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WO2018172503A2 - Liquid laundry detergent comprising modified saccharide or polysaccharide - Google Patents

Liquid laundry detergent comprising modified saccharide or polysaccharide Download PDF

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Publication number
WO2018172503A2
WO2018172503A2 PCT/EP2018/057396 EP2018057396W WO2018172503A2 WO 2018172503 A2 WO2018172503 A2 WO 2018172503A2 EP 2018057396 W EP2018057396 W EP 2018057396W WO 2018172503 A2 WO2018172503 A2 WO 2018172503A2
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WO
WIPO (PCT)
Prior art keywords
liquid laundry
laundry detergent
saccharide
weight
cmc
Prior art date
Application number
PCT/EP2018/057396
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French (fr)
Other versions
WO2018172503A3 (en
Inventor
Markus Meise
Eva-Maria REIS-WALTHER
Till GRUENDLING
Volker SETTELS
Thomas Wesley Holcombe
Alejandra Garcia Marcos
Natalia SHABELINA
Michael Bernhard SCHICK
Thomas Kaiser
Dagmar Pascale Kunsmann-Keitel
Giovanni DANDOLA
Original Assignee
Basf Se
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Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2018172503A2 publication Critical patent/WO2018172503A2/en
Publication of WO2018172503A3 publication Critical patent/WO2018172503A3/en

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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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C317/18—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/228—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with phosphorus- or sulfur-containing groups
    • 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

  • Liquid laundry detergent comprising modified saccharide or polysaccharide
  • the present invention relates to a liquid laundry detergent comprising the adduct of a) a vinyl sulfone monomer of formula I
  • R is an organic radical with up to 500 carbon atoms and R may comprise heteroatoms selected from O, N or S and b) a saccharide having a solubility in water of at least 10 parts by weight of saccharide in 100 parts by weight of water at 20°C and 1 bar.
  • laundry detergents may comprise anti greying additives.
  • Native or modified saccharides or polysaccharides are known as anti greying additives which reduce redeposition of soil on textile fabrics during the washing process.
  • CMC Carboxymethylcellulose
  • US 9523064 addresses the problem of low compatibility of cellulose ethers such as CMC in liquid laundry detergents, such low compatibility being obvious either from viscosity increase, phase separation or from precipitation.
  • US 9523064 discloses the use of sulfoethyl cellulose.
  • Vinyl sulfone monomers are known in the art. Margherita et al. disclose the preparation of poly (ethylene glycol) vinyl sulfone in Bioconjugate Chem.1996, 7, 363-368. The same method for the preparation of poly (ethylene glycol) vinyl sulfone is described in EP 0728 155 B1 . Neither Bioconjugate Chem.1996, 7, 363-368 nor EP 0728 155 B1 disclose vinyl sulfone monomers with a terminal hydroxyl group. It was an object of the present invention to provide anti-greying additives which are useful in liquid laundry detergents.
  • the anti-greying additives should have a good compatibility in liquid laundry detergents or at least a reduced precipitation or turbidity compared with anti-greying additives of the art. Furthermore, the anti-greying additives should have a high anti greying effect in the washing process.
  • liquid laundry detergent defined above has been found.
  • compounds have been found that are useful as anti-greying additives in liquid laundry compositions.
  • the vinyl sulfone monomer in a) is a monomer of formula I
  • R is an organic radical with up to 500 carbon atoms and R may comprise het- eroatoms selected from O, N or S.
  • R may, for example, comprise oxygen in form of ether, alcohol or carbonyl groups.
  • R may, for example, comprise nitrogen in form of primary, secondary or tertiary amino groups.
  • R may, for example, comprise sulfur in form of thioether groups.
  • R does not comprise nitrogen nor sulfur atoms but may comprise oxygen atoms, in particular oxygen atoms in form of ether or hydroxyl groups or both.
  • a particularly preferred monomer is the vinyl sulfone monomer of formula la
  • X and Y independently from each other are an alkylene group with 2 to 10 carbon atoms
  • Z is hydrogen or an alkyl group with 1 to 10 carbon atoms
  • n is 0 or an integral number from 1 to 200.
  • X is an alkylene group with 2 to 4 carbon atoms.
  • alkylene- groups as ethylene, n-propylen, iso-propylen and n-butylene may be mentioned.
  • X is an ethylene group.
  • Y is an alkylene group with 2 to 4 carbon atoms.
  • alkylene groups as ethylene, n-propylen, iso-propylen and n-butylene may be mentioned.
  • X is an ethylene or isopropylene group.
  • Y is an ethylene group as well.
  • Z is hydrogen or an alkyl group with 1 to 4 carbon atoms such as a methyl, ethyl or propyl or butyl group.
  • n is 0 or an integral number from 1 to 150. In a most preferred embodiment n is an integral number from 1 to 150. In a particularly preferred embodiment n is an integral number from 1 to 100, respectively from 2 to 80.
  • a preferred monomer is the vinyl sulfone monomer according to formula la wherein X and Y independently from each other are an alkylene group with 2 to 10 carbon atoms, Z is hydrogen and n is an integral number from 1 to 100.
  • a most preferred monomer is the vinyl sulfone monomer according to formula la with both X and Y being an ethylene group and Z being hydrogen and n is an integral num- ber from 1 to 100, in particular from 2 to 80.
  • Vinyl sulfone monomers wherein Z is an alkyl group are known in the art as mentioned above. Vinyl monomers wherein Z is a hydrogen and hence have a terminal hydroxyl group may be produced accordingly.
  • a preferred process for the preparation of the above vinyl sulfone monomers starts with vinyl mercapto alkanol.
  • Vinyl sulfone monomers of formula la and lb are preferably produced by first alkoxylat- ing the hydroxyl group of vinyl mercapto alkanol, preferably vinyl mercapto ethanol, and thereafter oxidizing the sulfur atom to become a sulfone group.
  • Alkoxylation of vinyl mercapto alkanol may be performed as known in the art and described for example in WO 2015/063194.
  • the alkylation is performed with epoxides such as ethylene epoxide or propylene epoxides as alkylation agents in the presence of basic catalysts.
  • Preferred basic catalysts are alkali metal alcoholates such as sodium methylate or potassium methylate.
  • the obtained alkoxylated vinyl mercapto alkanol is oxidized to the corresponding alkoxylated vinyl sulfone monomer.
  • Oxidation may be performed as known in the art.
  • peroxides such as hydrogen peroxide, alkali metal peroxides or transition metal peroxides may be used.
  • oxidation catalysts may be used. The use of catalysts may be helpful in the production of sulfone monomers of formula la wherein n has a value of at least 5.
  • Catalysts are, for example alkali metal chromate, alkali metaldichromate or alkali metal tungstate.
  • the saccharide in b) has a solubility in water of at least 10 parts by weight of saccharide in 100 parts by weight of water at 20°C and 1 bar.
  • the saccharide has a solubility of at least 20 parts by weight, in particular of at least 30 parts by weight of saccharide in 100 parts by weight of water at 20°C and 1 bar.
