WO2001016261A2 - Composition et procede de blanchiment d'un substrat - Google Patents

Composition et procede de blanchiment d'un substrat Download PDF

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Publication number
WO2001016261A2
WO2001016261A2 PCT/EP2000/008078 EP0008078W WO0116261A2 WO 2001016261 A2 WO2001016261 A2 WO 2001016261A2 EP 0008078 W EP0008078 W EP 0008078W WO 0116261 A2 WO0116261 A2 WO 0116261A2
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WO
WIPO (PCT)
Prior art keywords
alkyl
ligand
bleaching
complex
composition according
Prior art date
Application number
PCT/EP2000/008078
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English (en)
Other versions
WO2001016261A3 (fr
Inventor
Riccardo Filippo Carina
Stephen Paul Fox
Robertus Everardus Kalmeijer
Kenneth Daniel Karlin
Rob Thijssen
Robin Stefan Twisker
Original Assignee
Unilever Plc
Unilever Nv
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 claimed from PCT/GB1999/002878 external-priority patent/WO2000012808A1/fr
Priority claimed from PCT/GB1999/002876 external-priority patent/WO2000012667A1/fr
Priority claimed from GB0006961A external-priority patent/GB0006961D0/en
Application filed by Unilever Plc, Unilever Nv, Hindustan Lever Limited filed Critical Unilever Plc
Priority to CA002383935A priority Critical patent/CA2383935A1/fr
Priority to AU65716/00A priority patent/AU6571600A/en
Priority to BR0013737-5A priority patent/BR0013737A/pt
Priority to EP00953179A priority patent/EP1208185A2/fr
Publication of WO2001016261A2 publication Critical patent/WO2001016261A2/fr
Publication of WO2001016261A3 publication Critical patent/WO2001016261A3/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

