WO2023031328A1 - Catalyseurs de blanchiment, systèmes de blanchiment et compositions de nettoyage - Google Patents

Catalyseurs de blanchiment, systèmes de blanchiment et compositions de nettoyage Download PDF

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Publication number
WO2023031328A1
WO2023031328A1 PCT/EP2022/074314 EP2022074314W WO2023031328A1 WO 2023031328 A1 WO2023031328 A1 WO 2023031328A1 EP 2022074314 W EP2022074314 W EP 2022074314W WO 2023031328 A1 WO2023031328 A1 WO 2023031328A1
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WIPO (PCT)
Prior art keywords
bleach
aminopolycarboxylate
composition
acid
cleaning composition
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PCT/EP2022/074314
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English (en)
Inventor
Katherine Mary Thompson
Original Assignee
Unilever Ip Holdings B.V.
Unilever Global Ip Limited
Conopco, Inc., D/B/A Unilever
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Publication of WO2023031328A1 publication Critical patent/WO2023031328A1/fr

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    • 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
    • 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
    • C11D3/33—Amino carboxylic acids

Definitions

  • the present invention relates to a novel bleach catalyst comprising aminopolycarboxylic acid metal complexes comprising an aminopolycarboxylic acid and one or more datively bound metal cations, a bleach system comprising said catalyst, and further, cleaning compositions comprising the bleach catalyst / system.
  • Cleaning compositions comprise bleach to remove stains by oxidizing the stain components.
  • Bleach systems tackle difficult to remove colored stains, such as teastains.
  • Bleach systems beside a source of bleach, may contain bleach activator and bleach catalyst to provide effective bleaching also at low wash temperatures.
  • One known effective bleach catalyst is based on a manganese complex of the formula [L n Mn m Xp] z Yq, as described in EP0458397A2.
  • the invention provides a bleach catalyst comprising an aminopolycarboxylate-metal complex comprising an aminopolycarboxylate comprising GLDA, MGDA or a combination thereof, datively bonded to one or more metal cations comprising Fe 2+ , Fe 3+ , Co 2+ , Co 3+ or mixtures thereof.
  • the invention provides a bleach system including a bleach catalyst a bleach catalyst of the first aspect.
  • the bleach catalyst and bleach system have particular application in cleaning formulations to form a new and improved bleach composition.
  • the invention provides a cleaning composition comprising:
  • the cleaning component may comprise a detersive surfactant.
  • the invention provides use of a composition comprising an aminopolycarboxylate-metal complex comprising GLDA, MGDA or a combination thereof datively bonded to at least one metal cation comprising Fe2+, Fe3+, Co2+, Co3+ or mixtures thereof for cleaning a substrate.
  • the metal cation comprises Fe 2+ , Fe 3+ , and Co 2+ , Co 3+ or mixtures thereof, preferably comprises Fe 2+ , Fe 3+ or any combination I mixture thereof.
  • the composition comprises at most 1 wt. % of phosphonate (based on total weight of the composition.
  • the pH of a solution of 1 wt. % of the cleaning composition in water as measured at 25 degrees Celsius is from 7.0 to 12.0.
  • aminopolycarboxylic acid or ‘organic acid’ are used these encompass their corresponding salts (and vice versa).
  • aminopolycarboxylate-metal cation complexes of the invention can be effective in promoting bleaching of dyes in solution by having bleach catalyst activity.
  • the invention relates to the use of a composition comprising an aminopolycarboxylate-metal cation complex comprising an aminopolycarboxylate datively bonded to one or more metal cations for cleaning, especially bleaching a substrate.
  • Aminopolycarboxylates are sometimes referred to as aminopolycarboxylic acid chelants. They are generally appreciated as being strong builders. Suitable aminopolycarboxylic acids include glutamic acid N,N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA), ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDS), iminodimalic acid (IDM), ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethyliminodiacetic acid (HEIDA) aspartic acid diethoxysuccinic acid (AES) aspartic acid-N,N-diacetic acid (ASDA) , hydroxyethylene-diaminetetraacetic acid (HEDTA), hydroxyethylethylenediaminetriacetic acid
  • Preferred aminopolycarboxylates are GLDA, MGDA, EDDS, IDS, IDM or a mixture thereof, more preferred are GLDA, MGDA, EDDS or a mixture thereof and even more preferred are GLDA and MGDA or a mixture thereof.
  • GLDA is especially preferred as it can be made from bio-based materials (e.g. monosodium glutamate, which itself can be made as by-product from corn fermentation).
  • GLDA itself is highly biodegradable.
  • MGDA is more preferred in view of it being somewhat less hygroscopic, which improves detergent stability during storage. 4
  • the cleaning composition/bleach system according to the invention preferably comprises from 0 to 40 wt. % free acid equivalent of total aminopolycarboxylate not bound to any metal cation.
