WO2001016269A1 - Blanchiment de textiles taches - Google Patents

Blanchiment de textiles taches Download PDF

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Publication number
WO2001016269A1
WO2001016269A1 PCT/EP2000/007563 EP0007563W WO0116269A1 WO 2001016269 A1 WO2001016269 A1 WO 2001016269A1 EP 0007563 W EP0007563 W EP 0007563W WO 0116269 A1 WO0116269 A1 WO 0116269A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
pyridin
ligand
optionally substituted
bis
Prior art date
Application number
PCT/EP2000/007563
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 BR0013592-5A priority Critical patent/BR0013592A/pt
Priority claimed from PCT/GB1999/002878 external-priority patent/WO2000012808A1/fr
Priority claimed from GBGB0004847.0A external-priority patent/GB0004847D0/en
Application filed by Unilever Plc, Unilever N.V., Hindustan Lever Limited filed Critical Unilever Plc
Priority to CA002382115A priority patent/CA2382115A1/fr
Priority to EP00960390A priority patent/EP1208187A1/fr
Priority to AU72720/00A priority patent/AU7272000A/en
Publication of WO2001016269A1 publication Critical patent/WO2001016269A1/fr

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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
    • D06L4/13—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using inorganic agents
    • 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 washing a stained fabric in an aqueous wash liquor in the presence of a wash additive 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 as a wash additive for addition to an aqueous wash liquor for bleaching stains on fabrics .
  • 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 washing a stained fabric in an aqueous wash liquor in the presence of a wash additive, wherein: the wash additive 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 wash additive 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, on a carrier as a wash additive for addition to an aqueous wash liquor for bleaching stains on fabrics.
  • 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
  • a peroxygen bleach such as hydrogen peroxide, or a peroxy-based or -generating bleach system
  • a peroxygen bleach or a peroxy-based or -generating bleach system is present in the wash additive and is absent in the wash liquor. It will be appreciated that once the wash additive has been added to the wash liquor, additive materials such as the ligand or complex and, if present, peroxy bleach will migrate into the wash liquor medium.
  • 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 laundry fabrics and the wash additive is added to the wash liquor in a conventional wash cycle .
  • the wash additive will comprise at least the ligand or complex in combination with any suitable carrier.
  • the purpose of the carrier is simply to support or contain the additive active materials such as the ligand or complex and peroxy bleach, if present, and to allow delivery of the additive active materials into the wash liquor when the wash additive is added. It will be appreciated that any carrier suitable for this purpose may be used in accordance with the method of the invention.
  • the ligand or complex may conveniently be deposited on or impregnated into the carrier by any suitable means, for example as a liquid which is then optionally dried, or as a dry powder.
  • the ligand or complex is carried in or on the carrier in a composition that includes a solvent or carrier medium for the ligand or complex.
  • the composition may take any suitable form, such as a solid, powder, paste, gel or liquid.
  • the composition is in the form of a liquid.
  • the method according to the present invention is carried out on a laundry fabric using aqueous wash liquor.
  • the addition of the wash additive may be effected in, or as an adjunct to, an essentially conventional wash cycle for cleaning laundry.
  • the wash additive is added in an aqueous detergent wash liquor.
  • the ligand or complex can be delivered into the wash liquor from a carrier, which can be particulate, sheet-like or comprise a three-dimensional object.
  • the carrier can be dispersible or soluble in the wash liquor or may remain substantially intact.
  • the wash additive may, for example, be presented in the form of a body from which the complex is slowly released during the whole or part of the laundry process. Such release can occur over the course of a single wash or over the course of a plurality of washes. In the latter case it is envisaged that the complex can be released from a carrier substrate used in association with the wash process, e.g. from a body placed in the dispenser drawer of a washing machine, elsewhere in the delivery system or in the drum of the washing machine. When used in the drum of the washing machine the carrier can be freely moving or fixed relative to the drum. Such fixing can be achieved by mechanical means, for example by barbs that interact with the drum wall, or employ other forces, for example a magnetic force.
  • the wash additive can be presented in a form that is dispersed and preferably is soluble in the wash liquor.
  • the additive can take any of the physical forms used for wash additives, including powder, granule, pellet, sheet, tablet, block, bar or other such solid form or take the form of a paste, gel or liquid. Dosage of the additive can be unitary or in a quantity determined by the user. While it is envisaged that such additives can be used in the main washing cycle, the use of them in the conditioning or drying cycle is not hereby excluded.
  • the present invention is not limited to those circumstances in which a washing machine is employed, but can be applied where washing is performed in some alternative vessel.
  • the complex in the wash additive can be delivered by means of slow release from the bowl, bucket or other vessel which is being employed, or from any implement which is being employed, such as a brush, bat or dolly, or from any suitable applicator.
  • the present invention also extends to a commercial package comprising a ligand or complex as together with instructions for its use.
  • the present invention also extends to use of a ligand or complex in the manufacture of a wash additive.
  • 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(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 1- -alkyl, -F, -Cl, -Br or -I;
  • 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 ⁇ - 4 -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 o -C 2 o-alkyl, halo-C o -C 2 o- alkyl, nitroso, formyl-C 0 -C 2 o-alkyl , carboxyl-C 0 -C 2 o-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-Co-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 -C 0
  • 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 group U in formula (IA) represents a coordinating group of the general formula (IVA) :
