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WO2025131379A1 - Détergent à lessive liquide à couleur stable - Google Patents

Détergent à lessive liquide à couleur stable Download PDF

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Publication number
WO2025131379A1
WO2025131379A1 PCT/EP2024/080139 EP2024080139W WO2025131379A1 WO 2025131379 A1 WO2025131379 A1 WO 2025131379A1 EP 2024080139 W EP2024080139 W EP 2024080139W WO 2025131379 A1 WO2025131379 A1 WO 2025131379A1
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Prior art keywords
detergent
group
acid
water
detergents
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PCT/EP2024/080139
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German (de)
English (en)
Inventor
Frank Meier
Thorsten Ott
Leyla Eichholz
Dirk Weinrich
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of WO2025131379A1 publication Critical patent/WO2025131379A1/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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/43—Solvents
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the present invention relates to color-stable liquid detergents.
  • the invention relates to color-stable liquid detergents containing gluconic acid salt.
  • An important means of communicating the product quality and product promise of a liquid detergent is its appearance, for example the color of a liquid detergent or the shape and color of a portion unit containing the liquid detergent. This applies in particular to water-soluble film pouches, whose soluble films are usually transparent and allow a view of the solid or liquid detergent contained. Colored, i.e. non-white, liquid detergents can generally be produced easily by adding appropriate dyes to the liquid detergent.
  • the temporal stability of the achieved color impression is influenced by, among other factors, the ingredients of the liquid detergent and the addition of stabilizing agents.
  • the international application WO 93/09215 A1 describes the stabilization of dyes in liquid detergents by the addition of sulfur-containing compounds such as sulfites.
  • the ecological footprint of a liquid detergent is determined not only by the amount of energy and water used in its production, but also by the biodegradability of the ingredients and packaging materials used. Providing liquid detergents with high performance while continually reducing their ecological footprint is another objective in the development of detergents and cleaning products.
  • the application was based on the objective of providing a visually appealing, dye-containing liquid detergent characterized by high color stability.
  • the liquid detergent should be characterized by a high active ingredient concentration, be suitable for packaging in water-soluble foil pouches, and contain a high proportion of readily biodegradable ingredients.
  • a first subject matter of the application is a liquid detergent containing, based on its total weight, a) 22 to 50 wt.% anionic surfactant; b) 0.1 to 8 wt.% gluconic acid salt; c) 0.01 to 2 wt.% antioxidant; d) 5 to 25 wt.% organic solvent; e) 0.1 to 15 wt.% water; f) less than 0.1 wt.% organic phosphonate;
  • liquid detergents are characterized by surprising color stability when stored even under demanding conditions. This applies to both dye-free and dye-containing detergents, which retain their original coloration, as it occurs during production, even under demanding storage conditions.
  • the detergent is liquid under standard conditions (20°C, 1013 mbar).
  • Preferred detergents have a viscosity (21°C, Brookfield Viscometer Type DV-II. Pro, spindle no. 2, 20 rpm) above 400 mPas, preferably above 1000 mPas.
  • a first essential component of the liquid detergent is 12 to 45 wt.% anionic surfactant, with preferred liquid detergents containing, based on their total weight, 27 to 45 wt.%, preferably 32 to 40 wt.% anionic surfactant.
  • the anionic surfactant is preferably selected from the group comprising C9-C13 alkylbenzenesulfonates, olefinsulfonates, C12-C18 alkanesulfonates, estersulfonates, alk(en)yl sulfates, fatty alcohol ether sulfates, C12-C18 fatty acid salts, and mixtures thereof.
  • Compositions comprising C8-C18 alkylbenzenesulfonates and fatty alcohol ether sulfates as anionic surfactant have particularly good dispersing properties.
  • Suitable sulfonate-type surfactants are preferably C8-C18 alkylbenzenesulfonates, olefinsulfonates, i.e., mixtures of alkene and hydroxyalkanesulfonates, and disulfonates, such as those obtained, for example, from C12-C18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • compositions contain at least one anionic surfactant of formula (I), in the
  • R' and R" are independently H or alkyl and together contain 8 to 18, preferably 9 to 15 and in particular 9 to 13 C atoms and Y + represents a monovalent cation or the nth part of an n-valent cation (in particular monoethanolamine).
  • the group of alkyl ether sulfates includes fatty alcohol ether sulfates, for example the sulfuric acid monoesters of straight-chain or branched C7-C2i alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C12-18 fatty alcohols with 1 to 4 EO.
  • fatty alcohol ether sulfates for example the sulfuric acid monoesters of straight-chain or branched C7-C2i alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C12-18 fatty alcohols with 1 to 4 EO.
  • Alkyl ether sulfates with the formula (II) are preferred.
  • R 1 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical.
  • Preferred radicals R 1 of the formula (II) are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, with preference being given to those having an even number of carbon atoms.