  • a particularly preferred amount of free acid equivalent of aminopolycarboxylate is from 0.5 to 20 wt. %, more preferably from 1.0 to 15 wt. %, even more preferably from 2.0 to 10 wt. % and still even more preferably from 3.0 to 8 wt.%.
  • Preferred salts are alkali-based salts and more preferred are sodium-based salts.
  • aminopolycarboxylates are appreciated as strong builders and chelators. Hence these compounds naturally tend to scavenge cations in solution. The manufacture of aminopolycarboxylates with Fe and/or Co cations is therefore straightforward.
  • the preferred method of manufacture aminopolycarboxylates comprising one or more bound iron- (Fe) and/or cobalt- (Co) cations comprises the following steps: a) providing an aqueous solution comprising aminopolycarboxylate and Fe and/or Co cations, wherein the molar ratio of the aminopolycarboxylate and the cations is from 100:1 to 1 :3; and b) optionally adjusting the pH of the aqueous solution to the range of from 6 to 11 ; and c) removing water from the aqueous solution to provide a composition comprising aminopolycarboxylate with bound Fe and/or Co cations and the composition having water content of at most 60 wt.% or precipitating the complexes from aqueous solution by adding a non-aqueous solvent (preferably ethanol).
  • a non-aqueous solvent preferably ethanol
  • step c) water is removed until a solid is provided or a precipitated solid formed on addition of an organic solvent is separated from the supernatant solution by filtration and then air dried.
  • the aminopolycarboxylates comprising one or more datively bound iron- (Fe) and/or cobalt- (Co) cations is part of the ingredients to make a tablet or powder form of cleaning composition.
  • Suitable examples of such water-soluble salts are the chloride salts of Fe and/or Co.
  • the Fe 2+ , Fe 3+ and Co 2+ , Co 3+ are the preferred cations.
  • the cation is a Fe 2+ , Fe 3+ cation.
  • Preferred aminopolycarboxylates comprising a bound Fe and/or Co cation are MGDA, GLDA, EDDS and IDDS, whereof MGDA and GLDA are the more preferred.
  • Iron (II) and iron (III) catalysts are prepared by direct reaction of the iron (II) and iron (III) salts with the ligands in aqueous solution.
  • Preferred transition metal salts are the chlorides, sulphates and acetates.
  • Particularly suitable metal salts are ferrous sulphate, ferric chloride, ammonium ferric sulphate, cobalt (II) chloride, cobalt (III) chloride and their respective hydrates.
  • the metal to ligand ratio can vary depending on the individual metal ion change and ligand denticities. The generic method is as follows: 10 millimoles of the metal salt are dissolved in the minimum volume of water required for complete solubilisation.
  • ligand 10 or 30 millimoles of the ligand are dissolved in the water required for complete solubilisation, depending on whether the metal to ligand ratio is 1 :1 , 1 :2 or 1 :3.
  • the ligand solution is added dropwise to the metal salt solution at ambient temperature.
  • the pH of the reaction mixture is then adjusted by dropwise addition of 20% alkali (preferably sodium hydroxide solution, potassium hydroxide or ammonium hydroxide), to a value of pH 5-6 for iron (II) and iron (III) complexes.
  • alkali preferably sodium hydroxide solution, potassium hydroxide or ammonium hydroxide
  • reaction mixtures are magnetically stirred at ambient temperature (or optionally warmed to 50 0 C using a heating block or water bath for the EDDS, quinic acid and barbituric acid ligands) and allowed to react for 2 hours.
  • Complexes may precipitate directly from solution or if more water soluble be precipitated by cooling the reaction mixtures in an ice bath and adding ethanol solvent.
  • the precipitated solids are isolated by filtration and washed with ethanol before drying at ambient temperature in a fume hood.
  • cobalt (III) catalysts are typically prepared from cobalt (II) salts, preferably cobalt chloride hexahydrate, followed an analogous process but by oxidation to cobalt (III).
  • the generic method is as follows:
  • the molar ratio of aminopolycarboxylate and the cations can be from 100:1 to 1:3. Lower ratios will lead to only a part of the aminopolycarboxyate comprising bound Fe and/or Co ions. This can be beneficial since such an aminopolycarboxylate mixture can both contribute to effective bleaching as well as providing strong builder and chelating functionality in one go. Higher ratios are beneficial to provide a more targeted bleach catalyst activity and can allow for more than one Fe and/or Co cation to be bound to the aminopolycarboxylate. In this respect it is noted that many aminopolycarboxylates are capable of binding more than one Fe and/or Co cations.
  • Preferred coordination complexes include Fe 1 " (GLDA)’, Fe 1 " (GLDA) (OH) 2 ', Fe 1 "
  • the negatively charged complexes may be isolated as the acid, sodium, potassium or ammonium salts depending on the identity of the base used in the synthesis.
  • the positively charged complexes may be preferably isolated as sulphate or halide salts, preferably chloride salts. All complexes may be isolated as their respective hydrates.