  • the ligand is selected from:
  • Q3 Q and Q 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;
  • 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 R ⁇ 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,
  • R i; R 2 R 3 , R 4 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 , R3, 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 l f R 2 , R3, R 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 1 , Q 2 , Q3, 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 -Co-alkyl , halo-C o -C 2 o- alkyl, nitroso, formyl -C 0 -C 2 o-alkyl, carboxyl-C 0 -C 2 o-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-Co-C 8 -alkyl , carbonyl-C o
  • the ligand is of the general formula (IIB) :
  • R x , R 2 , R3, 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.
  • Ri, R , R3, R 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 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 ⁇ -10 optionally substituted alkyl, C ⁇ - 5 -furanyl , C ⁇ -5 optionally substituted benzylalkyl, benzyl, C 1 - 5 optionally substituted alkoxy, and C ⁇ -2 o optionally substituted N + Me 3 .
  • Ri 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; and
  • R C ⁇ _ 8 -alkyl
  • Ri 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 ⁇ - 5 - furanyl , C ⁇ - 5 optionally substituted benzylalkyl, benzyl, C ⁇ - 5 optionally substituted alkoxy, and C ⁇ -o optionally substituted N + Me 3 .
  • N-methyl-N,N' ,N' -tris (5-ethyl-pyridin-2 -ylmethyl) - ethylenediamine ; N-methyl-N,N' ,N' -tris (5-methyl-pyridin-2-ylmethyl) - ethylenediamine ; N-methyl-N,N' ,N' -tris (3 -methyl-pyridin-2-ylmethyl) - ethylenediamine ;
  • N-benzyl-N,N' ,N' -tris (3-methyl-pyridin-2-ylmethyl) - ethylenediamine
  • N-ethyl-N,N' ,N' -tris (3 -methyl-pyridin-2-ylmethyl) - ethylenediamine
  • 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-benzyl-N,N' ,N' -tris (5-ethyl-pyridin-2-ylmethyl) ethylene- 1, 2-diamine; and N- (2-methoxyethyl) -N,N' ,N' -tris (5-ethyl-pyridin-2- ylmethyl) ethylene- 1, 2-diamine .
  • More preferred ligands are:
  • N-methyl-N,N' ,N' -tris (3-methyl-pyridin-2 -ylmethyl) ethylene- 1, 2-diamine
  • N-ethyl-N,N' ,N' -tris (3 -methyl-pyridin-2-ylmethyl) ethylene- 1, 2-diamine
  • Zi, 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;
  • 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(O)-, 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.
  • Zi, 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 .
  • Zi, Z 2 and Z 3 each represent optionally substituted pyridin-2 -yl .
  • Optional substituents for the groups Zi, Z 2 and Z 3 are preferably selected from C ⁇ - 4 -alkyl, aryl, arylalkyl, heteroaryl, methoxy, hydroxy, nitro, amino, carboxyl, halo, and carbonyl , preferably methyl .
  • each Q 1# 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 2 o-alkyl, halo-C 0 -Co- alkyl, nitroso, formyl-C 0 -C 2 o-alkyl , carboxyl-C 0 -C 2 o-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 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 C2-3- alkylene optionally substituted by H, benzyl or C ⁇ -8 -alkyl;
  • Q ⁇ # Q2 and Q 3 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; 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 ⁇ -4 -alkyl, -F, -Cl, -Br or -I, provided that at least one, preferably at least two, of Ri, R 2 and R 3 is a coordinating group.
  • At least two, and preferably at least three, of Ri, 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 , 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 .
  • substituents for groups R lf 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 Qi, 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 - CH2CH2CH2-.
  • the groups R5, R6 , R7 , R8 preferably independently represent a group selected from -H, hydroxy-C 0 -C 2o -alkyl, halo-C 0 -C 2 o- alkyl, nitroso, formyl-C 0 -C 2o -alkyl , carboxyl-C 0 -C 2 o-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-Co-C 2 o-alkyl, aryl-C 0 -C 2 o-alkyl, C o -C 2 o-alky
  • the ligand is of the general formula (IID) :
  • Rl , R2 , R3 are as defined previously for R i# R 2 , R 3 , and Qi, Q 2 , Q 3 are as defined previously.
  • Preferred classes of ligands according to this preferred aspect are as follows :
  • Rl, 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 .
  • Rl, 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 .
  • Rl , 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 Rl, R2 , R3 represents a group selected from hydrogen, C ⁇ - ⁇ 0 optionally substituted alkyl, C ⁇ -5 -furanyl , C ⁇ -5 optionally substituted benzylalkyl, benzyl, C ⁇ -5 optionally substituted alkoxy, and C ⁇ - 2 o optionally substituted N + Me 3 .
  • the ligand is selected from:
  • QI 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) - (QI) r -] - group is independently defined;
  • Rl, 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 ⁇ -4 -alkyl, -F, -Cl, -Br or -I; or one of R1-R9 is a bridging group bound to another moiety
  • 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-C20- lkyl, halo-C 0 -C 2 o-alkyl , nitroso, formyl- Co-C 2 o-alkyl, carboxyl-C 0 -C 2 o-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 2 o-alkyl, amino-C 0 - C 2 o-alkyl, aryl-C 0 -C 2 o-alkyl , heteroaryl-C 0 -C 2 o-alkyl , C 0 -C 2 o- alkyl, alkoxy-C 0 -C 8 -alkyl, carbonyl-C 0
  • 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 QI , 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.
  • Rl , 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 .
  • Rl, 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 2o -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 Rl 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:
  • Rl , 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 , pyrimidinyl, 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.
  • 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.
  • 2-amino-ethyl containing 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:
  • N4Py N,N-bis (pyridin-2 -yl -methyl) -bis (pyridin-2 -yl) methylamine
  • MeN4Py N,N-bis (pyridin-2-yl-methyl) -1, 1-bis (pyridin-2 -yl) -1- aminoethane
  • BzN4Py N,N-bis (pyridin-2 -yl -methyl) -1, 1-bis (pyridin-2 -yl) -2-phenyl - 1-aminoethane, hereafter referred to as BzN4Py.
  • the ligand represents a pentadentate or hexadentate ligand of general formula (VE) : R ⁇ N-W-NR ⁇ 2
  • 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 -CH2CH2-, -CH 2 CH 2 CH 2 -, -CH2CH2CH2CH2-, -CH 2 -C 6 H 4 -CH 2 -, -CH 2 -C 6 H ⁇ 0 - CH 2 -, and -CH2-C10H6-CH2- ; 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 CH2-, -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 ⁇ 0 H 6 -CH 2 - (wherein -C 6 H 4 -, -C 6 H 10 -, -C ⁇ 0 H 6 - can be ortho- , para- , or meta-C 6 H 4 -, -C 6 H ⁇ 0 -, -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.