  • the term saccharide shall include monosaccharides, disaccharides, oligo- and poly saccharides. Mono- and disaccharides are commonly also referred to as sugars. As monosaccharides mentioned may be those with an aldehyde group (aldose) or a keto group (ketose).
  • the monosaccharides may consist of three carbon atoms (so called trioses), of four carbon atoms (so called tetroses), of five carbon atoms (so called pentoses) or of six carbon atoms (so called hexoses).
  • disaccharides, oligo- and polysaccharides are commonly referred to as polysaccharides. Accordingly, polysaccharides comprise at least two structural units of monosaccharides.
  • the saccharide is a C6 monosaccharide or a polysaccharide derived from a C6 monosaccharide.
  • the saccharide is cellulose or a cellulose derivative.
  • the cellulose or cellulose derivative such as carboxy methyl cellulose may, for exam- pie, have a weight average molecular weight of 1 .000 g/mol to 1 .000.000 g/mol.
  • the cellulose or cellulose derivative such as carboxy methyl cellulose has a weight average molecular weight of at least 10.000, in particular of at least
  • the weight average molecular weight is not higher than 500.000, in particular not higher than 300.000.
  • cellulose derivatives at least one hydrogen of one or more cellulose structural units is replaced by another molecular group.
  • Cellulose derivatives are in particular carboxy methyl cellulose or other hydrophilic modified cellulose, for example cellulose substituted by sulfo ethyl groups as disclosed in US 9523064.
  • a most preferred saccharide is carboxy methyl cellulose.
  • Polysaccharides of hexoses such as starch or cellulose have three hydroxyl groups per structural unit. The hydrogen atoms of these three hydroxyl groups are available for being substituted. The degree of substitution is defined to be the average substitution of each structural unit and has at maximum a value of 3.
  • the carboxy methyl cellulose has a degree of substitution by the carboxy methyl group of 0.1 to 2, in particular of 0.5 to 1.4 To the adduct of the vinyl sulfone monomer and the saccharide
  • the adduct of the vinyl sulfone monomer of formula I and the saccharide is a so called Michael adduct.
  • One of the free hydroxyl groups undergoes an addition reaction to the vinyl group of the vinyl sulfone monomer as shown in the reaction scheme below:
  • the adduct may be an adduct of saccharide with one defined vinyl sulfone monomer or an adduct of saccharide with a mixture of different vinyl sulfone monomers.
  • the adduct is a saccharide with a degree of substitution by the vinyl sulfone monomer or a mixture of vinyl sulfone monomers of 0.1 to 2, in particular of 0.2 to 1 .5.
  • the adduct is a carboxy methyl cellulose with a degree of substitution by the vinyl sulfone monomer or a mixture of vinyl sulfone monomers of 0.1 to 2, in particular of 0.2 to 1.5.
  • the adduct is formed by reacting the saccharide and the vinyl sulfone monomer.
  • reaction is performed in a solvent, in particular water.
  • a clear solution of the saccharide in the solvent is formed first followed by adding and reacting the vinyl sulfone monomer.
  • the pH value of the reaction mixture is preferably higher than 7, in particular from 8 to 12.
  • the pH may be adjusted by adding basic compounds such as tertiary amines.
  • the reaction may be performed at elevated temperatures, for example at temperatures of 20 to 80°C, in particular of 30 to 60°C.
  • the obtained adduct may be isolated from the solvent.
  • the isolated adduct or, alternatively, the obtained solution of the adduct may be used as additive to liquid laundry detergents.
  • the liquid laundry detergent of this invention comprises at least one surfactant, the above adduct of saccharide and vinyl sulfone monomer, preferably at least one builder, solvent and optionally further components.
  • the surfactant is preferably selected from anionic, nonionic, cationic, amphoteric and/or zwitterionic surfactants or mixtures thereof.
  • Suitable nonionic surfactants are in particular:
  • alkoxylated C8-C22-alcohols such as fatty alcohol
  • alkoxylates oxo alcohol alkoxylates and Guerbet alcohol alkoxylates: the alkoxyla- tion can be effected with C2-C20 alkylene oxides, preferably ethylene oxide, propylene oxide and/or butylene oxide.
  • Block copolymers or random copolymers may be present. Per mole of alcohol, they comprise typically from 2 to 50 mol, preferably from 3 to 20 mol of at least one alkylene oxide.
  • the preferred alkylene oxide is ethylene oxide.
  • the alcohols have preferably from 10 to 18 carbon atoms.
  • alkyl phenol alkoxylates especially alkylphenol ethoxylates which comprise C6-C14- alkyl chains and from 5 to 30 mol of alkylene oxide/mole,
  • alkylpolyglucosides which comprise Cs-C22-alkyl, preferably Cio-Cis-alkyl chains and generally from 1 to 20, preferably from 1 .1 to 5 glucoside units.
  • Suitable anionic surfactants are, for example:
  • alkoxylated C8-C22-alcohols alkyl ether sulfates: compounds of this type are prepared, for example, by first alkoxylating a C8-C22-alcohol, preferably a C10-
  • Cie-alcohol for example a fatty alcohol, and then sulfating the alkoxylation product.
  • alkoxylation for example a fatty alcohol
  • linear C8-C20 alkylbenzenesulfonat.es LAS
  • LAS linear C9-C13- alkylbenzenesulfonat.es and -alkyltoluenesulfonat.es.
  • alkanesulfonates especially C8-C24-alkanesulfonat.es, preferably C10-C18- alkanesulfonates.
  • - olefinsulfonates having from 8 to 22, preferably from 12 to 18, carbon atoms
  • isethionates especially acyl isethionates and N-acyl taurates.
  • N-acyl sarcosinates N-acyl sarcosinates.
  • sulfosuccinates (mono- or diesters of sulfosuccinic acid) and alkyl succinates
  • organic phosphate esters especially mixtures of mono- and diester phosphates of hydroxyl-terminated alkoxide condensates and salts thereof.
  • poly- oxalkylated alkylarylphosphate esters for example based on alkoxylated C8-C22- alcohols or alkoxylated
  • soaps such as the sodium and potassium salts of C8-C24-carboxylic acids.
  • the anionic surfactants are added to the detergent preferably in the form of salts.
  • Suitable salts are, for example, alkali metal salts such as sodium, potassium and lithium salts, and ammonium salts such as hydroxyethylammonium, di(hydroxyethyl) ammonium and tri(hydroxyethyl)ammonium salts.
  • Particularly suitable cationic surfactants include:
  • ester quats especially quaternary esterified mono-, di- and trialkanolamines which have been esterified with C8-C22-carboxylic acids;
  • Suitable amphoteric surfactants are derivatives of aliphatic or heterocyclic, secondary and tertiary amines in which the aliphatic radicals preferably have from 8 to 18 carbon atoms and at least one radical comprises one or more anionic water-soluble groups, for example one or more carboxylate, sulfonate, sulfate, phosphate or phosphonate groups.
  • amphoteric surfactants examples include:
  • alkylamino)propionates 3-(alkylamino)propionates, (alkylamino)acetates, 3-(dialkylamino)propionates and (dialkylamino) acetates, where preferably at least one alkyl group comprises from 8 to 18 carbon atoms.
