WO2024251400A1 - Nouvelles combinaisons de tensioactifs et agents de lavage et de nettoyage les contenant - Google Patents

Nouvelles combinaisons de tensioactifs et agents de lavage et de nettoyage les contenant Download PDF

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WO2024251400A1
WO2024251400A1 PCT/EP2024/057105 EP2024057105W WO2024251400A1 WO 2024251400 A1 WO2024251400 A1 WO 2024251400A1 EP 2024057105 W EP2024057105 W EP 2024057105W WO 2024251400 A1 WO2024251400 A1 WO 2024251400A1
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general formula
atoms
range
independently
weight
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English (en)
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Janine BIRNBACH
Peter Schmiedel
Caroline Hartwig
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele 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
    • 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
    • C11D2111/14—Hard surfaces

Definitions

  • the invention relates to a combination of non-ionic surfactant with anionic surfactant, which can be produced at least partially on the basis of renewable raw materials and which has superior washing performance on oily soiling.
  • the invention also relates to washing or cleaning agents which contain this surfactant combination.
  • surfactants to reduce the surface tension of water, to form dispersions and to facilitate solubilization has long been common knowledge in the field of detergents and cleaning agents. Although many surfactants are made entirely or partially from renewable raw materials, some powerful and widely used representatives are still petrochemically based. In addition, there is a constant desire to provide surfactants with outstanding application properties in order to achieve high performance even with low surfactant usage.
  • the object of the present invention is to provide surfactants which have advantageous application properties and can be produced, if possible, on the basis of renewable raw materials.
  • the surfactants should be well tolerated by the skin and can also be formulated together with other surfactants so that they are particularly suitable for use in washing and cleaning agents.
  • Rhamnolipids are compounds in which a mono- or dirhamnose unit is glycosidically linked to the hydroxyl group of a ß-hydroxyl-containing fatty acid, whereby the fatty acid can be esterified with a hydroxyl group of another hydroxyl-containing fatty acid molecule. They are obtained by fermentation of bacteria of the genus Pseudomonas, in particular Pseudomonas aeruginosa, preferably when they grow on hydrophobic substrates such as n-alkanes or vegetable oils. Due to their surface-active behavior and their origin, rhamnolipids belong to the so-called biosurfactants.
  • the 3-(hydroxydecanoyloxy)decanoic acid dirhamnoside for example, has the formula
  • Detergents are known from patent specification EP 0 499 434 B1 which contain 1 to 60% by weight of a surfactant which forms a micellar phase at pH 7.0 and 25°C in 1% by weight aqueous solution and a surfactant which forms a lamellar phase at pH 7.0 and 25°C in 1% by weight aqueous solution, where rhamnolipid can be both the surfactant which forms the micellar phase and the surfactant which forms the lamellar phase.
  • European patent specification EP 1 445 302 B1 relates to detergents which contain at least one glycolipid biosurfactant and at least one non-glycolipid surfactant, where these are in a micellar phase.
  • cleaning agents which contain at least 1% by weight of biosurfactant and an enzyme of bacterial origin.
  • the European patent application EP 0 605 308 A1 discloses compositions which contain 0.001% by weight to 99.99% by weight of anionic and/or nonionic surfactant and 0.001% by weight to 99.99% by weight of glycolipid, where the glycolipids can include, for example, sophorolipids, rhamnolipids, glucose lipids, trehalose lipids and cellobiose lipids.
  • cleaning agents which contain lipase and rhamnolipid, where the rhamnolipid consists of at least 50% by weight of mono-rhamnolipid.
  • Detergents are known from the international patent application WO 2012/010407 A1 which contain glycolipid surfactant and lipase of bacterial origin, wherein the glycolipid surfactant consists of at least 20% by weight of disaccharide acid group-containing glycolipid surfactant.
  • the European patent application EP 2 410 049 A1 discloses mono- and dirhamnolipid-containing cleaning agents in which the weight ratio of monorhamnolipid to dirhamnolipid is in the range from 95:5 to 45:55.
