydrogen; C1-C6-alkyl; Na; K; Mg; and Ca,
  • R is selected from: hydrogen; C1-C6-alkyl; Na; K; Mg; and Ca,
  • sulfone the group -S(0) 2 R, wherein R is selected from: hydrogen; Cl-C6-alkyl; benzyl and amine selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; Cl-C6-alkyl ; and benzyl, carboxylate derivative: the group -C(0)OR, wherein R is selected from hydrogen; Na; K; Mg; Ca; Cl-C6-alkyl; and benzyl ,
  • carbonyl derivative the group: -C(0)R, wherein R is selected from: hydrogen; Cl-C6-alkyl ; benzyl and amine selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl,
  • phosphonate the group -P(O) (0R) 2 / wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; benzyl; Na; K; Mg; and Ca,
  • phosphate the group -OP(O) (OR) 2 , wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; benzyl; Na; K; Mg; and Ca,
  • phosphine the group -P(R) 2 , wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl ,
  • phosphine oxide the group -P(0)R 2 , wherein R is independently selected from: hydrogen; Cl-C6-alkyl; benzyl and amine selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl .
  • Example 1 the iron perchlorate complex of MeN4Py
  • a pre-treatment system 2 ml of each, were added to either BC-1 or Pomarola/soya oil stains on cotton fabric, and left for either 0 or 60 minutes prior to washing in 1.75 g/1 detergent base in 15° FH (all Ca + ) water at 25 °C in a tergotometer (80 opm) .
  • the detergent base powder composition is given below:
  • ⁇ E aw [( ⁇ L) 2 +( ⁇ a) 2 + ( ⁇ b) 2 ] 1/2
  • ⁇ L is a measure for the difference in darkness between the washed and clean white cloth
  • ⁇ a and ⁇ b are measures for the difference in redness and yellowness respectively between both cloths.
  • CIE Commission International de l'Eclairage
  • Example 2 In Example 2 the iron chloride complex of MeN4py
  • FeMeN4pyCl 2 was used.
  • the iron chloride complex of MeN4py was prepared as follows from the MeN4py ligand synthesised as in EP 0909809. MeN4Py ligand (33.7 g; 88.5mmoles) was dissolved in 500ml dry methanol. Small portions of FeCl 2 .4H 2 0 (0.95eq; 16.7g; 84.0 mmoles) were added, yielding a clear red solution. After addition, the solution was stirred for 30 minutes at room temperature, after which the methanol was removed (rotary-evaporator) . The dry solid was ground and 150 ml of ethylacetate was added and the mixture was stirred until a fine red powder was obtained. This powder was washed twice with ethyl acetate, dried in the air and further dried under vacuum (40 °C) . El. Anal. Calc. for
  • Oils were applied on the BC-1 cloth by the following procedure. First an oil was dissolved in a heptane solution (40 mg liquid per ml heptane solution), then 0.72 ml of this solution was applied to a BC-1 (tea) cloth of 6x6 cm, yielding 5% oil on the cloth.
  • the two oils employed were medium chain triglyceride oil (fully saturated oil) and sunflower oil (SF) (poly-unsaturated oil containing a high quantity of 2 or 3 double bonds in the esterified fatty acid chains) .
  • the bleach results of the cloths, obtained after various periods of times are given in the table below.
  • the reflectance of the cloths was measured with a MinoltaTM 3700d spectrophotometer at 460 nm.
  • the difference in reflectance before and after the wash/storage is defined as a ⁇ R460 value; a higher value indicates a better bleaching of the BC-1 stain.
  • the bleaching values were determined immediately after the wash, after 4, 10, 17 and 24 days storage.
  • Table 3 bleaching performance of the iron catalyst on BC-1 in the absence of oil, in the presence of MCT oil and Sunflower oil .
  • the bleaching activity is expressed as a ⁇ R460 value (a higher value indicates a cleaner cloth) .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Pyridine Compounds (AREA)