  • alkylaminopropanesulfonates where the alkyl group preferably comprises from 8 to 18 carbon atoms.
  • Suitable zwitterionic surfactants are, for example:
  • amine oxides especially alkyldimethylamine oxides and alkyldiethylamine oxides, where the alkyl group preferably comprises from 8 to 18 carbon atoms, betaines, especially carbobetaines, sulfobetaines and phosphobetaines, such as: R 6 (R 7 ) 2 N + (CH 2 )nCOO- with the following preferred definition of the variables:
  • R 6 Ce-Cie-alkyl
  • R 7 Ci-C 3 -alkyl
  • n from 1 to 5.
  • R 6 CONH(CH 2 )m(R 7 )2N + (CH 2 )nCOO- with the following preferred definition of the variables:
  • R 6 C7-Ci7-alkyl;
  • R 7 Ci-C3-alkyl;
  • n, m each independently from 1 to 5.
  • R 6 (R 7 )2N + (CH2)nS03- with the following preferred definition of the variables:
  • R 6 Ce-Cie-alkyl
  • R 7 Ci-C 3 -alkyl
  • n from 1 to 5.
  • the adduct of saccharide and vinyl sulfone monomer is effective as anti greying additive in the liquid laundry detergent.
  • the liquid laundry detergent comprises the adduct of saccharide and vinyl sulfone monomer in an amount of 0.1 to 30% parts by weight, in particular in amounts of 5 to 20 parts by weight on 100 parts by weight of surfactants.
  • the liquid laundry detergent may comprise at least one builder.
  • the liquid laundry detergent comprises at least one builder.
  • no disctinction will be made between builders and such components elsewhere called "co-builders".
  • builders are complexing agents, ion exchange compounds, and precipitating agents.
  • Builders are, for example, selected from citrates, phosphates, silicates, carbonates, phosphonates, amino carboxylates and polycarbox- ylates.
  • the liquid laundry detergent comprises builders in an amount of 0.1 to 90 parts by weight, in particular in an amount of 5 to 70 parts by weight on 100 parts by weight of surfactants.
  • the solvent in the liquid laundry detergent is preferably water, solvents mixable with water or combinations thereof. Most preferred is water as solvent or mixtures of water with water-mixable solvents.
  • Water mixable solvents are preferably organic solvents which form homogeneous mixtures with water at 20°C in any mix ratio.
  • Such mixable solvents are preferably selected from monovalent or polyvalent alcohols, alkanolamines or glycol ethers.
  • Preferred water mixable solvents are ethanol, n- propanol or isopropanol, butanol, ethylene glycol, butanediol, glycerol, diethylene glycol, 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, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1 -butoxyethoxy-2-propano
  • the liquid laundry detergent contains water, water mixable organic solvents or mixtures of water and organic, water mixable solvents in an amount that the liquid laundry detergent has the fluidity and viscosity desired.
  • the liquid laundry detergent may comprise further optional ingredients such as, for example, viscosity modifiers, foam boosting or foam reducing agents, perfumes, dyes, optical brighteners, dye transfer inhibiting agents, preservatives and basic compounds such as alkali metal salts to adjust the pH value.
  • Liquid laundry detergents may further comprise enzymes. Examples of useful enzymes are, for example, lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, and any combinations thereof.
  • the liquid laundry detergent may also comprise one or more bleaching agents .
  • Preferred bleaching agents are selected from sodium perborate, anhydrous or, for example, as the monohydrate or as the tetrahydrate or so-called dihydrate, sodium per- carbonate, anhydrous or, for example, as the monohydrate, and sodium persulfate, where the term "persulfate" in each case includes the salt of the peracid H2SO5 and also the peroxodisulfate.
  • the liquid laundry detergent may also comprise one or more bleach catalysts.
  • Bleach catalysts can be selected from oxaziridinium-based bleach catalysts, bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes.
  • Transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes.
  • Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and also cobalt-, iron-, copper- and ruthenium-amine complexes can also be used as bleach catalysts.
  • the liquid laundry detergent may also comprise one or more bleach activators, for ex- ample tetraacetyl ethylene diamine, tetraacetylmethylenediamine, tetraacetylglycoluril, tetraacetylhexylenediamine, acylated phenolsulfonates such as for example n- nonanoyl- or isononanoyloxybenzene sulfonates, N-methylmorpholinium-acetonitrile salts ("MMA salts”), trimethylammonium acetonitrile salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1 ,5-diacetyl-2,2-dioxohexahydro-1 ,3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
  • bleach activators for ex- ample tetraacety
  • the liquid laundry detergent may also comprise one or more corrosion inhibitors.
  • corrosion inhibitors include triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, also phenol derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.
  • Further suitable surfactants, builders and other components of liquid laundry detergents are disclosed in WO 2015/091 160 and are included herein by reference.
  • a liquid laundry detergent ready to be used, for example, in washing machines may comprise
  • a liquid laundry detergent ready to be used, for example, in washing machines preferably comprises 5 to 80 5 by weight of surfactants
  • solvent which are preferably water or mixtures of water with water mixable organic solvents whereby all components add to 100 % by weight.
  • the liquid laundry detergent may be used for any type of laundry made from any type of fibers.
  • Fibers can be of natural or synthetic origin, or they can be mixtures of natural of natural and synthetic fibers. Examples of fibers of natural origin are cotton and wool. Examples for fibers of synthetic origin are polyurethane fibers such as Spandex® or Lycra®, polyester fibers, or polyamide fibers. Fibers may be single fibers or parts of textiles such as knitwear, wovens, or nonwovens.
  • the soil or dirt to be removed can be proteins, grease, fat, oil, sebum, non-polar soils like soot and byproducts of incomplete hydrocarbon combustion, particulate stains such as pigments and clays, or mixtures of at least two of the foregoing.
  • liquid laundry detergent at a temperature in the range of from 15 to 90°C, preferably in the range of from 20 to 60°C.
  • the liquid laundry detergent may be used manually but it is preferred to use it in a mechanical device, for example in a washing machine.
  • the adduct of saccharide and the vinyl sulfone monomer of formula I has good solubility in liquid laundry detergents. In the preparation of the liquid laundry detergent the adduct does cause no or at least less problems with precipitation or turbidity. The adduct is very effective as anti-greying additive in liquid laundry detergents. Examples
  • Vinyl sulfone monomer of formula la with X and Y being an ethylene group and n 10, shortly referred to as VSM 1 1
  • VME vinyl mercapto ethanol
  • VSM 10 100 g of ethoxylated VME were dissolved in 50 g of water. Sodium tungstate (2.83 g) was added. Thereafter hydrogen peroxide (137.34 g, 50% aq. solution) was added over a period of 1 h. The obtained reaction mixture was stirred for further 30 min. Formation of VSM 10 was confirmed by 1 H-NMR.
  • VME vinyl mercapto ethanol
  • VSM 5 was con- firmed by 1 H-NMR.
  • CMC Carboxymethyl cellulose
  • the CMC used was obtained from Aldrich and had a weight average molecular weight of 90.000 g/mol.