  • the European patent application EP 2 787 065 A1 discloses mono- and dirhamnolipid-containing textile detergents in which the weight ratio of dirhamnolipid to monorhamnolipid is greater than 51:49.
  • rhamnolipid mixtures which contain 51 wt.% to 95 wt.% of a specific dirhamnolipid and 0.5 wt.% to 9 wt.% of a specific monorhamnolipid, in which the weight ratio of dirhamnolipid to monorhamnolipid is greater than 91:9.
  • Washing or cleaning agents containing rhamnolipid and N-containing polymer are known from the international patent application WO 2016/096478 A1.
  • the present invention relates, in a first embodiment, to a surfactant combination of a first alkyl polyglycol ether of the general formula (Ia) or (Ib) with a second alkyl polyglycol ether of the general formula (IIa) or (Hb) and with a rhamnolipid of the general formula (III) or its salt,
  • R is a linear or branched alkyl group having 2 to 4 C atoms, in particular 2 C atoms
  • m is a number from 9 to 15
  • x and y independently of one another are numbers from 0 to 12
  • z is a number from 1 to 4, where the sum x + y + z is in the range from 10 to 16
  • n is a number from 1 to 5
  • a is a number from 2 to 7, where a is at least 1 greater than n
  • o 2, 1 or 0, p is 0 or 1
  • R 1 and R 2 independently of one another are identical or different organic radicals having 2 to 24, in particular 5 to 13 carbon atoms.
  • surfactants of the general formula (Ib) or the general formula (IIb) are less preferred than surfactants of the general formula (Ia) or the general formula (Ia), since they are only obtainable from a renewable raw material basis with comparatively great effort.
  • Preferred surfactants of the general formula (Ia) or the general formula (Ila) are those in which m is a number in the range from 11 to 15 and/or n is a number in the range from 2 to 4 and/or a is a number in the range from 4 to 7.
  • Surfactants of the general formula (la), (Ib), (lla) or (llb) can be prepared in a known manner by r T OH L I J z
  • Alkoxylation of alcohols CH3(CH2)m-OH or L Jy where when alcohol mixtures are used the indices m, x, y and z here and in the compounds of the general formula (la), (Ib), (lla) or (llb) can also be non-integer.
  • Ethylene oxide is preferably used for the alkoxylation. Since homolog mixtures are generally formed during the alkoxylation of the alcohols, the average degree of alkoxylation n or a in the compounds of the general formula (la), (Ib), (lla) or (llb) can also be non-integer.
  • the alcohol CH3(CH 2 )m-OH is preferably a fatty alcohol and thus also comes from a renewable raw material base.
  • the particularly preferred surfactants of the general formula (la) include the linear Ci2 alcohol with 3 ethylene oxide groups and the linear Cu alcohol with 4 ethylene oxide groups as well as the technical alkoxylates which are formed by reacting 1 molar equivalent of linear Ci2 alcohol or linear Cu alcohol with 2, 3 or 4 molar equivalents of ethylene oxide.
  • the particularly preferred surfactants of the general formula (lla) include the linear Ci2-alcohol with 5 ethylene oxide groups and the linear Cu-alcohol with 7 ethylene oxide groups as well as the technical alkoxylates which are formed by reacting 1 mole equivalent of linear Ci2-alcohol or linear Cu-alcohol with 5, 6 or ? mole equivalents of ethylene oxide
  • the weight ratio of alkyl polyglycol ether to rhamnolipid is preferably in the range from 50:50 to 99:1, in particular from 70:30 to 95:5 and particularly preferably from 80:20 to 90:10. If the surfactant combinations contain mixtures of compounds of the general formula (Ia) and the general formula (Ib), those of the general formula (Ia) are preferably present in larger weight proportions than those of the general formula (Ib).
  • the surfactant combination essential to the invention develops its advantageous effect even at low temperatures
  • it or an agent containing it is preferably used in processes for washing laundry or for cleaning hard surfaces which are carried out at temperatures in the range from 20 °C to 40 °C, in particular up to a maximum of 30 °C.