Definitions

  • This invention relates to compositions and methods for catalytically bleaching substrates with atmospheric oxygen, more particularly using a defined class of ligand or complex as catalyst, and further relates to ligands and complexes useful m such compositions and methods.
  • This invention also relates to a method of treating textiles, such as laundry fabrics, using the defined class of ligand or complex as catalyst, more specifically to a method whereby bleaching by atmospheric oxygen is catalysed after the treatment.
  • Peroxygen bleaches are well known for their ability to remove stains from substrates.
  • the substrate is subjected to hydrogen peroxide, or to substances which can generate hydroperoxyl radicals, such as inorganic or organic peroxides.
  • these systems must be activated.
  • One method of activation is to employ wash temperatures of 60 °C or higher. However, these high temperatures often lead to inefficient cleaning, and can also cause premature damage to the substrate.
  • a preferred approach to generating hydroperoxyl bleach radicals is the use of inorganic peroxides coupled with organic precursor compounds. These systems are employed for many commercial laundry powders. For example, various European systems are based on tetraacetyl ethylenediamme (TAED) as the organic precursor coupled with sodium perborate or sodium percarbonate, whereas in the United States laundry bleach products are typically based on sodium nonanoyloxybenzenesulfonate (SNOBS) as the organic precursor coupled with sodium perborate.
  • TAED tetraacetyl ethylenediamme
  • SNOBS sodium nonanoyloxybenzenesulfonate
  • Precursor systems are generally effective but still exhibit several disadvantages. For example, organic precursors are moderately sophisticated molecules requiring multi-step manufacturing processes resulting m high capital costs. Also, precursor systems have large formulation space requirements so that a significant proportion of a laundry powder must be devoted to the bleach components, leaving less room for other active ingredients and complicating the development of concentrated powders. Moreover, precursor systems do not bleach very efficiently m countries where consumers have wash habits entailing low dosage, short wash times, cold temperatures and low wash liquor to substrate ratios .
  • hydrogen peroxide and peroxy systems can be activated by bleach catalysts, such as by complexes of iron and the ligand N4Py (i.e. N, N- bis (pyr ⁇ dm-2 -yl-methyl) -bis (pyr ⁇ dm-2-yl) methylamme) disclosed m 095/34628, or the ligand Tpen ( i . e . N, N, N' , N' -tetra (pyr ⁇ dm-2 -yl-methyl) ethylenediamme) disclosed m W097/48787.
  • molecular oxygen may be used as the oxidant as an alternative to peroxide generating systems.
  • aldehydes A broad range of aliphatic, aromatic and heterocyclic aldehydes is reported to be useful, particularly para-substituted aldehydes such as 4-methyl-, 4 -ethyl- and 4 -isopropyl benzaldehyde, whereas the range of initiators disclosed includes N-hydroxysuccmimide, various peroxides and transition metal coordination complexes.
  • the aldehyde component and radical initiators such as peroxides are consumed during the bleachmg process .
  • These components must therefore be included m the composition m relatively high amounts so as not to become depleted before completion of the bleachmg process the wash cycle.
  • the spent components represent a waste of resources as they can no longer participate m the bleachmg process.
  • the present invention provides a bleaching composition comprising, m an aqueous medium, atmospheric oxygen and a ligand which forms a complex with a transition metal, the complex catalysing bleaching of a substrate by the atmospheric oxygen, wherein the aqueous medium is substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system.
  • the medium is therefore preferably insensitive or stable to catalase, which acts on peroxy species.
  • the present invention provides a method of bleaching a substrate comprising applying to the substrate, m an aqueous medium, a ligand which forms a complex with a transition metal, the complex catalysing bleaching of the substrate by atmospheric oxygen.
  • the present invention provides the use of a ligand which forms a complex with a transition metal as a catalytic bleaching agent for a substrate m an aqueous medium substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system, the complex catalysing bleaching of the substrate by the atmospheric oxygen.
  • the present invention provides a method of treating a textile by contacting the textile with a ligand which forms a complex with a transition metal, whereby the complex catalyses bleaching of the textile by atmospheric oxygen after the treatment.
  • the present invention provides a dry textile havmg a ligand as defined above applied or deposited thereon, whereby bleaching by atmospheric oxygen is catalysed on the textile.
  • the present invention provides ligands and complexes, as defined further below.
  • the method according to the present invention permits all or the majority of the bleaching species m the medium (on an equivalent weight basis) to be derived from atmospheric oxygen.
  • the medium can be made wholly or substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system.
  • the complex is a catalyst for the bleaching process and, as such, is not consumed but can continue to participate the bleaching process.