  • the cleaning composition comprises from 0.002-20.0% of free acid equivalent of one or more aminopolycarboxylate comprising one or more datively bound Fe and/or Co cations.
  • a further beneficial amount is from 0.1 to 20 wt. %, more preferably from 0.2 to 10 wt. %, even more preferably from 0.3 to 5 wt. % and still even more preferably from 0.4 to 4 wt. % 7
  • aminopolycarboxylate datively bound to one or more Fe and/or Co cations
  • further aminopolycarboxylate may be present which does not comprise such datively bound Fe, Mn and/or Co cations.
  • aminopolycarboxylate comprising one or more datively bound Fe or Co cations versus aminopolycarboxylate not comprising such, is considered to be from 1 :4000 to 100:1, more preferably from 1 :100 to 20:1, even more preferably from 1 :50 to 1:1 and still even more preferably from 1:20 to 1:10.
  • Such ratios provide a balanced bleach catalyst activity and a builder activity.
  • the I composition does not comprise further poorly biodegradable bleach catalyst and beneficially comprises essentially no further bleach catalyst (biodegradable or not). pH profile
  • the cleaning composition I bleach system provides a pH of a solution of 1 wt.% of the cleaning composition I bleach system in water as measured at 25 degrees Celsius of from 7.0 to 12.0, preferably of from 8.5 to 11.0 and even more preferably of from 9.0 to 10.5.
  • the cleaning composition I bleach system preferably comprises from 0.1 to 25 wt. % of bleach.
  • Inorganic and/or organic bleaches can be used.
  • Bleach may be selected from peroxides, organic peracids, salts of organic peracids and combinations thereof.
  • the bleach is selected from peroxides (including peroxide salts such as sodium percarbonate), organic peracids, salts of organic peracids and combinations thereof. More preferably, the bleach is a peroxide.
  • the bleach is hydrogen peroxide or a percarbonate. Further preferred, the bleach is a coated percarbonate.
  • Tetraacetylethylenediamine (TAED) may be included as a peracetic acid precursor. More preferred amounts of bleach are from 1.0 to 25 wt.%, even more preferably at from 2.0 to 20 wt. % and still even more preferably from 5 to 15 wt.%. 8
  • the improved bleaching composition has particular application in detergent formulations to form a new and improved detergent bleach composition within the purview of the invention, comprising the bleach catalyst, the bleach, a surface-active material, and usually also detergency builders and other known ingredients of such formulations, as well as in the industrial bleaching of yarns, textiles, paper, woodpulp and the like. These are discussed in more detail below.
  • the cleaning composition I bleach system may comprise further ingredients, such as further detergent active components.
  • Alkyl means an unsubstituted or substituted saturated hydrocarbon chain having from 1 to 18 carbon atoms.
  • the chain may be linear or branched.
  • “Dative bond” is used interchangeably with co-ordinate bond or a dative covalent bond or coordinate covalent bond. It is a covalent bond (a shared pair of electrons) in which both electrons come (are donated) from the same atom.
  • M + ” “M1 + ” or “M2 + denote metal ions with unspecified positive charge and for the sake of clarity the “+” sign does not imply only monovalent ions- but also divalent, trivalent, tetravalent etc., and other multiply charged metal cations (whether free ions e.g. in solution or a bound ion a complex). Conversely where the ion is specified such as Ca 2+ this implies a specific charge, here +2 (divalent ion).
  • “Textiles” can include woven fabrics, non-woven fabrics, and knitted fabrics; and can include natural or synthetic fibres such as silk fibres, linen fibres, cotton fibres, polyester fibres, polyamide fibres such as nylon, acrylic fibres, acetate fibres, and blends thereof including cotton and polyester blends.
  • compositions that is "substantially free of” or “substantially free from” refers to either the complete absence of an ingredient or a minimal amount thereof merely as impurity or unintended byproduct of another ingredient.
  • a composition that is "substantially free” of/from a component means that the composition comprises less than 0.5%, 0.25%, 0.1%, 0.05%, or 0.01%, or even 0%, by weight of the composition, of the component.
  • Substrate preferably is any suitable substrate and includes but is not limited to fabric substrates and dishes. Fabric substrates includes clothing, linens and other household textiles etc. In the context of fabrics, wherein the term “linen” is used to describe certain types of laundry items including bed sheets, pillow cases, towels, tablecloths, table napkins and uniforms and the term “textiles” can include woven fabrics, nonwoven fabrics, and knitted fabrics; and can include natural or synthetic fibres such as silk fibres, linen fibres, cotton fibres, polyester fibres, polyamide fibres such as nylon, acrylic fibres, acetate fibres, and blends thereof including cotton and polyester blends.
  • Dishes is meant generically and encompasses essentially any items which may be found in a dishwashing load, including crockery chinaware, glassware, plasticware, 10 hollowware and cutlery, including silverware.