  • a washing or cleaning agent according to the invention preferably contains 5% to 70% by weight, in particular 10% to 50% by weight and particularly preferably 12% to 40% by weight of the surfactant combination defined above.
  • the washing or cleaning agent can contain other ingredients which further improve the application and/or aesthetic properties of the agent.
  • the agent preferably additionally contains one or more substances from the group of non-ionic surfactants, anionic surfactants, builders, bleaches, bleach activators, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, anti-redeposition agents, graying inhibitors, shrinkage inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial agents, non-aqueous solvents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bitter agents, ironing aids, phobic and impregnating agents, skin care agents, swelling and anti-slip agents, softening components and UV absorbers.
  • a washing or cleaning agent according to the invention can contain up to 30% by weight of additional surfactant in addition to the surfactant combination essential to the invention, with the additional surfactants preferably being obtainable from renewable raw materials.
  • additional surfactants preferably being obtainable from renewable raw materials.
  • no additional surfactant is present in addition to the surfactant combination essential to the invention.
  • alkyl glycosides of the general formula R 7 O(G) q can also be used as further nonionic surfactants, in which R 7 corresponds to a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical with 8 to 22, preferably 12 to 18 C atoms and G is the symbol which stands for a glycose unit with 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization q which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; Preferably q is between 1.2 and 1.4.
  • nonionic surfactants which are used either as the sole additional nonionic surfactant or in combination with other additional nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
  • Non-ionic surfactants of the amine oxide type for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides can also be used.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula in which R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst.
  • An agent according to the invention preferably contains at least one water-soluble and/or water-insoluble, organic and/or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methyl glycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N,N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid), lysinetetra(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly)carboxylic acids
  • the relative average molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g/mol and 200,000 g/mol, that of the copolymers between 2,000 g/mol and 200,000 g/mol, preferably 50,000 g/mol to 120,000 g/mol, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular mass of 50,000 to 100,000.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • Terpolymers which contain two unsaturated acids and/or their salts as monomers and vinyl alcohol and/or a vinyl alcohol derivative or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated Cs-Cs-carboxylic acid and preferably from a C3-C4-monocarboxylic acid, in particular from (meth)acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C4-C8-dicarboxylic acid, with maleic acid being particularly preferred.
  • the third monomeric unit is in this case formed from vinyl alcohol and/or preferably an esterified vinyl alcohol.
  • Vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of Ci-C4-carboxylic acids, with vinyl alcohol are particularly preferred.
  • Preferred polymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight of (meth)acrylic acid or (meth)acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate, as well as 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, of vinyl alcohol and/or vinyl acetate.
  • Very particular preference is given to polymers in which the weight ratio of (meth)acrylic acid or (meth)acrylate to maleic acid or maleate is between 1:1 and 4:1, preferably between 2:1 and 3:1 and in particular 2:1 and 2.5:1.
  • the second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is substituted in the 2-position with an alkyl radical, preferably with a Ci-C4-alkyl radical, or an aromatic radical, which is preferably derived from benzene or benzene derivatives.
  • Preferred terpolymers contain 40 wt.% to 60 wt.%, in particular 45 to 55 wt.% (meth)acrylic acid or (meth)acrylate, particularly preferably acrylic acid or acrylate, 10 wt.% to 30 wt.%, preferably 15 wt.% to 25 wt.% methallylsulfonic acid or Methallylsulfonate and as a third monomer 15 wt.% to 40 wt.%, preferably 20 wt.% to 40 wt.% of a carbohydrate.
  • This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, with mono-, di- or oligosaccharides being preferred. Sucrose is particularly preferred.
  • the use of the third monomer presumably builds predetermined breaking points into the polymer, which are responsible for the good biodegradability of the polymer.
  • These terpolymers generally have a relative average molecular mass of between 1,000 g/mol and 200,000 g/mol, preferably between 200 g/mol and 50,000 g/mol.