  • the catalytically activated bleaching system of the type m accordance with the present invention which is based on atmospheric oxygen, is therefore both cost-effective and environmentally friendly.
  • the bleachmg system is operable under unfavourable wash conditions which include low temperatures, short contact times and low dosage requirements.
  • the method is effective an aqueous medium and is therefore particularly applicable to bleaching of laundry fabrics. Therefore, whilst the composition and method according to the present invention may be used for bleaching any suitable substrate, the preferred substrate is a laundry fabric.
  • the bleaching method may be carried out by simply leaving the substrate m contact with the medium for a sufficient period of time. Preferably, however, the aqueous medium on or containing the substrate is agitated.
  • An advantage of the method according to the fourth aspect of the invention is that, by enabling a bleaching effect even after the textile has been treated, the benefits of bleaching can be prolonged on the textile. Furthermore, since a bleaching effect is conferred to the textile after the treatment, the treatment itself, such as a laundry wash cycle, may for example be shortened. Moreover, since a bleachmg effect is achieved by atmospheric oxygen after treatment of the textile, hydrogen peroxide or peroxy-based bleach systems can be omitted from the treatment substance.
  • the present invention also extends to a commercial package comprising a ligand or complex as defined below together with instructions for its use.
  • the present invention also extends to use of a ligand or complex as defined below m the manufacture of a bleaching composition, the bleaching composition substantially devoid of peroxygen bleach or a peroxy-based or peroxy-generatmg bleach system.
  • the ligand may be present as a preformed complex of a ligand and a transition metal.
  • the composition 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 composition may also be formulated as 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 ligand forms a complex of the general formula (Al) :
  • M represents a metal selected from Mn (II) - (III) - (IV) - (V), Cu(I) - (ID- (HI) , 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 selected from Fe (II) - (III) - (IV) - (V) ;
  • L represents a ligand as herein defined, 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, preferably selected from O 2" , RB0 2 2” , RCOO “ , RCONR “ , OH “ , N0 3 ⁇ NO, S 2" , RS “ , P0 4 3” , P0 3 OR 3 ⁇ , H 2 0, C0 3 2" , HC0 3 " , ROH, N(R) 3 , ROO “ , 0 2 2” , 0 2 " , RCN, Cl “ , Br “ , OCN “ , SCN “ , CN “ , N 3 ⁇ , F “ , I “ , RO “ , C10 “ , and CF3SO3 “ , and more preferably selected from O 2” , RB0 2 2” , RCOO “ , OH “ , N0 3 “ , S ⁇ , RS “
  • Y represents any non-coordinated counter ion, preferably selected from Cl0 4 " , BR 4 " , [MX 4 ] “ , [MX 4 ] 2" , PF 6 “ , RCOO “ , N0 3 “ , RO “ , N + (R) 4 , ROO “ , 0 2 2” , 0 2 “ , Cl “ , Br “ , F “ , I “ , CF 3 S0 3 “ , S 2 O e 2” , OCN “ , SCN “ , H 2 0, RB0 2 2” , BF 4 “ and BPh 4 " , and more preferably selected from C10 4 " , BR 4 “ , [FeCl 4 ] “ , PF 6 “ , RCOO “ , N0 3 “ , RO “ , N + (R) 4 , Cl “ , Br “ , F “ , I “ , CF 3 SO 3 “ , S 2 0 6 2”
  • the ligand L is of the general formula (I) :
  • 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 py ⁇ dme, py ⁇ midme, pyrazme, pyrazole, lmidazole, benzimidazole, qu olme, qumoxalme, triazole, isoqumolme, carbazole, mdole, isomdole, oxazole and thiazole;
  • Qi / C , 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 selecte 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 togethei 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.
  • Zi, Z 2 and Z 3 each represent a coordinating group, preferably selected from optionally substituted py ⁇ dm-2-yl , optionally substituted ⁇ m ⁇ dazol-2-yl , optionally substituted ⁇ m ⁇ dazol-4-yl , optionally substituted pyrazol-1-yl , and optionally substituted qumolm-2-yl .
  • Z 1; Z 2 and Z 3 each represent optionally substituted py ⁇ dm-2-yl.
  • Optional substituents for the groups Z X l Z 2 and Z 3 are preferably selected from C ⁇ -4 -alkyl, aryl, arylalkyl, heteroaryl, methoxy, hydroxy, nitro, ammo, carboxyl, halo, and carbonyl, preferably methyl.
  • the groups R5-R8 are preferably independently selected from -H, hydroxy-C 0 -C 20 -alkyl, halo-C 0 -C 20 -alkyl , nitroso, for yl- 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 2 o-alkyl and esters and salts thereof, sulfamoyl-C 0 -C 20 -alkyl , ammo-C 0 -C 20 -alkyl , aryl-C 0 -C 20 -alkyl, C 0 -C 2 o-alkyl , alkoxy-C 0 -C 8 -alkyl , carbonyl - C 0 -C 6 -alk
  • each Qi, Q 2 and Q 3 independently represent C ⁇ 4 - alkylene, more preferably a group selected from -CH 2 - and - CH 2 CH 2 -.
  • the ligand L is selected from tris (py ⁇ dm-2- ylmethyl ) am e , tris (3-methyl-pynd ⁇ n-2-ylmethyl) am e, t ⁇ s (5-methyl -py ⁇ dm-2 -ylmethyl) amme, tris (4 -t-butyl- pyridm-2 -ylmethyl) amme and tris (6-methyl-pyr ⁇ dm-2- ylmethyl) amme .
  • 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 amon 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 4 , PF 6 , RS0 3 (m 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 m a solvent mixture comprising a salt of the metal M and the ligand L or ligand L-generatmg species.
  • the catalyst may be formed in situ from suitable precursors for the complex, for example a solution or dispersion containing the precursor materials.