  • Substrate may also include any inanimate “household surface”, “household hard surface”, it is meant herein any kind of surface typically found in and around houses like kitchens, bathrooms, e.g., floors, walls, tiles, tile grouting windows, cupboards, sinks, showers, shower plastified curtains, wash basins, WCs, fixtures and fittings and the like made of different materials like ceramic, vinyl, no-wax vinyl, linoleum, melamine, glass, Inox®, Formica®, vitroceramic, any plastics, plastified wood, metal or any painted or varnished or sealed surface and the like.
  • Household hard surfaces also include household appliances including, but not limited to refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on.
  • “Cleaning” includes any of washing, soaking, soil removal, stain removal, mould removal, and any combination thereof and may comprise pretreatment or direct treatment of substrates, and may utilise a detersive surfactant.
  • component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
  • the cleaning composition I bleach system may be in any suitable form.
  • the cleaning composition I bleach system may be in particulate form.
  • the term "particulate” in this context means free-flowing or compacted solid forms such as powders, granules, ribbon, noodle, pellets, flakes, pastille bars, briquettes or tablets.
  • the composition is in the form of powder, granules or a tablet.
  • the composition may be in the form of a unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet.
  • composition according to the present invention may be made via a variety of conventional methods known in the art and those which includes but is not limited to the mixing of ingredients, including dry-mixing, compaction such as agglomerating, extrusion, tableting, or spray-drying of the various compounds comprised in the detergent component, or mixtures of these techniques, whereby the components herein also can be made by for example compaction, including extrusion and agglomerating, or spray-drying.
  • the cleaning composition I bleach system may be made by any of the conventional processes, especially preferred is the technique of slurry making and spray drying.
  • compositions preferably have a density of more than 350 grams/litre, more preferably more than 450 grams/litre or even more than 570 grams/litre.
  • Solid e.g. particulate compositions may also incorporate non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers, fillers.
  • the cleaning composition I bleach system may be a liquid or a gel.
  • liquid in the context of this invention denotes that a continuous phase or predominant part of the composition is liquid and that the composition is flowable at 15°C and above. Accordingly, the term “liquid” may encompass emulsions, suspensions, and compositions having flowable yet stiffer consistency, known as gels 12 or pastes.
  • the viscosity of the composition may suitably range from about 200 to about 10,000 mPa.s at 25°C at a shear rate of 21 sec 1 . This shear rate is the shear rate that is usually exerted on the liquid when poured from a bottle.
  • Pourable liquid compositions generally have a viscosity of from 100 to 2,500 mPa.s, preferably from 100 to 1500 mPa.s.
  • Liquid compositions which are pourable gels generally have a viscosity of from 1,500 mPa.s to 6,000 mPa.s, preferably from 1 ,500 mPa.s to 2,000 mPa.s.
  • a liquid laundry cleaning composition I bleach system according to the invention may generally comprise from 5 to 95%, preferably from 10 to 90%, more preferably from 15 to 85% water (by weight based on the total weight of the composition).
  • the composition may also incorporate from 0.1 to 15% (by weight based on the total weight of the composition) of non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers.
  • compositions comprising a bleach catalyst together with a bleach, where such compositions comprise water
  • the bleach is segregated from the bleach catalyst for example using separate containers or encapsulation or other segregation means.
  • Cleaning composition I bleach systems may comprise a surfactant.
  • the surfactant may be present at 5 to 40%, preferably 15 to 35% (by weight based on the total weight of the composition). Alternatively, the surfactant may be present up to 60% (by weight based on the total weight of the composition).
  • the surfactant is a detersive surfactant.
  • Preferred detersive surfactants may be selected from non-soap anionic surfactants, nonionic surfactants and mixtures thereof.
  • Suitable non-soap anionic surfactants include salts of organic sulfates and sulfonates having alkyl radicals containing from about 8 -22, preferably 10 - 18, carbon atoms; e.g. alkyl sulfates, alkyl ether sulfates, alkaryl sulfonates, alpha-olefin sulfonates and 13 mixtures thereof.
  • the alkyl radicals may be saturated.
  • the alkyl ether sulfates may contain from one to ten ethylene oxide or propylene oxide units per molecule, and preferably contain one to three ethylene oxide units per molecule.
  • the counterion for anionic surfactants is generally an alkali metal such as sodium or potassium; or an ammoniacal counterion such as monoethanolamine, (MEA) diethanolamine (DEA) or triethanolamine (TEA). Mixtures of such counterions may also be employed.
  • a preferred class of non-soap anionic surfactant for use in the invention includes alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates (LAS) with an alkyl chain length of from 10 to 18 carbon atoms.
  • LAS linear alkylbenzene sulfonates
  • Commercial LAS is a mixture of closely related isomers and homologues alkyl chain homologues, each containing an aromatic ring sulfonated at the “para" position and attached to a linear alkyl chain at any position except the terminal carbons.
  • the linear alkyl chain typically has a chain length of from 11 to 15 carbon atoms, preferably about C12.