  • CMC (7.5g) was dissolved in water (143g) at room temperature. The solution was heated to 40 °C and kept at this temperature until the solution was clear. Then the pH was set to 10 by addition of triethyl amine (1.6g). Afterwards the VSM or a mixture of different VSM was added within 20 min. The amount of VSM used was 0.33 equivalent (eq.) per unit of CMC (resulting in substituted CMC with a DS of 0.33), 0.66 eq.
  • Lauryl benzene sulfonate (LAS), coconaut fatty acid, propylene glycol and water were introduced in a vessel as initial charge, heated to 40°C and neutralized with KOH (as 50% strength solution). After cooling, Lutensol® AO 7 which is a C13-C15 alcohol eth- oxylated with 7 EO, and ethanol and finally water were added.
  • the composition of the obtained liquid laundry detergent is found in Table 1 .
  • CMC-VSM adducts were added to liquid detergent in an amount of 1 , 2 or 3 parts by weight per 100 parts by weight of the liquid laundry detergent of Table 1 .
  • the amounts of CMC-VSM added and the results of the greying test are found in Table 2. For comparison, the test has been made without further additive or with CMC as additive.
  • the greying test consists of the repeat washes, in which, in each cycle, rinsing is carried out and fresh soiled fabric is used for each cycle.
  • Washing device Launder-Ometer from Atlas, Chicago, USA
  • Soiled fabric total liquor 1 : 10
  • White fabric cotton: wfkl OA, wfk80A, wfk12A, EMPA221
  • Test fabrics are available, for example from Wfk-Testgewebe GmbH, Christenfeld 10, D-41379 Brueggen and EMPA Testmaterialien Agm Moverstrasse 12, CH-9015 St. Gallen.
  • the fabric After rinsing, spinning is carried out and the fabric is hung up separately to dry. To determine the secondary detergency, the reflectance of the white fabric is measured before and after washing using a photometer (Elrpho) from Datacolor AG, CH-8305 Dietikon, Switzerland).
  • the reflectance values are determined at 460 nm, with in each case four measurement points being averaged per fabric type.
  • test fabric without the addition of any further additives and test fabric with the addition of carboxymethyl cellulose (CMC, 90kDa from Aldrich) at a dosage rate of 1 , respectively 3% was washed.
  • CMC carboxymethyl cellulose
  • Delta R reflectance of the white fabric washed with polymer addition minus reflectance of the white fabric washed with the liquid detergent without polymer
  • a high delta R value corresponds to a good greyness inhibition.

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Abstract

A liquid laundry detergent comprising the adduct of a) a vinyl sulfone monomer of formula (I) wherein R is an organic radical with up to 500 carbon atoms and R may comprise heteroatoms selected from O, N or S and b) a saccharide having a solubility in water of at least 10 parts by weight of sac- charide in 100 parts by weight of water at 20°C and 1 bar.

Description

Liquid laundry detergent comprising modified saccharide or polysaccharide
The present invention relates to a liquid laundry detergent comprising the adduct of a) a vinyl sulfone monomer of formula I
Figure imgf000002_0001
wherein R is an organic radical with up to 500 carbon atoms and R may comprise heteroatoms selected from O, N or S and b) a saccharide having a solubility in water of at least 10 parts by weight of saccharide in 100 parts by weight of water at 20°C and 1 bar. During the washing process of laundry, redeposition of soil may occur which leads to a greying of textiles. Therefore, laundry detergents may comprise anti greying additives. Native or modified saccharides or polysaccharides are known as anti greying additives which reduce redeposition of soil on textile fabrics during the washing process. The use of native or modified polysaccharides in liquid laundry detergents is limited since most of them typically have a high viscosity in water and tend to form a gel or precipitate when formulated in liquid laundry detergents. Therefore, most of them can only be used in powder laundry detergent compositions. Carboxymethylcellulose (CMC) is known as anti-greying additive which can be added to liquid laundry detergents or to laundry detergents in form of powder, see e.g. EP 2 135 933 A1. However, CMC often shows incompatibility with liquid laundry detergents and the use of CMC in liquid laundry detergents does not or not easily result in clear solutions.
US 9523064 addresses the problem of low compatibility of cellulose ethers such as CMC in liquid laundry detergents, such low compatibility being obvious either from viscosity increase, phase separation or from precipitation. US 9523064 discloses the use of sulfoethyl cellulose.
Vinyl sulfone monomers are known in the art. Margherita et al. disclose the preparation of poly (ethylene glycol) vinyl sulfone in Bioconjugate Chem.1996, 7, 363-368. The same method for the preparation of poly (ethylene glycol) vinyl sulfone is described in EP 0728 155 B1 . Neither Bioconjugate Chem.1996, 7, 363-368 nor EP 0728 155 B1 disclose vinyl sulfone monomers with a terminal hydroxyl group. It was an object of the present invention to provide anti-greying additives which are useful in liquid laundry detergents. In particular, the anti-greying additives should have a good compatibility in liquid laundry detergents or at least a reduced precipitation or turbidity compared with anti-greying additives of the art. Furthermore, the anti-greying additives should have a high anti greying effect in the washing process.
Accordingly, the liquid laundry detergent defined above has been found. In addition, compounds have been found that are useful as anti-greying additives in liquid laundry compositions. To the vinyl sulfone monomer
The vinyl sulfone monomer in a) is a monomer of formula I
Figure imgf000003_0001
wherein R is an organic radical with up to 500 carbon atoms and R may comprise het- eroatoms selected from O, N or S.
R may, for example, comprise oxygen in form of ether, alcohol or carbonyl groups. R may, for example, comprise nitrogen in form of primary, secondary or tertiary amino groups.
R may, for example, comprise sulfur in form of thioether groups.
In a preferred embodiment R does not comprise nitrogen nor sulfur atoms but may comprise oxygen atoms, in particular oxygen atoms in form of ether or hydroxyl groups or both.
A particularly preferred monomer is the vinyl sulfone monomer of formula la
Figure imgf000004_0001
wherein X and Y independently from each other are an alkylene group with 2 to 10 carbon atoms, Z is hydrogen or an alkyl group with 1 to 10 carbon atoms and n is 0 or an integral number from 1 to 200.
Preferably, X is an alkylene group with 2 to 4 carbon atoms. As examples alkylene- groups as ethylene, n-propylen, iso-propylen and n-butylene may be mentioned. In a more preferred embodiment of the invention X is an ethylene group. Preferably, Y is an alkylene group with 2 to 4 carbon atoms. As examples alkylene groups as ethylene, n-propylen, iso-propylen and n-butylene may be mentioned. In a more preferred embodiment of the invention X is an ethylene or isopropylene group. In a most preferred embodiment Y is an ethylene group as well. Preferably, Z is hydrogen or an alkyl group with 1 to 4 carbon atoms such as a methyl, ethyl or propyl or butyl group.
In a most preferred embodiment Z is hydrogen. Preferably, n is 0 or an integral number from 1 to 150. In a most preferred embodiment n is an integral number from 1 to 150. In a particularly preferred embodiment n is an integral number from 1 to 100, respectively from 2 to 80.
