WO2003014280A1 - Compositions de blanchiment - Google Patents

Compositions de blanchiment Download PDF

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Publication number
WO2003014280A1
WO2003014280A1 PCT/EP2002/008538 EP0208538W WO03014280A1 WO 2003014280 A1 WO2003014280 A1 WO 2003014280A1 EP 0208538 W EP0208538 W EP 0208538W WO 03014280 A1 WO03014280 A1 WO 03014280A1
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WIPO (PCT)
Prior art keywords
composition according
metal
group
ligand
enhancer
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PCT/EP2002/008538
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English (en)
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WO2003014280A8 (fr
Inventor
Peter Leslie Gratton
John Oakes
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Unilever Plc
Unilever Nv
Hindustan Lever Limited
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Publication of WO2003014280A1 publication Critical patent/WO2003014280A1/fr
Publication of WO2003014280A8 publication Critical patent/WO2003014280A8/fr

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Classifications

    • 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
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3481—Organic compounds containing sulfur containing sulfur in a heterocyclic ring, e.g. sultones or sulfolanes
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • 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

  • the present invention relates to the use of certain macrocyclic metal -ligand complexes as catalytic bleaching agents.
  • the invention will be particularly described with reference to bleaching in the context of fabric washing and laundry, although other and broader aspects of the invention are not intended to be excluded.
  • O-A-94/12619, WO-A-94/12620 and O-A-94/12621 disclose the use of simple substituted phenols, benzidine derivatives, phenothiazine derivatives and azino compounds as 'enhancers' for peroxidases and/or laccases.
  • O-A-97/06244 (Ciba) also discloses various enhancers, such as substituted naphthols, barbituric acids, and substituted coumarins .
  • Oxidation catalysts comprising non-enzyme (i.e. non-peptide) metal -complexes are also known. Such catalysts have been used in laundry compositions as components of a bleaching system. They have also been used in other chemical processes such as in the pulp and paper industry and in the cleaning of hard surfaces. These catalysts generally activate H 2 O 2 or other peroxygen sources in water, and are effective at neutral to basic pH, Some of these catalysts are even effective with oxygen itself as the source of oxidising equivalents.
  • a specific bleaching catalyst is disclosed in WO 98/03263, filed 21 July 1997, (Collins) .
  • This comprises a macrocyclic (tetra) amido N-donor.
  • the macrocycle is capable of complexing with a metal ion, for example an iron III or IV.
  • United States Patent 5,853,428, filed 24 Feb 1997, (Collins) discloses use of similar catalysts in laundry detergent compositions .
  • non-enzyme bleaching catalysts are of particular utility in the prevention of so-called 'dye transfer' in a laundry process. This occurs when dyestuffs are released from one region of a cloth article during laundering and are later re-adsorbed at another location or on another article. It is advantageous to bleach the dyestuff while it is in aqueous solution, thereby preventing or reducing its transfer.
  • a first aspect of the present invention provides a composition comprising:
  • a non-enzyme, metal -complexing ligand which is capable, in its complexed form and in the presence of a source of oxidising equivalents of oxidising dyestuffs and/or chromophoric soils, and,
  • compositions according to the present invention will comprise a ligand which is pre-complexed with a metal. While in some circumstances the conditions of use may be such that the environment is rich enough in a suitable metal, and the complex may form with sufficient ease to allow for metal-ligand formation in situ, it is preferable to provide the complex ab-initio.
  • the metal-ligand complex can form an activated species in the presence of oxidising equivalents. This activated species then interacts with the enhancer to form an activated species of enhancer. This activated species of enhancer can then interact with a dyestuff or another coloured material and bring about discolouration of that material .
  • the enhancers are nitrogen-containing organic molecules. More preferably, the enhancer compounds are of the general formula one, shown below:
  • Z 1 -Z 2 are electron-withdrawing groups, independently selected from the group consisting of optionally substituted alkyl/ (hetero) (poly)aryl-, -sulfone, -sulfoxide, - sulfonate, -carbonyl, -oxalyl, -amidoxalyl, -hydrazidoxalyl , -carboxyl and esters and salts thereof, -amidyl, - hydrazidyl, and nitrile.
  • Z 3 and Z 4 are hydrogen, or are absent when the bonding between Z or Z 2 and the adjacent nitrogen in the general form is a pi-bond.
  • azino enhancers are molecules of the general formula given below:
  • This molecule is known as 2 , 2 ' -Azino-bis (3 -ethyl - benzthiazoline-6-sulphonate) diammonium salt. Its CA registry number is 30931-67-0.
  • Preferred hydrazino enhancers may contain one or more than one of the hydrazino structures.
  • the general formulae of two particularly preferred enhancers are given below:
  • PTP phenothiazine-10-propionate
  • the activated enhancer is a relatively long-lived species, that its low molecular weight (as compared with the metal-ligand complex) promotes diffusion of the activated enhancer and that it will be effective in heterogeneous environments. It is also believed that the activated enhancer is effective at low pH's.
  • the bleach catalyst per se may be selected from a wide range of transition metal complexes of organic molecules.
  • Suitable organic molecules (ligands) for forming complexes and complexes thereof are found, for example in: GB 9906474.3; GB 9907714.1; GB 98309168.7, GB 98309169.5; GB 9027415.0 and GB 9907713.3; DE 19755493; EP 999050; WO-A-9534628; EP-A-458379; EP 0909809; United States Patent 4,728,455; WO-A-98/39098 ; WO-A-98/39406 , WO 9748787, WO 0029537; WO 0052124, and WO0060045 the complexes and organic molecule (ligand) precursors of which are herein incorporated by reference.
  • Preferred metal -complexed ligands are those having the structure as shown in general formula 2
  • B 3 and B 4 each represent a bridging group having zero, one two or three carbon containing nodes for substitution
  • B 2 represents a bridging group having at least one carbon containing node for substitution
  • each said node containing a C (R) , C(R ⁇ ) (R 2 ) or C (R) 2 / each R substituent is the same is the same or different from the remaining R substituents
  • (i) is selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl , aryl , alkynyl, alkylaryl, halogen, alkoxy, phenoxy and combinations thereof, or
  • M is a transition metal ion
  • Q is an alkali metal or tetra-alkyl ammonium or tetra- phenyl phosphonium counter-ion.
  • the axial ligand is selected from the group consisting of water and halide.
  • Particularly preferred axial ligands are water and chloride.
  • M is selected from the group consisting of Fe, Mn, Cr, Cu, Co, Ni, Mo, V, Zn and W.
  • complexes are of far lower molecular weight that enzymes and are consequently believed to be more weight efficient as regards activation of the enhancer.
  • complexes tend to be expensive to synthesise and consequently, their use in combination with a relatively inexpensive enhancer leads to a more cost effective system.
  • alkyl linear and branched Cl-C8-alkyl, preferably
  • alkenyl C2-C8 -alkenyl, preferably C3-C6; cycloalkyl : C3-C8 -cycloalkyl, preferably C6-C8; cycloalkenyl C4- 12 -cycloalkenyl (preferably C4-C8) having a single cyclic ring or multiple condensed rings and at least one point of internal unsaturation which can be optionally substituted with from 1 to 3 Cl-C8-alkyl groups ; aryl : selected from homoaromatic compounds having a molecular weight under 300, preferably selected from group consisting of: phenyl ; biphenyl; naphthalenyl ; anthracenyl ; and phenanthrenyl ; alkynyl C2-C12 -alkynyl; alkylaryl : Cl-12-alkylaryl , wherein the aryl selected from homoaromatic compounds having a molecular weight under
  • halogen selected from the group consisting of: F;
  • the present invention extends to fully formulated laundry products containing the catalysts and enhancers disclosed herein.
  • Such products will generally contain a detergent active and will typically contain one or more builders together with the typical additives used in detergent compositions.
  • the present invention also extends to a packaged laundry treatment composition comprising a bleach activator as defined together with an enhancer as defined, and instructions for its use.
  • compositions of the present invention will comprise a peroxygen source.
  • a preferred ligand is that described with reference to general formula 2.