  • Each alkyl chain homologue consists of a mixture of all the possible sulfophenyl isomers except for the 1 -phenyl isomer.
  • LAS is normally formulated into compositions in acid (i.e. HLAS) form and then at least partially neutralized in-situ.
  • alkyl ether sulfates having a straight or branched chain alkyl group having 10 to 18, more preferably 12 to 14 carbon atoms and containing an average of 1 to 3EO units per molecule.
  • a preferred example is sodium lauryl ether sulfate (SLES) in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 3EO units per molecule.
  • alkyl sulfate surfactant may be used, such as non-ethoxylated primary and secondary alkyl sulfates with an alkyl chain length of from 10 to 18.
  • a preferred mixture of non-soap anionic surfactants for use in the invention comprises linear alkylbenzene sulfonate (preferably Cn to C15 linear alkyl benzene sulfonate) and sodium lauryl ether sulfate (preferably C10 to C18 alkyl sulfate ethoxylated with an average of 1 to 3 EO). 14
  • the total level of non-soap anionic surfactant may suitably range from 5 to 30% (by weight based on the total weight of the composition).
  • Nonionic surfactants may be present, polyoxyalkylene compounds, i.e. the reaction product of alkylene oxides (such as ethylene oxide or propylene oxide or mixtures thereof) with starter molecules having a hydrophobic group and a reactive hydrogen atom which is reactive with the alkylene oxide.
  • Such starter molecules include alcohols, acids, amides or alkyl phenols.
  • the reaction product is known as an alcohol alkoxylate.
  • the polyoxyalkylene compounds can have a variety of block and heteric (random) structures. For example, they can comprise a single block of alkylene oxide, or they can be diblock alkoxylates or triblock alkoxylates.
  • the blocks can be all ethylene oxide or all propylene oxide, or the blocks can contain a heteric mixture of alkylene oxides.
  • examples of such materials include aliphatic alcohol ethoxylates such as Cs to Cis primary or secondary linear or branched alcohol ethoxylates with an average of from 2 to 40 moles of ethylene oxide per mole of alcohol.
  • Preferred nonionics are aliphatic Cs to Cis, more preferably C12 to C15 primary linear alcohol ethoxylates with an average of from 3 to 20, more preferably from 5 to 10 moles of ethylene oxide per mole of alcohol.
  • the nonionic may be present at 0 to 25% (by weight based on the total weight of the composition).
  • One or more cosurfactants may be used in addition to the surfactants described above.
  • Specific cationic surfactants include C8 to C18 alkyl dimethyl ammonium halides and derivatives thereof in which one or two hydroxyethyl groups replace one or two of the methyl groups, and mixtures thereof.
  • Cationic surfactant when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).
  • amphoteric (zwitterionic) surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, having alkyl radicals containing from about 8 to about 22 carbon atoms, the term “alkyl” being used to include the alkyl portion of higher acyl radicals.
  • Amphoteric (zwitterionic) surfactant when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).
  • the cleaning composition I bleach system may comprise polymeric cleaning boosters, such as antiredeposition polymers, soil release polymers and mixtures thereof.
  • Anti-redeposition polymers stabilise the soil in the wash solution thus preventing redeposition of the soil.
  • Suitable anti-redeposition polymers for use in the invention include alkoxylated polyethyleneimines.
  • Polyethyleneimines are materials composed of ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units.
  • Preferred alkoxylated polyethylenimines for use in the invention have a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight (M w ).
  • the polyethyleneimine backbone may be linear or branched. It may be branched to the extent that it is a dendrimer.
  • the alkoxylation may typically be ethoxylation or propoxylation, or a mixture of both.
  • a nitrogen atom is alkoxylated
  • a preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25 alkoxy groups per modification.
  • a preferred material is ethoxylated polyethyleneimine, with an average degree of ethoxylation being from 10 to 30, preferably from 15 to 25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone.
  • the polyamine is a soil release agent comprising a polyamine backbone corresponding to the formula:
  • the polyamine backbone prior to modification has a molecular weight greater than about 200 daltons.
