WO2019034490A1 - Rhamnolipid-containing detergents and cleaning agents - Google Patents

Rhamnolipid-containing detergents and cleaning agents Download PDF

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Publication number
WO2019034490A1
WO2019034490A1 PCT/EP2018/071468 EP2018071468W WO2019034490A1 WO 2019034490 A1 WO2019034490 A1 WO 2019034490A1 EP 2018071468 W EP2018071468 W EP 2018071468W WO 2019034490 A1 WO2019034490 A1 WO 2019034490A1
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Prior art keywords
acid
weight
sodium
rhamnolipid
mixtures
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PCT/EP2018/071468
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German (de)
French (fr)
Inventor
Alexander Schulz
Michael Dreja
Michael STROTZ
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Henkel Ag & Co. Kgaa
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Publication of WO2019034490A1 publication Critical patent/WO2019034490A1/en

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/37Mixtures of compounds all of which are anionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/04Carboxylic acids or salts thereof
    • C11D1/06Ether- or thioether carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to detergents and cleaners containing certain rhamnolipids.
  • Modern detergents which are often used in liquid form, are often used at low temperatures down to room temperature or below.
  • the surfactant system contained therein serves for the removal of, in particular, greasy soiling.
  • Typical surfactants used are petrochemically based linear alkylbenzenesulfonate, oleochemically or petrochemically based alcohol ether sulfate and petro- or oleochemically derived nonionic surfactants such as alcohol ethoxylates.
  • biosurfactants which can be obtained, for example, from sugar or other carbohydrate sources, are commercially available. However, the performance profile of biosurfactants in some cases does not readily meet the demands made of a modern detergent.
  • Rhamnolipids are compounds in which a mono- or dirhamnose unit is glycosidically linked to the hydroxyl group of a fatty acid containing ⁇ -hydroxyl groups, it being possible for the fatty acid to 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 in their growth on hydrophobic substrates such as n-alkanes or vegetable oils. Rhamnolipids belong to the so-called biosurfactants because of their surface-active behavior and their origin.
  • the 3- (hydroxydecanoyloxy) decanoic acid dirhomonoside for example, has the formula
  • rhamnolipids in addition to O-carboxylic acids and / or hydroxycarboxylic acids, there are also longer-chain, for example C 12 -carboxylic acids and / or -hydroxycarboxylic acids.
  • the patent EP 0 499 434 B1 discloses detergents which contain 1 to 60% by weight of a surfactant which forms a micellar phase at pH 7.0 and 25 ° C. in 1% strength by weight aqueous solution and one at pH 7.0 and 25 ° C in 1 weight percent aqueous solution containing a lamellar phase-forming surfactant, wherein rhamnolipid may be both the micellar phase as well as the lamellar phase forming surfactant.
  • European Patent Specification EP 1 445 302 B1 relates to detergents containing at least one glycolipid biosurfactant 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.
  • European Patent Application EP 0 605 308 A1 discloses compositions containing from 0.001% to 99.99% by weight of anionic and / or nonionic surfactant and from 0.001% to 99.99% by weight of glycolipid, wherein The glycolipids may be, for example, sophorolipids, rhamnolipids, glucoselipids, trehaloselipids and cellobioselipids.
  • International patent application WO 2012/010406 A1 discloses laundry detergents containing lipase and rhamnolipid, the rhamnolipid consisting of at least 50% by weight of mono-rhamnolipid.
  • International Patent Application WO 2012/010407 A1 discloses laundry detergents which contain 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 rhamnolipid disclosed there consists of about 30% by weight of mono-rhamnolipid and about 70% by weight of di-rhamnolipid.
  • European Patent Application EP 2 410 039 A1 relates to mono- and di-rhamnolipid-containing detergents in which the weight ratio of mono-rhamnolipid to di-rhamnolipid ranges from 95: 5 to 45:55; Specifically disclosed are agents in which the weight ratio of mono-rhamnolipid to di-rhamnolipid is 50:50 and for comparison is about 25:75.
  • European Patent Application EP 2 787 065 A1 relates to mono- and di-rhamnolipid-containing laundry detergents in which the weight ratio of di-rhamnolipid to mono-rhamnolipid is greater than 51:49; in the specifically disclosed rhamnolipid composition of P.
  • the weight ratio of mono rhamnolipids to di-rhamnolipids is 1:99, the di-rhamnolipid being about 18% by weight di-rhamnolipid having at least one C 12 Carboxylic acid.
  • European patent application EP 2 786 743 A1 discloses rhamnolipid mixtures which contain 51% by weight to 95% by weight of a certain di-rhamnolipid and 0.5% by weight to 9% by weight of a certain mono-rhamnolipid in which the weight ratio of di-rhamnolipid to mono-rhamnolipid is greater than 91: 9.
  • the invention therefore relates to a washing or cleaning agent containing a rhamnolipid mixture of from 35% by weight to 45% by weight of 3 - ( ⁇ 3 - [(6-deoxy-aL-mannopyranosyl) oxy] decanoyl ⁇ oxy) decanoic acid and / or its sodium, potassium, ammonium, alkylammonium and / or hydroxyalkylammonium salt (CioCio-mono-rhamnolipid) and 55% by weight to 65% by weight of 3 - [(3- ⁇ [6-deoxy-2-0- (6-deoxy-aL-mannopyranosyl) -al-mannopyranosyl] oxy ⁇ decanoyl) oxy] decanoic acid and / or its
  • the rhamnolipid mixture is preferably free from other rhamnolipids.
  • Rhamnolipid mixtures which can be used according to the invention are commercially available, for example, under the name NatSurFact®.
  • the alkyl groups in the alkylammonium ions are preferably those having in each case 1 to 4 C atoms and mixtures thereof, and the alkyl groups in the hydroxyalkylammonium ions are preferably those having in each case 2 to 4 C atoms and mixtures thereof.
  • Another object of the invention is the use of said Rhamnolipidgemisches to increase the washing or cleaning performance of detergents or cleaners.
  • the use according to the invention can be carried out, for example, by adding the rhamnolipid mixture to a washing or cleaning agent-containing aqueous liquor or introducing it as a constituent of a washing or cleaning agent into the aqueous liquor, and objects to be washed or cleaned at temperatures of, for example, 10 ° C. to 60 ° C or, for example, 20 ° C to 40 ° C in contact with the liquor.
  • An inventive washing or cleaning agent preferably contains 0.000001 wt .-% to 50 wt .-%, in particular 0, 1 wt .-% to 20 wt .-% of said Rhamnolipidgemischs in addition to conventional constituents of such agents.
  • the agents according to the invention may in particular be builder substances, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, dye transfer inhibitors, gray scale inhibitors, wrinkle-reducing and form-retaining polymeric active compounds, and other auxiliaries, such as optical brighteners, foam regulators, dyes and fragrances.
  • compositions may contain, in addition to the rhamnolipid mixture, one or more additional surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but cationic and / or amphoteric surfactants may also be present. It is preferred if the means in addition to the rhamnolipid mixture at least 3, in particular at least 4 other surfactants, wherein if desired, for example, 10 other surfactants may be present.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical 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 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 7 -n-alcohol with 7 EO, cis-is alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-i4-alcohol with 3 EO and Ci2-is-alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • nonionic surfactants it is also possible to use fatty alcohols with more than 12 EO. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • other nonionic surfactants which can also be employed are alkylglycosides of the general formula R 5 O (G) x in which R 5 is a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical containing 8 to 22, preferably 12 to 18 carbon atoms.
  • R 5 is a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical containing 8 to 22, preferably 12 to 18 carbon atoms.
  • Corresponds to atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl N, N-dimethylamino oxide and N-tallow alkyl N, N-dihydroxyethyl amine oxide, and the fatty acid alkanolamides can also be used.
  • surfactants are polyhydroxy fatty acid amides of the formula
  • R is an aliphatic acyl radical having 6 to 22 carbon atoms
  • R 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 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 R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 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 oxy-alkyl radical having 1 to 8 carbon atoms, with ⁇ -4-alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives thereof residue.
  • [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 catalyst.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • Preferred surfactants of the sulfonate type are C9-i3-alkylbenzenesulfonates, olefin-sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C12-C18-monoolefins having a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained, 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 for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of glycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are included the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • alkyl sulfates and ether sulfates are alkyl sulfates and ether sulfates.
  • An alkyl sulfate is to be understood as meaning a salt of a sulfuric acid half-ester of an alcohol which has a linear, branched-chain or cyclic saturated hydrocarbon radical having 10 to 22 carbon atoms.
  • a counter cation is present, in particular a sodium or potassium ion or an ammonium, alkylammonium or hydroxyalkylammonium ion.
  • Preferred alcohol radicals are derived from native C 12-18 fatty alcohols, such as, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 OXO alcohols or secondary alcohols of these chain lengths.
  • alkyl sulfates of said chain length which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • Ci2-Ci6-alkyl sulfates, Ci2-Ci5-alkyl sulfates and Ci4-Ci5-alkyl sulfates are particularly preferred.
  • Ether sulfates are analogous to the alkyl sulfates of sulfuric monoesters of alkoxylated alcohols, the average number of alkoxy groups per alcohol function being generally from 1 to 10, preferably from 3 to 7.
  • Preferred alkoxy groups are the ethoxy group, the propoxy group and mixtures thereof.
  • the sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight or branched C7-21 alcohols such as 2-methyl-branched C9-n-alcohols having an average of 3.5 moles of ethylene oxide (EO) or Ci2-i8 fatty alcohols with 1 up to 4 EO, are suitable.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are 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 -is-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 again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration. 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 anionic surfactants, including the soaps 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.
  • cationic active substances for example, cationic compounds of the following formulas can be used:
  • Such surfactants which can be used in addition to rhamnolipid are present in agents according to the invention in amounts of preferably from 5% by weight to 50% by weight, in particular from 10% by weight to 30% by weight, but may also be completely absent if desired.
  • Textile softening compounds can be used to care for the textiles and to improve the textile properties such as a softer "feel” (avivage) and reduced electrostatic charge (increased wear comfort) .
  • the active ingredients of these formulations are quaternary ammonium compounds with two hydrophobic radicals, such as Disteraryldime- thylammonium chloride, which, however, due to its insufficient biodegradability increasingly replaced by quaternary ammonium compounds containing ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.
  • esters with improved biodegradability are obtainable, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products in a manner known per se with alkylating agents.
  • Suitable as a finishing agent is dimethylolethyleneurea.
  • 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 methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1, 1 diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular by oxidation of polysaccharides or dextrins accessible polycarboxylates, and / or polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which also contain polymerized small amounts of polymerizable
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, each based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight.
  • Terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer may also be used as water-soluble organic builder substances.
  • the first acidic monomer or its salt is derived from a monoethylically unsaturated C 3 -C 5 -carboxylic acid and preferably from a C 3 -C 4 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, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Such polymers generally have a molecular weight between 1,000 and 200,000.
  • Further preferred copolymers are those which contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
  • the organic builders may, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form 30 to 50 weight percent aqueous solutions are used. 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 in the upper half of said ranges are preferably used in pasty or liquid, in particular water-containing agents.
  • Suitable water-soluble inorganic builder materials are, in particular, polymeric alkali metal phosphates, which may be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of these are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic builder materials.
  • aluminosilicates especially zeolite A, P and optionally X. Quantities close to the stated 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 capacity is generally in the range of 100 mg to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1, 1 to 1: 12, and may be present in amorphous or crystalline form.
  • 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. In particular, both .beta.
  • .delta.-sodium disilicates Na.sub.2Si.sub.20.sub.y H.sub.2O
  • amorphous alkali 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.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in another preferred embodiment used.
  • a granular compound of alkali metal silicate and alkali carbonate is used, as it is commercially available, for example, under the name Nabion® 15.
  • alkali metal aluminosilicate, in particular zeolite is also present as an additional builder substance
  • the weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances is preferably 1:10 to 10: 1.
  • the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
  • Builder substances are preferably contained in detergents in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
  • the agent comprises a water-soluble builder block.
  • builder block is intended to express that the agents contain no further builder substances than those which are water-soluble, ie all builder substances contained in the agent are combined in the "block” characterized in this way, the amounts at most being Substances are excluded, which may be contained as impurities or stabilizing additives in small amounts in the other ingredients of the means commercially available manner.
  • water-soluble is to be understood as meaning that the builder block dissolves without leaving a residue at the concentration which results from the use of the agent containing it under the usual conditions, preferably at least 15% by weight and up to 55% by weight %, in particular 25 wt .-% to 50 wt .-% of water-soluble builder block contained in the agents.This is preferably composed of the components
  • the water-soluble builder block contains at least 2 of the components b), c), d) and e) in amounts greater than 0 wt .-%.
  • component a) in a preferred embodiment, 15% by weight to 25% by weight of alkali carbonate, which may be replaced at least proportionally by alkali metal bicarbonate, and up to 5% by weight, in particular 0.5% by weight, bis 2.5% by weight of citric acid and / or Al contain kalicitrat.
  • component a) 5 wt .-% to 25 wt .-%, in particular 5 wt .-% to 15 wt .-% citric acid and / or alkali citrate and up to 5 wt .-%, in particular 1 wt .-% to 5 wt .-% alkali carbonate, which may be at least partially replaced by alkali metal bicarbonate included.
  • component a) comprises alkali metal carbonate and alkali metal bicarbonate, preferably in a weight ratio of 10: 1 to 1: 1.
  • component b in a preferred embodiment, 1 wt .-% to 5 wt .-% alkali metal silicate with a modulus in the range of 1, 8 to 2.5 included.
  • phosphonic acid and / or alkali metal phosphonate in a preferred embodiment, from 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate is contained.
  • Phosphonic acids are also understood as meaning optionally substituted alkylphosphonic acids, which may also have a plurality of phosphonic acid groups (so-called polyphosphonic acids).
  • They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali salts, for example dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1 -Hydroxyethane-1, 1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediaminetrakis (methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any mixtures.
  • dimethylaminomethanediphosphonic acid 3-aminopropane-1-hydroxy-1,1-diphosphonic acid
  • 1-amino-1-phenylmethanediphosphonic acid 1 -Hydroxyethane-1
  • 1-diphosphonic acid amino-tris (methylenephosphonic acid), N, N, N ',
  • alkali metal phosphate in particular trisodium polyphosphate, are contained.
  • Alkaliphosphat is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric (HP03) n and orthophosphoric H3PO4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate NaH2PÜ4 exists as dihydrate (density 1, 91 like 3 , melting point 60 °) and as monohydrate (density 2.04 like 3 ). Both salts are white, very soluble in water powders, which lose the water of crystallization on heating and at 200 ° C in the weak acid diphosphate (disodium hydrogendiphosphate, ⁇ ), at higher temperature in sodium trimetaphosphate (Na3P3Ü9) and Madrell's salt. NaH2PÜ4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (potassium phosphate monobasic or potassium monobasic potassium phosphate, KDP), KH2PO4, is a white salt with a density of 2.33, preferably 3 , with a melting point of 253 ° (decomposed to form (KPÜ3) x, potassium polyphosphate) and is readily soluble in Water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na2HP4, is a colorless, very slightly water-soluble crystalline salt.