A preferred monomer is the vinyl sulfone monomer according to formula la wherein X and Y independently from each other are an alkylene group with 2 to 10 carbon atoms, Z is hydrogen and n is an integral number from 1 to 100.
A most preferred monomer is the vinyl sulfone monomer according to formula la with both X and Y being an ethylene group and Z being hydrogen and n is an integral num- ber from 1 to 100, in particular from 2 to 80.
As examples vinyl sulfone monomers of formula la with n = 5 (shortly referred to as VSM 6 as the total number of ethylene groups is 6), with n= 10 (shortly referred to as VSM 1 1 as the total number of ethylene groups is 1 1 ) or with n = 25 (shortly referred to as VSM 26 as the total number of ethylene groups is 26) may be mentioned. Vinyl sulfone monomers wherein Z is an alkyl group are known in the art as mentioned above. Vinyl monomers wherein Z is a hydrogen and hence have a terminal hydroxyl group may be produced accordingly. A preferred process for the preparation of the above vinyl sulfone monomers starts with vinyl mercapto alkanol. The preferred starting material is vinyl mercapto ethanol which has the formula H2C=CH-S-CH2-CH2-OH.
The sulfur atom in the vinyl mercapto alkanol has to be oxidized to become a sulfone group (0=S=0) and the alcohol group may be further reacted to become the desired group R respectively group Z.
Vinyl sulfone monomers of formula la and lb are preferably produced by first alkoxylat- ing the hydroxyl group of vinyl mercapto alkanol, preferably vinyl mercapto ethanol, and thereafter oxidizing the sulfur atom to become a sulfone group.
Alkoxylation of vinyl mercapto alkanol may be performed as known in the art and described for example in WO 2015/063194. In a preferred embodiment the alkylation is performed with epoxides such as ethylene epoxide or propylene epoxides as alkylation agents in the presence of basic catalysts. Preferred basic catalysts are alkali metal alcoholates such as sodium methylate or potassium methylate. The amount of epoxide used determines the value of n. n is known to be an average value. Reacting, for example 5 moles ethylene oxide per mole of vinyl mercapto alkanol finally results in a value of n = 5, taking into account, however, that some of the alkoxylated chains may be longer and others shorter.
In a second step the obtained alkoxylated vinyl mercapto alkanol is oxidized to the corresponding alkoxylated vinyl sulfone monomer. Oxidation may be performed as known in the art. In particular, peroxides such as hydrogen peroxide, alkali metal peroxides or transition metal peroxides may be used. In addition oxidation catalysts may be used. The use of catalysts may be helpful in the production of sulfone monomers of formula la wherein n has a value of at least 5. Catalysts are, for example alkali metal chromate, alkali metaldichromate or alkali metal tungstate. To the saccharide
The saccharide in b) has a solubility in water of at least 10 parts by weight of saccharide in 100 parts by weight of water at 20°C and 1 bar. Preferably, the saccharide has a solubility of at least 20 parts by weight, in particular of at least 30 parts by weight of saccharide in 100 parts by weight of water at 20°C and 1 bar. The term saccharide shall include monosaccharides, disaccharides, oligo- and poly saccharides. Mono- and disaccharides are commonly also referred to as sugars. As monosaccharides mentioned may be those with an aldehyde group (aldose) or a keto group (ketose). The monosaccharides may consist of three carbon atoms (so called trioses), of four carbon atoms (so called tetroses), of five carbon atoms (so called pentoses) or of six carbon atoms (so called hexoses). Herein, disaccharides, oligo- and polysaccharides are commonly referred to as polysaccharides. Accordingly, polysaccharides comprise at least two structural units of monosaccharides.
Preferably, the saccharide is a C6 monosaccharide or a polysaccharide derived from a C6 monosaccharide.
In a preferred embodiment, the saccharide is cellulose or a cellulose derivative.
The cellulose or cellulose derivative such as carboxy methyl cellulose, may, for exam- pie, have a weight average molecular weight of 1 .000 g/mol to 1 .000.000 g/mol. Preferably, the cellulose or cellulose derivative such as carboxy methyl cellulose, has a weight average molecular weight of at least 10.000, in particular of at least
30.000 g/mol. In a preferred embodiment, the weight average molecular weight is not higher than 500.000, in particular not higher than 300.000.
In cellulose derivatives at least one hydrogen of one or more cellulose structural units is replaced by another molecular group.
Cellulose derivatives are in particular carboxy methyl cellulose or other hydrophilic modified cellulose, for example cellulose substituted by sulfo ethyl groups as disclosed in US 9523064.
A most preferred saccharide is carboxy methyl cellulose. Polysaccharides of hexoses such as starch or cellulose have three hydroxyl groups per structural unit. The hydrogen atoms of these three hydroxyl groups are available for being substituted. The degree of substitution is defined to be the average substitution of each structural unit and has at maximum a value of 3.
Preferably, the carboxy methyl cellulose has a degree of substitution by the carboxy methyl group of 0.1 to 2, in particular of 0.5 to 1.4 To the adduct of the vinyl sulfone monomer and the saccharide
The adduct of the vinyl sulfone monomer of formula I and the saccharide is a so called Michael adduct. One of the free hydroxyl groups undergoes an addition reaction to the vinyl group of the vinyl sulfone monomer as shown in the reaction scheme below:
Saccharid-OH + H2C=CH-S(=0)2-R→ Saccharid-0-CH2-CH2-S(=0)2-R
In case of cellulose the maximum degree of substitution by the vinyl sulfone monomer is 3 as each structural unit of cellulose has three hydroxyl groups.
In case of carboxy methyl cellulose the maximum degree of substitution is lower, as some of the hydroxyl groups are already consumed according to the degree of substitution by the carboxy methyl groups (see above).
The adduct may be an adduct of saccharide with one defined vinyl sulfone monomer or an adduct of saccharide with a mixture of different vinyl sulfone monomers.
Preferably, the adduct is a saccharide with a degree of substitution by the vinyl sulfone monomer or a mixture of vinyl sulfone monomers of 0.1 to 2, in particular of 0.2 to 1 .5.
In a most preferred embodiment, the adduct is a carboxy methyl cellulose with a degree of substitution by the vinyl sulfone monomer or a mixture of vinyl sulfone monomers of 0.1 to 2, in particular of 0.2 to 1.5.
The adduct is formed by reacting the saccharide and the vinyl sulfone monomer.
Preferably the reaction is performed in a solvent, in particular water.
In a preferred procedure a clear solution of the saccharide in the solvent is formed first followed by adding and reacting the vinyl sulfone monomer.
The pH value of the reaction mixture is preferably higher than 7, in particular from 8 to 12. The pH may be adjusted by adding basic compounds such as tertiary amines. The reaction may be performed at elevated temperatures, for example at temperatures of 20 to 80°C, in particular of 30 to 60°C.
The obtained adduct may be isolated from the solvent. The isolated adduct or, alternatively, the obtained solution of the adduct may be used as additive to liquid laundry detergents. To the liquid laundry detergent
The liquid laundry detergent of this invention comprises at least one surfactant, the above adduct of saccharide and vinyl sulfone monomer, preferably at least one builder, solvent and optionally further components.