  • radicals R 1 of the formula (II) are derived from fatty alcohols having 12 to 18 carbon atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or from oxo alcohols having 10 to 20 carbon atoms.
  • AO represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group.
  • the index n in formula (I) is an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. n is very particularly preferably 2, 3, 4, 5, 6, 7 or 8.
  • X is a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions and among them Na + or K + , with Na + being extremely preferred. Further cations X+ can be selected from NHT, 1Zn2 + , 14Mg2 + , 14Ca2 + , 14Mn2 + , and mixtures thereof, as well as primary and secondary amines, in particular monoethanolamine.
  • the stated degree of ethoxylation represents a statistical mean, which can be a whole or fractional number for a specific product.
  • the stated degrees of alkoxylation represent statistical mean, which can be a whole or fractional number for a specific product.
  • Preferred alkoxylates/ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • preferred liquid detergents contain anionic surfactant selected from the group of Cs-18-alkylbenzenesulfonates, Cs-18-olefinsulfonates, Cs-12-18-alkanesulfonates, Cs-18-estersulfonates, Cs-18-alkylsulfates, Cs-18-alkenylsulfates, fatty alcohol ether sulfates and C12-18 fatty acid salts, preferably from the group of Cs-18-alkylbenzenesulfonates, Cs-18-alkylsulfates, fatty alcohol ether sulfates and C12-18 fatty acid salts and in particular from the group of Cs-18-alkylbenzenesulfonates and C12-18 fatty acid salts.
  • anionic surfactant selected from the group of Cs-18-alkylbenzenesulfonates, Cs-18-olefinsulfonates, Cs-12-18-alkanesulfonates, Cs
  • anionic surfactants from the group of alkanolamine-Cs-is-alkylbenzenesulfonates has proven to be particularly advantageous for the storage stability of liquid detergents.
  • the anionic surfactant is selected from the group of alkanolamine Cs-18-alkylbenzenesulfonates with alkanolamine from the group monoethanolamine, monoisopropanolamine, diisopropanolamine, preferably from the group monoethanolamine.
  • C12-18 fatty acid salts are selected from the group of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and mixtures thereof.
  • the anionic surfactant is selected from the group of alkanolamine Ci2-18 fatty acid salts with alkanolamine from the group monoethanolamine, monoisopropanolamine, diisopropanolamine, preferably from the group monoethanolamine.
  • the C12-18 fatty acid salts are classified in the application as anionic surfactants.
  • the weight ratio of Cs-18-alkylbenzenesulfonate to C12-18 fatty acid salts is 8:1 to 2:1, preferably 7:1 to 5:2 and in particular 6:1 to 3:1.
  • Particularly preferred detergents are those in which the weight ratio of alkanolamine Cs-18-alkylbenzenesulfonate to alkanolamine C12-18 fatty acid salt is 8:1 to 2:1, preferably 7:1 to 5:2 and in particular 6:1 to 3:1.
  • the detergents contain a nonionic surfactant as a preferred optional ingredient. Its weight fraction of the total weight of the detergent is preferably 12 to 36 wt.%, particularly preferably 15 to 33 wt.%, and especially 18 to 30 wt.%.
  • non-ionic surfactants from the group of alkyl ethoxylates is particularly preferred, with preferred alkyl ethoxylates being selected from the group of ethoxylated primary Cs-18 alcohols, preferably ethoxylated primary Cs-18 alcohols with a degree of alkoxylation of 4 to 10, particularly preferably Cs-12-14 alcohols with 4 EO or 7 EO, Cs-18-n alcohols with 7 EO, Cs-13-15 alcohols with 5 EO, 7 EO or 8 EO, Cs-18 oxo alcohols with 7 EO, Cs-12-18 alcohols with 5 EO or 7 EO, in particular Cs-12-18 fatty alcohols with 7 EO or Cs-18 oxo alcohols with 7 EO.
  • preferred detergents contain, based on their total weight, 12 to 36% by weight, particularly preferably 15 to 33% by weight and in particular 18 to 30% by weight of nonionic surfactant from the group of ethoxylated primary Cs-is alcohols, preferably the ethoxylated primary Cs-is alcohols with a degree of alkoxylation of 4 to 10, particularly preferably the C12-14 alcohols with 4 EO or 7 EO, the Cg-n alcohols with 7 EO, the C18-is alcohols with 5 EO, 7 EO or 8 EO, the C18-is oxo alcohols with 7 EO, the Cs alcohols with 5 EO or 7 EO, in particular the C12-is fatty alcohols with 7 EO or the C18-is oxo alcohols with 7 EO.
  • non-ionic surfactant and anionic surfactant in a weight ratio of 3:1 to 1:3, preferably 2:1 to 1:2 and in particular 3:2 to 2:3.
  • Preferred polyalkoxylated amines have a weight-average molecular weight Mw in the range from 1300 g/mol to 6000 g/mol, in particular from 1400 g/mol to 4500 g/mol.