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K2HPO4, is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, sodium tertiary phosphate, NasPC are colorless crystals having a density of 1, 62, 3 and a melting point of 73-76 ° C (decomposition) as dodecahydrate, and a melting point of 100 ° as decahydrate (corresponding to 19-20% P2O5) C and in anhydrous form (corresponding to 39-40% P2O5) have a density of 2.536 like 3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K3PO4, is a white, deliquescent, granular powder of density 2.56, preferably 3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na4P20, exists in anhydrous form (density 2.534, 3 , melting point 988 °, also indicated as 880 °) and as decahydrate (density 1, 815-1, 836, 3 , melting point 94 °, with loss of water).
  • decahydrate Density 1, 815-1, 836, 3 , melting point 94 °, with loss of water.
  • Na4P2Ü7 is formed by heating disodium phosphate to> 200 ° C or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K4P2O7, exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33% 3 , which is soluble in water, the pH of the 1% solution being 25 ° 10, 4 is.
  • Condensation of NaH2PÜ4 or KH2PO4 gives rise to higher molecular weight sodium and potassium phosphates, which can be used to distinguish cyclic species, sodium or potassium metaphosphates, and chain types, sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches and Madrell- sches salt.
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentaka- Liumtriphosphat, K5P3O10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P2O5, 25% K2O) in the trade. There are also sodium potassium tripolyphosphates, which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:
  • sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two applicable are just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two applicable; It is also possible to use mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate.
  • the agent contains from 1.5% by weight to 5% by weight of polymeric polycarboxylate, in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid.
  • polymeric polycarboxylate in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid.
  • homopolymers of acrylic acid particularly preferred are those having an average molecular weight in the range from 5,000 D to 15,000 D (PA standard).
  • Suitable enzymes which can be used in the compositions are those from the class of lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof, for example amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl ® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast®, Lipozym® and / or Lipex®, cellulases such as Celluzyme® and / or Carezyme®.
  • amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl ® and / or Purafect® OxAm
  • lipases such as Lipolase®, Lipomax®, Lumafast®, Lipozym® and / or Lipex®
  • cellulases such
  • fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents.
  • the optionally used enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in the compositions in amounts of up to 5% by weight, in particular from 0.5% by weight to 2% by weight.
  • a preferred solvent in liquid agents of the invention is water.
  • the organic solvents which can be used in the compositions are alcohols having 1 to 4 C 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 the ethers derivable from the classes of compound mentioned.
  • Water-miscible solvents are preferably present in the compositions in amounts of from 1% to 60% by weight, especially from 2% to 40% by weight. Water can be used in inventive If desired, liquid agents may be present in amounts of up to 94% by weight. In preferred embodiments of low-water agents, the water content is not more than 15 wt .-%, in particular 1 wt .-% to 8 wt .-%.
  • Naturally derived polymers which can be used as thickening agents in aqueous liquid agents are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and Casein, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl and propyl cellulose, and polymers polysaccharide thickeners such as xanthan;
  • fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes are also suitable as thickeners.
  • the agents systemic 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 metal hydroxides.
  • Such pH regulators are preferably not more than 20 wt .-%, in particular from 1, 2 wt .-% to 17 wt .-%, contained in the means.
  • Soil release polymers are, for example, nonionic or cationic cellulosic derivatives, especially the polyester active soil release polymers Copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol, include those compounds which are formally accessible by esterification of two monomeric parts.
  • first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR-) a OH, which may also be present as a polymeric diol H- (O- (CHR-) a ) bOH
  • Ph is an o-, m- or p-phenyl enrest, which may carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R is hydrogen, an alkyl radical having 1 to 22 carbon atoms and mixtures thereof
  • a is a number from 2 to 6 and b is a number from 1 to 300.
  • the molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10.
  • the degree of polymerization b is preferably in the range from 4 to 200, in particular from 12 to 140.
  • the weight distribution of preferred soil release polyester is in the range from 250 to 100,000, in particular from 500 to 50,000.
  • the acid underlying Ph is preferably from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, methylitol, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof selected. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable.
  • acids having at least two carboxyl groups may be included in the soil release-capable polyester.
  • these include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • Preferred diols HO- (CHR-) a OH include those in which R is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R is hydrogen and the alkyl radicals have from 1 to 10 , in particular 1 to 3 C-atoms is selected.
  • R is hydrogen and a is a number from 2 to 6
  • a is 2 and R is hydrogen and the alkyl radicals have from 1 to 10 , in particular 1 to 3 C-atoms is selected.
  • those of the formula HO-CH 2 -CHR -OH in which R has the abovementioned meaning are particularly preferred.
  • diol components are ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
  • Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of 1000 to 6000. If desired, these polyesters may also be end developmentver consideration, with alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids in question as end groups.
  • the ester groups bonded via end groups can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, ela ostearic acid, arachic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidine acid, clupanodonic acid, lignoceric acid, cerotic acid
  • the end groups may also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and also o-, m- and p-hydroxybenzoic acid.
  • the hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group.
  • the number of hydroxymonocarboxylic acid units per end group is in the range from 1 to 50, in particular from 1 to 10.
  • the agents may contain anti-crease agents, since textile fabrics, in particular of rayon, wool, cotton and their mixtures, can tend to wrinkle, because the individual fibers are sensitive to bending, buckling, pressing and squeezing transverse to the fiber direction.
  • anti-crease agents include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
  • Graying inhibitors have the task of keeping suspended from the hard surface and in particular from the textile fiber suspended dirt 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 (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions used.
  • the agents may contain optical brighteners, among these in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • optical brighteners among these in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • 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 special silicone and / or paraffin-containing foam inhibitors, bound to a granular, water-soluble or dispersible carrier substance.
  • a granular, water-soluble or dispersible carrier substance e.g., mixtures of paraffins and bistearylethylenediamide are preferred.
  • peroxygen compounds come in particular organic peracids or pers acid salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide-releasing inorganic salts such as perborate, percarbonate and / or persilicate, into consideration.
  • Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. If 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.
  • alkali metal percarbonate alkali metal perborate monohydrate, alkali metal perborate tetrahydrate or, in particular in liquid media, hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide.
  • peroxygen compounds are present in detergents in amounts of up to 50% by weight, especially from 5% to 30% by weight.
  • customary bleach activators which form peroxocarboxylic acids or peroxoimidic acids under perhydrolysis conditions and / or customary bleach-activating transition metal complexes can be used.
  • the optional, especially in amounts of 0.5 wt .-% to 6 wt .-%, present component of the bleach activators include the commonly used N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetyl-ethylenediamine, acylated glycolurils, in particular Tetraacetylglycoluril, N-acylated hydantoins, Hy drazide, triazoles, urazoles, diketopiperazines, sulfururamides and cyanurates, also carboxylic anhydrides, especially phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonat, and acylated sugar derivatives, in particular pentaacetylglu
  • the bleach activators may have been coated or granulated in known manner with encapsulating substances, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1, 5 with the aid of carboxymethylcellulose. Diacetyl-2,4-dioxohexahydro-1, 3,5-triazine, and / or formulated in particulate trialkylammonium acetonitrile is particularly preferred.
  • Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.
  • compositions presents no difficulties and can be carried out in a manner known in the art, for example by spray-drying or granulation.
  • spray-drying or granulation For the preparation of the compositions with increased bulk density, in particular in the range of 650 g / l to 950 g / l, is an extrusion step preferred method.
  • Detergents in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
  • the agents in particular in concentrated liquid form, are present as a portion in a completely or partially water-soluble coating. Portioning makes it easier for the consumer to dose.
  • the funds can be packed, for example, in foil bags.
  • Pouches made of water-soluble film make it unnecessary for the consumer to tear open the packaging. In this way, a convenient dosing of a single, sized for a wash portion by inserting the bag directly into the washing machine or by throwing the bag into a certain amount of water, for example in a bucket, a bowl or hand basin, possible.
  • the film bag surrounding the washing portion dissolves without residue when it reaches a certain temperature.
  • thermoforming process thermoforming process
  • the water-soluble coatings do not necessarily consist of a film material, but can also represent dimensionally stable containers that can be obtained for example by means of an injection molding process.
  • a seal takes place.
  • the filling material is injected into the forming capsule, wherein the injection pressure of the filling liquid presses the polymer bands in the Kugelschalenkavticianen.
  • a process for preparing water-soluble capsules, initially filling and then sealing, is based on the so-called Bottle-Pack ® method. In this case, a tubular preform is guided into a two-part cavity. The cavity is closed, the lower tube portion is sealed, then the tube is inflated to form the capsule shape in the cavity, filled and finally sealed.
  • the shell material used for the preparation of the water-soluble portion is preferably a water-soluble polymeric thermoplastic, more preferably selected from the group (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, blends and composites, inorganic salts and mixtures of said materials, preferably hydroxypropylmethylcellulose and / or polyvinyl alcohol blends.
  • Polyvinyl alcohols are commercially available, for example under the trade name Mowiol ® (Clariant).
  • polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88, Mowiol ® 8-88 and Clariant L648.
  • the water-soluble thermoplastic used to prepare the portion may additionally optionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures of the above polymers.
  • the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol "1 , preferably from 1,000 to 90,000 gmol " 1 , more preferably from 12,000 to 80,000 gmol and especially from 13,000 to 70,000 gmol , It is further preferred if the thermoplastics are used in amounts of at least 50% by weight, preferably of at least 70% by weight, more preferably of at least 80% by weight and in particular of at least 90% by weight, based in each case on the weight the water-soluble polymeric thermoplastic.
  • a water-based liquid detergent containing 5.5% by weight of C 9-13 Na alkylbenzenesulfonate, 5.5% by weight of C 12-18 fatty alcohol 7 EO, and 5% by weight of C 12-14 Na alcohol was used 2 EO sulphate (V1) and an otherwise uniformly mixed liquid detergent which additionally contained 2% by weight of C10C10 mono- and di-rhamnolipid (NatSurFact® 90LCBS-4) (M1); Compensation for the amount of water contained.
  • the values given in Table 2 below show the differences in the ⁇ values of the remission measurement between the agent M1 and the agent V1, higher values meaning that the soiling was better washed out by the use of the agent according to the invention.

Abstract

The aim of the invention is to improve the washing power of detergents and cleaning products, in particular with respect to soiling containing oil and/or grease. This was essentially achieved by the use of a rhamnolipid mixture composed of 35 wt% to 45 wt% of C10C10 monorhamnolipid and 55 wt% to 65 wt% of C10C10 dirhamnolipid.

Description

Rhamnolipidhaltige Wasch- und Reinigungsmittel  Rhamnolipid-containing detergents and cleaners
Die vorliegende Erfindung betrifft Wasch- und Reinigungsmittel, die bestimmte Rhamnolipide enthalten. The present invention relates to detergents and cleaners containing certain rhamnolipids.
Moderne Waschmittel, die oft in flüssiger Form eingesetzt werden, kommen oft bei tiefen Temperaturen bis herunter zu Raumtemperatur oder noch darunter zum Einsatz. Dabei dient vor allem das in ihnen enthaltene Tensidsystem zur Entfernung von insbesondere fettigen Anschmutzungen. Übliche dabei verwendete Tenside sind petrochemisch basiertes lineares Alkylbenzolsulfonat, oleochemisch oder petrochemisch basiertes Alkoholethersulfat sowie petro- oder oleochemisch gewonnene nichtionische Tenside wie Alkoholethoxylate. Es ist eine Herausforderung, ein leistungsfähiges Waschmittel zu entwickeln, welches Inhaltsstoffe auf Basis alternativer Rohstoffquellen enthält und das ein Leistungsspektrum aufweist, das mit einem Waschmittel auf Basis solcher herkömmlicher tensidischer Inhaltsstoffe konkurrieren kann. Seit einigen Jahren sind Biotenside, die zum Beispiel aus Zucker oder anderen Kohlenhydrat-Quellen gewonnen werden können, kommerziell verfügbar. Allerdings erfüllt das Leistungsprofil der Biotenside in manchen Fällen nicht ohne weiteres die Ansprüche, die an ein modernes Waschmittel gestellt werden. Modern detergents, which are often used in liquid form, are often used at low temperatures down to room temperature or below. In particular, the surfactant system contained therein serves for the removal of, in particular, greasy soiling. Typical surfactants used are petrochemically based linear alkylbenzenesulfonate, oleochemically or petrochemically based alcohol ether sulfate and petro- or oleochemically derived nonionic surfactants such as alcohol ethoxylates. It is challenging to develop a powerful detergent that contains ingredients based on alternative sources of raw materials and that has a performance spectrum that can compete with a detergent based on such conventional surfactant ingredients. For some years, biosurfactants, which can be obtained, for example, from sugar or other carbohydrate sources, are commercially available. However, the performance profile of biosurfactants in some cases does not readily meet the demands made of a modern detergent.