To surfactants
The surfactant is preferably selected from anionic, nonionic, cationic, amphoteric and/or zwitterionic surfactants or mixtures thereof.
Suitable nonionic surfactants are in particular:
alkoxylated C8-C22-alcohols such as fatty alcohol
alkoxylates, oxo alcohol alkoxylates and Guerbet alcohol alkoxylates: the alkoxyla- tion can be effected with C2-C20 alkylene oxides, preferably ethylene oxide, propylene oxide and/or butylene oxide. Block copolymers or random copolymers may be present. Per mole of alcohol, they comprise typically from 2 to 50 mol, preferably from 3 to 20 mol of at least one alkylene oxide.
The preferred alkylene oxide is ethylene oxide. The alcohols have preferably from 10 to 18 carbon atoms.
alkyl phenol alkoxylates, especially alkylphenol ethoxylates which comprise C6-C14- alkyl chains and from 5 to 30 mol of alkylene oxide/mole,
alkylpolyglucosides which comprise Cs-C22-alkyl, preferably Cio-Cis-alkyl chains and generally from 1 to 20, preferably from 1 .1 to 5 glucoside units.
- N-alkylglucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates and block copolymers of ethylene oxide, propylene oxide and/or butylene oxide.
Suitable anionic surfactants are, for example:
- sulfates of (fatty) alcohols having from 8 to 22, preferably from 10 to 18 carbon atoms, especially CgCu-alcohol sulfates, Ci2Ci4-alcohol sulfates, Ci2-Ci8-alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fat alcohol sulfate.
sulfated alkoxylated C8-C22-alcohols (alkyl ether sulfates): compounds of this type are prepared, for example, by first alkoxylating a C8-C22-alcohol, preferably a C10-
Cie-alcohol, for example a fatty alcohol, and then sulfating the alkoxylation product. For the alkoxylation,
preference is given to using ethylene oxide.
linear C8-C20 alkylbenzenesulfonat.es (LAS), preferably linear C9-C13- alkylbenzenesulfonat.es and -alkyltoluenesulfonat.es.
alkanesulfonates, especially C8-C24-alkanesulfonat.es, preferably C10-C18- alkanesulfonates. fatty acid ester sulfonates of the formula R1CH(S03M)C02R2 in which R1 is C6-C2o- alkyl, preferably C8-Ci6-alkyl, and R2 is Ci-C4-alkyl, preferably methyl or ethyl, and M is hydrogen, a water-soluble cation, for example alkali metal cation or ammonium ion.
- olefinsulfonates having from 8 to 22, preferably from 12 to 18, carbon atoms,
isethionates, especially acyl isethionates and N-acyl taurates.
N-acyl sarcosinates.
sulfosuccinates (mono- or diesters of sulfosuccinic acid) and alkyl succinates, organic phosphate esters, especially mixtures of mono- and diester phosphates of hydroxyl-terminated alkoxide condensates and salts thereof. These include poly- oxalkylated alkylarylphosphate esters, for example based on alkoxylated C8-C22- alcohols or alkoxylated
phenol derivatives.
soaps such as the sodium and potassium salts of C8-C24-carboxylic acids.
The anionic surfactants are added to the detergent preferably in the form of salts. Suitable salts are, for example, alkali metal salts such as sodium, potassium and lithium salts, and ammonium salts such as hydroxyethylammonium, di(hydroxyethyl) ammonium and tri(hydroxyethyl)ammonium salts.
Particularly suitable cationic surfactants include:
C7-C25 alkylamines;
N, N-dimethyl-N-(C7-C25-hydroxyalkyl)ammonium salts;
mono- and di(C7-C25-alkyl)dimethylammonium compounds quaternized with alkyl- ating agents;
ester quats, especially quaternary esterified mono-, di- and trialkanolamines which have been esterified with C8-C22-carboxylic acids;
imidazoline quats. Suitable amphoteric surfactants are derivatives of aliphatic or heterocyclic, secondary and tertiary amines in which the aliphatic radicals preferably have from 8 to 18 carbon atoms and at least one radical comprises one or more anionic water-soluble groups, for example one or more carboxylate, sulfonate, sulfate, phosphate or phosphonate groups.
Examples of suitable amphoteric surfactants are:
3-(alkylamino)propionates, (alkylamino)acetates, 3-(dialkylamino)propionates and (dialkylamino) acetates, where preferably at least one alkyl group comprises from 8 to 18 carbon atoms.
- 3-[(3-alkylaminopropyl)amino]propionates and [(3- alkylaminopropyl)amino]acetates, where the alkyl group preferably comprises from 8 to 18 carbon atoms. [(2-acylaminoethyl)(2-hydroxyethyl)amino]acetates where the acyl group preferably comprises from 8 to 18 carbon atoms.
(alkylamino)propanesulfonates where the alkyl group preferably comprises from 8 to 18 carbon atoms.
Suitable zwitterionic surfactants are, for example:
amine oxides, especially alkyldimethylamine oxides and alkyldiethylamine oxides, where the alkyl group preferably comprises from 8 to 18 carbon atoms, betaines, especially carbobetaines, sulfobetaines and phosphobetaines, such as: R6(R7)2N+(CH2)nCOO- with the following preferred definition of the variables:
R6: Ce-Cie-alkyl; R7: Ci-C3-alkyl; n: from 1 to 5.
R6CONH(CH2)m(R7)2N+(CH2)nCOO- with the following preferred definition of the variables: R6: C7-Ci7-alkyl; R7: Ci-C3-alkyl; n, m: each independently from 1 to 5. R6(R7)2N+(CH2)nS03- with the following preferred definition of the variables:
R6: Ce-Cie-alkyl; R7: Ci-C3-alkyl; n: from 1 to 5.
cocoamidopropylbetaine.
To the adduct
The adduct of saccharide and vinyl sulfone monomer is effective as anti greying additive in the liquid laundry detergent.
Preferably, the liquid laundry detergent comprises the adduct of saccharide and vinyl sulfone monomer in an amount of 0.1 to 30% parts by weight, in particular in amounts of 5 to 20 parts by weight on 100 parts by weight of surfactants.
To builders The liquid laundry detergent may comprise at least one builder. Preferably the liquid laundry detergent comprises at least one builder. In the context of the present invention, no disctinction will be made between builders and such components elsewhere called "co-builders". Examples of builders are complexing agents, ion exchange compounds, and precipitating agents. Builders are, for example, selected from citrates, phosphates, silicates, carbonates, phosphonates, amino carboxylates and polycarbox- ylates.
In a preferred embodiment, the liquid laundry detergent comprises builders in an amount of 0.1 to 90 parts by weight, in particular in an amount of 5 to 70 parts by weight on 100 parts by weight of surfactants. To solvents
The solvent in the liquid laundry detergent is preferably water, solvents mixable with water or combinations thereof. Most preferred is water as solvent or mixtures of water with water-mixable solvents.
Water mixable solvents are preferably organic solvents which form homogeneous mixtures with water at 20°C in any mix ratio.