  • the average molecular weights given here and later for other polymers are These are weight-average molecular weights Mw, which can generally be determined by gel permeation chromatography with the aid of an RI detector, the measurement being advantageously carried out against an external standard.
  • They can be prepared in a known manner from ammonia, a monoalkylamine, a monoalkyl-monoalkanolamine or a monoalkyl-dialkanolamine or a mono-, di- or trialkanolamine, for example triethanolamine, methyl-, ethyl-, propyl- and isopropyl-diethanolamine, methyl-, ethyl-, propyl- and isopropyl-diisopropanolamine,
  • the polyalkoxylated amines obtainable in this way can be block or random structures. Particular preference is given, inter alia, to a polyalkoxylated amine obtainable by propoxylation of triethanolamine, preferably with a length of the three side arms of 15 propylene oxide units each. Likewise preferred is a polyalkoxylated amine obtainable by propoxylation of triisopropanolamine, preferably with a length of the three side arms of 15 propylene oxide units each.
  • polyalkoxylated monoalkylamines having a linear, branched, or cyclic alkyl group wherein the alkoxylation is carried out with an alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof, preferably with a mixture containing propylene oxide, particularly preferably with propylene oxide.
  • an alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof, preferably with a mixture containing propylene oxide, particularly preferably with propylene oxide.
  • a polyalkoxylated amine obtainable by propoxylation of tert-butylamine, preferably with a length of the two side arms of 12 propylene oxide units each.
  • a second essential component of detergents is the gluconic acid salt.
  • the weight fraction of the gluconic acid salt in the total weight of the detergent is preferably 0.2 to 6 wt.% and in particular 0.4 to 4 wt.%.
  • the addition of the gluconic acid salt has proven particularly advantageous for stabilizing the dye in the liquid detergent. Due to its availability and ease of processing, the use of sodium gluconate is particularly preferred.
  • antioxidants Another key ingredient in dye stabilization is the use of antioxidants.
  • An antioxidant is a molecule that can slow or prevent the oxidation of other molecules. Oxidation reactions can produce free radicals, which in turn can trigger degradation chain reactions. Antioxidants stop these chain reactions by removing the free radical intermediates and inhibiting other oxidation reactions, as well as being oxidized themselves. Therefore, antioxidants are often reducing agents.
  • the antioxidant is preferably selected from the group consisting of butylhydroxyltoluene (BHT), butylhydroxylanisole (BHA), trimethoxybenzoic acid (TMBA), ⁇ -, ⁇ -, ⁇ - and ⁇ -tocopherol (vitamin E acetate), 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox), 1,2, benzisothiazolin-3-one (Proxel GLX), tannic acid, galic acid, Tinoguard AO-6, Tinoguard TS, ascorbic acid, alkylated phenol, ethoxyquin 2,2,4-trimethyl,1-2-dihydroquinoline, lignosulfonic acid and its salts, benzofuran, benzopyran, tocopherol sorbate, butylhydroxylbenzoic acid and its salts, galic acid and its alkyl esters, uric acid, its salts and alkyl esters,
  • antioxidants are selected from the group of sulfites, hydrogen sulfites and disulfites, preferably from the group sodium sulfite, sodium hydrogen sulfite and sodium disulfite, in particular from the group containing sodium sulfite and sodium disulfite.
  • antioxidants from the disulfite group preferably from the sodium disulfite group
  • the weight proportion of the antioxidant in the total weight of the detergent is preferably 0.02 to 1 wt% and in particular 0.05 to 0.5 wt%.
  • the detergent contains 5 to 25 wt.% organic solvent.
  • the proportion of the organic solvent in the total weight of the detergent is preferably 7 to 20 wt.% and in particular 10 to 18 wt.%.
  • Preferred organic solvents are selected from the group consisting of ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether,
  • the detergent contains water.
  • Preferred detergents are those containing 5 to 15, preferably 8 to 15, wt.% water based on their total weight.
  • the weight fraction of organic phosphonate in the total weight of the detergent is less than 0.1 wt.%.
  • Preferred detergents contain no organic phosphonate, in particular no phosphonate at all.
  • Examples of phosphonate compounds that are preferably not present in the detergent are phosphonates from the group of hydroxyalkane and/or aminoalkanephosphonates, in particular from the group of 1-hydroxyethane-1,1-diphosphonate (HEDP), ethylenediaminetetramethylenephosphonate (EDTMP), and diethylenetriaminepentamethylenephosphonate (DTPMP).
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • ETMP ethylenediaminetetramethylenephosphonate
  • DTPMP diethylenetriaminepentamethylenephosphonate
  • the detergents are characterized by surprisingly high color stability, even under demanding storage conditions. This applies to both dye-free and dye-containing detergents.
  • Preferred detergents contain dye as an optional component.