  • the counter ions 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 “ , C10 “ , 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 RC00 “ , C10 4 “ , BF 4 “ , PF 6 “ , RSO3 “ (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 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.
  • both of the wash additive and the wash liquor may be 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.
  • the wash additive 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 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; (ii) 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;
  • 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.
  • MPS potassium monopersulphate
  • 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.
  • the wash additive 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 that 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: 2- (N,N,N-trimethyl ammonium) ethyl sodium-4 -sulphophenyl carbonate chloride - (SPCC) ;
  • 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.
  • 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-amides; 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 wash additive composition.
  • the method of the present invention has particular application 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 wash additive may also include a surface- active material, optionally together with detergency builder.
  • the wash additive 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 ⁇ 8 ) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (Cg- C 2 o) benzene sulphonates, particularly sodium linear secondary alkyl (C ⁇ 0 -C 15 ) 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 of
  • the preferred anionic detergent compounds are sodium (C ⁇ 0 -C ⁇ 5 ) alkylbenzene sulphonates, and sodium (C ⁇ 6 -C ⁇ 8 ) alkyl ether sulphates .
  • suitable 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 3 -C2) 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 .
  • 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 wash additive will preferably comprise from 1 to 15 % wt of anionic surfactant and from 10 to 40 % by weight of nonionic surf ctant.
  • the detergent active system is free from C ⁇ 6 -C 12 fatty acid soaps.
  • the wash additive 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,
  • precipitating builder materials examples 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.
  • 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 wash additive 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 wash additive 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 wash additive 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 was additive containing the catalyst is preferably substantially, and more preferably completely, devoid of transition metal sequestrants (other than the catalyst ligand) .
  • generic groups have been used, for example alkyl, alkoxy, aryl. Unless otherwise specified the following are preferred group restrictions that may be applied to generic groups found within compounds disclosed herein:
  • alkyl Cl-C6-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-propylene; 1 , 2-propylene;
  • aryl selected from homoaromatic compounds having a molecular weight under 300
  • arylene selected from the group consisting of: 1,2- benzene; 1,3 -benzene; 1,4-benzene; 1 , 2 -naphthalene; 1,3- naphthalene; 1, 4 -naphthalene; 2, 3 -naphthalene; phenol-2,3 - diyl; phenol -2 , 4-diyl; phenol-2 , 5-diyl ; and phenol -2, -6- diyl ,
  • heteroaryl selected from the group consisting of: pyridinyl; pyrimidinyl ; pyrazinyl; triazolyl, pyridazinyl; 1 , 3 , 5-triazinyl ; quinolinyl; isoquinolinyl ; quinoxalinyl ; imidazolyl; pyrazolyl; benzimidazolyl ; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl,
  • heteroarylene selected from the group consisting of 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-1,3- diyl ; pyrazol -3 , 5-diyl ; triazole-3 , 5-diyl ; triazole-1 , 3- diyl ; pyrazin-2 , 5-diyl ; and imidazole-2 , 4-diyl , heterocycloalkyl: selected from the group
  • amine the group -N(R) 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, halogen: selected from the group consisting of: F; Cl ; Br and I,
  • R is selected from: hydrogen; C1-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca,
  • R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5 ; Li; Na; K; Cs; Mg; and Ca,
  • sulphone the group -S(0) 2 R, wherein R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5 and amine (to give sulphonamide) selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen;
  • 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 ; M ; and Ca,
  • carbonyl derivative the group -C(0)R, wherein R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-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 Cl-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,
  • phosphonate the group -P(0) (OR) 2 , wherein 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 (0) (0R) 2 , wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs ; Mg; and Ca,
  • 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; Cl-C6-alkyl ; C1-C6- alkyl-C6H5; and phenyl, wherein when both R 1 are Cl-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 C1-C4 -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 ; and 1,4- butylene,
  • aryl selected from group consisting of: phenyl; biphenyl , naphthalenyl; anthracenyl ; and phenanthrenyl ,
  • arylene selected from the group consisting of: 1,2- benzene, 1,3 -benzene, 1,4 -benzene, 1, 2 -naphthalene, 1,4- naphthalene, 2 , 3 -naphthalene and phenol-2 , 6-diyl ,
  • heteroaryl selected from the group consisting of: pyridinyl; pyrimidinyl ; quinolinyl; pyrazolyl; triazolyl; isoquinolinyl ; imidazolyl ; and oxazolidinyl,
  • 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 ; and piperazinyl, amine: the group -N(R) 2 wherein 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,
  • sulphate the group -OS (O) 2 OR, wherein R is selected from: hydrogen; Cl-C6-alkyl; Na; K; Mg; and Ca,
  • sulphone 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 1 is independently selected from-, hydrogen; C1-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 .
  • each R is independently selected from: hydrogen; Cl-C6-alkyl, benzyl; Na; K; Mg; and Ca
  • phosphate the group -OP(O) (0R) 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 .
  • FeMeN4Py was obtained according to the procedure found in EP-A-0909809 A.
  • the change in colour was measured after leaving the cloths for 24 h in the dark with an Ultrascan XE spectrophotometer (ex Hunterlab) .
  • the change in colour (including bleaching) is expressed as the ⁇ E aw value relative to clean white cotton.
  • the measured colour difference ( ⁇ E aw ) between the washed cloth and the clean white cotton cloth is defined as follows :
  • ⁇ 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