  • Particularly preferred ligands of general formula 2 have R methyl.
  • B3 and B4 are preferably absent, the two related sides of the ring being derived from a 'classical' amino acid in which the amino group is located on the alpha- carbon.
  • a preferred starting amino acid is 2 -amino iso- butyric acid. (H 2 N-C (CH 3 ) 2 -COOH) .
  • the transition metal is preferably selected from groups VI, VII, VIII, IX, X and XI of the periodic table. More preferably the metal is selected from the group consisting of Fe, Mn, Cr, Cu, Co, Ni, Mo, V, Zn and W. Particularly preferably the metal is selected from the group comprising: Fe, Mn, Cu and Co. Iron is the most preferred metal.
  • Suitable counter ions are tetra-alkyl ammonium, tetra-phenyl phosphonium, K, Li or Na, most preferably lithium.
  • the most preferred catalyst is that in which the ligand is 5, 6-benzo-3, 8, 11, 13-tetraoxo-2 , 2 , 9, 9, 12, 12-hexamethyl-
  • the axial ligand 'L' is water or preferably chloride.
  • the counter-ion 'Q' is preferably lithium.
  • the ligand is also known as 3 , 4 , 8 , 9-tetrahydro-3 , 3 , 6 , 6 , 9, 9-hexa-methyl-lH- 1,4,8, ll-benzotetraazocyclotridecane-2, 5, 7, 10 (6H, 11H) tetrone .
  • the composition is preferably used in laundry wash liquor, preferably an aqueous wash liquor.
  • the amount of catalyst in the composition according to the present invention is sufficient to provide a concentration in the wash liquor of generally 0.005 ⁇ m to 100 ⁇ m, preferably from 0.025 ⁇ M to 50 ⁇ M, more preferably from 0.05 ⁇ M to 10 ⁇ M.
  • compositions of the present invention are pre-formulated with a source of hydroperoxyl species. It is preferable that the composition contains a peroxygen bleach or a peroxy-based or -generating system.
  • the peroxygen bleach is preferably a compound which is capable of yielding hydrogen peroxide in aqueous solution although it is possible to use more complex systems which involve peracids and/or peracid precursors.
  • Hydrogen peroxide sources are well known in the art. They include the inorganic peroxides, for example alkali metal peroxides, organic peroxides for example 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.
  • Typical levels of peroxygen source in fully formulated composition will range from 0.05-55 wt . % with 1-40 wt . % being particularly preferred and 1-25 wt . % being most particularly preferred.
  • Typical levels of peroxygen source (as hydrogen peroxide equivalents) in fully formulated composition will be such that the in-use concentration will range from 0.005mM to lOOmM with 0.025mM to 50mM being particularly preferred and 0.05mM to lOmM being most particularly preferred.
  • Preferred peroxygen sources include percarbonate and perborate .
  • 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 .
  • Another suitable hydrogen peroxide generating system is a combination of a C 1 -C 4 alkanol oxidase and a C 1 -C 4 alkanol, especially a combination of methanol oxidase (MOX) and ethanol .
  • MOX methanol oxidase
  • Alkylhydroxy peroxides are another class of peroxy bleaching compounds. Examples of these materials include cumene hydroperoxide and t-butyl hydroperoxide.
  • Organic peroxyacids may also be suitable as components of the bleaching system.
  • 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:
  • aliphatic, substituted aliphatic and arylalkyl monoperoxyacids e.g. peroxylauric acid, peroxystearic acid and N,N-phthaloylaminoperoxy caproic acid (PAP) ; and
  • Typical diperoxyacids useful herein include, for example:
  • 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
  • Peroxyacid bleach precursors are also 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.
  • 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
  • peracid precursors TAED and SNOBS are preferred.
  • Hydrogen peroxide based bleaching systems according to the present invention are markedly preferred to peroxyacid based systems.
  • the precursors are typically used in an amount of up to 12%, more preferably from 0.5 - 5% by weight of the composition.
  • compositions of the invention comprise one or more dye transfer inhibition (DTI) agents.
  • DTI agents include peroxidases, pthalocyanines and polymers.
  • Nitrogen-containing, dye binding, DTI polymers are preferred. Of these polymers and co-polymers of cyclic amines such as vinyl pyrrolidone, and/or vinyl imidazole are preferred. Suitable polymers include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, and polymers of N-carboxymethyl-4-vinylpyridinium chloride .
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7 , more preferably pKa ⁇ 6.