Abstract

L'invention concerne un procédé de blanchiment pour textiles tachés, consistant à prétraiter le textile taché avant le lavage, à l'aide d'une composition de prétraitement qui comprend un ligand formant un complexe de métal de transition en tant que catalyseur de blanchiment. Ce complexe catalyse le blanchiment des taches par l'oxygène atmosphérique. La composition de prétraitement comprend de préférence un complexe de fer contenant le ligand N,N-bis (pyridin-2-yl-méthyle)-1,1-bis(pyridin-2-yl)-1-aminoéthane. La composition de prétraitement et/ou la lessive de lavage sont sensiblement exempts d'agent de blanchiment peroxydé ou d'un système à base de peroxy ou générant du peroxy. Ce prétraitement permet un blanchiment amélioré des taches ou couvrant un profil de taches plus étendu.
PCT/EP2000/007561 1999-09-01 2000-08-04 Pretraitement et blanchiment de textiles taches WO2001016268A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR0013593-3A BR0013593A (pt) 1999-09-01 1999-09-01 Método para alvejar manchas de tecido
AU64400/00A AU777434B2 (en) 1999-09-01 2000-08-04 Method of pretreating and bleaching stained fabrics
EP00951477A EP1208184A1 (fr) 1999-09-01 2000-08-04 Pretraitement et blanchiment de textiles taches
CA002382114A CA2382114A1 (fr) 1999-09-01 2000-08-04 Pretraitement et blanchiment de textiles taches

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GBPCT/GB99/02878 1999-09-01
PCT/GB1999/002878 WO2000012808A1 (fr) 1998-09-01 1999-09-01 Procede de traitement d'un textile
GB0004844.7 2000-02-29
GBGB0004844.7A GB0004844D0 (en) 2000-02-29 2000-02-29 Method of pretreating and bleaching stained fabrics

Publications (1)

Publication Number Publication Date
WO2001016268A1 true WO2001016268A1 (fr) 2001-03-08

Family

ID=26243762

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/007561 WO2001016268A1 (fr) 1999-09-01 2000-08-04 Pretraitement et blanchiment de textiles taches

Country Status (5)

Country Link
EP (1) EP1208184A1 (fr)
CN (1) CN1384869A (fr)
AU (1) AU777434B2 (fr)
CA (1) CA2382114A1 (fr)
WO (1) WO2001016268A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002050229A1 (fr) * 2000-12-18 2002-06-27 Unilever Plc Amelioration de catalyseurs de blanchiment a l'air
US6551977B2 (en) * 2001-03-14 2003-04-22 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Air bleaching catalysts with enhancer and moderating agent
US6586383B2 (en) * 2001-03-14 2003-07-01 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Air bleaching catalysts with moderating agent
WO2008139341A2 (fr) * 2007-05-10 2008-11-20 Kimberly-Clark Worldwide, Inc. Agent neutralisant de colorant
US9161869B2 (en) 2012-03-30 2015-10-20 Kimberly-Clark Worldwide, Inc. Absorbent articles with decolorizing agents
US9161868B2 (en) 2009-09-04 2015-10-20 Kimberly-Clark Worldwide, Inc. Removal of colored substances from aqueous liquids
US9237975B2 (en) 2013-09-27 2016-01-19 Kimberly-Clark Worldwide, Inc. Absorbent article with side barriers and decolorizing agents

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3693450A1 (fr) * 2019-02-08 2020-08-12 The Procter & Gamble Company Procédé de traitement de tissus comportant un prétraitement automatique de l'eau

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4217105A (en) * 1977-03-28 1980-08-12 The Procter & Gamble Company Photoactivated bleach-compositions and processes
WO1996026999A1 (fr) * 1995-02-28 1996-09-06 The Procter & Gamble Company Pretraitement du linge avec des chelateurs contenant un agent de blanchiment peroxyde pour le fer, le cuivre ou le manganese, pour diminuer la deterioration du tissu
EP0909809A2 (fr) * 1997-10-01 1999-04-21 Unilever Plc Activation de blanchiment
WO2000012667A1 (fr) * 1998-09-01 2000-03-09 Unilever Plc Composition et procede de blanchiment d'un substrat