Rhamnolipide sind Verbindungen, in denen eine Mono- oder Dirhamnoseeinheit glycosidisch mit der Hydroxylgruppe einer ß-hydroxylgruppenhaltigen Fettsäure verbunden ist, wobei die Fettsäure mit einer Hydroxylgruppe eines weiteren hydroxylgruppenhaltigen Fettsäuremoleküls verestert sein kann. Man erhält sie durch Fermentation von Bakterien der Gattung Pseudomonas, insbesondere von Pseudomonas aeruginosa, bevorzugt bei deren Wachstum auf hydrophoben Substraten wie n- Alkanen oder Pflanzenölen. Rhamnolipide gehören wegen ihres oberflächenaktiven Verhaltens und ihrer Herkunft zu den sogenannten Biotensiden. Das 3-(Hydroxydecanoyloxy)decansäure-dirham- nosid zum Beispiel besitzt die Formel Rhamnolipids are compounds in which a mono- or dirhamnose unit is glycosidically linked to the hydroxyl group of a fatty acid containing β-hydroxyl groups, it being possible for the fatty acid to 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 in their growth on hydrophobic substrates such as n-alkanes or vegetable oils. Rhamnolipids belong to the so-called biosurfactants because of their surface-active behavior and their origin. The 3- (hydroxydecanoyloxy) decanoic acid dirhomonoside, for example, has the formula
Figure imgf000002_0001
In üblichen Rhamnolipiden liegen neben Oo-Carbonsäuren und/oder -Hydroxycarbonsäuren auch längerkettige, beispielsweise Ci2-Carbonsäuren und/oder -Hydroxycarbonsäuren, vor. Aus der Patentschrift EP 0 499 434 B1 sind Waschmittel bekannt, die 1 bis 60 Gew.-% eines bei pH 7,0 und 25 °C in 1 gewichtsprozentiger wässriger Lösung eine micellare Phase ausbildendes Tensid und ein bei pH 7,0 und 25 °C in 1 gewichtsprozentiger wässriger Lösung eine lamellare Phase ausbildendes Tensid enthalten, wobei Rhamnolipid sowohl das die micellare Phase wie auch das die lamellare Phase ausbildende Tensid sein kann. Die europäische Patentschrift EP 1 445 302 B1 betrifft Waschmittel, die mindestens ein Glykolipid-Biotensid und mindestens ein Nicht-Glykolipid-Tensid enthalten, wobei diese sich in einer micellaren Phase befinden. Aus der internationalen Patentanmeldung WO 2012/010405 A1 sind Reinigungsmittel bekannt, die mindestens 1 Gew.-% Biotensid und ein Enzym bakterieller Herkunft enthalten. Die europäische Patentanmeldung EP 0 605 308 A1 offenbart Zusammensetzungen, die 0,001 Gew.-% bis 99,99 Gew.-% anionisches und/oder nichtionisches Tensid und 0,001 Gew.-% bis 99,99 Gew.-% Glykolipid enthalten, wobei unter den Glykolipiden zum Beispiel Sophorolipide, Rhamnolipide, Glucoselipide, Trehaloselipide und Cellobioselipide sein können. Aus der internationalen Patentanmeldung WO 2012/010406 A1 sind Waschmittel bekannt, die Lipase und Rhamnolipid enthalten, wobei das Rhamnolipid zu mindestens 50 Gew.-% aus Mono- Rhamnolipid besteht. Aus der internationalen Patentanmeldung WO 2012/010407 A1 sind Waschmittel bekannt, die Glykolipid-Tensid und Lipase bakterieller Herkunft enthalten, wobei das Glykoli- pid-Tensid zu mindestens 20 Gew.-% aus disaccharidischem säuregruppen-aufweisenden Glykolipid-Tensid besteht; das dort offenbarte Rhamnolipid besteht zu ca. 30 Gew.-% aus Mono-Rhamno- lipid und zu ca. 70 Gew.-% aus Di-Rhamnolipid. Die europäische Patentanmeldung EP 2 410 039 A1 betrifft mono- und di-rhamnolipidhaltige Reinigungsmittel, in denen das Gewichtsverhältnis von Mono-Rhamnolipid zu Di-Rhamnolipid im Bereich von 95:5 bis 45:55 liegt; konkret offenbart werden Mittel, in denen das Gewichtsverhältnis von Mono-Rhamnolipid zu Di-Rhamnolipid bei 50:50 und zum Vergleich bei etwa 25:75 liegt. Die europäische Patentanmeldung EP 2 787 065 A1 betrifft mono- und di-rhamnolipidhaltige Textilwaschmittel, in denen das Gewichtsverhältnis von Di-Rhamnolipid zu Mono-Rhamnolipid größer als 51 :49 ist; in der dort konkret offenbarten Rhamnolipidzu- sammensetzung aus P. putida liegt das Gewichtsverhältnis von Mono-Rhamnolipiden zu Di-Rham- nolipiden bei 1 :99, wobei das Di-Rhamnolipid zu etwa 18 Gew.-% aus Di-Rhamnolipid mit mindestens einer Ci2-Carbonsäure besteht. Aus der europäischen Patentanmeldung EP 2 786 743 A1 sind Rhamnolipidmischungen bekannt, die 51 Gew.-% bis 95 Gew.-% eines bestimmten Di-Rhamnolipids und 0,5 Gew.-% bis 9 Gew.-% eines bestimmten Mono-Rhamnolipids enthalten, in denen das Gewichtsverhältnis von Di-Rhamnolipid zu Mono-Rhamnolipid größer als 91 :9 ist.
Figure imgf000002_0001
In customary rhamnolipids, in addition to O-carboxylic acids and / or hydroxycarboxylic acids, there are also longer-chain, for example C 12 -carboxylic acids and / or -hydroxycarboxylic acids. The patent EP 0 499 434 B1 discloses detergents which contain 1 to 60% by weight of a surfactant which forms a micellar phase at pH 7.0 and 25 ° C. in 1% strength by weight aqueous solution and one at pH 7.0 and 25 ° C in 1 weight percent aqueous solution containing a lamellar phase-forming surfactant, wherein rhamnolipid may be both the micellar phase as well as the lamellar phase forming surfactant. European Patent Specification EP 1 445 302 B1 relates to detergents containing at least one glycolipid biosurfactant 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. European Patent Application EP 0 605 308 A1 discloses compositions containing from 0.001% to 99.99% by weight of anionic and / or nonionic surfactant and from 0.001% to 99.99% by weight of glycolipid, wherein The glycolipids may be, for example, sophorolipids, rhamnolipids, glucoselipids, trehaloselipids and cellobioselipids. International patent application WO 2012/010406 A1 discloses laundry detergents containing lipase and rhamnolipid, the rhamnolipid consisting of at least 50% by weight of mono-rhamnolipid. International Patent Application WO 2012/010407 A1 discloses laundry detergents which contain 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 rhamnolipid disclosed there consists of about 30% by weight of mono-rhamnolipid and about 70% by weight of di-rhamnolipid. European Patent Application EP 2 410 039 A1 relates to mono- and di-rhamnolipid-containing detergents in which the weight ratio of mono-rhamnolipid to di-rhamnolipid ranges from 95: 5 to 45:55; Specifically disclosed are agents in which the weight ratio of mono-rhamnolipid to di-rhamnolipid is 50:50 and for comparison is about 25:75. European Patent Application EP 2 787 065 A1 relates to mono- and di-rhamnolipid-containing laundry detergents in which the weight ratio of di-rhamnolipid to mono-rhamnolipid is greater than 51:49; in the specifically disclosed rhamnolipid composition of P. putida, the weight ratio of mono rhamnolipids to di-rhamnolipids is 1:99, the di-rhamnolipid being about 18% by weight di-rhamnolipid having at least one C 12 Carboxylic acid. European patent application EP 2 786 743 A1 discloses rhamnolipid mixtures which contain 51% by weight to 95% by weight of a certain di-rhamnolipid and 0.5% by weight to 9% by weight of a certain mono-rhamnolipid in which the weight ratio of di-rhamnolipid to mono-rhamnolipid is greater than 91: 9.
Überraschenderweise wurde gefunden, dass der Einsatz von bestimmte Rhamnolipide mit ange- passtem Verhältnis von Mono-Rhamnolipid zu Di-Rhamnolipid zu einer überlegenen Waschleistung führt. Gegenstand der Erfindung ist daher ein Wasch- oder Reinigungsmittel, enthaltend ein Rhamnolipid- gemisch aus 35 Gew.-% bis 45 Gew.-% 3-({3-[(6-deoxy-a-L-mannopyranosyl)oxy]decano- yl}oxy)decansäure und/oder deren Natrium-, Kalium-, Ammonium-, Alkylammonium- und/oder Hy- droxyalkylammoniumsalz (CioCio-Mono-Rhamnolipid) und 55 Gew.-% bis 65 Gew.-% 3-[(3-{[6-de- oxy-2-0-(6-deoxy-a-L-mannopyranosyl)-a-L-mannopyranosyl]oxy}decanoyl)oxy]decansäure und/oder deren Natrium-, Kalium-, Ammonium-, Alkylammonium- und/oder Hydroxyalkylammoni- umsalz (CioCio-Di-Rhamnolipid). Das Rhamnolipidgemisch ist vorzugsweise frei von anderen Rham- nolipiden. Erfindungsgemäß brauchbare Rhamnolipidgemische sind beispielsweise unter der Bezeichnung NatSurFact® kommerziell erhältlich. Bei den Alkylgruppen in den Alkylammoniumionen handelt es vorzugsweise um solche mit jeweils 1 bis 4 C-Atomen und deren Mischungen, und bei den Alkylgruppen in den Hydroxyalkylammoniumionen handelt es vorzugsweise um solche mit jeweils 2 bis 4 C-Atomen und deren Mischungen. Surprisingly, it has been found that the use of certain rhamnolipids with an adjusted ratio of mono-rhamnolipid to di-rhamnolipid leads to a superior washing performance. The invention therefore relates to a washing or cleaning agent containing a rhamnolipid mixture of from 35% by weight to 45% by weight of 3 - ({3 - [(6-deoxy-aL-mannopyranosyl) oxy] decanoyl} oxy) decanoic acid and / or its sodium, potassium, ammonium, alkylammonium and / or hydroxyalkylammonium salt (CioCio-mono-rhamnolipid) and 55% by weight to 65% by weight of 3 - [(3- { [6-deoxy-2-0- (6-deoxy-aL-mannopyranosyl) -al-mannopyranosyl] oxy} decanoyl) oxy] decanoic acid and / or its sodium, potassium, ammonium, alkylammonium and / or Hydroxyalkylammoni- umsalz (CioCio-di-rhamnolipid). The rhamnolipid mixture is preferably free from other rhamnolipids. Rhamnolipid mixtures which can be used according to the invention are commercially available, for example, under the name NatSurFact®. The alkyl groups in the alkylammonium ions are preferably those having in each case 1 to 4 C atoms and mixtures thereof, and the alkyl groups in the hydroxyalkylammonium ions are preferably those having in each case 2 to 4 C atoms and mixtures thereof.
Ein weiterer Gegenstand der Erfindung ist die Verwendung des genannten Rhamnolipidgemisches zur Erhöhung der Wasch- oder Reinigungsleistung von Wasch- oder Reinigungsmitteln. Die erfindungsgemäße Verwendung kann beispielsweise derart ausgeführt werden, dass man das Rhamnolipidgemisch einer wasch- oder reinigungsmittelhaltigen wässrigen Flotte zusetzt oder es als Bestandteil eines Wasch- oder Reinigungsmittels in die wässrige Flotte einbringt, und zu waschende oder reinigende Gegenstände bei Temperaturen von beispielsweise 10 °C bis 60 °C oder beispielsweise 20 °C bis 40 °C mit der Flotte in Kontakt bringt. Another object of the invention is the use of said Rhamnolipidgemisches to increase the washing or cleaning performance of detergents or cleaners. The use according to the invention can be carried out, for example, by adding the rhamnolipid mixture to a washing or cleaning agent-containing aqueous liquor or introducing it as a constituent of a washing or cleaning agent into the aqueous liquor, and objects to be washed or cleaned at temperatures of, for example, 10 ° C. to 60 ° C or, for example, 20 ° C to 40 ° C in contact with the liquor.
Ein erfindungsgemäßes Wasch- oder Reinigungsmittel enthält vorzugsweise 0,000001 Gew.-% bis 50 Gew.-%, insbesondere 0, 1 Gew.-% bis 20 Gew.-% des genannten Rhamnolipidgemischs neben herkömmlichen Bestandteilen solcher Mittel. An inventive washing or cleaning agent preferably contains 0.000001 wt .-% to 50 wt .-%, in particular 0, 1 wt .-% to 20 wt .-% of said Rhamnolipidgemischs in addition to conventional constituents of such agents.
Die erfindungsgemäßen Mittel können insbesondere Buildersubstanzen, oberflächenaktive Tenside, wassermischbare organische Lösungsmittel, Enzyme, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren, Polymere mit Spezialeffekten, wie soil release-Polymere, Farbübertragungsinhibitoren, Ver- grauungsinhibitoren, knitterreduzierende und formerhaltende polymere Wirkstoffe, und weitere Hilfsstoffe, wie optische Aufheller, Schaumregulatoren, Färb- und Duftstoffe enthalten. The agents according to the invention may in particular be builder substances, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, dye transfer inhibitors, gray scale inhibitors, wrinkle-reducing and form-retaining polymeric active compounds, and other auxiliaries, such as optical brighteners, foam regulators, dyes and fragrances.
Die Mittel können neben dem Rhamnolipidgemisch ein oder mehrere zusätzliche Tenside enthalten, wobei insbesondere anionische Tenside, nichtionische Tenside und deren Gemische in Frage kommen, aber auch kationische und/oder amphotere Tenside enthalten sein können. Dabei ist bevorzugt, wenn die Mittel neben dem Rhamnolipidgemisch mindestens 3, insbesondere mindestens 4 weitere Tenside enthalten, wobei gewunschtenfalls beispielsweise 10 weitere Tenside anwesend sein können. Als nichtionische Tenside können alle dem Fachmann bekannten nichtionischen Tenside eingesetzt werden. Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann oder lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkohol- ethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 Mol EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise Ci2-i4-Alkohole mit 3 EO oder 4 EO, Cg-n-Alkohol mit 7 EO, Cis-is-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-18- Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus Ci2-i4-Alkohol mit 3 EO und Ci2-is-Alkohol mit 5 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt einer ganzen oder einer gebrochenen Zahl entsprechen können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow ränge ethoxylates, NRE). The compositions may contain, in addition to the rhamnolipid mixture, one or more additional surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but cationic and / or amphoteric surfactants may also be present. It is preferred if the means in addition to the rhamnolipid mixture at least 3, in particular at least 4 other surfactants, wherein if desired, for example, 10 other surfactants may be present. As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical 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. In particular, however, 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 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 7 -n-alcohol with 7 EO, cis-is alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-i4-alcohol with 3 EO and Ci2-is-alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
Alternativ oder zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO. Außerdem können als weitere nichtionische Tenside auch Alkylglykoside der allgemeinen Formel R50(G)x eingesetzt werden, in der R5 einem primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen entspricht und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosi- den und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1 ,2 bis 1 ,4. Alternatively or in addition to these nonionic surfactants, it is also possible to use fatty alcohols with more than 12 EO. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. In addition, other nonionic surfactants which can also be employed are alkylglycosides of the general formula R 5 O (G) x in which R 5 is a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical containing 8 to 22, preferably 12 to 18 carbon atoms. Corresponds to atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; preferably x is 1, 2 to 1, 4.
Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette. Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylami- noxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können eingesetzt werden. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl N, N-dimethylamino oxide and N-tallow alkyl N, N-dihydroxyethyl amine oxide, and the fatty acid alkanolamides can also be used.
Weitere geeignete Tenside sind Polyhydroxyfettsäureamide der Formel, Further suitable surfactants are polyhydroxy fatty acid amides of the formula
R1 R1
I  I
R-C O-N— [Z] in der R für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch re- duktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alka- nolamin und nachfolgender Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können. Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel
Figure imgf000006_0001
in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R2 für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei Ο-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes. [Z] wird vorzugsweise durch reduktive Aminierung eines reduzierten Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.
RC ON- [Z] R is an aliphatic acyl radical having 6 to 22 carbon atoms, R 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. The 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
Figure imgf000006_0001
R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 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 oxy-alkyl radical having 1 to 8 carbon atoms, with Ο-4-alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives thereof residue. [Z] is preferably obtained by reductive amination of 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 catalyst.