  • Other preferred copolymers are those which have acrolein and acrylic acid/acrylic acid salts or vinyl acetate as monomers.
  • the organic builder substances can be used, particularly for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, particularly their alkali salts.
  • Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts in the upper half of the ranges mentioned are preferably used in paste-like or liquid, in particular water-containing, agents.
  • Polyphosphates preferably sodium triphosphate, are particularly suitable as water-soluble inorganic builder materials.
  • Crystalline or amorphous, water-dispersible alkali aluminosilicates are particularly used as water-insoluble inorganic builder materials, in amounts of not more than 25% by weight, preferably from 3% by weight to 20% by weight and in particular in amounts of from 5% by weight to 15% by weight.
  • crystalline sodium aluminosilicates in detergent quality in particular zeolite A, zeolite P and zeolite MAP and optionally zeolite X, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, particulate agents.
  • Suitable aluminosilicates in particular do not have any particles with a grain size of more than 30 pm and preferably consist of at least 80% by weight of particles with a size of less than 10 pm.
  • Their calcium binding capacity is generally in the range from 100 to 200 mg CaO per gram.
  • water-soluble inorganic builder materials can be included.
  • polyphosphates such as sodium triphosphate
  • these include in particular the water-soluble crystalline and/or amorphous alkali silicate builders.
  • Such water-soluble inorganic builder materials are preferably included in the agents in amounts of 1 wt.% to 20 wt.%, in particular 5 wt.% to 15 wt.%
  • the alkali silicates that can be used as builder materials preferably have a molar ratio of alkali oxide to SiO2 of less than 0.95, in particular 1:1.1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na2O:SiC>2 of 1:2 to 1:2.8.
  • crystalline silicates which can be present alone or in a mixture with amorphous silicates, preferably crystalline layered silicates of the general formula Na2Si x C>2x+iy H2O are used, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates are those in which x in the general formula mentioned assumes the values 2 or 3.
  • both ß- and 5-sodium disilicates are preferred.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be made from sand and soda.
  • Sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further embodiment.
  • a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.
  • Suitable peroxidic bleaching agents include, in particular, organic peracids or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid, monoperoxyphthalic acid and diperdodecanedioic acid, as well as their salts such as magnesium monoperoxyphthalate, diacyl peroxides, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the conditions of use, such as alkali perborate, alkali percarbonate and/or alkali persilicate, and hydrogen peroxide inclusion compounds such as H2C>2-urea adducts, as well as mixtures of these.
  • organic peracids or peracidic salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid, monoperoxyphthalic acid and diperdodecanedioic acid, as well as their salts such as magnesium monoperoxyphthalate, diacyl peroxides, hydrogen peroxide and inorganic
  • Hydrogen peroxide can also be produced with the aid of an enzymatic system, i.e. an oxidase and its substrate. If solid peroxygen compounds are to be used, these can be used in the form of powders or granules, which can also be coated in a manner known in principle. Alkali percarbonate, alkali perborate monohydrate or hydrogen peroxide are particularly preferred.
  • a detergent that can be used in the context of the invention contains peroxidic bleach in amounts of preferably up to 60% by weight, in particular from 5% by weight to 50% by weight and particularly preferably from 15% by weight to 30% by weight or alternatively from 2.5% by weight to 20% by weight, with hydrogen peroxide being the particularly preferred peroxidic bleach in liquid agents and sodium percarbonate being the particularly preferred peroxidic bleach in solid agents.
  • Peroxidic bleach particles preferably have a particle size in the range from 10 pm to 5000 pm, in particular from 50 pm to 1000 pm and/or a density of 0.85 g/cm 3 to 4.9 g/cm 3 , in particular from 0.91 g/cm 3 to 2.7 g/cm 3 .
  • bleach-activating compounds which yield peroxocarboxylic acid under perhydrolysis conditions
  • compounds which yield optionally substituted perbenzoic acid and/or aliphatic peroxocarboxylic acids having 1 to 12 C atoms, in particular 2 to 4 C atoms, alone or in mixtures.