  • the dye is preferably selected from the group of water-soluble dyes, in particular from the group of water-soluble acid dyes, water-soluble direct dyes, and water-soluble polymer dyes, in particular water-soluble polymer dyes.
  • Suitable dyes are Acid Red 18 (CI 16255), Acid Red 26, Acid Red 27, Acid Red 33, Acid Red 51, Acid Red 87, Acid Red 88, Acid Red 92, Acid Red 95, Acid Red 249 (CI 18134), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet 48, Acid Violet 54, Acid Yellow 1, Acid Yellow 3 (CI 47005), Acid Yellow 11, Acid Yellow 23 (CI 19140), Acid Yellow 3, Direct Blue 199 (CI 74190), Direct Yellow 28 (CI 19555), Food Blue 2 (CI 42090), Food Blue 5:2 (CI 42051 :2), Food Red 7(01 16255), Food Yellow 13 (CI 47005), Food Yellow 3 (CI 15985), Food Yellow 4 (CI 19140), Reactive Green 12, Solvent Green 7 (CI 59040).
  • Preferred dyes are also water-soluble acid dyes, for example Food Yellow 13 (Acid Yellow 3, CI 47005), Food Yellow 4 (Acid Yellow 23, CI 19140), Food Red 7 (Acid Red 18, CI 16255), Food Blue 2 (Acid Blue 9, CI 42090), Food Blue 5 (Acid Blue 3, CI 42051), Acid Red 249 (CI 18134), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet48, Acid Blue 80(01 61585), Acid Blue 182, Acid Blue 182, Acid Green 25 (CI 61570), Acid Green 81.
  • Water-soluble direct dyes such as Direct Yellow 28 (CI 19555), Direct Blue 199 (CI 74190) and water-soluble reactive dyes, such as Reactive Green 12, as well as the dyes Food Yellow 3 (CI 15985), Acid Yellow 184 can also be used.
  • water-soluble polymer dyes for example Liquitint, Liquitint Blue HP (CAS No. 162874-54-6), Liquitint Blue MC, Liquitint Blue 65, Liquitint Cyan 15 (CAS No. 888888-03-0), Liquitint Patent Blue (CAS No. 162874-57-9), Liquitint Violet 129 (CAS No. 888888-06-7), Liquitint Royal Blue (CAS No. 162874-58-0), Liquitint Red ET (CAS No. 888888-02-9), Liquitint Experimental Yellow 8949-43, Liquitint Green HMC, Liquitint Yellow LP, Liquitint Yellow II), Liquitint Aquamarine, (CAS No.
  • Water-soluble polymer dyes from the group Liquitint Cyan 15 (CAS No. 888888-03-0), Liquitint Blue HP (CAS No. 162874-54-6), Liquitint Violet 129 (CAS No. 888888-06-7) and Liquitint Red ET (CAS No. 888888-02-9) are particularly preferred.
  • the weight proportion of the dye in the total weight of dye-containing detergents is preferably 0.001 to 0.5 wt.%, more preferably 0.002 to 0.3 wt.% and in particular 0.005 to 0.2 wt.%.
  • particularly preferred liquid detergents contain, based on their total weight, a) 22 to 50 wt.% anionic surfactant from the group of alkanolamine Cs-is alkylbenzenesulfonates and alkanolamine Cs fatty acid salts; b) 0.1 to 8 wt.% gluconic acid salt; c) 0.01 to 2 wt.% antioxidant from the group of sodium sulfite and sodium disulfite; d) 5 to 25 wt.% organic solvent; e) 0.1 to 15 wt.% water; f) no organic phosphonate; g) 0.001 to 0.5 wt.% water-soluble polymer dye.
  • the detergents do not contain any dye.
  • Corresponding particularly preferred liquid detergents contain, based on their total weight, a) 22 to 50 wt.% anionic surfactant from the group of alkanolamine Cs-18 alkylbenzenesulfonates and alkanolamine Cs fatty acid salts; b) 0.1 to 8 wt.% gluconic acid salt; c) 0.01 to 2 wt.% antioxidant from the group of sodium sulfite and sodium disulfite; d) 5 to 25 wt.% organic solvent; e) 0.1 to 15 wt.% water; f) no organic phosphonate; g) no dye.
  • Preferred detergents contain washing or cleaning-active polymers.
  • Particularly preferred washing or cleaning-active polymers are selected from the group of soil release polymers, dye transfer inhibitors, graying inhibitors, and anti-redeposition agents.
  • Soil release agents are components that positively influence the ability of textiles to be washed out of oil and grease. This effect is particularly evident when a textile is soiled that has already been washed several times with an agent containing this oil and grease-dissolving component.