Als anionische Tenside werden beispielsweise solche vom Typ der Sulfonate und Sulfate eingesetzt. Als Tenside vom Sulfonat-Typ kommen dabei vorzugsweise C9-i3-Alkylbenzolsulfonate, Olefinsulfo- nate, das heißt Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus Ci2-i8-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonie- ren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfo- nierungsprodukte erhält, in Betracht. Geeignet sind auch Alkansulfonate, die aus Ci2-is-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse oder Neutralisation gewonnen werden. Ebenso sind auch die Ester von α-Sulfofettsäuren (Estersulfonate), zum Beispiel die α-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren geeignet. As anionic surfactants, for example, those of the sulfonate type and sulfates are used. Preferred surfactants of the sulfonate type are C9-i3-alkylbenzenesulfonates, olefin-sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C12-C18-monoolefins having a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained, into consideration. Also suitable are alkanesulfonates which are obtained from C 12 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
Weitere geeignete Aniontenside sind sulfierte Fettsäureglycerinester. Unter Fettsäureglycerinestern sind die Mono-, Di- und Triester sowie deren Gemische zu verstehen, wie sie bei der Herstellung durch Veresterung von Glycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden. Bevorzugte sulfierte Fettsäureglycerinester sind dabei die Sulfierprodukte von gesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen, beispielsweise der Capronsäure, Caprylsäure, Caprinsäure, Myristinsäure, Laurinsäure, Palmitinsäure, Stearinsäure oder Behensäure. Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of glycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are included the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
Weitere geeignete Aniontenside sind Alkylsulfate und Ethersulfate. Unter einem Alkylsulfat ist ein Salz eines Schwefelsäurehalbesters eines Alkohols zu verstehen, der einen linearen, verzweigtket- tigen oder cyclischen gesättigten Kohlenwasserstoffrest mit 10 bis 22 C-Atomen aufweist. Zur Ladungsneutralisation des Schwefelsäurehalbesters ist ein Gegenkation vorhanden, insbesondere ein Natrium- oder Kaliumion oder ein Ammonium-, Alkylammonium- oder Hydroxyalkylammoniumion. Bevorzugte Alkoholreste leiten sich von nativen Ci2-Ci8-Fettalkoholen, wie beispielsweise von Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol, oder den C10-C20-OXO- alkoholen oder sekundären Alkoholen dieser Kettenlängen ab. Weiterhin bevorzugt sind Alkylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. Ci2-Ci6-Alkylsulfate, Ci2-Ci5-Alkylsulfate sowie Ci4-Ci5-Alkylsulfate sind besonders bevorzugt. Ethersulfate sind analog den Alkylsulfaten Schwefelsäurehalbester alkoxylierter Alkohole, wobei die durchschnittliche Anzahl von Alkoxygrup- pen pro Alkoholfunktion in der Regel 1 bis 10, vorzugsweise 3 bis 7, beträgt. Bevorzugte Alkoxy- gruppen sind die Ethoxygruppe, die Propoxygruppe und deren Mischungen. Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-21- Alkohole, wie 2-Methyl-verzweigte C9-n-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder Ci2-i8-Fettalkohole mit 1 bis 4 EO, sind geeignet. Further suitable anionic surfactants are alkyl sulfates and ether sulfates. An alkyl sulfate is to be understood as meaning a salt of a sulfuric acid half-ester of an alcohol which has a linear, branched-chain or cyclic saturated hydrocarbon radical having 10 to 22 carbon atoms. For charge neutralization of the sulfuric acid half-ester, a counter cation is present, in particular a sodium or potassium ion or an ammonium, alkylammonium or hydroxyalkylammonium ion. Preferred alcohol radicals are derived from native C 12-18 fatty alcohols, such as, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 OXO alcohols or secondary alcohols of these chain lengths. Also preferred are alkyl sulfates of said chain length, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Ci2-Ci6-alkyl sulfates, Ci2-Ci5-alkyl sulfates and Ci4-Ci5-alkyl sulfates are particularly preferred. Ether sulfates are analogous to the alkyl sulfates of sulfuric monoesters of alkoxylated alcohols, the average number of alkoxy groups per alcohol function being generally from 1 to 10, preferably from 3 to 7. Preferred alkoxy groups are the ethoxy group, the propoxy group and mixtures thereof. Also, the sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight or branched C7-21 alcohols, such as 2-methyl-branched C9-n-alcohols having an average of 3.5 moles of ethylene oxide (EO) or Ci2-i8 fatty alcohols with 1 up to 4 EO, are suitable.
Weitere geeignete Aniontenside sind auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen, darstellen. Bevorzugte Sulfosuccinate enthalten Cs -is-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen. Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen. Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cs -is-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 again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
Als weitere anionische Tenside kommen insbesondere Seifen in Betracht. Geeignet sind gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierte Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengemische. Die anionischen Tenside einschließlich der Seifen können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor. As further anionic surfactants are particularly soaps into consideration. 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 anionic surfactants, including the soaps, 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.
An Stelle der genannten Tenside oder in Verbindung mit ihnen können auch kationische und/oder amphotere Tenside eingesetzt werden. Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and / or amphoteric surfactants.
Als kationische Aktivsubstanzen können beispielsweise kationische Verbindungen der nachfolgenden Formeln eingesetzt werden: As cationic active substances, for example, cationic compounds of the following formulas can be used:
Ri Ri
-N-(C H2)n-T- (C H2)n-T-R2 -N- (CH 2 ) n -T- (CH 2 ) n -T -R 2
Figure imgf000008_0001
Figure imgf000008_0002
worin jede Gruppe R unabhängig voneinander ausgewählt ist aus Ο-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R2 unabhängig voneinander ausgewählt ist aus Cs-28-Alkyl- oder -Alkenylgruppen; R3 = R oder (CH2)n-T-R2; R4 = R oder R2 oder (CH2)n-T-R2; T = -CH2-, -O- CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.
Figure imgf000008_0001
Figure imgf000008_0002
wherein each R group is independently selected from Ο-6 alkyl, alkenyl or hydroxyalkyl groups; each R 2 group is independently selected from Cs-28 alkyl or alkenyl groups; R 3 = R or (CH 2) NTR 2; R 4 = R or R 2 or (CH 2 ) nTR 2 ; T = -CH 2 -, -O-CO- or -CO-O- and n is an integer from 0 to 5.
Derartige zusätzlich zu Rhamnolipid einsetzbare Tenside sind in Mengen von vorzugsweise 5 Gew.-% bis 50 Gew.-%, insbesondere von 10 Gew.-% bis 30 Gew.-%, in erfindungsgemäßen Mitteln enthalten, können gewünschtenfalls aber auch ganz fehlen. Such surfactants which can be used in addition to rhamnolipid are present in agents according to the invention in amounts of preferably from 5% by weight to 50% by weight, in particular from 10% by weight to 30% by weight, but may also be completely absent if desired.
Zur Pflege der Textilien und zur Verbesserung der Textileigenschaften wie einem weicheren "Griff (Avivage) und verringerter elektrostatischer Aufladung (erhöhter Tragekomfort) können textil- weichmachende Verbindungen eingesetzt werden. Die Wirkstoffe dieser Formulierungen sind quar- täre Ammoniumverbindungen mit zwei hydrophoben Resten, wie beispielsweise das Disteraryldime- thylammoniumchlorid, welches jedoch wegen seiner ungenügenden biologischen Abbaubarkeit zunehmend durch quartäre Ammoniumverbindungen ersetzt wird, die in ihren hydrophoben Resten Estergruppen als Sollbruchstellen für den biologischen Abbau enthalten. Textile softening compounds can be used to care for the textiles and to improve the textile properties such as a softer "feel" (avivage) and reduced electrostatic charge (increased wear comfort) .The active ingredients of these formulations are quaternary ammonium compounds with two hydrophobic radicals, such as Disteraryldime- thylammonium chloride, which, however, due to its insufficient biodegradability increasingly replaced by quaternary ammonium compounds containing ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.
Derartige "Esterquats" mit verbesserter biologischer Abbaubarkeit sind beispielsweise dadurch erhältlich, dass man Mischungen von Methyldiethanolamin und/oder Triethanolamin mit Fettsäuren verestert und die Reaktionsprodukte anschließend in an sich bekannter Weise mit Alkylierungsmit- teln quaterniert. Als Appreturwirkstoff geeignet ist Dimethylolethylenharnstoff. Such "esterquats" with improved biodegradability are obtainable, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products in a manner known per se with alkylating agents. Suitable as a finishing agent is dimethylolethyleneurea.
Ein erfindungsgemäßes Mittel enthält vorzugsweise mindestens einen wasserlöslichen und/oder wasserunlöslichen, organischen und/oder anorganischen Builder. Zu den wasserlöslichen organischen Buildersubstanzen gehören Polycarbonsäuren, insbesondere Citronensäure und Zuckersäuren, monomere und polymere Aminopolycarbonsäuren, insbesondere Methylglycindiessigsäure, Nitrilotriessigsäure und Ethylendiamintetraessigsäure sowie Polyasparaginsäure, Polyphosphonsäuren, insbesondere Aminotris(methylenphosphonsäure), Ethylendiamintetrakis(methylenphos- phonsäure) und 1-Hydroxyethan-1 ,1-diphosphonsäure, polymere Hydroxyverbindungen wie Dextrin sowie polymere (Poly-)carbonsäuren, insbesondere durch Oxidation von Polysacchariden beziehungsweise Dextrinen zugänglichen Polycarboxylate, und/oder polymere Acrylsäuren, Methacryl- säuren, Maleinsäuren und Mischpolymere aus diesen, die auch geringe Anteile polymerisierbarer Substanzen ohne Carbonsäurefunktionalität einpolymerisiert enthalten können. Die relative Molekülmasse der Homopolymeren ungesättigter Carbonsäuren liegt im allgemeinen zwischen 5 000 und 200 000, die der Copolymeren zwischen 2 000 und 200 000, vorzugsweise 50 000 bis 120 000, jeweils bezogen auf freie Säure. Ein besonders bevorzugtes Acrylsäure-Maleinsäure-Copolymer weist eine relative Molekülmasse von 50 000 bis 100 000 auf. Geeignete, wenn auch weniger bevorzugte Verbindungen dieser Klasse sind Copolymere der Acrylsäure oder Methacrylsäure mit Vinylethern, wie Vinylmethylethern, Vinylester, Ethylen, Propylen und Styrol, in denen der Anteil der Säure mindestens 50 Gew.-% beträgt. Als wasserlösliche organische Buildersubstanzen können auch Terpo- lymere eingesetzt werden, die als Monomere zwei ungesättigte Säuren und/oder deren Salze sowie als drittes Monomer Vinylalkohol und/oder einem veresterten Vinylalkohol oder ein Kohlenhydrat enthalten. Das erste saure Monomer beziehungsweise dessen Salz leitet sich von einer monoethyl- enisch ungesättigten C3-Cs-Carbonsäure und vorzugsweise von einer C3-C4-Monocarbonsäure, insbesondere von (Meth)-acrylsäure ab. Das zweite saure Monomer beziehungsweise dessen Salz kann ein Derivat einer C4-Cs-Dicarbonsäure, wobei Maleinsäure besonders bevorzugt ist, und/oder ein Derivat einer Allylsulfonsäure, die in 2-Stellung mit einem Alkyl- oder Arylrest substituiert ist, sein. Derartige Polymere weisen im Allgemeinen eine relative Molekülmasse zwischen 1 000 und 200 000 auf. Weitere bevorzugte Copolymere sind solche, die als Monomere Acrolein und Acrylsäure/Acryl- säuresalze beziehungsweise Vinylacetat aufweisen. Die organischen Buildersubstanzen können, insbesondere zur Herstellung flüssiger Mittel, in Form wässriger Lösungen, vorzugsweise in Form 30- bis 50-gewichtsprozentiger wässriger Lösungen eingesetzt werden. Alle genannten Säuren werden in der Regel in Form ihrer wasserlöslichen Salze, insbesondere ihre Alkalisalze, eingesetzt. 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 methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1, 1 diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular by oxidation of polysaccharides or dextrins accessible polycarboxylates, and / or polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality can. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, each based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. Terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer may also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylically unsaturated C 3 -C 5 -carboxylic acid and preferably from a C 3 -C 4 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, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical. Such polymers generally have a molecular weight between 1,000 and 200,000. Further preferred copolymers are those which contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. The organic builders may, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form 30 to 50 weight percent aqueous solutions are used. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
Derartige organische Buildersubstanzen können gewünschtenfalls in Mengen bis zu 40 Gew.-%, insbesondere bis zu 25 Gew.-% und vorzugsweise von 1 Gew.-% bis 8 Gew.-% enthalten sein. Mengen in der oberen Hälfte der genannten Bereiche werden vorzugsweise in pastenförmigen oder flüssigen, insbesondere wasserhaltigen Mitteln eingesetzt. If desired, such 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 in the upper half of said ranges are preferably used in pasty or liquid, in particular water-containing agents.
Als wasserlösliche anorganische Buildermaterialien kommen insbesondere polymere Alkaliphosphate, die in Form ihrer alkalischen neutralen oder sauren Natrium- oder Kaliumsalze vorliegen können, in Betracht. Beispiele hierfür sind Tetranatriumdiphosphat, Dinatriumdihydrogendiphosphat, Pentanatriumtriphosphat, sogenanntes Natriumhexametaphosphat sowie die entsprechenden Kaliumsalze beziehungsweise Gemische aus Natrium- und Kaliumsalzen. Als wasserunlösliche, was- serdispergierbare anorganische Buildermaterialien werden insbesondere kristalline oder amorphe Alkalialumosilikate, in Mengen von bis zu 50 Gew.-%, vorzugsweise nicht über 40 Gew.-% und in flüssigen Mitteln insbesondere von 1 Gew.-% bis 5 Gew.-%, eingesetzt. Unter diesen sind die kristallinen Natriumalumosilikate in Waschmittelqualität, insbesondere Zeolith A, P und gegebenenfalls X, bevorzugt. Mengen nahe der genannten Obergrenze werden vorzugsweise in festen, teilchenför- migen Mitteln eingesetzt. Geeignete Alumosilikate weisen insbesondere keine Teilchen mit einer Korngröße über 30 μιη auf und bestehen vorzugsweise zu wenigstens 80 Gew.-% aus Teilchen mit einer Größe unter 10 μιη. Ihr Calciumbindevermögen liegt in der Regel im Bereich von 100 mg bis 200 mg CaO pro Gramm. Suitable water-soluble inorganic builder materials are, in particular, polymeric alkali metal phosphates, which may be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of these are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic builder materials. %, used. Among these, preferred are the detergent grade crystalline sodium aluminosilicates, especially zeolite A, P and optionally X. Quantities close to the stated upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 μm, and preferably consist of at least 80% by weight of particles having a size of less than 10 μm. Their calcium binding capacity is generally in the range of 100 mg to 200 mg CaO per gram.