  • Suitable bleaching agents are activators which carry O- and/or N-acyl groups, in particular of the stated number of C atoms and/or optionally substituted benzoyl groups.
  • acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids thereof, in particular nonanoyl or isononanoyl or lauroyloxybenzenesulfonate (NOBS or iso-NOBS or LOBS) or decanoyloxybenzoate (DOBA), their formal carbonic acid ester derivatives such as 4-(2-decanoyloxyethoxycarbonyloxy)benz
  • bleach-activating compounds such as nitriles from which perimidic acids are formed under perhydrolysis conditions may be present.
  • These include in particular aminoacetonitrile derivatives with a quaternized nitrogen atom according to the formula in which R 1 is -H, -CH3, a C2-24-alkyl or -alkenyl radical, a substituted Ci-24-alkyl or C2-24-alkenyl radical with at least one substituent from the group -CI, -Br, -OH, -NH2, -CN and - N (+) -CH2-CN, an alkyl or alkenylaryl radical with a Ci-24-alkyl group, or a substituted alkyl or alkenylaryl radical with at least one, preferably two, optionally substituted Ci-24-alkyl group(s) and optionally further substituents on the aromatic ring, R 2 and R 3 are
  • Bleach activators which form peroxocarboxylic acids or perimidic acids under perhydrolysis conditions are preferably present in amounts of up to 25% by weight, in particular 0.1% by weight to 10% by weight, in agents according to the invention.
  • Bleach activator particles preferably have a particle size in the range from 10 pm to 5000 pm, in particular from 50 pm to 1000 pm and/or a density of 0.85 g/cm 3 to 4.9 g/cm 3 , in particular from 0.91 g/cm 3 to 2.7 g/cm 3 .
  • bleach-catalyzing transition metal complexes in addition to or instead of the bleach activators mentioned, is possible. These are preferably selected from among the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes.
  • Both inorganic and organic compounds can be used as ligands in such transition metal complexes, which include, in addition to carboxylates, in particular compounds with primary, secondary and/or tertiary amine and/or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, triazole, 2,2'-bispyridylamine, tris-(2-pyridylmethyl)amine, 1,4,7-triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl-1,5,9-triazacyclododecane, (bis-((1-methylimidazol-2-yl)-methyl))-(2-pyridylmethyl)-amine, N,N'-(bis-(1-methylimidazol-2-yl)-methyl)-ethylenediamine, N-bis-(2-benzimidazolylmethyl)-a
  • the inorganic neutral ligands include in particular ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, the complex contains further, preferably anionic, and among these in particular mono- or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO2) group, i.e. a nitro ligand or a nitrito ligand.
  • the (NO2) group can also be bound to a transition metal in a chelating manner or it can bridge two transition metal atoms asymmetrically or pl-O.
  • the transition metal complexes can also carry other, usually simpler ligands, in particular mono- or polyvalent anion ligands.
  • ligands are nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, oxalate, perchlorate and complex anions such as hexafluorophosphate.
  • the anion ligands are intended to ensure charge balance between the transition metal central atom and the ligand system.
  • the presence of oxo ligands, peroxo ligands and imino ligands is also possible.
  • Such ligands in particular can also have a bridging effect, so that multinuclear complexes are formed.
  • both metal atoms in the complex do not have to be the same.
  • the use of binuclear complexes in which the two transition metal central atoms have different oxidation numbers is also possible. If anion ligands are missing or the presence of anion ligands does not lead to charge balance in the grain plex, anionic counterions are present in the transition metal complex compounds to be used according to the invention, which neutralize the cationic transition metal complex.
  • anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, oxalate, benzoate or citrate.