  • Any polymer backbone can be used provided the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferably 1,000 to 500,000; most preferably 5,000 to 100,000. This preferred class of materials is referred to herein as "PVNO" .
  • a preferred polyamine N-oxide is poly (4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
  • PVP/PVI Block or random copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers
  • the PVP/PVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000, as determined by light scattering as described in Barth, et al . , Chemical Analysis, Vol. 113. "Modern Methods of Polymer Characterization").
  • the preferred PVP/PVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1.
  • These copolymers can be either linear or
  • Suitable PVP/PVI polymers include Sokalan HP56, available commercially from BASF, Ludwigshafen, Germany.
  • PVP polyvinylpyrrolidone polymers
  • Suitable PVP polymers include Sokalan HP50, available commercially from BASF.
  • Compositions containing PVP can also contain polyethylene glycol ("PEG") having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
  • modified polyethyleneimine polymers are water-soluble or dispersible, modified polyamines .
  • Modified polyamines are further disclosed in US-A-4 , 548 , 744 ; US-A-4 , 597 , 898 ; US-A- 4,877,896; US-A- 4,891, 160; US-A- 4,976,879;
  • the bleaching composition according to the present invention comprises a dye transfer inhibition agent selected from poly vinyl -pyrridine N-oxide (PVPy-NO) , polyvinyl pyrrolidone (PVP), polyvinyl imidazole, N-vinylpyrrolidone and N-vinylimidazole copolymers (PVP/PVI), copolymers thereof, and mixtures thereof.
  • a dye transfer inhibition agent selected from poly vinyl -pyrridine N-oxide (PVPy-NO) , polyvinyl pyrrolidone (PVP), polyvinyl imidazole, N-vinylpyrrolidone and N-vinylimidazole copolymers (PVP/PVI), copolymers thereof, and mixtures thereof.
  • the amount of dye transfer inhibition agent in the composition according to the present invention will be from 0.01 to 10 %, preferably from 0.02 to 5 %, more preferably from 0.03 to 2 %, by weight of the composition.
  • the present invention has particular application in detergent bleaching, especially for laundry cleaning.
  • composition preferably contains a surface- active material, optionally together with detergency builder.
  • the composition may contain a surface-active material in an amount, for example, of from 10 to 50% by weight.
  • the surface-active material may comprise materials which are 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 ⁇ -Ci ⁇ ) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (C 9 -C 20 ) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 -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 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;
  • the preferred anionic detergent compounds are sodium (C 10 -C 15 ) alkylbenzene sulphonates (C10-C15 LAS) , and sodium (Ci 6 -C ⁇ ) alkyl ether sulphates (C16-C18 LES) .
  • nonionic surface-active compounds which may be used, preferably together with the anionic surface- active compounds, include, in particular, the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C 6 -C 22 ) phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule; and the condensation products of aliphatic (Cs-Cis) 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.
  • composition will preferably comprise from 1 to 15 % wt of anionic surfactant and from 10 to 40 % by weight of nonionic surfactant .
  • Preferred embodiments of the present invention comprise a mixed active system which comprises both anionic and nonionic surfactants. It is believed that the catalysts become less effective as the level of nonionic approaches 100% on surfactant. Conversely, where nitrogen-containing, dye binding, DTI polymers are used, the effectiveness of these polymers is reduced at high levels of anionic surfactant .
  • the level of anionic surfactant (on total surfactant) ranges from 10-90%wt and that the level of nonionic ranges from 90-10%wt (on total surfactant). It is especially preferred to use 30-60%wt/surfactant of anionic surfactant selected from: LAS, PAS, soap and mixtures thereof, together with 70-40%wt/surfactant of ethoxylated alcohol nonionic surfactant .
  • the formulation can contain 100% Anionic surfactant.
  • composition may also contain a detergency builder, for example in an amount of from about 5 to 80 % by weight, preferably from about 10 to 60 % by weight.
  • Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
  • Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid and its water- soluble salts; the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid; and polyacetal carboxylates as disclosed in US-A-4, 144,226 and US-A-4 , 146, 495.
  • alkali metal polyphosphates such as sodium tripolyphosphate
  • nitrilotriacetic acid and its water- soluble salts the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid
  • polyacetal carboxylates as disclosed in US-A-4,
  • 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 composition 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 composition 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 .
  • the composition contains not more than 5 % by weight of a carbonate buffer, expressed as sodium carbonate, more preferable not more than 2.5% by weight to substantially nil, if the composition pH lies in the lower alkaline region of up to 10.
  • a carbonate buffer expressed as sodium carbonate
  • transition metal sequestrants such as EDTA and the phosphonic acid derivatives, e.g.
  • ethylene diamine tetra- (methylene phosphonate) -EDTMP- are of special importance, as not only do they improve the stability of the catalyst/H 2 O 2 system and sensitive ingredients, such as enzymes, fluorescent agents, perfumes and the like, but also improve the bleach performance, especially at the higher pH region of above 10, particularly at pH 10.5 and above.
  • Other suitable transition metal sequestrants are known and can be chosen by those skilled in the art, for example aminocarboxylates, aminophosphonates, and polyfunctionally substituted aromatic chelating agents, as disclosed further in WO-A-98/39406. If present, the sequestrants are generally present in amounts of 0.001 to 15%, more preferably 0.01 to 3.0%, by weight of the composition.
  • the present invention may be conveniently embodied in a solid form of product, which includes both a powder or tablet form of product. Both of these forms may be homogeneous or non-homogeneous .
  • tablets may comprise a plurality of discrete regions which include some ingredients only, while powders may comprise mixed granules of differing compositions.
  • the catalyst referred to in the examples is the Fe complex of 3,4,8, 9-tetrahydro-3, 3,6,6,9, 9-hexamethyl-lH-l, 4 , 8, 11- benzotetraazocyclotri-decane -2,5,7,10 (6H,11H) tetrone, with lithium as the counter-ion and water as the axial ligand. This was synthesised in accordance with the method set out in our co-pending patent application GB 0020846.2.
  • the model detergent used in the examples was such that the wash liquor contained lg/L of a 50/50 mixture of LAS and the nonionic Synperonic A7 , lg/L of sodium tripolyphosphate, 0.4 g/L sodium carbonate and 20 microlitres of sequestrant (DequestTM 2047) .
  • Washes were simulated in a shaker-bath or Rotawash LinitesterTM at 40°C, using 30 minutes agitation in 100-200ml of wash liquor.
  • Each monitor was measured through one thickness of cloth with bleached, non- fluorescent mercerised white cotton sheeting as the reference standard. Each monitor was measured four times and the average of these four measurements was taken to be the value of that monitor. Reflectance values were taken and converted into delta E values by a computer software package which reported average delta E values according to the following equation:
  • levels of additional components are: 50 ⁇ M Enhancer, 500 ⁇ M H202 , l ⁇ M catalyst.
  • Table 1 shows that peroxide alone shows a very slight improvement over just detergent but has no significant effect on tomato stain, while the catalyst + H202 has significant stain removal benefits. It can be seen that, in particular, the enhancer ABTS greatly increases stain removal .
  • Table 1 Delta-E Values for Tomato Stained Cloth
  • delta-E represents the amount of dye which has been transferred from the green cloth to the white monitor. Therefore, lower levels of delta-E are representative of better results.
  • levels of additional components are: 100 ⁇ M ABTS, 500 ⁇ M H202, l ⁇ M catalyst.
  • Table 3 shows that addition of ABTS extends the pH profile to better bleaching at low pH.
  • the bleaching performance falls off with decreasing pH.
  • the enhancer is present, the performance does not fall off so quickly at lower pH.
  • delta-E represents the amount of dye which has been transferred from the green cloth to the white monitor. Therefore, lower levels of delta-E are representative of better results.
  • levels of additional components are: lOO ⁇ M PTP, lOOO ⁇ M H202, l ⁇ M catalyst.