Geeignete Substitute beziehungsweise Teilsubstitute für das genannte Alumosilikat sind kristalline Alkalisilikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können. Die als Gerüststoffe brauchbaren Alkalisilikate weisen vorzugsweise ein molares Verhältnis von Alkalioxid zu S1O2 unter 0,95, insbesondere von 1 : 1 , 1 bis 1 : 12 auf und können amorph oder kristallin vorliegen. Bevorzugte Alkalisilikate sind die Natriumsilikate, insbesondere die amorphen Natriumsilikate, mit einem molaren Verhältnis Na20:Si02 von 1 :2 bis 1 :2,8. Als kristalline Silikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können, werden vorzugsweise kristalline Schichtsilikate der allgemeinen Formel Na2Six02x+i y H2O eingesetzt, in der x, das sogenannte Modul, eine Zahl von 1 ,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Bevorzugte kristalline Schichtsilikate sind solche, bei denen x in der genannten allgemeinen Formel die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch δ-Natriumdisilikate (Na2Si20s y H2O) bevorzugt. Auch aus amorphen Alkalisilikaten hergestellte, praktisch wasserfreie kristalline Alkalisilikate der obengenannten allgemeinen Formel, in der x eine Zahl von 1 ,9 bis 2, 1 bedeutet, können eingesetzt werden. In einer weiteren bevorzugten Ausführungsform wird ein kristallines Natriumschichtsilikat mit einem Modul von 2 bis 3 eingesetzt, wie es n aus Sand und Soda hergestellt werden kann. Kristalline Natriumsilikate mit einem Modul im Bereich von 1 ,9 bis 3,5 werden in einer weiteren be- vorzugten Ausführungsform eingesetzt. In einer bevorzugten Ausgestaltung setzt man ein granuläres Compound aus Alkalisilikat und Alkalicarbonat ein, wie es zum Beispiel unter dem Namen Nabion® 15 im Handel erhältlich ist. Falls als zusätzliche Buildersubstanz auch Alkalialumosilikat, insbesondere Zeolith, vorhanden ist, beträgt das Gewichtsverhältnis Alumosilikat zu Silikat, jeweils bezogen auf wasserfreie Aktivsubstanzen, vorzugsweise 1 : 10 bis 10:1. In Mitteln, die sowohl amorphe als auch kristalline Alkalisilikate enthalten, beträgt das Gewichtsverhältnis von amorphem Alkalisilikat zu kristallinem Alkalisilikat vorzugsweise 1 :2 bis 2: 1 und insbesondere 1 :1 bis 2:1. Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1, 1 to 1: 12, and may be present in amorphous or crystalline form. 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. In particular, both .beta. And .delta.-sodium disilicates (Na.sub.2Si.sub.20.sub.y H.sub.2O) are preferred. Also prepared from amorphous alkali 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 a further preferred embodiment, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in another preferred embodiment used. In a preferred embodiment, a granular compound of alkali metal silicate and alkali carbonate is used, as it is commercially available, for example, under the name Nabion® 15. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is preferably 1:10 to 10: 1. In agents containing both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
Buildersubstanzen sind in Waschmitteln vorzugsweise in Mengen bis zu 60 Gew.-%, insbesondere von 5 Gew.-% bis 40 Gew.-%, enthalten. Builder substances are preferably contained in detergents in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
In einer bevorzugten Ausgestaltung weist das Mittel einen wasserlöslichen Builderblock auf. Durch die Verwendung des Begriffes„Builderblock" soll hierbei ausgedrückt werden, dass die Mittel keine weiteren Buildersubstanzen enthalten als solche, die wasserlöslich sind, das heißt sämtliche in dem Mittel enthaltenen Buildersubstanzen sind in dem so charakterisierten„Block" zusammengefasst, wobei allenfalls die Mengen an Stoffen ausgenommen sind, die als Verunreinigungen beziehungsweise stabilisierende Zusätze in geringen Mengen in den übrigen Inhaltsstoffen der Mittel handelsüblicher Weise enthalten sein können. Unter dem Begriff„wasserlöslich" soll dabei verstanden werden, dass sich der Builderblock bei der Konzentration, die sich durch die Einsatzmenge des ihn enthaltenden Mittels bei den üblichen Bedingungen ergibt, rückstandsfrei löst. Vorzugsweise sind mindestens 15 Gew.-% und bis zu 55 Gew.-%, insbesondere 25 Gew.-% bis 50 Gew.-% an wasserlöslichem Builderblock in den Mitteln enthalten. Dieser setzt sich vorzugsweise zusammen aus den Komponenten In a preferred embodiment, the agent comprises a water-soluble builder block. The use of the term "builder block" is intended to express that the agents contain no further builder substances than those which are water-soluble, ie all builder substances contained in the agent are combined in the "block" characterized in this way, the amounts at most being Substances are excluded, which may be contained as impurities or stabilizing additives in small amounts in the other ingredients of the means commercially available manner. The term "water-soluble" is to be understood as meaning that the builder block dissolves without leaving a residue at the concentration which results from the use of the agent containing it under the usual conditions, preferably at least 15% by weight and up to 55% by weight %, in particular 25 wt .-% to 50 wt .-% of water-soluble builder block contained in the agents.This is preferably composed of the components
a) 5 Gew.-% bis 35 Gew.-% Citronensäure, Alkalicitrat und/oder Alkalicarbonat, welches auch zumindest anteilig durch Alkalihydrogencarbonat ersetzt sein kann, a) 5% by weight to 35% by weight of citric acid, alkali citrate and / or alkali metal carbonate, which may also be replaced at least proportionally by alkali metal bicarbonate,
b) bis zu 10 Gew.-% Alkalisilikat mit einem Modul im Bereich von 1 ,8 bis 2,5, b) up to 10% by weight of alkali silicate having a modulus in the range of 1.8 to 2.5,
c) bis zu 2 Gew.-% Phosphonsäure und/oder Alkaliphosphonat, c) up to 2% by weight of phosphonic acid and / or alkali phosphonate,
d) bis zu 50 Gew.-% Alkaliphosphat, und d) up to 50% by weight of alkali metal phosphate, and
e) bis zu 10 Gew.-% polymerem Polycarboxylat, e) up to 10% by weight of polymeric polycarboxylate,
wobei die Mengenangaben sich auf das gesamte Wasch- oder Reinigungsmittel beziehen. Dies gilt auch für alle voranstehenden oder noch folgenden Mengenangaben, sofern nicht ausdrücklich anders angegeben. wherein the quantities are based on the entire detergent or cleaning agent. This also applies to all quantities above or below, unless expressly stated otherwise.
In einer bevorzugten Ausführungsform enthält der wasserlösliche Builderblock mindestens 2 der Komponenten b), c), d) und e) in Mengen größer 0 Gew.-%. In a preferred embodiment, the water-soluble builder block contains at least 2 of the components b), c), d) and e) in amounts greater than 0 wt .-%.
Hinsichtlich der Komponente a) sind in einer bevorzugten Ausführungsform 15 Gew.-% bis 25 Gew.-% Alkalicarbonat, welches zumindest anteilig durch Alkalihydrogencarbonat ersetzt sein kann, und bis zu 5 Gew.-%, insbesondere 0,5 Gew.-% bis 2,5 Gew.-% Citronensäure und/oder AI- kalicitrat enthalten. In einer alternativen Ausführungsform sind als Komponente a) 5 Gew.-% bis 25 Gew.-%, insbesondere 5 Gew.-% bis 15 Gew.-% Citronensäure und/oder Alkalicitrat und bis zu 5 Gew.-% , insbesondere 1 Gew.-% bis 5 Gew.-% Alkalicarbonat, welches zumindest anteilig durch Alkalihydrogencarbonat ersetzt sein kann, enthalten. Falls sowohl Alkalicarbonat wie auch Alkalihy- drogencarbonat vorhanden sind , weist die Komponente a) Alkalicarbonat und Alkalihydrogencarbonat vorzugsweise im Gewichtsverhältnis von 10: 1 bis 1 : 1 auf. With regard to component a), in a preferred embodiment, 15% by weight to 25% by weight of alkali carbonate, which may be replaced at least proportionally by alkali metal bicarbonate, and up to 5% by weight, in particular 0.5% by weight, bis 2.5% by weight of citric acid and / or Al contain kalicitrat. In an alternative embodiment, as component a) 5 wt .-% to 25 wt .-%, in particular 5 wt .-% to 15 wt .-% citric acid and / or alkali citrate and up to 5 wt .-%, in particular 1 wt .-% to 5 wt .-% alkali carbonate, which may be at least partially replaced by alkali metal bicarbonate included. If both alkali metal carbonate and alkali metal bicarbonate are present, component a) comprises alkali metal carbonate and alkali metal bicarbonate, preferably in a weight ratio of 10: 1 to 1: 1.
Hinsichtlich der Komponente b) sind in einer bevorzugten Ausführungsform 1 Gew.-% bis 5 Gew.-% Alkalisilikat mit einem Modul im Bereich von 1 ,8 bis 2,5 enthalten. With regard to component b), in a preferred embodiment, 1 wt .-% to 5 wt .-% alkali metal silicate with a modulus in the range of 1, 8 to 2.5 included.
Hinsichtlich der Komponente c) sind in einer bevorzugten Ausführungsform 0,05 Gew.-% bis 1 Gew.-% Phosphonsäure und/oder Alkaliphosphonat enthalten. Unter Phosphonsäuren werden dabei auch gegebenenfalls substituierte Alkylphosphonsäuren verstanden, die auch mehrere Phos- phonsäuregruppierungen aufweisen könne (sogenannte Polyphosphonsäuren). Bevorzugt werden sie ausgewählt aus den Hydroxy- und/oder Aminoalkylphosphonsäuren und/oder deren Alkalisalzen, wie zum Beispiel Dimethylaminomethandiphosphonsäure, 3-Aminopropan-1-hydroxy-1 , 1-diphos- phonsäure, 1-Amino-1-phenyl-methandiphosphonsäure, 1-Hydroxyethan-1 , 1-diphosphonsäure, Amino-tris(methylenphosphonsäure), N,N,N',N'-Ethylendiamin-tetrakis(methylenphosphonsäure) und acylierte Derivate der phosphorigen Säure, die auch in beliebigen Mischungen eingesetzt werden können. With regard to component c), in a preferred embodiment, from 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate is contained. Phosphonic acids are also understood as meaning optionally substituted alkylphosphonic acids, which may also have a plurality of phosphonic acid groups (so-called polyphosphonic acids). They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali salts, for example dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1 -Hydroxyethane-1, 1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediaminetrakis (methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any mixtures.