  • transition metal complex compounds are [N,N'-bis[(2-hydroxy-5-vinylphenyl)-methylene]-1,2-diamino-cyclohexane]-manganese-(III) chloride, [N,N'-bis[(2-hydroxy-5-nitrophenyl)-methylene]-1,2-diamino-cyclohexane]-manganese-(III) acetate, [N,N'-bis[(2-hydroxyphenyl)-methylene]-1,2-phenylenediamine]-manganese-(III) acetate, [N,N'-bis[(2-hydroxyphenyl)-methylene]-1,2-diaminocyclohexane]-manganese-(III) chloride, [N,N'-bis[(2-hydroxyphenyl)-methylene]-1,2-diaminoethane]-manganese-(III) chloride, [N,N'-bis[(2-
  • Enzymes that can be used in the agents are those from the class of proteases, amylases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof.
  • Enzymatic active substances obtained from fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus are particularly suitable.
  • the enzymes can be adsorbed on carriers and/or embedded in coating substances in order to protect them against premature inactivation. They are preferably contained in the washing or cleaning agents according to the invention in amounts of up to 5% by weight, in particular from 0.002% by weight to 4% by weight. If the agent according to the invention contains protease, it preferably has a proteolytic activity in the range from about 100 PE/g to about 10,000 PE/g, in particular 300 PE/g to 8,000 PE/g. If several enzymes are to be used in the agent according to the invention, this can be done by incorporating two or more separate enzymes or enzymes prepared separately in a known manner or by two or more enzymes prepared together in a granulate.
  • the agents according to the invention can contain system- and environmentally-compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and/or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali hydroxides.
  • Such pH regulators are contained in the agents according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • the purpose of graying inhibitors is to keep the dirt detached from the textile fiber suspended in the liquor.
  • Water-soluble colloids are suitable for this purpose, for example starch, glue, gelatin, salts of ethercarboxylic acids or ethersulfonic acids of starch or cellulose, or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Starch derivatives other than those mentioned above can also be used, for example aldehyde starches.
  • Cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof are preferred, for example in amounts of 0.1 to 5% by weight based on the agent.
  • the agents can contain a conventional color transfer inhibitor, preferably in amounts of up to 2% by weight, in particular 0.1% by weight to 1% by weight, which in a preferred embodiment is selected from the polymers of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or the copolymers thereof.
  • Enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance that provides hydrogen peroxide in water can also be used.
  • a mediator compound for the peroxidase for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, although the above-mentioned polymeric dye transfer inhibitor active ingredients can also be used in addition.
  • Polyvinylpyrrolidone preferably has an average molecular weight in the range from 10,000 g/mol to 60,000 g/mol, in particular in the range from 25,000 g/mol to 50,000 g/mol.
  • Detergents can contain, for example, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts as optical brighteners, although they are preferably free of optical brighteners for use as color detergents.
  • Suitable examples are salts of 4,4'-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2'-disulfonic acid or similarly structured compounds which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group.
  • the agent according to the invention is particulate and contains, in addition to the surfactant essential to the invention, builder, in particular in an amount in the range of 1 wt.% to 60 wt.%.
  • an agent according to the invention is liquid and contains up to 90% by weight, in particular 10% by weight to 85% by weight, preferably 25% by weight to 75% by weight, and particularly preferably 35% by weight to 65% by weight of water, water-miscible solvent or a mixture of water and water-miscible solvent.
  • Water-miscible solvents include, for example, monohydric alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols and triols with 2 to 4 carbon atoms, in particular ethylene glycol, propylene glycol and glycerin, as well as mixtures thereof and the ethers derivable from the above-mentioned classes of compounds.
  • Such water-miscible solvents are preferably present in the agents according to the invention in amounts not exceeding 30% by weight, in particular from 2% by weight to 20% by weight.
  • the agent according to the invention is portioned ready for individual dosing in a chamber made of water-soluble material; the agent then preferably contains less than 15% by weight, in particular in the range of 1% by weight to 12% by weight, of water.
  • a portion is an independent dosing unit with at least one chamber in which the product to be dosed is contained.
  • a chamber is a space delimited by walls (for example by a film) which can also be filled without the product to be dosed (if necessary with changes in the its shape).
  • a surface coating or a layer of a surface coating is therefore not a wall according to the present invention.