Such mixable solvents are preferably selected from monovalent or polyvalent alcohols, alkanolamines or glycol ethers. Preferred water mixable solvents are ethanol, n- propanol or isopropanol, butanol, ethylene glycol, butanediol, glycerol, diethylene glycol, 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, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1 -butoxyethoxy-2-propanol, 3-methyl- 3-methoxybutanol, propyl-ene glycol tert-butyl ether and any mixtures thereof.
Usually the liquid laundry detergent contains water, water mixable organic solvents or mixtures of water and organic, water mixable solvents in an amount that the liquid laundry detergent has the fluidity and viscosity desired.
To further components of the liquid laundry detergent The liquid laundry detergent may comprise further optional ingredients such as, for example, viscosity modifiers, foam boosting or foam reducing agents, perfumes, dyes, optical brighteners, dye transfer inhibiting agents, preservatives and basic compounds such as alkali metal salts to adjust the pH value. Liquid laundry detergents may further comprise enzymes. Examples of useful enzymes are, for example, lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, and any combinations thereof. The liquid laundry detergent may also comprise one or more bleaching agents .
Preferred bleaching agents are selected from sodium perborate, anhydrous or, for example, as the monohydrate or as the tetrahydrate or so-called dihydrate, sodium per- carbonate, anhydrous or, for example, as the monohydrate, and sodium persulfate, where the term "persulfate" in each case includes the salt of the peracid H2SO5 and also the peroxodisulfate. The liquid laundry detergent may also comprise one or more bleach catalysts. Bleach catalysts can be selected from oxaziridinium-based bleach catalysts, bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and also cobalt-, iron-, copper- and ruthenium-amine complexes can also be used as bleach catalysts.
The liquid laundry detergent may also comprise one or more bleach activators, for ex- ample tetraacetyl ethylene diamine, tetraacetylmethylenediamine, tetraacetylglycoluril, tetraacetylhexylenediamine, acylated phenolsulfonates such as for example n- nonanoyl- or isononanoyloxybenzene sulfonates, N-methylmorpholinium-acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1 ,5-diacetyl-2,2-dioxohexahydro-1 ,3,5-triazine ("DADHT") or nitrile quats (trimethylammonium acetonitrile salts).
The liquid laundry detergent may also comprise one or more corrosion inhibitors. In the present case, this is to be understood as including those compounds which inhibit the corrosion of metal. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, also phenol derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol. Further suitable surfactants, builders and other components of liquid laundry detergents are disclosed in WO 2015/091 160 and are included herein by reference.
Composition of Liquid laundry detergent
A liquid laundry detergent ready to be used, for example, in washing machines may comprise
0.1 to 85 % by weight of surfactants,
0.1 to 10 % by weight of the adduct of vinyl sulfone monomer and saccharide
0.1 to 70 % by weight of builders
0 to 60 % by weight of other components, which are in particular selected from those components listed above and
5 to 80 % by weight of solvent, which are preferably water or mixtures of water with water mixable organic solvents whereby all components add to 100 % by weight. A liquid laundry detergent ready to be used, for example, in washing machines preferably comprises 5 to 80 5 by weight of surfactants
0.2 to 5 % by weight of the adduct of vinyl sulfone monomer and saccharide
5 to 70 % by weight of builders
5 to 60 % by weight of other components, which are preferably selected from those components listed above and
5 to 70 % by weight of solvent, which are preferably water or mixtures of water with water mixable organic solvents whereby all components add to 100 % by weight.
To the use of the liquid laundry detergent
The liquid laundry detergent may be used for any type of laundry made from any type of fibers. Fibers can be of natural or synthetic origin, or they can be mixtures of natural of natural and synthetic fibers. Examples of fibers of natural origin are cotton and wool. Examples for fibers of synthetic origin are polyurethane fibers such as Spandex® or Lycra®, polyester fibers, or polyamide fibers. Fibers may be single fibers or parts of textiles such as knitwear, wovens, or nonwovens.
The soil or dirt to be removed can be proteins, grease, fat, oil, sebum, non-polar soils like soot and byproducts of incomplete hydrocarbon combustion, particulate stains such as pigments and clays, or mixtures of at least two of the foregoing.
It is preferred to use the liquid laundry detergent at a temperature in the range of from 15 to 90°C, preferably in the range of from 20 to 60°C.
The liquid laundry detergent may be used manually but it is preferred to use it in a mechanical device, for example in a washing machine. The adduct of saccharide and the vinyl sulfone monomer of formula I has good solubility in liquid laundry detergents. In the preparation of the liquid laundry detergent the adduct does cause no or at least less problems with precipitation or turbidity. The adduct is very effective as anti-greying additive in liquid laundry detergents. Examples
Preparation of compounds Example 1 :
Vinyl sulfone monomer of formula la with X and Y being an ethylene group and n = 10, shortly referred to as VSM 1 1
In a first step vinyl mercapto ethanol (VME) was ethoxylated according to
WO 2015/063194 with 10 mols of ethylene oxide (EO) per mol of VME.
In a second step the obtained ethoxylated VME was oxidized to VSM 10.
100 g of ethoxylated VME were dissolved in 50 g of water. Sodium tungstate (2.83 g) was added. Thereafter hydrogen peroxide (137.34 g, 50% aq. solution) was added over a period of 1 h. The obtained reaction mixture was stirred for further 30 min. Formation of VSM 10 was confirmed by 1H-NMR.
Example 2:
Vinyl sulfone monomer of formula la with X and Y being an ethylene group and n = 25, shortly referred to as VSM 26
The procedure of example 1 was repeated using 25 mols of EO instead of 10.
Example 3:
Vinyl sulfone monomer of formula la with X and Y being an ethylene group and n = 5, shortly referred to as VSM 6
In a first step vinyl mercapto ethanol (VME) was ethoxylated according to
WO 2015/063194 with 5 mols of EO per mol of VME.
In a second step the obtained ethoxylated VME was oxidized to VSM 5.
100 g of ethoxylated VME were dissolved in 50 g of water. At room temperature hydrogen peroxide (137.34 g, 50% aq. solution) was added over a period of 1 h. The obtained reaction mixture was stirred for further 30 min. Formation of VSM 5 was con- firmed by 1H-NMR.
Example 4:
Michael-Addition of VSM onto Carboxymethyl cellulose (CMC) The CMC used was obtained from Aldrich and had a weight average molecular weight of 90.000 g/mol. CMC (7.5g) was dissolved in water (143g) at room temperature. The solution was heated to 40 °C and kept at this temperature until the solution was clear. Then the pH was set to 10 by addition of triethyl amine (1.6g). Afterwards the VSM or a mixture of different VSM was added within 20 min. The amount of VSM used was 0.33 equivalent (eq.) per unit of CMC (resulting in substituted CMC with a DS of 0.33), 0.66 eq. per unit of CMC (resulting in a substituted CMC with a DS of 0.66) or 1 eq. per unit of CMC (resulting in substituted CMC with a DS of 1 ). The solution was stirred for additional 60 min. The adduct has not to be separated from the solution. The obtained solution of the adduct may be used as additive to liquid laundry detergents.