Hinsichtlich der Komponente d) sind in einer bevorzugten Ausführungsform 15 Gew.-% bis 35 Gew.- % Alkaliphosphat, insbesondere Trinatriumpolyphosphat, enthalten. Alkaliphosphat ist dabei die summarische Bezeichnung für die Alkalimetall- (insbesondere Natrium- und Kalium-) -Salze der verschiedenen Phosphorsäuren, bei denen man Metaphosphorsäuren (HP03)n und Orthophosphorsäure H3PO4 neben höhermolekularen Vertretern unterscheiden kann. Die Phosphate vereinen dabei mehrere Vorteile in sich: Sie wirken als Alkaliträger, verhindern Kalkbeläge auf Maschinenteilen bzw. Kalkinkrustationen in Geweben und tragen überdies zur Reinigungsleistung bei. Natriumdihy- drogenphosphat, NaH2PÜ4, existiert als Dihydrat (Dichte 1 ,91 gern 3, Schmelzpunkt 60°) und als Mo- nohydrat (Dichte 2,04 gern 3). Beide Salze sind weiße, in Wasser sehr leicht lösliche Pulver, die beim Erhitzen das Kristallwasser verlieren und bei 200°C in das schwach saure Diphosphat (Dinatrium- hydrogendiphosphat, ΝΒΣΗΣΡΣΟ), bei höherer Temperatur in Natiumtrimetaphosphat (Na3P3Ü9) und Madrellsches Salz übergehen. NaH2PÜ4 reagiert sauer; es entsteht, wenn Phosphorsäure mit Natronlauge auf einen pH-Wert von 4,5 eingestellt und die Maische versprüht wird. Kaliumdihydrogen- phosphat (primäres oder einbasiges Kaliumphosphat, Kaliumbiphosphat, KDP), KH2PO4, ist ein weißes Salz der Dichte 2,33 gern 3, hat einen Schmelzpunkt 253° (Zersetzung unter Bildung von (KPÜ3)x, Kaliumpolyphosphat) und ist leicht löslich in Wasser. Dinatriumhydrogenphosphat (sekundäres Natriumphosphat), Na2HPÜ4, ist ein farbloses, sehr leicht wasserlösliches kristallines Salz. Es existiert wasserfrei und mit 2 Mol (Dichte 2,066 gern-3, Wasserverlust bei 95°), 7 Mol (Dichte 1 ,68 gern 3, Schmelzpunkt 48° unter Verlust von 5 H2O) und 12 Mol Wasser (Dichte 1 ,52 gern 3, Schmelzpunkt 35° unter Verlust von 5 H2O), wird bei 100° wasserfrei und geht bei stärkerem Erhitzen in das Diphosphat Na4P20 über. Dinatriumhydrogenphosphat wird durch Neutralisation von Phosphorsäure mit Sodalösung unter Verwendung von Phenolphthalein als Indikator hergestellt. Dikaliumhy- drogenphosphat (sekundäres oder zweibasiges Kaliumphosphat), K2HPO4, ist ein amorphes, weißes Salz, das in Wasser leicht löslich ist. Trinatriumphosphat, tertiäres Natriumphosphat, NasPC , sind farblose Kristalle, die als Dodecahydrat eine Dichte von 1 ,62 gern 3 und einen Schmelzpunkt von 73- 76°C (Zersetzung), als Decahydrat (entsprechend 19-20% P2O5) einen Schmelzpunkt von 100°C und in wasserfreier Form (entsprechend 39-40% P2O5) eine Dichte von 2,536 gern 3 aufweisen. Trinatriumphosphat ist in Wasser unter alkalischer Reaktion leicht löslich und wird durch Eindampfen einer Lösung aus genau 1 Mol Dinatriumphosphat und 1 Mol NaOH hergestellt. Trikaliumphosphat (tertiäres oder dreibasiges Kaliumphosphat), K3PO4, ist ein weißes, zerfließliches, körniges Pulver der Dichte 2,56 gern 3, hat einen Schmelzpunkt von 1340° und ist in Wasser mit alkalischer Reaktion leicht löslich. Es entsteht z.B. beim Erhitzen von Thomasschlacke mit Kohle und Kaliumsulfat. Trotz des höheren Preises werden die leichter löslichen, daher hochwirksamen, Kaliumphosphate gegenüber entsprechenden Natrium-Verbindungen vielfach bevorzugt. Tetranatriumdiphosphat (Natri- umpyrophosphat), Na4P20, existiert in wasserfreier Form (Dichte 2,534 gern 3, Schmelzpunkt 988°, auch 880° angegeben) und als Decahydrat (Dichte 1 ,815-1 ,836 gern 3, Schmelzpunkt 94° unter Wasserverlust). Bei Substanzen sind farblose, in Wasser mit alkalischer Reaktion lösliche Kristalle. Na4P2Ü7 entsteht beim Erhitzen von Dinatriumphosphat auf >200° oder indem man Phosphorsäure mit Soda im stöchiometrischem Verhältnis umsetzt und die Lösung durch Versprühen entwässert. Das Decahydrat komplexiert Schwermetall-Salze und Härtebildner und verringert daher die Härte des Wassers. Kaliumdiphosphat (Kaliumpyrophosphat), K4P2O7, existiert in Form des Trihydrats und stellt ein farbloses, hygroskopisches Pulver mit der Dichte 2,33 gern 3 dar, das in Wasser löslich ist, wobei der pH-Wert der 1 %igen Lösung bei 25° 10,4 beträgt. Durch Kondensation des NaH2PÜ4 oder des KH2PO4 entstehen höhermolekulare Natrium- und Kaliumphosphate, bei denen man cyclische Vertreter, die Natrium- oder Kaliummetaphosphate und kettenförmige Typen, die Natrium- oder Kaliumpolyphosphate, unterscheiden kann. Insbesondere für letztere sind eine Vielzahl von Bezeichnungen in Gebrauch: Schmelz- oder Glühphosphate, Grahamsches Salz, Kurrolsches und Madrell- sches Salz. Alle höheren Natrium- und Kaliumphosphate werden gemeinsam als kondensierte Phosphate bezeichnet. Das technisch wichtige Pentanatriumtriphosphat, NasPsO-io (Natriumtripolyphos- phat), ist ein wasserfrei oder mit 6 H2O kristallisierendes, nicht hygroskopisches, weißes, wasserlösliches Salz der allgemeinen Formel NaO-[P(0)(ONa)-0]n-Na mit n=3. In 100 g Wasser lösen sich bei Zimmertemperatur etwa 17 g, bei 60° ca. 20 g, bei 100° rund 32 g des kristallwasserfreien Salzes; nach zweistündigem Erhitzen der Lösung auf 100° entstehen durch Hydrolyse etwa 8% Ortho- phosphat und 15% Diphosphat. Bei der Herstellung von Pentanatriumtriphosphat wird Phosphorsäure mit Sodalösung oder Natronlauge im stöchiometrischen Verhältnis zur Reaktion gebracht und die Lösung, durch Versprühen entwässert. Ähnlich wie Grahamsches Salz und Natriumdiphosphat löst Pentanatriumtriphosphat viele unlösliche Metall-Verbindungen (auch Kalkseifen usw.). Pentaka- liumtriphosphat, K5P3O10 (Kaliumtripolyphosphat), kommt beispielsweise in Form einer 50 Gew.-%- igen Lösung (> 23% P2O5, 25% K2O) in den Handel. Weiter existieren auch Natriumkaliumtripoly- phosphate, welche ebenfalls im Rahmen der vorliegenden Erfindung einsetzbar sind. Diese entstehen beispielsweise, wenn man Natriumtrimetaphosphat mit KOH hydrolysiert: With regard to component d), in a preferred embodiment, 15% by weight to 35% by weight of alkali metal phosphate, in particular trisodium polyphosphate, are contained. Alkaliphosphat is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric (HP03) n and orthophosphoric H3PO4 in addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance. Sodium dihydrogen phosphate, NaH2PÜ4, exists as dihydrate (density 1, 91 like 3 , melting point 60 °) and as monohydrate (density 2.04 like 3 ). Both salts are white, very soluble in water powders, which lose the water of crystallization on heating and at 200 ° C in the weak acid diphosphate (disodium hydrogendiphosphate, ΝΒΣΗΣΡΣΟ), at higher temperature in sodium trimetaphosphate (Na3P3Ü9) and Madrell's salt. NaH2PÜ4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate monobasic or potassium monobasic potassium phosphate, KDP), KH2PO4, is a white salt with a density of 2.33, preferably 3 , with a melting point of 253 ° (decomposed to form (KPÜ3) x, potassium polyphosphate) and is readily soluble in Water. Disodium hydrogen phosphate (secondary sodium phosphate), Na2HP4, is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 likes -3 , water loss at 95 °), 7 moles (density 1, 68 preferably 3 , melting point 48 ° with loss of 5 H2O) and 12 moles of water (density 1, 52 like 3 , melting point 35 ° with loss of 5 H2O), becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na4P20. Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K2HPO4, is an amorphous, white salt that is readily soluble in water. Trisodium phosphate, sodium tertiary phosphate, NasPC, are colorless crystals having a density of 1, 62, 3 and a melting point of 73-76 ° C (decomposition) as dodecahydrate, and a melting point of 100 ° as decahydrate (corresponding to 19-20% P2O5) C and in anhydrous form (corresponding to 39-40% P2O5) have a density of 2.536 like 3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K3PO4, is a white, deliquescent, granular powder of density 2.56, preferably 3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds. Tetrasodium diphosphate (sodium pyrophosphate), Na4P20, exists in anhydrous form (density 2.534, 3 , melting point 988 °, also indicated as 880 °) and as decahydrate (density 1, 815-1, 836, 3 , melting point 94 °, with loss of water). For substances are colorless, in water with alkaline reaction soluble crystals. Na4P2Ü7 is formed by heating disodium phosphate to> 200 ° C or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K4P2O7, exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33% 3 , which is soluble in water, the pH of the 1% solution being 25 ° 10, 4 is. Condensation of NaH2PÜ4 or KH2PO4 gives rise to higher molecular weight sodium and potassium phosphates, which can be used to distinguish cyclic species, sodium or potassium metaphosphates, and chain types, sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches and Madrell- sches salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates. The industrially important pentasodium triphosphate, NasPsO-io (sodium tripolyphosphate), is an anhydrous or water-soluble salt of the general formula NaO- [P (O) (ONa) -O] n- Na, which crystallizes with 6H 2 O, and which is non-hygroscopic n =. 3 In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentaka- Liumtriphosphat, K5P3O10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P2O5, 25% K2O) in the trade. There are also sodium potassium tripolyphosphates, which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:
(NaP03)3 + 2 KOH Na3K2P30io + H2O (NaPO 3 ) 3 + 2 KOH Na 3 K 2 P 30io + H 2 O
Diese sind genau wie Natriumtripolyphosphat, Kaliumtripolyphosphat oder Mischungen aus diesen beiden einsetzbar; auch Mischungen aus Natriumtripolyphosphat und Natriumkaliumtripolyphosphat oder Mischungen aus Kaliumtripolyphosphat und Natriumkaliumtripolyphosphat oder Gemische aus Natriumtripolyphosphat und Kaliumtripolyphosphat und Natriumkaliumtripolyphosphat sind einsetzbar. These are just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two applicable; It is also possible to use mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate.
Hinsichtlich der Komponente e) sind in einer bevorzugten Ausführungsform der Mittel 1 ,5 Gew.-% bis 5 Gew.-% polymeres Polycarboxylat, insbesondere ausgewählt aus den Polymerisations- beziehungsweise Copolymerisationsprodukten von Acrylsäure, Methacrylsäure und/oder Maleinsäure enthalten. Unter diesen sind die Homopolymere der Acrylsäure und unter diesen wiederum solche mit einer mittleren Molmasse im Bereich von 5 000 D bis 15 000 D (PA-Standard) besonders bevorzugt. With regard to component e), in a preferred embodiment, the agent contains from 1.5% by weight to 5% by weight of polymeric polycarboxylate, in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid. Among these, particularly preferred are the homopolymers of acrylic acid and, among these, those having an average molecular weight in the range from 5,000 D to 15,000 D (PA standard).
Als in den Mitteln verwendbare Enzyme kommen solche aus der Klasse der Lipasen, Cutinasen, Amylasen, Pullulanasen, Mannanasen, Cellulasen, Hemicellulasen, Xylanasen und Peroxidasen sowie deren Gemische in Frage, beispielsweise Amylasen wie Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® und/oder Purafect® OxAm, Lipasen wie Lipolase®, Lipomax®, Lumafast®, Lipozym® und/oder Lipex®, Cellulasen wie Celluzyme® und/oder Carezyme®. Besonders geeignet sind aus Pilzen oder Bakterien, wie Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes oder Pseudomonas cepacia gewonnene enzymatische Wirkstoffe. Die gegebenenfalls verwendeten Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Inaktivierung zu schützen. Sie sind in den Mitteln vorzugsweise in Mengen bis zu 5 Gew.-%, insbesondere von 0,5 Gew.-% bis 2 Gew.-%, enthalten. Suitable enzymes which can be used in the compositions are those from the class of lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof, for example amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl ® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast®, Lipozym® and / or Lipex®, cellulases such as Celluzyme® and / or Carezyme®. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents. The optionally used enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in the compositions in amounts of up to 5% by weight, in particular from 0.5% by weight to 2% by weight.
Ein bevorzugtes Lösungsmittel in flüssigen erfindungsgemäßen Mitteln ist Wasser. Zu den in den Mitteln, insbesondere wenn sie in flüssiger oder pastöser Form vorliegen, verwendbaren organischen Lösungsmitteln gehören Alkohole mit 1 bis 4 C-Atomen, insbesondere Methanol, Ethanol, Isopropanol und tert.-Butanol, Diole mit 2 bis 4 C-Atomen, insbesondere Ethylenglykol und Propy- lenglykol, sowie deren Gemische und die aus den genannten Verbindungsklassen ableitbaren Ether. Wassermischbare Lösungsmittel sind in den Mitteln vorzugsweise in Mengen von 1 Gew.-% bis 60 Gew.-%, insbesondere von 2 Gew.-% bis 40 Gew.-%, vorhanden. Wasser kann in erfindungsge- mäßen flüssigen Mitteln gewünschtenfalls in Mengen bis zu 94 Gew.-% enthalten sein. In bevorzugten Ausführungsformen wasserarmer Mittel beträgt der Wassergehalt nicht mehr als 15 Gew.-%, insbesondere 1 Gew.-% bis 8 Gew.-%. A preferred solvent in liquid agents of the invention is water. Among the organic solvents which can be used in the compositions, in particular if they are in liquid or pasty form, are alcohols having 1 to 4 C 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 the ethers derivable from the classes of compound mentioned. Water-miscible solvents are preferably present in the compositions in amounts of from 1% to 60% by weight, especially from 2% to 40% by weight. Water can be used in inventive If desired, liquid agents may be present in amounts of up to 94% by weight. In preferred embodiments of low-water agents, the water content is not more than 15 wt .-%, in particular 1 wt .-% to 8 wt .-%.
Aus der Natur stammende Polymere, die in wässrigen flüssigen Mitteln als Verdickungsmittel Verwendung finden können, sind beispielsweise Agar-Agar, Carrageen, Tragant, Gummi arabicum, Al- ginate, Pektine, Polyosen, Guar-Mehl, Johannisbrotbaumkernmehl, Stärke, Dextrine, Gelatine und Casein, Cellulosederivate wie Carboxymethylcellulose, Hydroxyethyl- und -propylcellulose, und po- lymere Polysaccharid-Verdickungsmittel wie Xanthan; daneben kommen auch vollsynthetische Polymere wie Polyacryl- und Polymethacryl-Verbindungen, Vinylpolymere, Polycarbonsäuren, Po- lyether, Polyimine, Polyamide und Polyurethane als Verdicker in Frage. Naturally derived polymers which can be used as thickening agents in aqueous liquid agents are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and Casein, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl and propyl cellulose, and polymers polysaccharide thickeners such as xanthan; In addition, fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes are also suitable as thickeners.
Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH-Werts können die Mittel System- und umweltverträgliche Säuren, insbesondere Citronensäure, Essigsäure, Weinsäure, Äpfelsäure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure, oder Basen, insbesondere Ammonium- oder Alkalihydroxide, enthalten. Derartige pH-Regulatoren sind in den Mitteln vorzugsweise nicht über 20 Gew.-%, insbesondere von 1 ,2 Gew.-% bis 17 Gew.-%, enthalten. To establish a desired, not by itself resulting from the mixture of the other components of the pH, the agents systemic 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 metal hydroxides. Such pH regulators are preferably not more than 20 wt .-%, in particular from 1, 2 wt .-% to 17 wt .-%, contained in the means.
