WO2024251401A1 - Nouvelle combinaison de tensioactifs, et détergents et agents de nettoyage la contenant - Google Patents

Nouvelle combinaison de tensioactifs, et détergents et agents de nettoyage la contenant Download PDF

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Publication number
WO2024251401A1
WO2024251401A1 PCT/EP2024/057106 EP2024057106W WO2024251401A1 WO 2024251401 A1 WO2024251401 A1 WO 2024251401A1 EP 2024057106 W EP2024057106 W EP 2024057106W WO 2024251401 A1 WO2024251401 A1 WO 2024251401A1
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atoms
general formula
rhamnolipid
weight
independently
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German (de)
English (en)
Inventor
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
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the invention relates to a combination of non-ionic surfactant with two different anionic surfactants, 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 an alkyl polyglycol ether of the general formula (Ia) or (Ib) with a rhamnolipid of the general formula (II) 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 7 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 2 to 10
  • o is 2, 1 or
  • 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
  • a further anionic surfactant which is different from the rhamnolipid
  • the salts of the compounds of the general formula (II) which are suitable here are preferably those in which the carboxyl H atom is replaced by an alkali metal cation or the grouping N + R 3 R 4 R 5 R 6 , in which R 3 , R 4 , R 5 and R 6 independently of one another represent hydrogen, an alkyl group having 1 to 6 C atoms or a hydroxyalkyl group having 2 to 6 C atoms, i.e. the carboxylic acid group is present as a carboxylate anion.
  • Surfactants of the general formula (Ib) are less preferred than surfactants of the general formula (Ia), since they are relatively difficult to obtain from a renewable raw material base.
  • Preferred surfactants of the general formula (Ia) 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 4 to 7.
  • Surfactants of the general formula (la) or (Ib) can be prepared in a known manner by alkoxylation of alcohols CH3(CH2)m-OH or produce, whereby when using
  • Alcohol mixtures, the indices m, x, y and z here and in the compounds of the general formula (la) or (Ib) 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 in the compounds of the general formula (la) or (Ib) can also be non-integer.
  • the alcohol CH3(CH2)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 C12 alcohol with 3 ethylene oxide groups and the linear Ci4 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 Ci4 alcohol with 2, 3 or 4 molar equivalents of ethylene oxide.
  • surfactants of the sulfonate type are C9-C13 alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of alkene and hydroxyalkanesulfonates, and disulfonates, such as those obtained, for example, from Ci2-Cis monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from Ci2-Cis alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of a-sulfofatty acids for example the a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which are produced by a-sulfonation of the methyl esters of fatty acids of vegetable and/or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble monosalts.
  • a-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids although sulfonation products of unsaturated fatty acids, for example oleic acid, can also be present in small amounts, preferably in amounts not exceeding about 2 to 3% by weight.
  • a-sulfofatty acid alkyl esters which have an alkyl chain with no more than 4 C atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters.
  • the methyl esters of a-sulfofatty acids (MES) and their saponified disalts are used with particular advantage.
  • Suitable anionic surfactants are also sulfated fatty acid glycerol esters, which are mono-, di- and triesters as well as mixtures thereof, as obtained in the production by esterification using a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • alkali and in particular the sodium salts of the sulfuric acid half esters of the Ci2-Ci8 fatty alcohols for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Cio-C2o oxo alcohols and those half esters of secondary alcohols of this chain length are preferred as alk(en)yl sulfates.
  • alk(en)yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis, which have a degradation behavior similar to that of the corresponding compounds based on oleochemical raw materials.
  • Ci2-Ci6-alkyl sulfates and Ci2-Ci5-alkyl sulfates as well as Ci4-Ci5-alkyl sulfates are particularly preferred.
  • sulfuric acid monoesters of the straight-chain or branched C7-C2i-alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched Cg-Cn-alcohols with an average of 3.5 mol of ethylene oxide (EO) or Ci2-Ci8-fatty alcohols with 1 to 4 EO.
  • the preferred other anionic surfactants also include the salts of alkyl sulfosuccinic acid, which are also referred to as sulfosuccinates or sulfosuccinic acid esters, and the monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain Cs to Cis fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue that is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk(en)ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof.
  • alk(en)ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof.
  • Other anionic surfactants that can be considered are fatty acid derivatives of amino acids, for example N-methyltaurine (taurides) and/or N-methylglycine (sarcosides).
  • sarcosides or sarcosinates especially sarcosinates of higher and given if monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.
  • Other anionic surfactants that can be considered are soaps.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the well-known alkenyl succinic acid salts can also be used together with these soaps or as a substitute for soaps.
  • the other anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. They are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the other anionic surfactants are contained in detergents in proportions of normally 0.1% by weight to 70% by weight, in particular from 1% by weight to 20% by weight.
  • 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).
  • surfactant combinations according to the invention are outstandingly suitable as ingredients in washing and cleaning agents, cosmetics such as shampoos, toothpastes, and for the other fields of application in which anionic surfactants have usually been used to date, such as in the food industry, geosciences, tertiary oil production, plastics technology, metalworking, photography, paper recycling, tool cleaning, and firefighting.
  • the surfactant combination defined above for producing washing or cleaning agents the use of the surfactant combination defined above for increasing the performance of washing or cleaning agents when washing laundry or cleaning hard surfaces, and the washing or cleaning agents which contain a surfactant combination defined above.
  • 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.
  • the agent according to the invention can contain additional nonionic surfactants.
  • Suitable nonionic surfactants include alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof.
  • 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.