  • the framed film in question is immersed in 800 ml of distilled water tempered to 20 °C in a 1 liter beaker with a circular bottom surface (Schott, Mainz, beaker 1000 ml, low form) so that the surface of the clamped film is arranged at a right angle to the bottom surface of the beaker, the upper edge of the frame is 1 cm below the water surface and the lower edge of the frame is aligned parallel to the bottom surface of the beaker in such a way that the lower edge of the frame runs along the radius of the bottom surface of the beaker and the center of the lower edge of the frame is arranged above the center of the radius of the bottom of the beaker.
  • the material dissolves within 600 seconds when stirred (magnetic stirrer speed 300 rpm, stirring rod: 5 cm long) to such an extent that no individual solid particles are visible to the naked eye.
  • the thermoforming process generally includes forming a first layer of a water-soluble film material to form recesses for receiving a composition therein, filling the composition into the recesses, covering the composition-filled recesses with a second layer of a water-soluble film material, and sealing the first and second layers together at least around the recesses.
  • the water-soluble film material is preferably selected from polymers or polymer mixtures.
  • the casing can be formed from one or from two or more layers of water-soluble film material.
  • the water-soluble film materials of the first layer and the further layers, if present, can be the same or different.
  • the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer; more preferably it consists of polyvinyl alcohol or polyvinyl alcohol copolymer.
  • Water-soluble films for producing the water-soluble coating 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 .
  • Polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid, and/or mixtures of the above polymers can additionally be added to a film material suitable for producing the water-soluble coating.
  • the copolymerization of monomers underlying such polymers, individually or in mixtures of two or more, with vinyl acetate is also possible.
  • preferred polyvinyl alcohol copolymers comprise an ethylenically unsaturated carboxylic acid, its salt or its ester.
  • such polyvinyl alcohol copolymers particularly preferably contain acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof; among the esters, C 1-4 alkyl esters or hydroxyalkyl esters are preferred.
  • preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, ethylenically unsaturated dicarboxylic acids as further monomers. Suitable dicarboxylic acids are, for example, itaconic acid, maleic acid, fumaric acid and mixtures thereof, with itaconic acid being particularly preferred.
  • the washing or cleaning agent portion comprising the washing or cleaning agent and the water-soluble casing, can have one or more chambers.
  • the water-soluble casings with a chamber can have a substantially dimensionally stable spherical, spherical-ellipsoidal, cube-shaped, cuboid-shaped or pillow-shaped configuration with a circular, elliptical, square or rectangular basic shape.
  • the agent can be contained in one or more chambers, if present, of the water-soluble casing.
  • the water-soluble casing has two chambers.
  • both chambers can each contain a solid partial composition or each contain a liquid partial composition, or the first chamber contains a liquid partial composition and the second chamber contains a solid partial composition.
  • the proportions of the agents contained in the different chambers of a water-soluble casing with two or more chambers can have the same composition.
  • the agents in a water-soluble casing with at least two chambers have partial compositions that differ in at least one ingredient and/or in the content of at least one ingredient.
  • a partial composition of such agents according to the invention comprises enzyme and/or bleach activator and a separate further partial composition comprises peroxidic bleaching agent, in which case the first-mentioned partial composition in particular comprises no peroxidic bleaching agent and the second-mentioned partial composition in particular comprises no enzyme and no bleach activator.
  • a water-soluble coated portion preferably weighs 10 g to 35 g, in particular 12 g to 28 g and particularly preferably 12 g to 15 g, with the proportion of the water-soluble coating included in the weight specification accounting for 0.3 g to 2.5 g, in particular 0.7 g to 1.2 g.