Schmutzablösevermögende Polymere, die oft als "Soil Release' -Wirkstoffe oder wegen ihres Vermögens, die behandelte Oberfläche, zum Beispiel der Faser, schmutzabstoßend auszurüsten, als "Soil Repellents" bezeichnet werden, sind beispielsweise nichtionische oder kationische Cellulosederivate. Zu den insbesondere polyesteraktiven schmutzablösevermögenden Polymeren gehören Copolyester aus Dicarbonsäuren, beispielsweise Adipinsäure, Phthalsäure oder Terephthalsäure, Diolen, beispielsweise Ethylenglykol oder Propylenglykol, und Polydiolen, beispielsweise Polyethyl- englykol oder Polypropylenglykol. Zu den bevorzugt eingesetzten schmutzablösevermögenden Po- lyestern gehören solche Verbindungen, die formal durch Veresterung zweier Monomerteile zugänglich sind, wobei das erste Monomer eine Dicarbonsäure HOOC-Ph-COOH und das zweite Monomer ein Diol HO-(CHR -)aOH, das auch als polymeres Diol H-(0-(CHR -)a)bOH vorliegen kann, ist. Darin bedeutet Ph einen o-, m- oder p-Phenylenrest, der 1 bis 4 Substituenten, ausgewählt aus Alkyl- resten mit 1 bis 22 C-Atomen, Sulfonsäuregruppen, Carboxylgruppen und deren Mischungen, tragen kann, R Wasserstoff, einen Alkylrest mit 1 bis 22 C-Atomen und deren Mischungen, a eine Zahl von 2 bis 6 und b eine Zahl von 1 bis 300. Vorzugsweise liegen in den aus diesen erhältlichen Poly- estern sowohl Monomerdioleinheiten -0-(CHR -)aO- als auch Polymerdioleinheiten -(O- (CHR -)a)bO- vor. Das molare Verhältnis von Monomerdioleinheiten zu Polymerdioleinheiten beträgt vorzugsweise 100: 1 bis 1 :100, insbesondere 10: 1 bis 1 :10. In den Polymerdioleinheiten liegt der Polymerisationsgrad b vorzugsweise im Bereich von 4 bis 200, insbesondere von 12 bis 140. Das Molekulargewicht beziehungsweise das mittlere Molekulargewicht oder das Maximum der Moleku- largewichtsverteilung bevorzugter schmutzablösevermögender Polyester liegt im Bereich von 250 bis 100 000, insbesondere von 500 bis 50 000. Die dem Rest Ph zugrundeliegende Säure wird vorzugsweise aus Terephthalsäure, Isophthalsäure, Phthalsäure, Trimellithsäure, Meilithsäure, den Isomeren der Sulfophthalsäure, Sulfoisophthalsäure und Sulfoterephthalsäure sowie deren Gemischen ausgewählt. Sofern deren Säuregruppen nicht Teil der Esterbindungen im Polymer sind, liegen sie vorzugsweise in Salzform, insbesondere als Alkali- oder Ammoniumsalz vor. Unter diesen sind die Natrium- und Kaliumsalze besonders bevorzugt. Gewünschtenfalls können statt des Monomers HOOC-Ph-COOH geringe Anteile, insbesondere nicht mehr als 10 Mol-% bezogen auf den Anteil an Ph mit der oben gegebenen Bedeutung, anderer Säuren, die mindestens zwei Carboxylgruppen aufweisen, im schmutzablösevermögenden Polyester enthalten sein. Zu diesen gehören beispielsweise Alkylen- und Alkenylendicarbonsäuren wie Malonsäure, Bernsteinsäure, Fumarsäure, Maleinsäure, Glutarsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure und Sebacinsäure. Zu den bevorzugten Diolen HO-(CHR -)aOH gehören solche, in denen R Wasserstoff und a eine Zahl von 2 bis 6 ist, und solche, in denen a den Wert 2 aufweist und R unter Wasserstoff und den Alkylresten mit 1 bis 10, insbesondere 1 bis 3 C-Atomen ausgewählt wird. Unter den letztgenannten Diolen sind solche der Formel HO-CH2-CHR -OH, in der R die obengenannte Bedeutung besitzt, besonders bevorzugt. Beispiele für Diolkomponenten sind Ethylenglykol, 1 ,2-Propylenglykol, 1 ,3-Propylengly- kol, 1 ,4-Butandiol, 1 ,5-Pentandiol, 1 ,6-Hexandiol, 1 ,8-Octandiol, 1 ,2-Decandiol, 1 ,2-Dodecandiol und Neopentylglykol. Besonders bevorzugt unter den polymeren Diolen ist Polyethylenglykol mit einer mittleren Molmasse im Bereich von 1000 bis 6000. Gewünschtenfalls können diese Polyester auch endgruppenverschlossen sein, wobei als Endgruppen Alkylgruppen mit 1 bis 22 C-Atomen und Ester von Monocarbonsäuren in Frage kommen. Den über Esterbindungen gebundenen Endgruppen können Alkyl-, Alkenyl- und Arylmonocarbonsäuren mit 5 bis 32 C-Atomen, insbesondere 5 bis 18 C-Atomen, zugrunde liegen. Zu diesen gehören Valeriansäure, Capronsäure, Önanthsäure, Caprylsäure, Pelargonsäure, Caprinsäure, Undecansäure, Undecensäure, Laurinsäure, Laurolein- säure, Tridecansäure, Myristinsäure, Myristoleinsäure, Pentadecansäure, Palmitinsäure, Stearinsäure, Petroselinsäure, Petroselaidinsäure, Ölsäure, Linolsäure, Linolaidinsäure, Linolensäure, Elä- ostearinsäure, Arachinsäure, Gadoleinsäure, Arachidonsäure, Behensäure, Erucasäure, Brassidin- säure, Clupanodonsäure, Lignocerinsäure, Cerotinsäure, Melissinsäure, Benzoesäure, die 1 bis 5 Substituenten mit insgesamt bis zu 25 C-Atomen, insbesondere 1 bis 12 C-Atomen tragen kann, beispielsweise tert.-Butylbenzoesäure. Den Endgruppen können auch Hydroxymonocarbonsäuren mit 5 bis 22 C-Atomen zugrunde liegen, zu denen beispielsweise Hydroxyvaleriansäure, Hydroxyca- pronsäure, Ricinolsäure, deren Hydrierungsprodukt Hydroxystearinsäure sowie o-, m- und p-Hydro- xybenzoesäure gehören. Die Hydroxymonocarbonsäuren können ihrerseits über ihre Hydroxylgruppe und ihre Carboxylgruppe miteinander verbunden sein und damit mehrfach in einer Endgruppe vorliegen. Vorzugsweise liegt die Anzahl der Hydroxymonocarbonsäureeinheiten pro Endgruppe, das heißt ihr Oligomerisierungsgrad, im Bereich von 1 bis 50, insbesondere von 1 bis 10. In einer bevorzugten Ausgestaltung der Erfindung werden Polymere aus Ethylenterephthalat und Po- lyethylenoxid-terephthalat, in denen die Polyethylenglykol-Einheiten Molgewichte von 750 bis 5000 aufweisen und das Molverhältnis von Ethylenterephthalat zu Polyethylenoxid-terephthalat 50:50 bis 90:10 beträgt, allein oder in Kombination mit Cellulosederivaten verwendet. Soil release polymers, often referred to as "soil release" agents or because of their ability to render the treated surface, e.g., the fiber, "soil repellents", are, for example, nonionic or cationic cellulosic derivatives, especially the polyester active soil release polymers Copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol, include those compounds which are formally accessible by esterification of two monomeric parts. wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR-) a OH, which may also be present as a polymeric diol H- (O- (CHR-) a ) bOH Ph is an o-, m- or p-phenyl enrest, which may carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R is hydrogen, an alkyl radical having 1 to 22 carbon atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, in the polyesters obtainable from these, both monomer diol units -0- (CHR -) a O- and also polymeric diol units - (O- (CHR-) a ) bO- in front. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. In the polymer diol units, the degree of polymerization b is preferably in the range from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight The weight distribution of preferred soil release polyester is in the range from 250 to 100,000, in particular from 500 to 50,000. The acid underlying Ph is preferably from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, methylitol, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof selected. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable. If desired, in place of the monomer HOOC-Ph-COOH small proportions, in particular not more than 10 mol% based on the proportion of Ph having the meaning given above, of other acids having at least two carboxyl groups may be included in the soil release-capable polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. Preferred diols HO- (CHR-) a OH include those in which R is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R is hydrogen and the alkyl radicals have from 1 to 10 , in particular 1 to 3 C-atoms is selected. Among the latter diols, those of the formula HO-CH 2 -CHR -OH in which R has the abovementioned meaning are particularly preferred. Examples of diol components are ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2-decanediol, 1, 2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of 1000 to 6000. If desired, these polyesters may also be endgruppenverschlossen, with alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids in question as end groups. The ester groups bonded via end groups can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, ela ostearic acid, arachic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidine acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms , for example, tert-butylbenzoic acid. The end groups may also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and also o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. Preferably, the number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units Molar weights from 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used alone or in combination with cellulose derivatives.
Die Mittel können Knitterschutzmittel enthalten, da textile Flächengebilde, insbesondere aus Reyon, Wolle, Baumwolle und deren Mischungen, zum Knittern neigen können, weil die Einzelfasern gegen Durchbiegen, Knicken, Pressen und Quetschen quer zur Faserrichtung empfindlich sind. Hierzu zählen beispielsweise synthetische Produkte auf der Basis von Fettsäuren, Fettsäureestern, Fettsäu- reamiden, -alkylolestern, -alkylolamiden oder Fettalkoholen, die meist mit Ethylenoxid umgesetzt sind, oder Produkte auf der Basis von Lecithin oder modifizierter Phosphorsäureester. The agents may contain anti-crease agents, since textile fabrics, in particular of rayon, wool, cotton and their mixtures, can tend to wrinkle, because the individual fibers are sensitive to bending, buckling, pressing and squeezing transverse to the fiber direction. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
Vergrauungsinhibitoren haben die Aufgabe, den von der harten Oberfläche und insbesondere von der Textilfaser abgelösten Schmutz in der Flotte suspendiert zu halten. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise Stärke, Leim, Gelatine, Salze von Ether- carbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich andere als die obengenannten Stärkederivate verwenden, zum Beispiel Aldehydstärken. Bevorzugt werden Celluloseether, wie Car- boxymethylcellulose (Na-Salz), Methylcellulose, Hydroxyalkylcellulose und Mischether, wie Methyl- hydroxyethylcellulose, Methylhydroxypropylcellulose, Methylcarboxymethylcellulose und deren Gemische, beispielsweise in Mengen von 0, 1 bis 5 Gew.-%, bezogen auf die Mittel, eingesetzt. Graying inhibitors have the task of keeping suspended from the hard surface and in particular from the textile fiber suspended dirt 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. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions used.
Die Mittel können optische Aufheller, unter diesen insbesondere Derivate der Diaminostilbendisul- fonsäure beziehungsweise deren Alkalimetallsalze, enthalten. Geeignet sind zum Beispiel Salze der 4,4'-Bis(2-anilino-4-morpholino-1 ,3,5-triazinyl-6-amino)stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholino-Gruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ der substituierten Diphenylstyryle anwesend sein, zum Beispiel die Alkalisalze des 4,4'-Bis(2-sulfostyryl)-diphenyls, 4,4'-Bis(4-chlor-3-sulfostyryl)-diphenyls, oder 4-(4- Chlorstyryl)-4'-(2-sulfostyryl)-diphenyls. Auch Gemische der vorgenannten optischen Aufheller können verwendet werden. The agents may contain optical brighteners, among these in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. For example, 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. Further, 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.
Insbesondere beim Einsatz in maschinellen Waschverfahren kann es von Vorteil sein, den Mitteln übliche Schauminhibitoren zuzusetzen. Als Schauminhibitoren eignen sich beispielsweise Seifen natürlicher oder synthetischer Herkunft, die einen hohen Anteil an Cis-C24-Fettsäuren aufweisen. Geeignete nichttensidartige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure oder Bisfettsäurealkylendiamiden. Mit Vorteilen werden auch Gemische aus verschiedenen Schauminhibitoren verwendet, zum Beispiel solche aus Silikonen, Paraffinen oder Wachsen. Vorzugsweise sind die Schauminhibitoren, insbe- sondere Silikon- und/oder Paraffin-haltige Schauminhibitoren, an eine granuläre, in Wasser lösliche beziehungsweise dispergierbare Trägersubstanz gebunden. Insbesondere sind dabei Mischungen aus Paraffinen und Bistearylethylendiamid bevorzugt. In particular when used in automatic washing processes, it may be advantageous to add conventional foam inhibitors to the compositions. 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. Preferably, the foam inhibitors, in particular special silicone and / or paraffin-containing foam inhibitors, bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.
Als in den Mitteln, insbesondere den Mitteln in fester Form, gegebenenfalls enthaltene Persauerstoffverbindungen kommen insbesondere organische Persäuren oder persaure Salze organischer Säuren, wie Phthalimidopercapronsäure, Perbenzoesäure oder Salze der Diperdodecandisäure, Wasserstoffperoxid und unter den Waschbedingungen Wasserstoffperoxid abgebende anorganische Salze, wie Perborat, Percarbonat und/oder Persilikat, in Betracht. Wasserstoffperoxid kann dabei auch mit Hilfe eines enzymatischen Systems, das heißt einer Oxidase und ihres Substrats, erzeugt werden. Sofern feste Persauerstoffverbindungen eingesetzt werden sollen, können diese in Form von Pulvern oder Granulaten verwendet werden, die auch in im Prinzip bekannter Weise umhüllt sein können. Besonders bevorzugt wird Alkalipercarbonat, Alkaliperborat-Monohydrat, Alkaliperborat-Tetrahydrat oder, insbesondere in flüssigen Mitteln, Wasserstoffperoxid in Form wässriger Lösungen, die 3 Gew.-% bis 10 Gew.-% Wasserstoffperoxid enthalten, eingesetzt. Vorzugsweise sind Persauerstoffverbindungen in Mengen von bis zu 50 Gew.-%, insbesondere von 5 Gew.-% bis 30 Gew.-%, in Waschmitteln vorhanden. As in the means, in particular the agents in solid form, optionally contained peroxygen compounds come in particular organic peracids or pers acid salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide-releasing inorganic salts such as perborate, percarbonate and / or persilicate, into consideration. Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. If 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, alkali metal perborate tetrahydrate or, in particular in liquid media, hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide. Preferably, peroxygen compounds are present in detergents in amounts of up to 50% by weight, especially from 5% to 30% by weight.
Zusätzlich können übliche Bleichaktivatoren, die unter Perhydrolysebedingungen Peroxocarbonsäu- ren oder Peroxoimidsäuren bilden, und/oder übliche die Bleiche aktivierende Übergangsmetallkomplexe eingesetzt werden. Die fakultativ, insbesondere in Mengen von 0,5 Gew.-% bis 6 Gew.-%, vorhandene Komponente der Bleichaktivatoren umfasst die üblicherweise verwendeten N- oder O- Acylverbindungen, beispielsweise mehrfach acylierte Alkylendiamine, insbesondere Tetraacetyl- ethylendiamin, acylierte Glykolurile, insbesondere Tetraacetylglykoluril, N-acylierte Hydantoine, Hy- drazide, Triazole, Urazole, Diketopiperazine, Sulfurylamide und Cyanurate, außerdem Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, Carbonsäureester, insbesondere Natrium-iso- nonanoyl-phenolsulfonat, und acylierte Zuckerderivate, insbesondere Pentaacetylglukose, sowie kationische Nitrilderivate wie Trimethylammoniumacetonitril-Salze. Die Bleichaktivatoren können zur Vermeidung der Wechselwirkung mit den Persauerstoffverbindungen bei der Lagerung in bekannter Weise mit Hüllsubstanzen überzogen beziehungsweise granuliert worden sein, wobei mit Hilfe von Carboxymethylcellulose granuliertes Tetraacetylethylendiamin mit mittleren Korngrößen von 0,01 mm bis 0,8 mm, granuliertes 1 ,5-Diacetyl-2,4-dioxohexahydro-1 ,3,5-triazin, und/oder in Teilchenform konfektioniertes Trialkylammoniumacetonitril besonders bevorzugt ist. In Waschmitteln sind derartige Bleichaktivatoren vorzugsweise in Mengen bis zu 8 Gew.-%, insbesondere von 2 Gew.-% bis 6 Gew.-%, jeweils bezogen auf gesamtes Mittel, enthalten. In addition, customary bleach activators which form peroxocarboxylic acids or peroxoimidic acids under perhydrolysis conditions and / or customary bleach-activating transition metal complexes can be used. The optional, especially in amounts of 0.5 wt .-% to 6 wt .-%, present component of the bleach activators include the commonly used N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetyl-ethylenediamine, acylated glycolurils, in particular Tetraacetylglycoluril, N-acylated hydantoins, Hy drazide, triazoles, urazoles, diketopiperazines, sulfururamides and cyanurates, also carboxylic anhydrides, especially phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonat, and acylated sugar derivatives, in particular pentaacetylglucose, and cationic nitrile derivatives such as trimethylammoniumacetonitrile salts. To avoid interaction with the peroxygen compounds, the bleach activators may have been coated or granulated in known manner with encapsulating substances, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1, 5 with the aid of carboxymethylcellulose. Diacetyl-2,4-dioxohexahydro-1, 3,5-triazine, and / or formulated in particulate trialkylammonium acetonitrile is particularly preferred. Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.