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  • 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)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un procédé de blanchiment pour textiles tachés. Ce procédé consiste à laver un textile taché dans une lessive aqueuse en présence d'un additif de lavage comprenant un ligand qui forme un complexe de métal de transition agissant comme catalyseur de blanchiment. Ce complexe catalyse le blanchiment des taches par l'oxygène atmosphérique. L'additif de lavage comprend de préférence un complexe de fer contenant le ligand N, N-bis (pyridin-2-yl-méhyle)-1,1-bis(pyridin-2-yl)-1-aminoéthane. L'additif de lavage ou/et la lessive sont sensiblement exempts d'agents de blanchiment peroxygéné ou de systèmes à base de peroxy ou générant du peroxy. Cet additif de lavage permet un blanchiment amélioré ou couvrant un profil de taches plus étendu.
PCT/EP2000/007563 1999-09-01 2000-08-04 Blanchiment de textiles taches WO2001016269A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR0013592-5A BR0013592A (pt) 1999-09-01 1999-09-01 Embalagem comercial para alvejar manchas de tecido em um licor de lavagem aquoso, e, uso da mesma
CA002382115A CA2382115A1 (fr) 1999-09-01 2000-08-04 Blanchiment de textiles taches
EP00960390A EP1208187A1 (fr) 1999-09-01 2000-08-04 Blanchiment de textiles taches
AU72720/00A AU7272000A (en) 1999-09-01 2000-08-04 Method of bleaching stained fabrics

