WO2016066464A1 - Détergents à base de mannosylérythritollipide - Google Patents

Détergents à base de mannosylérythritollipide Download PDF

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WO2016066464A1
WO2016066464A1 PCT/EP2015/074143 EP2015074143W WO2016066464A1 WO 2016066464 A1 WO2016066464 A1 WO 2016066464A1 EP 2015074143 W EP2015074143 W EP 2015074143W WO 2016066464 A1 WO2016066464 A1 WO 2016066464A1
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acid
weight
branched
linear
range
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PCT/EP2015/074143
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German (de)
English (en)
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Hendrik Hellmuth
Nicole BODE
Michael Dreja
Andreas Buhl
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Henkel Ag & Co. Kgaa
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Publication of WO2016066464A1 publication Critical patent/WO2016066464A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • 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
    • C11D1/662—Carbohydrates or derivatives
    • C11D2111/12—

Definitions

  • the present invention relates to detergents containing mannosylerythritol lipid.
  • Mannosylerythntollipids are compounds in which a mannose unit esterified with at least one fatty acid is glycosidically linked to an erythritol residue.
  • the hydroxyl group at C2 is esterified with octylic acid
  • the hydroxyl group at C3 with a C12-18 carboxylic acid
  • the hydroxyl groups at C4 and C6 with acetic acid
  • R Cn-17-alkyl.
  • They are obtained from so-called brand mushrooms of the genera Pseudozyma and Ustilago, in particular the fungi Pseudozyma antarctica and Ustilago maydis.
  • Special cultivation and processing strategies for the optimized production of mannosylerythritol lipids by Ustilago maydis mutants which do not produce cellobioselipids are known from Chem. Ing. Tech. 82, 2010, 1215-1221.
  • Mannosylerythntollipids belong to the so-called biosurfactants because of their surface-active behavior and their origin.
  • the patent application EP 0 499 434 A1 discloses detergents which contain a micellar phase-forming surfactant and a further lamellar phase-forming surfactant, at least one of these two surfactants comprising a glycolipid biosurfactant, in particular a rhamnolipid, glucoselipid, sophoroselipid, Trehaloselipid and / or Cellobioselipid must be.
  • European patent application EP 1 445 302 A1 relates to detergents containing at least one glycolipid biosurfactant, in particular sophorolipid and / or rhamnolipid, and at least one non-glycolipid surfactant, these being in a micellar phase.
  • International patent application WO 2012/010405 A1 discloses cleaning compositions which contain at least 1% by weight of biosurfactant and an enzyme of bacterial origin.
  • International patent application WO 2012/010407 A1 discloses laundry detergents which comprise glycolipid surfactant and lipase of bacterial origin, the glycolipid surfactant consisting of at least 20% by weight of disaccharide acid glycol-containing glycolipid surfactant.
  • the invention therefore relates to a detergent containing mannosylerythritol lipid of the general formula (I),
  • Ac is an acetyl group and R is a linear or branched-chain hydrocarbon radical having 1 1 to 17 C atoms.
  • the detergent contains 0.01 wt .-% to 23 wt .-%, in particular 3 wt .-% to 6 wt .-% Mannosylerythritollipid.
  • the agent may additionally comprise further surfactants, the combinations of mannosylerythritolollipid with ethersulfates mentioned below, ethoxylation products of linear or branched alcohols having in each case 12 to 18 C atoms in the alkyl moiety and 3 to 20, in particular 4 to 10 ethyl ether groups and / or C9 Ci3 alkyl benzene sulfonates are particularly preferred.
  • the weight ratio of mannosyl erythritol lipid to the further surfactant or surfactants is preferably in the range of 1:18 to 10:18, more preferably 1: 6 to 1: 3.
  • the detergent is liquid and has a water content in the range of 6 wt .-% to 95 wt .-%, in particular from 55 wt .-% to 90 wt .-% to.
  • Mannosylerythritollipid the general formula (I) to enhance the cleaning performance of detergents in the washing provided with greasy and / or oily soils textiles.
  • the use of mannosyl erythritol lipids removes greasy and oily soiling from textiles even at temperatures in the range from 10 ° C. to 30 ° C., in particular from 17 ° C. to 25 ° C.
  • a further subject of the invention is therefore a process for washing textiles provided with greasy and / or oily soiling by contacting the textiles with an aqueous surfactant-containing liquor Temperature range from 10 ° C to 30 ° C, especially from 20 ° C to 25 ° C, which is characterized in that the aqueous liquor Mannosylerythritol- lipid of the general formula (I) contains.
  • the process can be carried out by separate addition of mannosylerythritol lipid to a customary wash liquor or preferably by use of a mannosyl erythrinolipid-containing wash detergent. It can be done manually or using a conventional washing machine.
  • the concentration of mannosylerythritol lipid in the aqueous liquor is preferably in the range from 0.075 g / l to 0.3 g / l, in particular from 0.8 g / l to 0.25 g / l.
  • Detergents which may be in the form of homogeneous solutions or suspensions, in particular in powdered solids, in densified particle form, may in principle contain, in addition to the active ingredient used according to the invention, all known ingredients customary in such agents.
  • the agents according to the invention or used in the process according to the invention may in particular be builders, other surfactants, bleaches based on organic and / or inorganic peroxygen compounds, bleach activators, water, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical Brightener, grayness inhibitors, foam regulators and dyes and fragrances included.
  • the agents preferably contain, in addition to the mannosylerythritol lipid, another surfactant or several other surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
  • Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 5 to 12 C atoms in the alkyl radical.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols for example C12-Ci4 alcohols containing 3 EO or 4 EO, C 9 include -CN alcohols containing 7 EO, C 3 -Ci5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, CI2 C18-alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 7 EO.
  • the stated degrees of ethoxylation represent statistical averages, which for a particular product may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • agents for use in mechanical processes usually extremely low-foam compounds are used. These include preferably Ci2-Ci8-alkylpolyethylenglykol-polypropylene glycol ethers each with at 8 mol ethylene oxide and propylene oxide in the molecule.
  • low-foam nonionic surfactants such as, for example, C12-C18-alkylpolyethylene glycol-polybutylene glycol ethers having up to 8 moles of ethylene oxide and butylene oxide units in the molecule as well as end-capped alkylpolyalkylene glycol mixed ethers.
  • hydroxyl-containing alkoxylated alcohols so-called hydroxymic ethers.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G represents a glycose unit with 5 or 6 C atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number - which, as a variable to be determined analytically, can also be of a fractional value - between 1 and 10; preferably x is 1, 2 to 1, 4.
  • R is CO for an aliphatic acyl radical having 6 to 22 carbon atoms
  • R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula
  • R 3 -CO-N- [Z] in the R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms
  • R 5 is a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein Ci-C4-alkyl or phenyl radicals are preferred
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this radical is available.
  • [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as 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 catalyst.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • nonionic surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called “spacer.” This spacer is usually a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart to act independently of one another generally by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water In exceptional cases, the term gemini surfactants not only such "dimer”, but also corresponding to "trimeric” surfactants understood.
  • Surfactants are, for example, sulfated hydroxymix ethers or dimer alcohol bis- and trimer alcohol trisulfates and ether sulfates
  • End-capped dimeric and trimeric mixed ethers are particularly distinguished by their bi- and multifunctionality, for example, the end-capped surfactants mentioned have good wetting properties and are included Low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups.
  • surfactants of the sulfonate type are preferably C9-C13 alkylbenzenesulfonates, olefin sulfonates, that is, mixtures of alkene and hydroxyalkanesulfonates As well as disulfonates, as obtained for example from Ci2-Ci8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration.
  • alkanesulfonates which are obtained from C 12 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by ⁇ -sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 C -Atomen in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are prepared, into consideration.
  • ⁇ -sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids although sulfonated products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt. %, can be present.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 C atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester.
  • the methyl esters of ⁇ -sulfo fatty acids (MES), but also their saponified disalts are used.
  • Suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 Mole of glycerol can be obtained.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12-18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters of secondary alcohols this chain length is preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • Ci2-Ci6-alkyl sulfates and Ci2-Ci5-alkyl sulfates and Cw-Cis-alkyl sulfates are particularly preferred.
  • ether sulfates the sulfuric acid monoesters of the straight-chain or branched C 7 -C 20 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9 -C 20 -alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 -C 18 -alcohol.
  • EO ethylene oxide
  • the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as 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 derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly important prefers.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides).
  • sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.
  • anionic surfactants are particularly soaps into consideration.
  • 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. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Surfactants are present in detergents in proportions of normally from 1% by weight to 50% by weight, in particular from 5% by weight to 30% by weight.
  • a detergent 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, methylglycine diacetic 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), lysine tetra (methylenephosphonic acid) and 1-hydroxyethane-1, 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (polycarboxylic acids, in particular by
  • 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 vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight.
  • vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene
  • water-soluble organic builders can terpolymers are also used which contain as unsaturated monomers two unsaturated acids and / or salts thereof and as the third monomer vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C3-Cs carboxylic acid and preferably from a C3-C4 monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C4-Cs-dicarboxylic acid, with maleic acid being particularly preferred.
  • the third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. Particularly preferred are vinyl alcohol derivatives which are an ester of short chain carboxylic acids, for example, C1-C4 carboxylic acids, with vinyl alcohol.
  • Preferred polymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% 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 lies.