  • the active catalyst may be formed m si tu m a mixture comprising a salt of the metal M and the ligand L, or a ligand L-generatmg species, m a suitable solvent.
  • M is iron
  • an iron salt such as FeS0 4 can be mixed m solution with the ligand L, or a ligand L-generatmg species, to form the active complex.
  • the ligand L in another such example, can be mixed with metal M ions present m the substrate or wash liquor to form the active catalyst in si tu .
  • Suitable ligand L-generatmg 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 bleaching compositions according to the present invention may be used for laundry cleaning, hard surface cleaning (including cleaning of lavatories, kitchen work surfaces, floors, mechanical ware washing etc.) .
  • bleaching compositions are also employed m waste-water treatment, pulp bleaching during the manufacture of paper, leather manufacture, dye transfer inhibition, food processing, starch bleaching, sterilisation, whitening m oral hygiene preparations and/or contact lens disinfection.
  • bleaching should be understood as relating generally to the decolou ⁇ sation 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 bleachmg mechanism or process that does not require the presence of light or activation by light.
  • photobleachmg compositions and processes relying on the use of photobleach catalysts or photobleach activators and the presence of light are excluded from the present invention.
  • the level of the catalyst is such that the m-use level is from 0.05 ⁇ M to 50mM, with preferred m-use levels for domestic laundry operations falling m the range 0.5 ⁇ M to 100 ⁇ M, more preferably from 1 ⁇ M to 10 ⁇ M. Higher levels may be desired and applied m industrial bleaching processes, such as textile and paper pulp bleaching.
  • the aqueous medium has a pH m 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, m particular from pH 9 to 10.
  • the bleaching composition of the present invention has particular application detergent formulations, especially for laundry cleaning. Accordingly, m another preferred embodiment, the present invention provides a detergent bleach composition comprising a bleaching composition as defined above and additionally a surface-active material, optionally together with detergency builder.
  • the bleach composition according to the present invention may for example contain a surface-active material in an amount 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. Many suitable actives are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
  • Typical synthetic anionic surface-actives are usually water- soluble alkali metal salts of organic sulfates and sulfonates 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 sulfates, especially those obtained by sulfating higher (C 8 -C ⁇ 8 ) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (C 9 -
  • C 0 ) benzene sulfonates particularly sodium linear secondary alkyl (C 10 -C ⁇ 5 ) benzene sulfonates; sodium alkyl glyceryl ether sulfates, especially those ethers of the higher alcohols derived from tallow or coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium and ammonium salts of sulfuric acid esters of higher (C 9 -C 18 ) 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 methyl taurine; alkane monosulfonates such as those derived by reacting alpha- olefins (C 8 -C 20 ) with sodium bisulfite and those derived by reacting paraffins with S0 2 and Cl 2 and then hydrolys
  • nonionic surface-active compounds which may be used, preferably together with the anionic surface- active compounds, include, m 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 18 ) 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 18 ) 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 amme oxides, long-chain tertiary phosphme oxides and dialkyl sulfoxides .
  • Amphoteric or zwitterionic surface-active compounds can also be used m 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 m small amounts m compositions based on - It
  • the detergent bleach composition of the invention 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 16 -C 12 fatty acid soaps.
  • the bleach composition of the present invention may also contains a detergency builder, for example m 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; nitrilot ⁇ acetic acid and its water- soluble salts; the alkali metal salts of carboxymethyloxy succmic acid, ethylene diamme tetraacetic acid, oxydisuccmic acid, mellitic acid, benzene polycarboxylic acids, citric acid; and polyacetal carboxylates as disclosed m US-A-4, 144, 226 and US-A-4 , 146 , 495.
  • alkali metal polyphosphates such as sodium tripolyphosphate
  • the alkali metal salts of carboxymethyloxy succmic acid ethylene diamme tetraacetic acid, oxydisuccmic acid, mellitic acid, benzene polycarboxylic acids, citric acid
  • polyacetal carboxylates as disclosed m 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.
  • compositions of the invention 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 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 bleach composition of the present invention 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 phosphomc acid derivatives ( .e.