  • Preferred soil release agents include, for example, non-ionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a methoxyl group content of 15 to 30 wt.% and a hydroxypropoxyl group content of 1 to 15 wt.%, based in each case on the non-ionic cellulose ether, as well as the polymers of phthalic acid and/or terephthalic acid or their derivatives with monomeric and/or polymeric diols known from the prior art, in particular polymers of ethylene terephthalates and/or polyethylene glycol terephthalates or anionically and/or non-ionically modified derivatives thereof.
  • Anionic or non-ionic polyesters of Polypropylene terephthalates are commercially available, for example, under the trade name Texcare®.
  • preferred detergents are those containing washing- or cleaning-active polymers from the group of phthalic acid and/or terephthalic acid or derivatives thereof with monomeric and/or polymeric diols, preferably from the group of polymers of ethylene terephthalates and/or polyethylene glycol terephthalates and/or polypropylene terephthalates or anionically and/or nonionically modified derivatives thereof, particularly preferably from the group of anionic or nonionic polyesters of polypropylene terephthalates.
  • Particularly preferred dye transfer inhibitors are polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), or copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI).
  • the polyvinylpyrrolidones (PVP) used preferably have an average molecular weight of 2,500 to 400,000 and are commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60, or PVP K 90, or from BASF as Sokalan® HP 50 or Sokalan® HP 53.
  • the copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI) used preferably have a molecular weight in the range of 5,000 to 100,000 g/mol.
  • a PVP/PVI copolymer is commercially available, for example, from BASF under the name Sokalan® HP 56.
  • Cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose, and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose, and mixtures thereof are preferred.
  • the weight proportion of this ethoxylated polyethyleneimine in the total weight of the detergent preferably 1 to 10 wt.%, more preferably 1.2 to 7 wt.%, and in particular 1.5 to 4 wt.%.
  • the polyalkyleneimine has primary amino functions at the ends and preferably both secondary and tertiary amino functions in the interior; if appropriate, it can also have only secondary amino functions in the interior, resulting in a linear rather than a branched-chain polyalkyleneimine.
  • the ratio of primary to secondary amino groups in the polyalkyleneimine is preferably in the range from 1:0.5 to 1:1.5, in particular in the range from 1:0.7 to 1:1.
  • the ratio of primary to tertiary amino groups in the polyalkyleneimine is preferably in the range from 1:0.2 to 1:1, in particular in the range from 1:0.5 to 1:0.8.
  • the N atoms in the polyalkyleneimine are separated from one another by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, although not all alkylene groups need to have the same number of C atoms. Particular preference is given to ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and mixtures thereof.
  • the primary amino functions in the polyalkyleneimine can carry 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, although not every amino function needs to be substituted by an alkoxy group.
  • the average number of alkoxy groups per primary and secondary amino function in the ethoxylated polyalkyleneimine is preferably 5 to 100, in particular 10 to 50.
  • the ethoxylated polyalkyleneimines are obtainable by reacting the polyalkyleneimines with ethylene oxide.
  • particularly preferred detergents contain washing or cleaning-active polymers from the group of carboxymethylcelluloses, non-ionic cellulose ethers, polyalkoxylated polyethyleneimines and (co)polymers of phthalic acid or terephthalic acid.
  • preferred detergents contain, based on their total weight, 0.5 to 7 wt.%, preferably 1.0 to 6 wt.% enzyme preparations.
  • an enzyme preparation comprises other components such as enzyme stabilizers, carrier materials or fillers.
  • the enzyme protein usually only forms a fraction of the total weight of the enzyme preparation.
  • Preferably used enzyme preparations contain between 0.1 and 40 wt.%, preferably between 0.2 and 30 wt.%, more preferably between 0.4 and 20 wt.% and most preferably between 0.8 and 10 wt.% of the enzyme protein.
  • a Enzyme stabilizer may be present in an amount of 0.05 to 35 wt.%, preferably 0.05 to 10 wt.%, based on the total weight in the enzyme composition.
  • the protein concentration can be determined using known methods, such as the BCA method (bicinchoninic acid; 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method.
  • the active protein concentration is determined by titrating the active sites using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)) and determining the residual activity.
  • a suitable irreversible inhibitor for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)
  • the detergents preferably contain at least one enzyme preparation, particularly preferably at least three enzyme preparations of enzymes from the group consisting of lipase, mannanase, amylase, protease, cellulase, hexosaminidase, preparations of a pectinolytic enzyme and endoglucanase.
  • Detergents preferred in terms of their cleaning performance contain, based on their total weight, 0.1 to 0.4 wt.% and in particular 0.2 to 0.3 wt.% of hexosaminidase preparation, particularly preferably ß-hexosaminidase preparation.
  • hexosaminidase refers to a polypeptide with hexosaminidase activity (hexosaminidases) and includes enzymes that catalyze the hydrolysis of N-acetyl-D-hexosamine or N-acetyl-glucosamine polymers.