  • Table 3 shows the effective diffusion coefficients from dynamic surface tension measurements (maximum bubble pressure) at room temperature; the surfactant mixtures were used in amounts of 1 g/L each in citrate buffer at pH 8, and the effective diffusion coefficients were obtained by fitting the first data points with the Ward-Tordai equation.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne des combinaisons tensioactives d'un premier éther d'alkylpolyglycol de formule générale (la) ou (Ib) et d'un second éther d'alkylpolyglycol de formule générale (IIa) ou (IIb) et d'un rhamnolipide de formule générale (III) ou de son sel, CH3 (CH2)m(-o-R)n-OH (Ia), formule (Ib), CH3 (CH2)m(-o-R)a-OH (IIa), formule (IIb), formule (II), dans laquelle R est un groupe alkyle linéaire ou ramifié ayant 2 à 4 atomes de C, m est un nombre de 9 à 15, x et y sont indépendamment l'un de l'autre sont des nombres de 0 à 12, z est un nombre de 1 à 4, la somme de x + y + z se situant dans la plage de 10 à 16, n est un nombre de 1 à 5 et a est un nombre de 2 à 7, et a est supérieur à n d'au moins 1, o est 2, 1 ou 0, p est 0 ou 1, et R1 et R2 indépendamment l'un de l'autre sont des groupes organiques identiques ou différents avec 2 à 24 atomes de carbone. Ces combinaisons de tensioactifs peuvent être bien incorporées dans des agents de lavage et de nettoyage, présentent d'excellentes propriétés d'utilisation et peuvent être produites à partir de matières premières renouvelables.
PCT/EP2024/057105 2023-06-05 2024-03-18 Nouvelles combinaisons de tensioactifs et agents de lavage et de nettoyage les contenant Pending WO2024251400A1 (fr)

Applications Claiming Priority (2)

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DE102023205205.9A DE102023205205A1 (de) 2023-06-05 2023-06-05 Neue Tensidkombination und Wasch- und Reinigungsmittel, welche diese enthalten
DE102023205205.9 2023-06-05

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EP0605308A1 (fr) 1992-12-30 1994-07-06 Institut Francais Du Petrole Composition contenant un composé tensio-actif et des glycolipides et procédé de décontamination d'un milieu poreux pollué
WO2003006146A1 (fr) * 2001-07-13 2003-01-23 Cognis France S.A. Preparations aqueuses
EP1445302A1 (fr) * 2003-01-28 2004-08-11 Ecover Belgium Compositions détergentes
EP2410049A1 (fr) 2002-02-26 2012-01-25 Third Wave Technologies, Inc. Enzymes de détection d'ARN
WO2012010405A1 (fr) 2010-07-22 2012-01-26 Unilever Plc Compositions de détergent comprenant un biosurfactant et une enzyme
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EP2787065A1 (fr) 2013-04-02 2014-10-08 Evonik Industries AG Composition détergente pour textiles contenant des rhamnolipides ayant une teneur majoritaire en di-rhamnolipides
EP2786743A1 (fr) 2013-04-02 2014-10-08 Evonik Industries AG Composition de mélange contenant des rhamnolipides
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EP0499434B1 (fr) 1991-02-12 1995-07-19 Unilever Plc Compositions détergentes
EP0605308A1 (fr) 1992-12-30 1994-07-06 Institut Francais Du Petrole Composition contenant un composé tensio-actif et des glycolipides et procédé de décontamination d'un milieu poreux pollué
WO2003006146A1 (fr) * 2001-07-13 2003-01-23 Cognis France S.A. Preparations aqueuses
EP2410049A1 (fr) 2002-02-26 2012-01-25 Third Wave Technologies, Inc. Enzymes de détection d'ARN
EP1445302B1 (fr) 2003-01-28 2006-06-07 Ecover Belgium Compositions détergentes
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WO2012010406A1 (fr) 2010-07-22 2012-01-26 Unilever Plc Combinaisons de rhamnolipides et d'enzymes pour nettoyage amélioré
EP2787065A1 (fr) 2013-04-02 2014-10-08 Evonik Industries AG Composition détergente pour textiles contenant des rhamnolipides ayant une teneur majoritaire en di-rhamnolipides
EP2786743A1 (fr) 2013-04-02 2014-10-08 Evonik Industries AG Composition de mélange contenant des rhamnolipides
WO2016096478A1 (fr) 2014-12-15 2016-06-23 Henkel Ag & Co. Kgaa Agent de lavage et de nettoyage

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