  • Dequest ® types fabric softening agents; inorganic salts and alkaline buffering agents, such as sodium sulfate and sodium silicate; and, usually m 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 phosphomc acid derivatives such as EDTMP (ethylene diamme tetra (methylene phosphonate) ) may also be included, m addition to the 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 composition according to the present invention containing the ligand is preferably substantially, and more preferably completely, devoid of transition metal sequestrants (other than the ligand) .
  • the present invention is based on the catalytic bleachmg of a substrate by atmospheric oxygen or air, it will be appreciated that small amounts of hydrogen peroxide or peroxy-based or -generating systems may be included m the composition, if desired. Therefore, by “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. Preferably, however, 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 bleachmg of the substrate is effected by oxygen sourced from the air.
  • the catalyst may be contacted to the textile fabric m any suitable manner.
  • it may be applied m dry form, such as in powder form, or m a liquor that is then dried, for example as an aqueous spray-on fabric treatment fluid or a wash liquor for laundry cleaning, or a non-aqueous dry cleaning fluid or spray-on aerosol fluid.
  • m dry form such as in powder form
  • m a liquor that is then dried
  • aqueous spray-on fabric treatment fluid or a wash liquor for laundry cleaning or a non-aqueous dry cleaning fluid or spray-on aerosol fluid.
  • Other suitable means of contacting the catalyst to the textile may be used, as further explained below.
  • any suitable textile that is susceptible to bleaching or one that one might wish to subject to bleachmg may be used.
  • the textile is a laundry fabric or garment.
  • the bleaching method of the fourth aspect may be carried out by simply leaving the substrate contact with the catalyst for a sufficient period of time.
  • the catalyst is m an aqueous medium, and the aqueous medium on or containing the substrate is agitated.
  • the treated textile is dried, by allowing it to dry under ambient temperature or at elevated temperatures .
  • the method according to the fourth aspect is carried out on a laundry fabric using aqueous treatment liquor.
  • the treatment may be effected in, or as an adjunct to, an essentially conventional wash cycle for cleaning laundry. More preferably, the treatment is carried out m an aqueous detergent wash liquor.
  • the catalyst can be delivered into the wash liquor from a powder, granule, pellet, tablet, block, bar or other such solid form.
  • the solid form can comprise 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 catalyst can be delivered into the wash liquor from a paste, gel or liquid concentrate.
  • the catalyst used m the method of the fourth aspect makes use of atmospheric oxygen in its bleaching activity. This avoids the requirement that peroxygen bleaches and/or other relatively large quantities of reactive substances need be used m the treatment process. Consequently, only a relatively small quantity of bleach active substance need be employed and this allows dosage routes to be exploited which could previously not be used.
  • a washing process such as a pre-treatment , main-wash, conditioning composition or ironing aid
  • other means for ensuring that the catalyst is present m the wash liquor may be envisaged.
  • the catalyst can be presented in the form of a body from which it 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.
  • the catalyst can be released from a carrier substrate used in association with the wash process, e.g. from a body placed m the dispenser drawer of a washing machine, elsewhere m the delivery system or 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 catalyst can be presented m the form of a wash additive that preferably is soluble.
  • 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 m a quantity determined by the user. While it is envisaged that such additives can be used m the mam washing cycle, the use of them m 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 m some alternative vessel.
  • the catalyst 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.
  • Suitable pre-treatment means for application of the catalyst to the textile material prior to the mam wash include sprays, pens, roller-ball devices, bars, soft solid applicator sticks and impregnated cloths or cloths containing microcapsules .
  • Such means are well known m the analogous art of deodorant application and/or m spot treatment of textiles. Similar means for application are employed m those embodiments where the catalyst is applied after the mam washing and/or conditioning steps have been performed, e.g. prior to or after ironing or drying of the cloth.
  • the catalyst may be applied using tapes, sheets or sticking plasters coated or impregnated with the substance, or containing microcapsules of the substance.
  • the catalyst may for example be incorporated into a drier sheet so as to be activated or released during a tumble-drier cycle, or the substance can be provided an impregnated or microcapsule-containing sheet so as to be delivered to the textile when ironed.
  • alkyl linear and branched Cl-C8-alkyl
  • alkenyl C2-C6-alkenyl
  • cycloalkyl C3 -C8 -cycloalkyl
  • alkoxy Cl-C6-alkoxy
  • alkylene selected from the group consisting of: methylene
  • 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 ; 1-hydroxy-2 , 3-phenylene; 1-hydroxy-2 , 4-phenylene; 1-hydroxy- 2 , 5-phenylene; and l-hydroxy-2 , 6 -phenylene,