  • V units are terminal units having the formula: ii) W units are backbone units having the formula iii) Y units are branching units having the formula: and iv) Z units are terminal units having the formula: 17
  • backbone linking R units are selected from the group consisting of C2-C12 alkylene, -(R1O)xR3 (OR1)x-, -(CH2CH(OR2)CH 2 O)z(R1O)yR1(OCH 2 CH(OR2)CH2)w-, -CH2CH(OR2)CH2- and mixtures thereof, provided that when R comprises C1-C12 alkylene R also comprises at least one - (R1O)xR3(OR1)x-, -(CH 2 CH(OR2)CH 2 O)z(R1O)yR1- (OCH 2 CH(OR2)CH 2 )w-, or - CH 2 CH(OR2)CH 2 -unit;
  • R1 is C2-C6 alkylene and mixtures thereof;
  • R2 is hydrogen, (R1O)XB, and mixtures thereof;
  • R3 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene, -C(O)-, -C(O)NHR5NHC(O)-, C(O)(R4)rC(O)-, - CH2CH(OH)CH 2 O(R1O)yR1O-CH 2 CH(OH)CH2-, and mixtures thereof;
  • R4 is C1-C12 alkylene, C4-C12 alkenylene, C8-C12 arylalkylene, C6-C10 arylene, and mixtures thereof;
  • R5 is C2-C12 alkylene or C6 C12 arylene
  • E units are selected from the group consisting of (CH2)p-CO2M, - (CH 2 )qSO 3 M, -CH(CH 2 CO2M)CO2l ⁇ /l, (CH 2 )pPO 3 M, -(R1O)xB, and mixtures thereof,
  • B is hydrogen, -(CH 2 )qSO 3 M, -(CH 2 )pCO 2 M, -(CH 2 )q CH(SO 3 M)CH 2 SO 3 M, - (CH 2 )qCH(SO 2 M)CH 2 SO 3 M, - (CH2)pPO 3 M, -PO 3 M, and mixtures thereof, 18
  • M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance
  • X is a water soluble anion
  • k has the value from 0 to about 20;
  • m has the value from 4 to about 400;
  • n has the value from 0 to about 200;
  • p has the value from 1 to 6,
  • q has the value from 0 to 6;
  • r has the value 0 or 1;
  • w has the value 0 or 1 ;
  • x has the value from 1 to 100;
  • y has the value from 0 to 100;
  • z has the value 0 or 1.
  • the overall level of anti-redeposition polymer when included, may range from 0.05 to 6%, more preferably from 0.1 to 5% (by weight based on the total weight of the composition).
  • Suitable anti-redeposition polymer for use in the invention includes cellulose esters and ethers, for example sodium carboxymethyl cellulose.
  • Soil release polymers help to improve the detachment of soils from fabric by modifying the fabric surface during washing.
  • the adsorption of an SRP over the fabric surface is promoted by an affinity between the chemical structure of the SRP and the target fibre.
  • SRPs for use in the invention may include a variety of charged (e.g. anionic) as well as non-charged monomer units and structures may be linear, branched or star-shaped.
  • the SRP structure may also include capping groups to control molecular weight or to alter polymer properties such as surface activity.
  • (M w ) of the SRP may suitably range from about 1000 to about 20,000 and preferably ranges from about 1500 to about 10,000.
  • SRPs for use in the invention may suitably be selected from copolyesters of dicarboxylic acids (for example adipic acid, phthalic acid or terephthalic acid), diols (for example ethylene glycol or propylene glycol) and polydiols (for example polyethylene glycol or polypropylene glycol).
  • the copolyester may also include monomeric units substituted with anionic groups, such as for example sulfonated isophthaloyl units.
  • oligomeric esters produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”) and poly(ethyleneglycol) (“PEG”); partly- and fully-anionic-end-capped oligomeric esters such as oligomers from ethylene glycol (“EG”), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; nonionic-capped block polyester oligomeric compounds such as those produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na- dimethyl-5-sulfoisophthalate, and copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate
  • cellulosic derivatives such as hydroxyether cellulosic polymers, C1-C4 alkylcelluloses and C4 hydroxyalkyl celluloses
  • Preferred SRPs for use in the invention include copolyesters formed by condensation of terephthalic acid ester and diol, preferably 1 ,2 propanediol, and further comprising an end cap formed from repeat units of alkylene oxide capped with an alkyl group.
  • Examples of such materials have a structure corresponding to general formula (II): in which R 1 and R 2 independently of one another are X-(OC2H4)n-(OC3H6) m ; in which X is C1-4 alkyl and preferably methyl; n is a number from 12 to 120, preferably from 40 to 50; m is a number from 1 to 10, preferably from 1 to 7; and a is a number from 4 to 9.
  • n, n and a are not necessarily whole numbers for the polymer in bulk.
  • the overall level of SRP when included, may range from 0.1 to 10%, preferably from 0.3 to 7%, more preferably from 0.5 to 5% (by weight based on the total weight of the composition).
  • Detergent may in some cases contain one or more fatty acids and/or salts thereof.
  • Suitable fatty acids in the context of this invention include aliphatic carboxylic acids of formula RCOOH, where R is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond.
  • R is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond.
  • saturated C12-18 fatty acids such as lauric acid, myristic acid, palmitic acid or stearic acid
  • fatty acid mixtures in which 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids.
  • Such mixtures may typically be derived from natural fats and/or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow). 21
  • the fatty acids may be present in the form of their sodium, potassium or ammonium salts and/or in the form of soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • Fatty acids and/or their salts when included, may be present in an amount ranging from about 0.25 to 5%, more preferably from 0.5 to 5%, most preferably from 0.75 to 4% (by weight based on the total weight of the composition).