  • the second acidic monomer or its salt may also be a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives is.
  • Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight.
  • % preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate.
  • This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Particularly preferred is sucrose.
  • the use of the third monomer presumably incorporates predetermined breaking points into the polymer which are responsible for the good biodegradability of the polymer.
  • terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol.
  • Further preferred copolymers are those which have acrolein as monomers and acrylic acid / acrylic acid salts or vinyl acetate.
  • the organic builder substances can be used, in particular for the preparation 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, in particular their alkali metal salts.
  • organic builder substances may 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. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.
  • Suitable water-soluble inorganic builder materials are, in particular, polyphosphates, preferably sodium triphosphate.
  • water-insoluble inorganic builder materials are in particular crystalline or amorphous, water-dispersible alkali metal aluminosilicates, in amounts not exceeding 25 wt .-%, preferably from 3 wt .-% to 20 wt .-% and in particular in amounts of 5 wt .-% to 15 wt. -% used.
  • preference is given to the detergent-grade crystalline sodium aluminosilicates in particular zeolite A, zeolite P and zeolite MAP and optionally zeolite X.
  • Amounts near the above upper limit are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 ⁇ m, and preferably consist of at least 80% by weight of particles having a size of less than 10 ⁇ m.
  • Their calcium binding inhibitor is usually in the range of 100 to 200 mg CaO per gram.
  • 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 metal silicate builders.
  • Such water-soluble inorganic builder materials are preferably present in the compositions in amounts of from 1% to 20% by weight, in particular from 5% to 15% by weight.
  • the alkali metal silicates useful as builder materials preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1, 1 to 1: 12, and may be amorphous or crystalline.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of from 1: 2 to 1: 2.8.
  • Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na.sub.2SixO.sub.2.sup.x + H.sub.2O.sub.2, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both .beta. And .delta.-sodium disilicates (Na.sub.2Si.sub.20.sub.y H.sub.2O) are preferred.
  • Also prepared from amorphous alkali metal silicates practically anhydrous crystalline alkali silicates of the above general formula in which x is a number from 1, 9 to 2.1, can be used in the compositions.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda.
  • Sodium silicates with a modulus in the range of 1.9 to 3.5 are used in another embodiment.
  • a granular compound of alkali silicate and alkali carbonate is used, as it is commercially available, for example, under the name Nabion® 15.
  • the compositions may also contain bleaches, especially those based on peroxygen.
  • Suitable peroxygen compounds are, in particular, organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid, monoperoxyphthalic acid and diperdodecanedioic acid and salts thereof such as magnesium monoperoxyphthalate, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the conditions of use, such as perborate, percarbonate and / or persilicate, and Hydrogen peroxide inclusion compounds, such as H 2 O 2 urea adducts. Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate.
  • solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate or hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide. If a detergent which can be used in the context of the invention contains peroxygen compounds, these are present in amounts of preferably up to 50% by weight, in particular from 2% by weight to 45% by weight and more preferably from 5% by weight to 20% Wt .-% present.
  • Preferred peroxygen concentrations (calculated as H2O2) in the liquor are in the range from 0.001 g / l to 10 g / l, in particular from 0.02 g / l to 1 g / l and particularly preferably from 0.03 g / l to 0, 5 g / l.
  • peroxycarboxylic acid-yielding compound in particular compounds which give under perhydrolysis conditions optionally substituted perbenzoic acid and / or aliphatic peroxycarboxylic acids having 1 to 12 C-atoms, in particular 2 to 4 C-atoms, alone or in mixtures, are used.
  • Suitable bleach activators which carry O- and / or N-acyl groups, in particular of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated 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 of these, especially nonanoyl or Isononanoyl- or Lauroyloxybenzolsulfonat (NOBS or iso-NOBS or LOBS) or Decanoyloxybenzoat (DOBA), their formal carbonic ester derivatives such as 4- (2-decanoyloxyethoxycarbonyloxy) benz
  • bleach-activating compounds such as nitriles, from which perimide acids form under perhydrolysis conditions may be present.
  • nitriles include in particular aminoacetonitrile derivatives with quaternized nitrogen atom according to the formula
  • R 3 in the R represents -H, -CH 3 , a C2-24-alkyl or alkenyl radical, a substituted Ci-24-alkyl or C2-24-alkenyl radical having at least one substituent from the group -Cl, -Br , -OH, -NH2, -CN and -N (+) -CH2-CN, an alkyl or alkenylaryl radical having a Ci-24-alkyl group, or for a substituted alkyl or alkenylaryl radical having 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 independently selected from -CH 2-CN, -CH 3, -CH 2 -CH 3, -CH 2 -CH 2 -CH 3, -CH ( CH 3) -CH 3, -CH 2 -OH, -CH 2 -CH 2 OH, -CH (OH) -CH3, -CH2-CH2-
  • peroxycarboxylic or perimic acids forming bleach activators are preferably present in amounts above 0 wt .-% up to 10 wt .-%, in particular 1, 5 wt .-% to 5 wt .-% in the invention usable detergents.
  • Acylhydrazones and / or oxygen-transferring sulfonimines may also be used.
  • transition metal complexes are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes.