  • heteroaryl selected from the group consisting of: pyridmyl; pyrimidmyl; pyrazmyl; triazolyl; pyridazmyl; 1 , 3 , 5-tr ⁇ azmyl ; qumolmyl; lsoquinolmyl ; qumoxalmyl ; lmidazolyl; pyrazolyl ; benzimidazolyl ; thiazolyl; oxazolidmyl ; pyrrolyl ; carbazolyl ; mdolyl ; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom m the ring of the selected heteroaryl,
  • heteroarylene selected from the group consisting of: pyrid diyl ; qumolmdiyl ; pyrazodiyl ; pyrazoldiyl ; t ⁇ azolediyl ; pyrazmdiyl ; and lmidazolediyl , wherein the heteroarylene acts as a bridge m the compound via any atom m the ring of the selected heteroarylene, more specifically preferred are: pyr ⁇ dm-2 , 3 -diyl ; pyr ⁇ dm-2 , 4-diyl ; py ⁇ dm- 2,5-d ⁇ yl; py ⁇ dm-2 , 6-d ⁇ yl ; py ⁇ dm-3 , 4-diyl ; pyndm-3,5- diyl ; qumolm-2 , 3-d ⁇ yl ; qumolm-2 , 4 -diyl ; qumolm-2, 8- diyl; isoqumolm-l ,
  • heterocycloalkyl selected from the group consisting of: pyrrol yl; pyrrolidmyl ; morphol yl; piperidmyl ; piperazmyl; hexamethylene lmme; 1 , 4-p ⁇ perazmyl ; tetrahydrothiophenyl ; tetrahydrofuranyl ; 1,4,7- t ⁇ azacyclononanyl ; 1,4,8, 11-tetraazacyclotetradecanyl ;
  • 1,4,7,10, 13-pentaazacyclopentadecanyl 1, 4-d ⁇ aza-7-th ⁇ a- cyclononanyl ; 1 , 4-d ⁇ aza-7-oxa-cyclononanyl ; 1,4,7,10- tetraazacyclododecanyl ; 1 , 4-d ⁇ oxanyl ; 1 , 4 , 7-tr ⁇ th ⁇ a- cyclononanyl ; tetrahydropyranyl ; and oxazolidinyl , 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-1, 2-ylene; piperidin-2 , 6-ylene; piperidin-4 , 4- ylidene; 1 , 4-piperazin-l , 4-ylene ; 1 , 4-piperazin-2 , 3-ylene; 1, 4-piperazin-2 , 5-ylene; 1 , 4-piperazin-2 , 6-ylene; 1,4- piperazin-1, 2-ylene; 1 , 4-piperazin-l , 3 -ylene; 1 , 4-piperazin- 1,4-ylene; tetrahydrothiophen-2 , 5-ylene ; tetrahydrothiophen- 3, 4 -ylene; tetrahydrothiophen-2 , 3 -ylene ; tetrahydrofuran- 2, 5-ylene; tetrahydrofuran-3 , 4-ylene; tetrahydrofuran-2 , 3- ylene; pyrrolidin-2 , 5-ylene
  • 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,
  • 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 -0S(0) 2 0R, wherein R is selected from: hydrogen; C1-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 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,
  • 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 selec ed from: hydrogen; Cl-C6-alkyl ; phenyl; Cl-C6-alkyl- C6H5 and amme (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 chair, forming an alkyl substituent to the heterocyclic ring,
  • phosphonate the group -P(O) (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) (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
  • 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' 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 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-d ⁇ yl
  • 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 1-hydroxy-2 , 6- phenylene,
  • heteroaryl selected from the group consisting of: pyridmyl; pyrimidmyl; qumolmyl; pyrazolyl; triazolyl; lsoqumolmyl ; lmidazolyl; and oxazolidmyl , wherein the heteroaryl may be connected to the compound via any atom m the ring of the selected heteroaryl,
  • heteroarylene selected from the group consisting of: py ⁇ dm-2 , 3-d ⁇ yl; pyr ⁇ dm-2 , 4-diyl ; pyr ⁇ dm-2 , 6-d ⁇ yl ; pyr ⁇ dm-3 , 5-d ⁇ yl ; qumolm-2 , 3 -diyl ; qumolm-2 , 4 -diyl ; isoqumolm-l, 3 -diyl ; isoqumolm-l , 4-diyl ; pyrazol-3,5- diyl; and ⁇ m ⁇ dazole-2 , 4-diyl ,
  • heterocycloalkyl selected from the group consisting of: pyrrol ldmyl ; morpholmyl ; pipe ⁇ dmyl ; piper ldmyl ; 1,4- piperazmyl; tetrahydrof uranyl ; 1 , 4 , 7-tr ⁇ azacyclononanyl ; 1, 4 , 8, 11-tetraazacyclotetradecanyl; 1,4,7,10,13- pentaazacyclopentadecanyl ; 1,4,7, 10-tetraazacyclododecanyl ; and piperazmyl, wherein the heterocycloalkyl may be connected to the compound via any atom m the ring of the selected heterocycloalkyl, heterocycloalkylene : selected from the group consisting of: p ⁇ peridin-2 , 6-ylene ; piperidin-4 , 4 -ylidene ; 1,4- piperazin-1, 4-ylene; 1 , 4-piperazin-2 ,
  • amme 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
  • sulfonate the group -S(0) 2 OR, wherein R is selected from: hydrogen; Cl-C6-alkyl; Na; K; Mg; and Ca,
  • sulfate the group -OS(0) 2 OR, wherein R is selected from: hydrogen; Cl-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; C1-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 (0) (0R) 2 , wherein each R is independently selected from: hydrogen; Cl-C6-alkyl ; benzyl; Na; K; Mg; and Ca,
  • phosphate the group -OP (0) (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 amme selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl .
  • Compound 1-7 were tested for catalytic bleaching activity using air.
  • Tris (3-methyl-pyridm-2 -ylmethyl) amme and Tris (5-methyl- pyridm-2 -ylmethyl) amme were synthesised according to the literature (E.C. Wilkinson, et al . , J. Am. Chem. Soc . , 120, 955 (1998) and
  • Tris [ ( (4 - t -butyl ) -pyridm -2 -yl ) methyl] amme To a stirred solution of 2 -am omethyl -4 -t-butyl-pyridine • 2HC1 (1.18 g, 5.0 mmol) m water (10 ml), 2.35 g (10 mmol) of 2- chloromethyl-4-t-butyl-pyr ⁇ dme was added. A solution of NaOH (1.2 g, 30 mmol) m 4 ml of water was added at 0 °C. The reaction mixture was allowed to stir at room temperature for 12 hrs (whereupon the pH of the solution dropped to 7.0) .
  • ⁇ E [( ⁇ L) 2 +( ⁇ a) 2 +( ⁇ b) 2 ] 1/2
  • ⁇ L is a measure for the difference in darkness between the washed and unwashed test cloth; ⁇ a and ⁇ b are measures for the difference in redness and yellowness respectively between both cloths.
  • CIE Commission International de 1 'Eclairage