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
PCT/GB1999/002878 WO2000012808A1 (fr) 1998-09-01 1999-09-01 Procede de traitement d'un textile
GBPCT/GB99/02878 1999-09-01
GB0004847.0 2000-02-29
GBGB0004847.0A GB0004847D0 (en) 2000-02-29 2000-02-29 Method of bleaching stained fabrics

Publications (1)

Publication Number Publication Date
WO2001016269A1 true WO2001016269A1 (fr) 2001-03-08

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CN (1) CN1384870A (fr)
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WO (1) WO2001016269A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001046364A2 (fr) * 1999-12-22 2001-06-28 Unilever Plc Technique d'apport d'ameliorant
WO2002081613A1 (fr) * 2001-04-06 2002-10-17 Unilever Plc Composition de blanchiment et procede de blanchiment d'un substrat
US6586384B2 (en) 1999-12-22 2003-07-01 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Method of treating fabrics and apparatus used therein
US6991489B2 (en) 2003-03-19 2006-01-31 Benq Corporation Connection device
US7041793B2 (en) 1999-12-22 2006-05-09 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Detergent compositions comprising benefit agents

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103194894A (zh) * 2011-11-24 2013-07-10 东华大学 四吡啶基五氮金属配合物在纺织品低温练漂助剂中的应用
CN108948050B (zh) * 2018-06-29 2020-11-03 浙江理工大学 一种金属配合物及其制备方法和一种漂白工作液

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4532063A (en) * 1983-08-15 1985-07-30 S. C. Johnson & Son, Inc. Dissolvable bleach sheet
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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4532063A (en) * 1983-08-15 1985-07-30 S. C. Johnson & Son, Inc. Dissolvable bleach sheet
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 (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001046364A2 (fr) * 1999-12-22 2001-06-28 Unilever Plc Technique d'apport d'ameliorant
WO2001046364A3 (fr) * 1999-12-22 2002-06-20 Unilever Plc Technique d'apport d'ameliorant
US6586384B2 (en) 1999-12-22 2003-07-01 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Method of treating fabrics and apparatus used therein
US7041793B2 (en) 1999-12-22 2006-05-09 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Detergent compositions comprising benefit agents
WO2002081613A1 (fr) * 2001-04-06 2002-10-17 Unilever Plc Composition de blanchiment et procede de blanchiment d'un substrat
US6991489B2 (en) 2003-03-19 2006-01-31 Benq Corporation Connection device

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EP1208187A1 (fr) 2002-05-29
CN1384870A (zh) 2002-12-11
CA2382115A1 (fr) 2001-03-08
AU7272000A (en) 2001-03-26

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