  • Polypeptides with hexosaminidase activity include dispersins such as Dispersin B (DspB), which are ß-N-acetylglucosamine dispersins belonging to the glycoside hydrolase 20 family. Dispersins are produced by the periodontal pathogen Aggregatibacter actinomycetemcomitans, a Gram-negative oral bacterium. Dispersin B is a ß-hexosaminidase that specifically hydrolyzes ß-1,6-glycosidic bonds of acetylglucosamine polymers. The use of hexosaminidases from the ß-hexosaminidase group is preferred.
  • DspB Dispersin B
  • Dispersins are produced by the periodontal pathogen Aggregatibacter actinomycetemcomitans, a Gram-negative oral bacterium.
  • Dispersin B is a ß-hexosaminidase that specifically hydrolyze
  • the detergent contains at least one lipase preparation.
  • Lipases preferred according to the invention are selected from at least one enzyme from the group consisting of triacylglycerol lipase (E.C. 3.1.1.3), lipoprotein lipase (E.C. 3.1.1.34), and monoglyceride lipase (E.C. 3.1.1.23).
  • Lipase preparations according to the invention are the commercial products marketed by Amano Pharmaceuticals under the names Lipase M-AP10®, Lipase LE®, and Lipase F® (also Lipase JV®).
  • Lipase F® for example, is naturally present in Rhizopus oryzae.
  • Lipase M-AP10® for example, is naturally present in Mucor javanicus.
  • a highly preferred lipase is commercially available under the trade name Lipex® from Novozymes (Denmark) and can be advantageously used in the detergents according to the invention. Lipase Lipex® 100 L is particularly preferred.
  • the detergents preferably contain at least one amylase, in particular an ⁇ -amylase.
  • ⁇ -Amylases (E.C. 3.2.1.1) act as enzymes to hydrolyze internal ⁇ -1,4-glycosidic bonds of starch and starch-like polymers. Examples include the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, and from B. stearothermophilus, as well as their improved further developments for use in detergents or cleaning agents.
  • the enzyme from B. licheniformis is available from Novozymes under the trade name Termamyl® and from Genencor under the trade name Purastar®ST.
  • the detergent contains 0.01 to 1% by weight, preferably 0.02 to 0.3% by weight of a mannanase preparation.
  • a mannanase catalyzes the hydrolysis of 1,4-beta-D-mannosidic bonds in mannans, galactomannans, glucomannans, and galactoglucomannans. These mannanases are classified according to enzyme nomenclature as E.C. 3.2.1.78.
  • Cellulases suitable according to the invention include, for example, fungal, endoglucanase (EG)-rich compositions which are offered by the company Novozymes under the trade name Celluzyme®.
  • Other commercial products from this company that can be used are Cellusoft®, Renozyme® and Celluclean®.
  • the detergent according to the invention is characterized by high color stability and is therefore particularly suitable for packaging in transparent packaging.
  • Preferred detergents are packaged in transparent containers.
  • the transparent container allows the detergent to be perceived within the container.
  • Examples of such transparent packaging include transparent plastic bottles or transparent, water-soluble film bags.
  • Transparent or “transparency” means that the transmittance within the visible spectrum of light (410 to 800 nm) is greater than 20%, preferably greater than 30%, most preferably greater than 40%, and especially greater than 50%. Thus, as soon as a wavelength of the visible spectrum of light has a transmittance greater than 20%, it is considered transparent within the meaning of the invention.
  • a further preferred subject matter of this application is a detergent portion unit comprising i) a detergent; ii) a transparent water-soluble film which completely encloses the detergent.
  • the water-soluble film enclosing the detergent can comprise one or more structurally different water-soluble polymers.
  • Particularly suitable water-soluble polymers are polymers from the group of (optionally acetalized) polyvinyl alcohols (PVAL) and their copolymers.
  • Water-soluble films are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 gmol -1 , preferably from 20,000 to 500,000 gmol -1 , particularly preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol -1 .
  • polyvinyl alcohol and polyvinyl alcohol copolymers generally involves the hydrolysis of intermediate polyvinyl acetate.
  • Preferred polyvinyl alcohols and polyvinyl alcohol copolymers have a degree of hydrolysis of 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and especially 82 to 88 mol%.
  • Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt, or its ester.
  • such polyvinyl alcohol copolymers contain, in addition to vinyl alcohol, sulfonic acids such as 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, or mixtures thereof; among the esters, C 1-4 alkyl esters or hydroxyalkyl esters are preferred.
  • AMPS 2-acrylamido-2-methyl-1-propanesulfonic acid
  • Other suitable monomers include ethylenically unsaturated dicarboxylic acids, for example itaconic acid, maleic acid, fumaric acid, and mixtures thereof.
  • Suitable water-soluble films for use are marketed by MonoSol LLC, for example, under the designations M8630, M8720, M8310, C8400, or M8900.
  • Other suitable films include Solublon® PT, Solublon® GA, Solublon® KC, or Solublon® KL from Aicello Chemical Europe GmbH, or the VF-HP films from Kuraray.