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Abstract

L'invention se rapporte au blanchiment catalytique de substrats, notamment de tissus pour blanchissage, avec de l'oxygène atmosphérique ou de l'air. L'invention concerne un procédé de blanchiment d'un substrat, qui consiste à appliquer sur le substrat, dans un milieu aqueux, un ligand spécifié d'une classe sélectionnée, qui forme avec un métal de transition un complexe utilisant l'oxygène atmosphérique pour catalyser le blanchiment du substrat. Elle concerne également une composition de blanchiment aqueuse sensiblement dépourvue d'agent de blanchiment peroxygéné ou d'un système de blanchiment à base de peroxy ou générateur de peroxy. L'invention concerne en outre un procédé de traitement d'un textile, tel qu'un tissu pour blanchissage, qui met en oeuvre un complexe utilisant l'oxygène atmosphérique pour catalyser le blanchiment du textile après traitement. Le catalyseur peut être utilisé sous forme de poudre ou dans une liqueur qui est ensuite séchée, telle qu'un fluide aqueux d'apprêt thermique applicable par pulvérisation, ou une liqueur de lavage pour blanchisserie, ou un fluide non aqueux de nettoyage à sec, ou encore un fluide aérosol applicable par pulvérisation. Le procédé peut conférer des qualités de lavage au textile après traitement. L'invention concerne enfin un textile sec sur lequel un catalyseur est appliqué ou déposé, et dont le blanchiment est catalysé avec de l'oxygène atmosphérique.
PCT/EP2000/008078 1999-09-01 2000-08-16 Composition et procede de blanchiment d'un substrat WO2001016261A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA002383935A CA2383935A1 (fr) 1999-09-01 2000-08-16 Composition et procede de blanchiment d'un substrat
AU65716/00A AU6571600A (en) 1999-09-01 2000-08-16 Composition and method for bleaching a substrate
BR0013737-5A BR0013737A (pt) 1999-09-01 2000-08-16 Composição alvejante, processos de alvejamento de um substrato e de tratamento de um têxtil, uso de um ligando que forma um complexo com um metal de transição, ligando, e, complexo
EP00953179A EP1208185A2 (fr) 1999-09-01 2000-08-16 Composition et procede de blanchiment d'un substrat