Following adducts were produced:
CMC-VSM 6 (0.33eq)
CMC-VSM 6 (1 eq)
CMC-VSM 1 1 (0.66eq)
CMC- VSM 6/1 1/26 (1 eq, which are 0.33eq VSM 6; 0.33 eq VSM 1 1 and 0.33 eq VSM 26)
Preparation of the liquid laundry detergent
Lauryl benzene sulfonate (LAS), coconaut fatty acid, propylene glycol and water were introduced in a vessel as initial charge, heated to 40°C and neutralized with KOH (as 50% strength solution). After cooling, Lutensol® AO 7 which is a C13-C15 alcohol eth- oxylated with 7 EO, and ethanol and finally water were added. The composition of the obtained liquid laundry detergent is found in Table 1 .
Table 1 : composition of the liquid laundry detergent
Figure imgf000015_0001
The CMC-VSM adduct or just CMC (for comparison) was added to the liquid laundry detergent of Table 1 in amounts as detailed in the further examples. Solubility of CMC-VSM
0.6 parts by weight of each of CMC (for comparison) or of CMC-VSM 6 (0.33eq), CMC- VSM 6 (1 eq), CMC-VSM 1 1 (0.66eq) or CMC-VSM 6/1 1/26 were added to 100 parts by weight of the liquid laundry detergent prepared above. The mixtures were kept on a roll bock for 24 hours at 25 °C. Afterwards the mixtures were incubated for at least one hour to degas the solution. Then the optical appearance of the mixtures was checked visually. The mixture containing CMC was turbid, over time solids were settling and gel particles were formed at the bottom of the snap cover glass.
The mixtures comprising CMC-VSM 6 (0.33eq), CMC-VSM 6 (1 eq), CMC-VSM 1 1 (0.66eq) or CMC- VSM 6/1 1/26 were clear solutions without any precipitation and without any gel formation.
Greyness-inhibition
CMC-VSM adducts were added to liquid detergent in an amount of 1 , 2 or 3 parts by weight per 100 parts by weight of the liquid laundry detergent of Table 1 .
The amounts of CMC-VSM added and the results of the greying test are found in Table 2. For comparison, the test has been made without further additive or with CMC as additive. The greying test consists of the repeat washes, in which, in each cycle, rinsing is carried out and fresh soiled fabric is used for each cycle.
Washing conditions
Washing device: Launder-Ometer from Atlas, Chicago, USA
Water hardness: 2.5 mmol Ca++ + Mg++/I = 14° German hardness
Ca:Mg:NaHC03 ratio: 4:1 :8 mmol
Washing temperature: 40 °C
Washing time: 30 min (incl. heating time)
Wash cycles: 3
Liquid laundry detergent 1 .25 ml
Total liquor: 250 ml (= liquid laundry detergent detergent + washing water)
Soiled fabric: 5g EMPA 101 cotton fabric with soot/olive oil soiling
5g SBL 2004 (soiled ballast fabric)
or
5g BAF Clay
Soiled fabric: total liquor 1 : 10 White fabric: cotton: wfkl OA, wfk80A, wfk12A, EMPA221
synthetic: wfk30A, wfk20A, EMPA406
Test fabrics are available, for example from Wfk-Testgewebe GmbH, Christenfeld 10, D-41379 Brueggen and EMPA Testmaterialien Agm Moverstrasse 12, CH-9015 St. Gallen.
After rinsing, spinning is carried out and the fabric is hung up separately to dry. To determine the secondary detergency, the reflectance of the white fabric is measured before and after washing using a photometer (Elrpho) from Datacolor AG, CH-8305 Dietikon, Switzerland).
The reflectance values are determined at 460 nm, with in each case four measurement points being averaged per fabric type. For comparison, test fabric without the addition of any further additives and test fabric with the addition of carboxymethyl cellulose (CMC, 90kDa from Aldrich) at a dosage rate of 1 , respectively 3%, was washed. Delta R (reflectance of the white fabric washed with polymer addition minus reflectance of the white fabric washed with the liquid detergent without polymer) is evaluated see table 2. A high delta R value corresponds to a good greyness inhibition.
Table 2: washing results
Parts by
weight of
Soiled fabric Additiv additive Delta R sum for fabrics
EMPA SBL - 294
EMPA SBL CMC 1 363
EMPA SBL CMC-VSM 6 (0.33eq) 3 357
EMPA/SBL CMC-VSM 6 (1 eq) 3 356
EMPA/SBL CMC-VSM 6/1 1/26 (1 eq) 3 350
EMPA/SBL CMC-VME-1 1 (0.66eq) 3 362
Clay - 375
Clay CMC 1 379
Clay CMC-VSM 6 (0.33eq) 3 399
Clay CMC-VSM 6 (1 eq) 3 396
Clay CMC-VSM 6/1 1/26 (1 eq) 3 391
Clay CMC-VSM 1 1 (0.66eq) 3 374

Claims

Claims
1 . A liquid laundry detergent comprising the adduct of a) a vinyl sulfone monomer of formula I
Figure imgf000018_0001
wherein R is an organic radical with up to 500 carbon atoms and R may comprise heteroatoms selected from O, N or S and b) a saccharide having a solubility in water of at least 10 parts by weight of saccharide in 100 parts by weight of water at 20°C and 1 bar.
A liquid laundry detergent according to claim 1 , wherein the vinyl sulfone monomer of formula I is a monomer of formula la
Figure imgf000018_0002
wherein X and Y independently from each other are an alkylene group with 2 to 10 carbon atoms, Z is hydrogen or an alkyl group with 1 to 10 carbon atoms and n is 0 or an integral number from 1 to 200.
A liquid laundry detergent according to claim 2, wherein X and Y are an ethylene group.
A liquid laundry detergent according to any of claims 1 to 3 wherein the saccharide is a C6 monosaccharide or a polysaccharide derived from a C6 monosaccharide.
A liquid laundry detergent according to any of claims 1 to 4 wherein the saccharide is cellulose or a cellulose derivative.
6. A liquid laundry detergent according to any of claims 1 to 5 wherein the saccharide is carboxy methyl cellulose.
7. A liquid laundry detergent according to claim 6 wherein the carboxy methyl cellu- lose has a degree of substitution by the carboxy methyl group of from 0.1 to 2.
8. A liquid laundry detergent according to any of claims 1 to 7 wherein the adduct is a saccharide with a degree of substitution by the vinyl sulfone monomer of formula I of 0.1 to 2.
9. A liquid laundry detergent comprising from 0.1 to 30 parts by weight of the adduct on 100 parts by weight of surfactants.
10. A monomer of formula la
Figure imgf000019_0001
wherein X and Y independently from each other are an alkylene group with 2 to 10 carbon atoms, Z is hydrogen and n is 0 or an integral number from 1 to 200.
PCT/EP2018/057396 2017-03-24 2018-03-23 Liquid laundry detergent comprising modified saccharide or polysaccharide WO2018172503A2 (en)

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EP2135933A1 (en) 2008-06-20 2009-12-23 The Procter and Gamble Company Laundry composition
WO2015063194A1 (en) 2013-10-30 2015-05-07 Basf Se Alkoxylates of s-vinylthioalkanols
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