  • Suitable ligands in such transition metal complexes are both inorganic and organic compounds, in addition to carboxylates in particular compounds having 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)) - (2-pyridyl
  • 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 (NO 2) - group, that is a nitro ligand or a nitrito ligand.
  • the (NO 2) - group may also be chelated to a transition metal or it may be asymmetric or two transition metal atoms -0-bridging.
  • the transition metal complexes may carry further, generally simpler ligands, in particular mono- or polyvalent anion ligands.
  • ligands for example, nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, oxalate, perchlorate and complex anions such as hexafluorophosphate are suitable.
  • the anion ligands should provide 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 act bridging, so that polynuclear complexes arise.
  • both metal atoms in the complex need not 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 anionic ligands does not result in charge balance in the complex, anionic counterions which neutralize the cationic transition metal complex are present in the transition metal complex compounds to be used according to the invention.
  • 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 , 4,7-trimethyl-1, 4,7-triazacyclononane) -di-hexafluorophosphate, [N, N'-bis [(2-hydroxy-5-vinylphenyl) -methylene] -1, 2-diaminocyclohexane] -manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-nitrophenyl) methylene] -1,2-diaminocyclohexane] 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-diaminocycl
  • Enzymes which can be used in the compositions are those from the class of amylases, proteases, Lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxides, and mixtures thereof. Particularly suitable are enzymatic agents 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.
  • the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in the detergents or cleaners according to the invention in amounts of up to 5% by weight, in particular from 0.2% by weight to 4% by weight. If the agent of the invention contains protease, it preferably has a proteolytic activity in the range of about 100 PE / g to about 10,000 PE / g, in particular 300 PE / g to 8000 PE / g. If several enzymes are to be used in the agent according to the invention, this can be carried out by incorporation of the two or more separate or in a known manner separately prepared enzymes or by two or more enzymes formulated together in a granule.
  • usable organic solvents in addition to water include alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C Atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived from the said classes of compounds ethers.
  • Such water-miscible solvents are preferably present in the compositions according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.
  • compositions of the invention system and environmentally friendly acids especially 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.
  • pH regulators are present in the compositions 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 have the task of keeping suspended from the textile fiber dirt suspended in the fleet.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • starch derivatives can be used, for example aldehyde starches.
  • cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropyl pylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of 0.1 to 5 wt .-%, based on the agents used.
  • Detergents may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners, although they are preferably free of optical brighteners for use as color washing agents.
  • optical brighteners for use as color washing agents.
  • salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or similarly constructed compounds which are substituted for the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Mixtures of the aforementioned optical brightener can be used.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of cis-C24 fatty acids.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes.
  • the foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance.
  • a granular, water-soluble or dispersible carrier substance In particular, mixtures of paraffins and bistearylethylenediamide are preferred.
  • compositions having an increased bulk density in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.
  • compositions in tablet form which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers
  • the procedure is preferably such that all components - optionally one layer at a time - in a mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric presses or rotary presses, with pressing forces in the range of about 50 to 100 kN, preferably compressed at 60 to 70 kN.
  • a tablet produced in this way has a weight of 10 g to 50 g, in particular 15 g up to 40 g.
  • the spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm.
  • the size of rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device of the washing machine, is dependent on the geometry and the volume of this metering device.
  • Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.
  • Liquid or pasty compositions in the form of conventional solvent-containing solutions are usually prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
  • liquid detergent M1 according to the invention and, for comparison, the liquid detergent V1 not according to the invention were prepared by simply mixing the ingredients indicated in Table 1 in the amounts indicated there (quantities in% by weight)
  • Cotton textile pieces provided with standardized stains listed in the following Table 2 were washed at 25 ° C. for 1 hour using a detergent (dosage 4.2 g / l) listed in Table 1, rinsed with water, dried and then their remission value spectrophotometrically ( Minolta CR400-1).
  • Table 2 shows the differences in the brightness values (Y values of the remission measurement) between the use of the agent M1 or M2 and the use of the agent V1 as averages of 5-fold determinations, with higher values indicating a better leachability.
  • Table 2 Brightness differences