  • the water-soluble films may contain additional active ingredients or fillers as well as plasticizers and/or solvents, especially water.
  • the group of other active substances includes, for example, materials that protect the ingredients of the preparation enclosed in the film material from decomposition or deactivation Protect against light exposure. Antioxidants, UV absorbers, and fluorescent dyes have proven particularly suitable for this purpose.
  • Plasticizers that can be used include, for example, glycerol, ethylene glycol, diethylene glycol, propanediol, 2-methyl-1,3-propanediol, sorbitol or mixtures thereof.
  • the surface of the water-soluble film of the detergent dispenser can optionally be dusted with a fine powder.
  • Sodium aluminosilicate, silicon dioxide, talc, and amylose are examples of suitable dusting agents.
  • the volume of the detergent portion unit is preferably from 10 to 30 ml, in particular from 12 to 25 ml.
  • Preferred detergent portion units have one to four receiving chambers, preferably three or four receiving chambers. In detergent portion units with two or more receiving chambers, preferably at least one of the receiving chambers, preferably the majority of the receiving chambers, is transparent. Preferred detergent portion units have three or four receiving chambers, and at least two of the chambers contain a detergent according to the invention.
  • Detergent portion unit comprising at least two receiving chambers surrounded by a water-soluble film, wherein one receiving chamber is filled with the detergent according to the invention and the further receiving chamber is filled with a second detergent different from the detergent according to the invention;
  • Detergent portion unit comprising at least three receiving chambers surrounded by a water-soluble film, wherein two receiving chambers are filled with the detergent according to the invention and the further receiving chamber is filled with a second detergent different from the detergent according to the invention;
  • Detergent portion unit at least four receiving chambers which are surrounded by a water-soluble film, wherein three receiving chambers are filled with the detergent according to the invention and the further receiving chamber is filled with a detergent different from the detergent according to the invention.
  • the detergent is particularly suitable for cleaning textiles in machine-based textile cleaning.
  • a further subject matter of this application is therefore a method for textile cleaning, in which a detergent or a detergent portion unit according to the invention is introduced into the washing liquor of a textile washing machine.
  • the mechanical textile cleaning process is preferably carried out at temperatures of 20°C to 60°C, preferably 30°C to 45°C.
  • This registration provides, among other things, the following items:
  • Liquid detergent containing, based on its total weight, a) 22 to 50 wt.% anionic surfactant; b) 0.1 to 8 wt.% gluconic acid salt; c) 0.01 to 2 wt.% antioxidant; d) 5 to 25 wt.% organic solvent; e) 0.1 to 15 wt.% water; f) less than 0.1 wt.% organic phosphonate.
  • the anionic surfactant is selected from the group of Cs-18-alkylbenzenesulfonates, Cs-18-olefinsulfonates, Cs-12-18-alkanesulfonates, Cs-18-estersulfonates, Cs-18-alkylsulfates, Cs-18-alkenylsulfates, fatty alcohol ether sulfates and fatty acid salts, preferably from the group of Cs-18-alkylbenzenesulfonates, Cs-18-alkylsulfates, fatty alcohol ether sulfates and C12-18 fatty acid salts and in particular from the group of Cs-18-alkylbenzenesulfonates and C12-18 fatty acid salts.
  • anionic surfactant is selected from the group of alkanolamine Cs-18-alkylbenzenesulfonates and alkanolamine Cs-12-18 fatty acid salts.
  • anionic surfactant is selected from the group of alkanolamine Cs-is-alkylbenzenesulfonates.
  • Detergent according to one of the preceding points wherein the detergent contains, based on its total weight, 27 to 45 wt.%, preferably 32 to 40 wt.% of anionic surfactant.
  • the detergent contains Cs-18 alkylbenzenesulfonate and C12-18 fatty acid salt and the weight ratio of Cs-18 alkylbenzenesulfonate to C12-18 fatty acid salt is 8:1 to 2:1, preferably 7:1 to 5:2 and in particular 6:1 to 3:1.
  • the detergent contains alkanolamine Cs-is-alkylbenzenesulfonate and alkanolamine Cs fatty acid salt and the weight ratio of alkanolamine Cs-is-alkylbenzenesulfonate to alkanolamine Cs fatty acid salt is 8:1 to 2:1, preferably 7:1 to 5:2 and in particular 6:1 to 3:1.
  • the detergent further contains, based on its total weight, 12 to 36 wt.%, preferably 15 to 33 wt.% and in particular 18 to 30 wt.% of non-ionic surfactant.