  • fatty acids and/or their salts are not included in the level of surfactant or in the level of builder.
  • the cleaning composition I bleach system may comprise an effective amount of one or more enzymes selected from the group comprising, pectate lyase, protease, amylase, cellulase, lipase, mannanase and mixtures thereof.
  • the enzymes are preferably present with corresponding enzyme stabilizers.
  • the level of each enzyme in the composition is from 0.0001 wt.% to 1 wt.% (of the composition). Total enzyme levels may be from 0.0001 to 5%.
  • Levels of enzyme present in the composition preferably relate to the level of enzyme as pure protein.
  • Preferred enzymes include those in the group consisting of: proteases, cellulases, alpha-amylases, peroxidases/oxidases, pectate lyases, and/or mannanases. Said preferred enzymes include a mixture of two or more of these enzymes.
  • the enzyme is selected from: proteases, cellulases, and/or alpha-amylases.
  • Preferred proteases are selected from the following group, serine, acidic, metallo- and cysteine proteases. More preferably the protease is a serine and/or acidic protease. 22
  • the protease is a serine protease. More preferably the serine protease is subtilisin type serine protease.
  • Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708.
  • a polyol such as propylene glycol or glycerol
  • a sugar or sugar alcohol lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid
  • the cleaning composition I bleach system preferably has a pH in the range of 7 - 12, more preferably 6 to 8, when measured on dilution of the composition to 1% (by weight based on the total weight of the composition) using demineralised water.
  • the cleaning composition I bleach system may contain further optional ingredients to enhance performance and/or consumer acceptability.
  • ingredients include fragrance oils, foam boosting agents, preservatives (e.g. bactericides), antioxidants, sunscreens, anticorrosion agents, colorants, pearlisers and/or opacifiers, and shading dye.
  • preservatives e.g. bactericides
  • sunscreens e.g. bactericides
  • anticorrosion agents colorants
  • pearlisers and/or opacifiers e.g. opacifiers
  • the cleaning composition I bleach system generally contains no more than 0.2%, preferably from 0 to 0.1%, more preferably from 0 to 0.01% and most preferably 0% (by weight based on the total weight of the composition) of transition metal ions selected from Fe(ll), Fe (III), Cr(ll - VI), Cu(ll), Co (II), Co (III), Mn (II), Mn (III), Ni(ll), Ce (III), Ce (IV) and Zn (II) and mixtures thereof.
  • transition metal ions selected from Fe(ll), Fe (III), Cr(ll - VI), Cu(ll), Co (II), Co (III), Mn (II), Mn (III), Ni(ll), Ce (III), Ce (IV) and Zn (II) and mixtures thereof.
  • the cleaning composition I bleach system generally contains no more than 0.2%, preferably no more than 0.1%, more preferably no more than 0.01% and most preferably 0% (by weight based on the total weight of the composition) of oxidising 23 agents selected from halogen-based bleaches (e.g. alkali metal hypochlorites and alkali metal salts of di- and tri-chloro and di- and tri-bromo cyanuric acids).
  • halogen-based bleaches e.g. alkali metal hypochlorites and alkali metal salts of di- and tri-chloro and di- and tri-bromo cyanuric acids.
  • the cleaning composition I bleach system may be packaged in any suitable form.
  • the cleaning composition I bleach system may be supplied in multidose plastics packs with a top or bottom closure.
  • a dosing measure may be supplied with the pack either as a part of the cap or as an integrated system.
  • Detergent methods may suitably be carried out in a top-loading or front-loading automatic washing machine or can be carried out by hand.
  • the dose of cleaning composition I bleach system is typically put into a dispenser and from there it is flushed into the machine by the water flowing into the machine, thereby forming the wash liquor.
  • a subsequent aqueous rinse step and drying the substrate is preferred. Any input of water during any optional rinsing step(s) is not included when determining the volume of the wash liquor. Drying can take place either in an automatic dryer or in the open air.
  • a solid composition according to the present invention may be made via a variety of conventional methods known in the art and those which includes but is not limited to the mixing of ingredients, including dry-mixing, compaction such as agglomerating, extrusion, tabletting, or spray-drying of the various compounds comprised in the detergent component, or mixtures of these techniques, whereby the components herein also can be made by for example compaction, including extrusion and agglomerating, or spray-drying.
  • the cleaning composition I bleach system may be made by any of the conventional processes, especially preferred is the technique of slurry making and spray drying.
  • the compositions preferably have a density of more than 350 grams/litre, more preferably more than 450 grams/litre or even more than 570 grams/litre.
  • the solid laundry cleaning composition I bleach system according to the present invention is preferably free flowing.
  • the composition is preferably a fully formulated cleaning composition I bleach system.
  • the composition is used for laundering fabrics using manual-washing method.
  • the composition of the present invention is a solid laundry cleaning composition I bleach system.
  • the composition is in the form of a spray -dried powder or particulate free-flowing form.