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Abstract

Composition de blanchiment pouvant être utilisée pour la lessive et contenant un complexe ligand métallique représenté de préférence par la structure (I) dans laquelle B1, B2, B3 et B4 représentent chacun un groupe de liaison, M représente un ion métal de transition, L représente un ligand axial et Q représente un contre-ion métal alcalin. Ces compositions contiennent également un ou plusieurs composés d'activation dudit complexe ligand métallique, ledit composé d'activation étant, de préférence, représenté par la formule (II) dans laquelle Z1-Z2 représentent des groupes de retrait d'électron, Z3 et Z4 représentent hydrogène ou sont absents quand la liaison entre Z1 ou Z2 et l'atome d'azote contigu de la formule générale est une liaison pi. Cette composition contient éventuellement un tensioactif, une source de peroxygène et une adjuvant.
PCT/EP2002/008538 2001-08-02 2002-07-30 Compositions de blanchiment WO2003014280A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0118934A GB0118934D0 (en) 2001-08-02 2001-08-02 Improvements relating to bleaching compositions
GB0118934.9 2001-08-02

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WO2003014280A1 true WO2003014280A1 (fr) 2003-02-20
WO2003014280A8 WO2003014280A8 (fr) 2003-11-20

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003074646A1 (fr) * 2002-03-06 2003-09-12 Carnegie Mellon University Composition de blanchiment
US7060818B2 (en) 2003-02-21 2006-06-13 Carnegie Mellon University Synthesis of macrocyclic tetraamido compounds and new metal insertion process
EP3009498A3 (fr) * 2014-10-13 2016-05-25 Henkel AG & Co. KGaA Lessive protegeant les couleurs

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994012621A1 (fr) * 1992-12-01 1994-06-09 Novo Nordisk Amelioration de reactions enzymatiques
US5445755A (en) * 1994-05-31 1995-08-29 The Procter & Gamble Company Detergent compositions containing a peroxidase/accelerator system without linear alkylbenzenesulfonate
WO1995031526A1 (fr) * 1994-05-11 1995-11-23 The Procter & Gamble Company Compositions pour inhiber le transfert des couleurs, contenant des catalyseurs constitues de complexes metalliques speciaux
US5474576A (en) * 1992-01-31 1995-12-12 The Procter & Gamble Company Detergent compositions inhibiting dye transfer in washing
US5785886A (en) * 1995-06-07 1998-07-28 Lever Brothers Company, Division Of Conopco, Inc. Bleaching compositions containing imine hydrogen peroxide and a transition metal catalyst
US5853428A (en) * 1996-07-22 1998-12-29 Carnegie Mellon University Metal ligand containing bleaching compositions
DE10200672A1 (de) * 2001-01-10 2002-07-11 Kao Corp Bleich-Formulierung

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5474576A (en) * 1992-01-31 1995-12-12 The Procter & Gamble Company Detergent compositions inhibiting dye transfer in washing
WO1994012621A1 (fr) * 1992-12-01 1994-06-09 Novo Nordisk Amelioration de reactions enzymatiques
WO1995031526A1 (fr) * 1994-05-11 1995-11-23 The Procter & Gamble Company Compositions pour inhiber le transfert des couleurs, contenant des catalyseurs constitues de complexes metalliques speciaux
US5445755A (en) * 1994-05-31 1995-08-29 The Procter & Gamble Company Detergent compositions containing a peroxidase/accelerator system without linear alkylbenzenesulfonate
US5785886A (en) * 1995-06-07 1998-07-28 Lever Brothers Company, Division Of Conopco, Inc. Bleaching compositions containing imine hydrogen peroxide and a transition metal catalyst
US5853428A (en) * 1996-07-22 1998-12-29 Carnegie Mellon University Metal ligand containing bleaching compositions
DE10200672A1 (de) * 2001-01-10 2002-07-11 Kao Corp Bleich-Formulierung

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003074646A1 (fr) * 2002-03-06 2003-09-12 Carnegie Mellon University Composition de blanchiment
US7060818B2 (en) 2003-02-21 2006-06-13 Carnegie Mellon University Synthesis of macrocyclic tetraamido compounds and new metal insertion process
EP3009498A3 (fr) * 2014-10-13 2016-05-25 Henkel AG & Co. KGaA Lessive protegeant les couleurs

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GB0118934D0 (en) 2001-09-26

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