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4217105A (en) * 1977-03-28 1980-08-12 The Procter & Gamble Company Photoactivated bleach-compositions and processes
WO1996026999A1 (fr) * 1995-02-28 1996-09-06 The Procter & Gamble Company Pretraitement du linge avec des chelateurs contenant un agent de blanchiment peroxyde pour le fer, le cuivre ou le manganese, pour diminuer la deterioration du tissu
EP0909809A2 (fr) * 1997-10-01 1999-04-21 Unilever Plc Activation de blanchiment
WO2000012667A1 (fr) * 1998-09-01 2000-03-09 Unilever Plc Composition et procede de blanchiment d'un substrat

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002050229A1 (fr) * 2000-12-18 2002-06-27 Unilever Plc Amelioration de catalyseurs de blanchiment a l'air
US6518231B2 (en) 2000-12-18 2003-02-11 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Enhancement of air bleaching catalysts
US6551977B2 (en) * 2001-03-14 2003-04-22 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Air bleaching catalysts with enhancer and moderating agent
US6586383B2 (en) * 2001-03-14 2003-07-01 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Air bleaching catalysts with moderating agent
WO2008139341A2 (fr) * 2007-05-10 2008-11-20 Kimberly-Clark Worldwide, Inc. Agent neutralisant de colorant
WO2008139341A3 (fr) * 2007-05-10 2009-11-19 Kimberly-Clark Worldwide, Inc. Agent neutralisant de colorant
US9657257B2 (en) 2007-05-10 2017-05-23 Kimberly-Clark Worldwide, Inc. Colorant neutralizer
US9161868B2 (en) 2009-09-04 2015-10-20 Kimberly-Clark Worldwide, Inc. Removal of colored substances from aqueous liquids
US9161869B2 (en) 2012-03-30 2015-10-20 Kimberly-Clark Worldwide, Inc. Absorbent articles with decolorizing agents
US9220646B2 (en) 2012-03-30 2015-12-29 Kimberly-Clark Worldwide, Inc. Absorbent articles with improved stain decolorization
US9283127B2 (en) 2012-03-30 2016-03-15 Kimberly-Clark Worldwide, Inc. Absorbent articles with decolorizing structures
US9237975B2 (en) 2013-09-27 2016-01-19 Kimberly-Clark Worldwide, Inc. Absorbent article with side barriers and decolorizing agents

Also Published As

Publication number Publication date
CA2382114A1 (fr) 2001-03-08
AU6440000A (en) 2001-03-26
EP1208184A1 (fr) 2002-05-29
AU777434B2 (en) 2004-10-14
CN1384869A (zh) 2002-12-11

Similar Documents

Publication Publication Date Title
US6302921B1 (en) Method of bleaching stained fabrics
US6610641B2 (en) Composition and method for bleaching a substrate
EP1208188A1 (fr) Composition et procede de blanchiment d'un substrat
US6537959B2 (en) Bleach catalyst and composition and method for bleaching a substrate
US6451752B1 (en) Method of pretreating and bleaching stained fabrics
WO2000060043A1 (fr) Composition et procede pour le blanchissage d'un substrat
AU777434B2 (en) Method of pretreating and bleaching stained fabrics
US20020013246A1 (en) Composition and method for bleaching laundry fabrics
US20020010121A1 (en) Bleaching and dye transfer inhibiting composition and method for laundry fabrics
EP1283861B1 (fr) Composition et procede de blanchiment d'un substrat
EP1208187A1 (fr) Blanchiment de textiles taches
AU2001250319A1 (en) Composition and method for bleaching a substrate
US6653271B2 (en) Composition and method for bleaching a substrate
EP1319061B1 (fr) Necessaire de blanchiment du linge et procede de blanchiment d'un substrat
US20020023303A1 (en) Method for reducing dye fading of fabrics in laundry bleaching compositions
AU7410400A (en) Composition and method for bleaching a substrate

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWE Wipo information: entry into national phase

Ref document number: 2000951477

Country of ref document: EP

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 200200934

Country of ref document: ZA

WWE Wipo information: entry into national phase

Ref document number: 64400/00

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: IN/PCT/2002/00196/MU

Country of ref document: IN

Ref document number: 2382114

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2002/00535

Country of ref document: TR

WWE Wipo information: entry into national phase

Ref document number: 00815029X

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 2000951477

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: JP

WWG Wipo information: grant in national office

Ref document number: 64400/00

Country of ref document: AU

WWW Wipo information: withdrawn in national office

Ref document number: 2000951477

Country of ref document: EP