  • a typical solid cleaning composition / (powder) includes the following:
  • a base solution was made by dispersing 0.005 wt. % of naphthol blue black dye (available from Sigma-Aldrich) in water and adjusting the pH to 7 (using phosphate). To this solution hydrogen peroxide was added to provide a level of 20mM. For testing either 25ppm of bleach catalyst according to the invention was added, or (not according to the invention) bare Fe 3+ (as water soluble sulphate) as control. The final solution was incubated at 20 degrees Celsius for 20 hours after which the absorbance was measured at 629nm. The results are given in the Table 1 below.
  • aminopolycarboxylate complexes of the invention can substantially improve dye bleaching at 20 degrees Celsius and a pH of 7 or 10, where complexes with GLDA and MGDA perform best. These conditions are relevant for detergent wash liquor conditions when operating at low temperatures.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un catalyseur de blanchiment comprenant un complexe aminopolycarboxylate-métal comprenant un GLDA, MGDA ou une combinaison de ceux-ci, liédativement à au moins un cation métallique comprenant Fe2+, Fe3+, Co2+, Co3+ ou des mélanges de ceux-ci. L'invention concerne également un système de blanchiment comprenant le catalyseur de blanchiment en combinaison avec un agent de blanchiment. L'invention concerne en outre une composition de nettoyage comprenant le catalyseur de blanchiment, un agent de blanchiment et un tensioactif détersif.
PCT/EP2022/074314 2021-09-01 2022-09-01 Catalyseurs de blanchiment, systèmes de blanchiment et compositions de nettoyage WO2023031328A1 (fr)

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EP21194363 2021-09-01

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4119557A (en) * 1975-12-18 1978-10-10 Lever Brothers Company Bleaching compositions and process for cleaning fabrics
EP0458397A2 (fr) 1990-05-21 1991-11-27 Unilever N.V. Activation du blanchiment
WO1992019708A1 (fr) 1991-04-30 1992-11-12 The Procter & Gamble Company Detergents liquides comprenant un ester de borate aromatique servant a inhiber l'enzyme proteolytique
WO1992019709A1 (fr) 1991-04-30 1992-11-12 The Procter & Gamble Company Detergents liquides contenant un adjuvant et un complexe polyol acide borique qui sert a inhiber l'enzyme proteolytique
EP1004571A1 (fr) * 1998-05-27 2000-05-31 Showa Denko Kabushiki Kaisha Procedes de preparation d'aminoacide ayant un groupe amino secondaire ou tertiaire et au moins trois groupes carboxyle et son sel
US6960330B1 (en) * 2002-07-12 2005-11-01 Cox Jr Henry Wilmore Method for reducing H2S contamination
WO2016055758A1 (fr) * 2014-10-06 2016-04-14 Nch Corporation Composition de produit dérouillant de ph neutre
US20170173204A1 (en) * 2010-10-08 2017-06-22 Stephen R. Temple Methods and Equipment for Treating Industrial Gas Streams and Biological Fouling
US20180371380A1 (en) * 2017-06-27 2018-12-27 Ecolab Usa Inc. Non-phosphorous transition metal control in laundry applications

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4119557A (en) * 1975-12-18 1978-10-10 Lever Brothers Company Bleaching compositions and process for cleaning fabrics
EP0458397A2 (fr) 1990-05-21 1991-11-27 Unilever N.V. Activation du blanchiment
WO1992019708A1 (fr) 1991-04-30 1992-11-12 The Procter & Gamble Company Detergents liquides comprenant un ester de borate aromatique servant a inhiber l'enzyme proteolytique
WO1992019709A1 (fr) 1991-04-30 1992-11-12 The Procter & Gamble Company Detergents liquides contenant un adjuvant et un complexe polyol acide borique qui sert a inhiber l'enzyme proteolytique
EP1004571A1 (fr) * 1998-05-27 2000-05-31 Showa Denko Kabushiki Kaisha Procedes de preparation d'aminoacide ayant un groupe amino secondaire ou tertiaire et au moins trois groupes carboxyle et son sel
US6960330B1 (en) * 2002-07-12 2005-11-01 Cox Jr Henry Wilmore Method for reducing H2S contamination
US20170173204A1 (en) * 2010-10-08 2017-06-22 Stephen R. Temple Methods and Equipment for Treating Industrial Gas Streams and Biological Fouling
WO2016055758A1 (fr) * 2014-10-06 2016-04-14 Nch Corporation Composition de produit dérouillant de ph neutre
US20180371380A1 (en) * 2017-06-27 2018-12-27 Ecolab Usa Inc. Non-phosphorous transition metal control in laundry applications

Non-Patent Citations (1)

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Title
AKZONOBEL: "Chelates Product Guide", 31 May 2017 (2017-05-31), XP055484377, Retrieved from the Internet <URL:https://chelates.akzonobel.com/siteassets/20170714-download-product-dissolvineproductguide2017web.pdf> [retrieved on 20180614] *

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