  • surfactants that may be suitable if desired are polyhydroxy fatty acid amides of the formula, in which R is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • Polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • 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 Ci-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, methylglycinediacetic 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, in particular polycarboxylates accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight 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-Cs-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, and 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight of vinyl alcohol and/or vinyl acetate.
  • 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. Both the amounts and the weight ratios are based on the acids.
  • 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 Residue which is preferably derived from benzene or benzene derivatives.
  • Preferred terpolymers contain 40% to 60% by weight, in particular 45 to 55% by weight of (meth)acrylic acid or (meth)acrylate, particularly preferably acrylic acid or acrylate, 10% to 30% by weight, preferably 15% to 25% by weight of methallylsulfonic acid or methallylsulfonate and, as a third monomer, 15% to 40% by weight, preferably 20% to 40% by weight 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 in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions, particularly for the production of liquid agents. All of the acids mentioned are generally used in the form of their water-soluble salts, particularly their alkali metal 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.
  • water-soluble inorganic builder materials may 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 listed in the Agents preferably contain them in amounts of 1 wt. % to 20 wt. %, in particular 5 wt. % to 15 wt. %.
  • the alkali silicates which 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 sodium silicates, in particular amorphous sodium silicates, with a molar ratio Na2O:SiO2 of 1:2 to 1:2.8.
  • a crystalline sodium layered 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 H2G2-urea adducts, as well as mixtures of these. 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 .
  • compounds which under perhydrolysis conditions yield optionally substituted perbenzoic acid and/or aliphatic peroxocarboxylic acids having 1 to 12 carbon atoms, in particular 2 to 4 carbon atoms, alone or in mixtures, can be used as bleach-activating compounds which yield peroxocarboxylic acid under perhydrolysis conditions.
  • Suitable bleach activators are those which carry O- and/or N-acyl groups, in particular of the stated number of carbon atoms, and/or optionally substituted benzoyl groups.
  • 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 from 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. In particular, such ligands 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 equalization in the complex, 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. ferric 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.
  • graying inhibitors The purpose of graying inhibitors is to keep the dirt detached from the textile fiber suspended in the liquor.
  • Water-soluble colloids usually of an organic nature, 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.
  • copolymers those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5:1 to 1:1 with an average molecular weight in the range from 5,000 g/mol to 50,000 g/mol, in particular 10,000 g/mol to 20,000 g/mol, are preferred.
  • the detergents are free of such additional dye transfer inhibitors.
  • Detergents can contain, for example, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts as optical brighteners, although they are not suitable for use as color detergents. tel are preferably free of optical brighteners. 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 constructed compounds which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group.
  • Brighteners of the substituted diphenylstyryl type can also be present, for example the alkali metal salts of 4,4'-bis(2-sulfostyryl)-diphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)-diphenyl, or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-diphenyl. Mixtures of the aforementioned optical brighteners can also be used.
  • Suitable foam inhibitors include, for example, soaps of natural or synthetic origin that have a high proportion of C1a-C24 fatty acids.
  • Suitable non-surfactant-type foam inhibitors include, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica, as well as paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica or bis-fatty acid alkylenediamides. Mixtures of different foam inhibitors are also advantageously used, for example those made from silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone and/or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or water-dispersible carrier substance. Mixtures of paraffins and bis-stearylethylenediamide are particularly preferred.
  • 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; then the agent contains preferably 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 exist without the product to be dosed (possibly by changing its shape).
  • a surface coating or a layer of a surface coating is therefore not a wall according to the present invention.
  • the walls of the chamber are made of a water-soluble material.
  • the water solubility of the material can be determined using a square film of the material in question (film: 22 x 22 mm with a thickness of 76 pm) fixed in a square frame (edge length on the inside: 20 mm) according to the following measurement protocol.
  • 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 walls of the chambers and thus the water-soluble casings of the detergents according to the invention are preferably formed by a water-soluble film material.
  • Such water-soluble packaging can be produced either by vertical form-fill-seal processes or by thermoforming processes.
  • 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. It is preferred that 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 .
  • Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • 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.
  • Suitable water-soluble films for use in the wrappers of the water-soluble packaging according to the invention are films sold by MonoSol LLC, for example under the designation M8630, C8400 or M8900.
  • Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the VF-HP films from Kuraray.
  • 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 one chamber can have a substantially dimensionally stable spherical, rotationally 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.
  • solid agents according to the invention presents no difficulties and can be carried out in a known manner, for example by spray drying or granulation, with enzymes and any other thermally sensitive ingredients such as bleaching agents being added separately later if necessary.
  • a process comprising an extrusion step is preferred.
  • Liquid or pasty compositions according to the invention in the form of solutions containing water and conventional solvents are generally prepared by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
  • the washing performance of surfactant combinations according to the invention was determined in comparison to conventional surfactant mixtures in a miniaturized washing device.
  • aqueous solutions of 1 g/l each of the mixtures specified in Table 1 below (which had the weight ratio of the individual surfactants specified in brackets) were used at 30 °C to wash cotton test fabrics with standardized oily soiling and the sum of the Y values across all test fabrics was determined after drying.
  • the values also specified in Table 1 were obtained.
  • a clear superiority of the surfactant mixtures E1 to E5 according to the invention is observed in comparison to the individual surfactants or other surfactant mixtures (V1 to V5).