  • the nonionic surfactant is selected from the group of ethoxylated primary Cs-18 alcohols, preferably ethoxylated primary Cs-18 alcohols with a degree of alkoxylation of 4 to 10, particularly preferably Cs-12-14 alcohols with 4 EO or 7 EO, Cs-18 alcohols with 7 EO, Cs-18 alcohols with 5 EO, 7 EO or 8 EO, Cs-13-15 oxo alcohols with 7 EO, Cs-12-18 alcohols with 5 EO or 7 EO, in particular Cs-12-18 fatty alcohols with 7 EO or Cs-13-18 oxo alcohols with 7 EO.
  • the nonionic surfactant is selected from the group of ethoxylated primary Cs-18 alcohols, preferably ethoxylated primary Cs-18 alcohols with a degree of alkoxylation of 4 to 10, particularly preferably Cs-12-14 alcohols with 4 EO or 7 EO, Cs-18 alcohols with 7 EO, Cs-18 alcohols with 5 EO, 7
  • the detergent contains, based on its total weight, 1 to 10 wt.%, preferably 1.2 to 7 wt.% and in particular 1.5 to 4 wt.% of polyalkoxylated amine having a weight-average molecular weight Mw in the range from 600 g/mol to 10,000 g/mol, which is obtainable by reacting ammonia or primary alkyl or hydroxyalkylamines which have a molecular weight below 200 g/mol with alkylene oxides.
  • Detergent according to item 11, wherein the polyalkoxylated amine is obtainable by reacting triethanolamine with alkylene oxides, preferably by reacting triethanolamine with ethylene oxide and propylene oxide.
  • Detergent according to one of the preceding points wherein the detergent contains, based on its total weight, 0.2 to 6 wt.% and in particular 0.4 to 4 wt.% of gluconic acid salt, preferably sodium gluconate.
  • the detergent contains antioxidants from the group of sulfites, hydrogen sulfites and disulfites, preferably from the group sodium sulfite, sodium hydrogen sulfite and sodium disulfite, in particular from the group sodium sulfite and sodium disulfite.
  • Detergent according to one of the preceding points wherein the detergent contains, based on its total weight, 0.02 to 1 wt.% and in particular 0.05 to 0.5 wt.% of antioxidant.
  • the detergent contains an organic solvent from the group consisting of ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerin, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxy
  • Detergent according to one of the preceding points wherein the detergent contains, based on its total weight, 7 to 20 wt.%, preferably 10 to 18 wt.% of organic solvent.
  • the detergent contains dye from the group of water-soluble dyes, in particular from the group of water-soluble acid dyes, water-soluble direct dyes and water-soluble polymer dyes, in particular water-soluble polymer dyes.
  • the detergent contains dye from the group Liquitint Blue HP (CAS No. 162874-54-6), Liquitint Cyan 15 (CAS No. 888888-03-0), Liquitint Patent Blue (CAS No. 162874-57-9), Liquitint Violet 129 (CAS No. 888888-06-7), Liquitint Royal Blue (CAS No. 162874-58-0), Liquitint Red ET (CAS No. 888888-02-9), Liquitint Aquamarine, (CAS No. 888888-04-4), Liquitint Blue (CAS No. 888888-02-6), Liquitint Bright Yellow Dye (CAS No. 888888-03-7), Liquitint Brilliant Orange Dye (CAS No.
  • the detergent contains washing or cleaning-active polymer from the group of carboxymethylcelluloses, non-ionic cellulose ethers, polyalkoxylated polyethyleneimines and (co)polymers of phthalic acid or terephthalic acid.

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Abstract

L'invention concerne un détergent à lessive liquide, contenant, par rapport à son poids total, a) 22 à 50 % en poids de tensioactif anionique ; b) 0,1 à 8 % en poids de sel d'acide gluconique ; c) 0,01 à 2 % en poids d'antioxydant ; d) 5 à 25 % en poids de solvant organique ; e) 0,1 à 15 % en poids d'eau ; et f) moins de 0,1 % en poids de phosphonate organique.
PCT/EP2024/080139 2023-12-21 2024-10-24 Détergent à lessive liquide à couleur stable Pending WO2025131379A1 (fr)

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DE102023213172.2A DE102023213172A1 (de) 2023-12-21 2023-12-21 Farbstabiles Flüssigwaschmittel
DE102023213172.2 2023-12-21

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993009215A1 (fr) 1991-11-07 1993-05-13 The Procter & Gamble Company Systeme de stabilisation des couleurs dans des compositions detergentes liquides
WO2022122480A1 (fr) * 2020-12-07 2022-06-16 Unilever Ip Holdings B.V. Compositions détergentes
EP4349946A1 (fr) * 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Produit de traitement de tissu en dose unitaire

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993009215A1 (fr) 1991-11-07 1993-05-13 The Procter & Gamble Company Systeme de stabilisation des couleurs dans des compositions detergentes liquides
WO2022122480A1 (fr) * 2020-12-07 2022-06-16 Unilever Ip Holdings B.V. Compositions détergentes
EP4349946A1 (fr) * 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Produit de traitement de tissu en dose unitaire

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
no. 888888-03-8

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