Applications Claiming Priority (6)

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/GB99/02876 1999-09-01
GBPCT/GB99/02878 1999-09-01
PCT/GB1999/002876 WO2000012667A1 (fr) 1998-09-01 1999-09-01 Composition et procede de blanchiment d'un substrat
GB0006961.7 2000-03-22
GB0006961A GB0006961D0 (en) 2000-03-22 2000-03-22 Composition and method for bleaching a substrate

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WO2001016261A3 WO2001016261A3 (fr) 2001-08-30

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
WO2002081613A1 (fr) * 2001-04-06 2002-10-17 Unilever Plc Composition de blanchiment et procede de blanchiment d'un substrat
WO2003104377A1 (fr) * 2002-06-06 2003-12-18 Unilever N.V. Perfectionnements apportes a des catalyseurs de blanchiment
WO2004111174A1 (fr) * 2003-06-09 2004-12-23 Unilever Plc Composition de blanchiment
WO2009013313A1 (fr) * 2007-07-23 2009-01-29 Henkel Ag & Co. Kgaa Dégradation du cot dans des eaux usées par des catalyseurs à métal de transition

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Publication number Priority date Publication date Assignee Title
WO1997048710A1 (fr) * 1996-06-21 1997-12-24 Regents Of The University Of Minnesota Complexes de fer destines a accelerer le blanchiment et utilises dans l'oxydation stereospecifique
DE19721886A1 (de) * 1997-05-26 1998-12-03 Henkel Kgaa Bleichsystem
WO2000029537A1 (fr) * 1998-11-13 2000-05-25 The Procter & Gamble Company Compositions de blanchiment

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
WO1997048710A1 (fr) * 1996-06-21 1997-12-24 Regents Of The University Of Minnesota Complexes de fer destines a accelerer le blanchiment et utilises dans l'oxydation stereospecifique
DE19721886A1 (de) * 1997-05-26 1998-12-03 Henkel Kgaa Bleichsystem
WO2000029537A1 (fr) * 1998-11-13 2000-05-25 The Procter & Gamble Company Compositions de blanchiment

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Title
DONG Y ET AL: "A HIGH-VALENT NONHEME IRON INTERMEDIATE. STRUCTURE AND PROPERTIES OF (Fe2(MU-O)2(5-Me-TPA)2)(ClO4)3" JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,US,AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC, vol. 117, 1995, pages 2778-2792, XP002040679 ISSN: 0002-7863 cited in the application *
ZANG Y ET AL: "MODELS FOR NONHEME IRON INTERMEDIATES: STRUCTURAL BASIS FOR TUNING THE SPIN STATES OF Fe(TPA) COMPLEXES" JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,US,AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC, vol. 119, 7 May 1997 (1997-05-07), pages 4197-4205, XP002040680 ISSN: 0002-7863 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002081613A1 (fr) * 2001-04-06 2002-10-17 Unilever Plc Composition de blanchiment et procede de blanchiment d'un substrat
WO2003104377A1 (fr) * 2002-06-06 2003-12-18 Unilever N.V. Perfectionnements apportes a des catalyseurs de blanchiment
WO2004111174A1 (fr) * 2003-06-09 2004-12-23 Unilever Plc Composition de blanchiment
WO2009013313A1 (fr) * 2007-07-23 2009-01-29 Henkel Ag & Co. Kgaa Dégradation du cot dans des eaux usées par des catalyseurs à métal de transition

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BR0013737A (pt) 2002-06-04

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