Abstract

L'invention vise à améliorer l'efficacité de détergents lors du lavage à basses températures de textiles présentant des taches grasses et/ou huileuses. Cet objectif est atteint essentiellement par l'utilisation de mannosylérythritollipide.
PCT/EP2015/074143 2014-10-28 2015-10-19 Détergents à base de mannosylérythritollipide WO2016066464A1 (fr)

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EP3290501A1 (fr) 2016-08-29 2018-03-07 Richli, Remo Compositions detergentes contentant des amides d'acides gras alcoxylés
EP3290500A1 (fr) 2016-08-29 2018-03-07 Richli, Remo Composition de lavage, de nettoyage et de soin contenant de carboxylate polyoxyalkyléné
EP3940049A1 (fr) 2020-07-13 2022-01-19 Dalli-Werke GmbH & Co. KG Lipide de mannosylérythritol comprenant des agents de rinçage liquides
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CN112105711A (zh) * 2018-05-11 2020-12-18 巴斯夫欧洲公司 包含鼠李糖脂和/或甘露糖赤藓糖醇脂的洗涤剂组合物

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EP3290500A1 (fr) 2016-08-29 2018-03-07 Richli, Remo Composition de lavage, de nettoyage et de soin contenant de carboxylate polyoxyalkyléné
EP3940049A1 (fr) 2020-07-13 2022-01-19 Dalli-Werke GmbH & Co. KG Lipide de mannosylérythritol comprenant des agents de rinçage liquides
CN114736741A (zh) * 2022-02-28 2022-07-12 温柱 一种环保型高浓缩洗衣液及其制备方法

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