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Detergent Compositions (AREA)

Abstract

L'invention concerne des combinaisons de tensioactifs comprenant : un éther de polyglycol d'alkyle de formule générale (Ia) ou (Ib) et un rhamnolipide de formule générale (III) ou son sel, CH3(CH2)m(-O-R)n-OH, formules (Ia), (Ib), (II), dans lesquelles R est un groupe alkyle linéaire ou ramifié ayant de 2 à 4 atomes de C, m est un nombre de 7 à 15, x et y sont indépendamment l'un de l'autre des nombres de 0 à 12, z est un nombre de 1 à 4, la somme de x + y + z étant dans la plage allant de 10 à 16, n est un nombre de 2 à 10, o est 2, 1 ou 0, p est 0 ou 1, et R1 et R2 sont indépendamment des groupes organiques identiques ou différents ayant de 2 à 24 atomes de carbone, en particulier de 5 à 13 atomes de carbone ; et un autre tensioactif anionique qui est différent du rhamnolipide. Ces combinaisons de tensioactifs peuvent être bien incorporées dans des détergents et des agents de nettoyage, ont d'excellentes propriétés d'utilisation et peuvent être produites, au moins dans une certaine mesure, à partir de matières premières renouvelables.
PCT/EP2024/057106 2023-06-05 2024-03-18 Nouvelle combinaison de tensioactifs, et détergents et agents de nettoyage la contenant Pending WO2024251401A1 (fr)

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