Die Herstellung fester Mittel bietet keine Schwierigkeiten und kann in im Prinzip bekannter Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen. Zur Herstellung der Mittel mit erhöhtem Schüttgewicht, insbesondere im Bereich von 650 g/l bis 950 g/l, ist ein einen Extrusionsschritt aufweisendes Verfahren bevorzugt. Waschmittel in Form wässriger oder sonstige übliche Lösungsmittel enthaltender Lösungen werden besonders vorteilhaft durch einfaches Mischen der Inhaltsstoffe, die in Substanz oder als Lösung in einen automatischen Mischer gegeben werden können, hergestellt. The preparation of solid compositions presents no difficulties and can be carried out in a manner known in the art, for example by spray-drying or granulation. For the preparation of the compositions with increased bulk density, in particular in the range of 650 g / l to 950 g / l, is an extrusion step preferred method. Detergents in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
In einer auch bevorzugten Ausführungsform liegen die Mittel, insbesondere in konzentrierter flüssiger Form, als Portion in einer ganz oder teilweise wasserlöslichen Umhüllung vor. Die Portionierung erleichtert dem Verbraucher die Dosierbarkeit. In an also preferred embodiment, the agents, in particular in concentrated liquid form, are present as a portion in a completely or partially water-soluble coating. Portioning makes it easier for the consumer to dose.
Die Mittel können dabei beispielsweise in Folienbeutel eingepackt vorliegen. Beutelverpackungen aus wasserlöslicher Folie machen ein Aufreißen der Verpackung durch den Verbraucher unnötig. Auf diese Weise ist ein bequemes Dosieren einer einzelnen, für einen Waschgang bemessenen Portion durch Einlegen des Beutels direkt in die Waschmaschine oder durch Einwerfen des Beutels in eine bestimmte Menge Wasser, beispielsweise in einem Eimer, einer Schüssel oder im Handwaschbecken, möglich. Der die Waschportion umgebende Folienbeutel löst sich bei Erreichen einer bestimmten Temperatur rückstandsfrei auf. The funds can be packed, for example, in foil bags. Pouches made of water-soluble film make it unnecessary for the consumer to tear open the packaging. In this way, a convenient dosing of a single, sized for a wash portion by inserting the bag directly into the washing machine or by throwing the bag into a certain amount of water, for example in a bucket, a bowl or hand basin, possible. The film bag surrounding the washing portion dissolves without residue when it reaches a certain temperature.
Im Stand der Technik existieren zahlreiche Verfahren zur Herstellung wasserlöslicher Waschmittelportionen, die grundsätzlich auch zur Herstellung von im Rahmen der vorliegenden Erfindung brauchbaren Mitteln geeignet sind. Bekannteste Verfahren sind dabei die Schlauchfolienverfahren mit horizontalen und vertikalen Siegelnähten. Weiterhin geeignet zur Herstellung von Folienbeuteln oder auch formstabilen Waschmittelportionen ist das Thermoformverfahren (Tiefziehverfahren). Die wasserlöslichen Umhüllungen müssen allerdings nicht zwangsläufig aus einem Folienmaterial bestehen, sondern können auch formstabile Behältnisse darstellen, die beispielsweise mittels eines Spritzguss-Verfahrens erhalten werden können. There are numerous processes in the prior art for producing water-soluble detergent portions, which are in principle also suitable for the production of agents useful in the context of the present invention. The best known methods are the tubular film processes with horizontal and vertical sealing seams. Also suitable for the production of film bags or dimensionally stable detergent portions is the thermoforming process (thermoforming process). However, the water-soluble coatings do not necessarily consist of a film material, but can also represent dimensionally stable containers that can be obtained for example by means of an injection molding process.
Weiterhin sind Verfahren zur Herstellung wasserlöslicher Kapseln aus Polyvinylalkohol oder Gelatine bekannt, die prinzipiell die Möglichkeit bieten, Kapseln mit einem hohen Befüllgrad bereitzustellen. Die Verfahren beruhen darauf, dass in eine formgebende Kavität das wasserlösliche Polymer eingeführt wird. Das Befüllen und Versiegeln der Kapseln erfolgt entweder synchron oder in nacheinander folgenden Schritten, wobei im letzteren Fall die Befüllung der Kapseln durch eine kleine Öffnung erfolgt. Die Befüllung der Kapseln erfolgt dabei beispielsweise durch einen Befüllkeil, der oberhalb von zwei sich gegeneinander drehenden Trommeln, die auf ihrer Oberfläche Kugelhalbschalen aufweisen, angeordnet ist. Die Trommeln führen Polymerbänder, die die Kugelhalbschalenkavitäten bedecken. An den Positionen, an denen das Polymerband der einen Trommel mit dem Polymerband der gegenüberliegenden Trommel zusammentrifft findet eine Versiegelung statt. Parallel dazu wird das Befüllgut in die sich ausbildende Kapsel injiziert, wobei der Injektionsdruck der Befüllflüssigkeit die Polymerbänder in die Kugelhalbschalenkavitäten presst. Ein Verfahren zur Herstellung wasserlöslicher Kapseln, bei dem zunächst die Befüllung und anschließend die Versiegelung erfolgt, basiert auf dem sogenannten Bottle-Pack®-Verfahren. Hierbei wird ein schlauchartiger Vorformling in eine zweiteilige Kavität geführt. Die Kavität wird geschlossen, wobei der untere Schlauchabschnitt versiegelt wird, anschließend wird der Schlauch aufgeblasen zur Ausbildung der Kapselform in der Kavität, befüllt und abschließend versiegelt. Furthermore, methods for producing water-soluble capsules of polyvinyl alcohol or gelatin are known, which in principle offer the possibility to provide capsules with a high degree of filling. The methods are based on introducing the water-soluble polymer into a shaping cavity. The filling and sealing of the capsules takes place either synchronously or in successive steps, in which case the filling of the capsules takes place through a small opening in the latter case. The filling of the capsules is carried out, for example, by a Befüllkeil, which is above two rotating against each other drums, which have spherical half shells on its surface. The drums carry polymer bands that cover the ball half-shell cavities. At the positions where the polymer band of one drum coincides with the polymer tape of the opposite drum, a seal takes place. In parallel, the filling material is injected into the forming capsule, wherein the injection pressure of the filling liquid presses the polymer bands in the Kugelhalbschalenkavitäten. A process for preparing water-soluble capsules, initially filling and then sealing, is based on the so-called Bottle-Pack ® method. In this case, a tubular preform is guided into a two-part cavity. The cavity is closed, the lower tube portion is sealed, then the tube is inflated to form the capsule shape in the cavity, filled and finally sealed.
Das für die Herstellung der wasserlöslichen Portion verwendete Hüllmaterial ist vorzugsweise ein wasserlöslicher polymerer Thermoplast, besonders bevorzugt ausgewählt aus der Gruppe (gegebenenfalls teilweise acetalisierter) Polyvinylalkohol, Polyvinylalkohol-Copolymere, Polyvinylpyrrolidon, Polyethylenoxid, Gelatine, Cellulose und deren Derivate, Stärke und deren Derivate, Blends und Verbünde, anorganische Salze und Mischungen der genannten Materialien, vorzugsweise Hydroxy- propylmethylcellulose und/oder Polyvinylalkohol-Blends. Polyvinylalkohole sind kommerziell verfügbar, beispielsweise unter dem Warenzeichen Mowiol® (Clariant). Im Rahmen der vorliegenden Erfindung besonders geeignete Polyvinylalkohole sind beispielsweise Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88, Mowiol® 8-88 sowie Clariant L648. Das zur Herstellung der Portion verwendete wasserlösliche Thermoplast kann zusätzlich gegebenenfalls Polymere ausgewählt aus der Gruppe, umfassend Acrylsäure-haltige Polymere, Polyacrylamide, Oxazolin-Polymere, Polystyrolsulfonate, Polyurethane, Polyester, Polyether und/oder Mischungen der vorstehenden Polymere, aufweisen. Bevorzugt ist, wenn das verwendete wasserlösliche Thermoplast einen Polyvinylalkohol umfasst, dessen Hydrolysegrad 70 bis 100 Mol-%, vorzugsweise 80 bis 90 Mol-%, besonders bevorzugt 81 bis 89 Mol-% und insbesondere 82 bis 88 Mol-% ausmacht. Weiter bevorzugt ist, dass das verwendete wasserlösliche Thermoplast einen Polyvinylalkohol umfasst, dessen Molekulargewicht im Bereich von 10.000 bis 100.000 gmol"1 , vorzugsweise von 1 1.000 bis 90.000 gmol"1 , besonders bevorzugt von 12.000 bis 80.000 gmol und insbesondere von 13.000 bis 70.000 gmol liegt. Weiterhin bevorzugt ist, wenn die Thermoplaste in Mengen von mindestens 50 Gew.-%, vorzugsweise von mindestens 70 Gew.-%, besonders bevorzugt von mindestens 80 Gew.-% und insbesondere von mindestens 90 Gew.-%, jeweils bezogen auf das Gewicht des wasserlöslichen polymeren Thermoplasts, vorliegt. The shell material used for the preparation of the water-soluble portion is preferably a water-soluble polymeric thermoplastic, more preferably selected from the group (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, blends and composites, inorganic salts and mixtures of said materials, preferably hydroxypropylmethylcellulose and / or polyvinyl alcohol blends. Polyvinyl alcohols are commercially available, for example under the trade name Mowiol ® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88, Mowiol ® 8-88 and Clariant L648. The water-soluble thermoplastic used to prepare the portion may additionally optionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures of the above polymers. It is preferred if the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%. It is further preferred that the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol "1 , preferably from 1,000 to 90,000 gmol " 1 , more preferably from 12,000 to 80,000 gmol and especially from 13,000 to 70,000 gmol , It is further preferred if the thermoplastics are used in amounts of at least 50% by weight, preferably of at least 70% by weight, more preferably of at least 80% by weight and in particular of at least 90% by weight, based in each case on the weight the water-soluble polymeric thermoplastic.
Beispiele Examples
Die in der nachfolgenden Tabelle angegebenen standardisierten Anschmutzungen (auf Baumwolle, wenn nicht anders angegeben, oder auf Polyester-Baumwoll-Mischgewebe) wurden gewaschen, dann gespült, getrocknet und anschließend ihr Remissionswert spektralphotometrisch (Minolta® CR400-1 ) vermessen und mit dem Remissionswert vor der Wäsche verglichen (Waschtemperatur 40°C, Waschzeit 90 Minuten, Waschmitteldosierung 4,06 g/l im Hauptwaschgang; Mittelwert aus einer 6-fach Bestimmung). The standardized stains (on cotton unless otherwise stated or on polyester-cotton blends) given in the table below were washed, then rinsed, dried and then their reflectance measured by spectrophotometric (Minolta® CR400-1) and pre-measured at the reflectance value compared to washing (washing temperature 40 ° C., washing time 90 minutes, detergent dosage 4.06 g / l in the main wash cycle, mean value from a 6-fold determination).
Tabelle 1 : Anschmutzungen Table 1: soiling
Figure imgf000021_0001
Figure imgf000021_0001
Zum Einsatz kam ein wasserhaltiges Flüssigwaschmittel mit 5,5 Gew.-% C9-13 Na-Alkylbenzolsulfo- nat, 5,5 Gew.-% C12-18 Fettalkohol-7 EO, und 5 Gew.-% C12-14 Na-Alkohol-2 EO-sulfat (V1 ), sowie ein ansonsten gleich zusammengesetztes Flüssigwaschmittel, das zusätzlich 2 Gew.-% C10C10- Mono- und Di-Rhamnolipid (NatSurFact® 90LCBS-4) enthielt (M1 ); Ausgleich über die enthaltene Wassermenge. Die in der nachfolgenden Tabelle 2 angegebenen Werte zeigen die Unterschiede der ΔΥ-Werte der Remissionsmessung zwischen dem Mittel M1 und dem Mittel V1 , wobei höhere Werte bedeuten, dass die Anschmutzung durch die Anwendung des erfindungsgemäßen Mittels besser ausgewaschen wurden.  A water-based liquid detergent containing 5.5% by weight of C 9-13 Na alkylbenzenesulfonate, 5.5% by weight of C 12-18 fatty alcohol 7 EO, and 5% by weight of C 12-14 Na alcohol was used 2 EO sulphate (V1) and an otherwise uniformly mixed liquid detergent which additionally contained 2% by weight of C10C10 mono- and di-rhamnolipid (NatSurFact® 90LCBS-4) (M1); Compensation for the amount of water contained. The values given in Table 2 below show the differences in the ΔΥ values of the remission measurement between the agent M1 and the agent V1, higher values meaning that the soiling was better washed out by the use of the agent according to the invention.
Tabelle 2: Helligkeitsunterschiedsdifferenzen Table 2: Brightness difference differences
Anschmutzung ΔΔΥ Soiling ΔΔΥ
A 3,4  A 3,4
B 7,2  B 7.2
C 2,1  C 2.1
D 1 ,9  D 1, 9
E 5,4  E 5.4

Claims

Patentansprüche claims
1. Wasch- oder Reinigungsmittel, enthaltend ein Rhamnolipidgemisch aus 35 Gew.-% bis 45 Gew.- % 3-({3-[(6-deoxy-a-L-mannopyranosyl)oxy]decanoyl}oxy)decansäure und/oder deren Natrium-, Kalium-, Ammonium-, Alkylammonium- und/oder Hydroxyalkylammoniumsalz und 55 Gew.-% bis 65 Gew.-% 3-[(3-{[6-deoxy-2-0-(6-deoxy-a-L-mannopyranosyl)-a-L-mannopyranosyl]oxy}deca- noyl)oxy]decansäure und/oder deren Natrium-, Kalium-, Ammonium-, Alkylammonium- und/oder Hydroxyalkylammoniumsalz. 1. washing or cleaning agent containing a rhamnolipid mixture of 35 wt .-% to 45 wt .-% 3 - ({3 - [(6-deoxy-aL-mannopyranosyl) oxy] decanoyl} oxy) decanoic acid and / or its sodium , Potassium, ammonium, alkylammonium and / or hydroxyalkylammonium salt and 55% to 65% by weight of 3 - [(3 - {[6-deoxy-2-0- (6-deoxy-aL-mannopyranosyl ) -α-L-mannopyranosyl] oxy} decanoyl) oxy] decanoic acid and / or its sodium, potassium, ammonium, alkylammonium and / or hydroxyalkylammonium salt.
2. Mittel nach Anspruch 1 , dadurch gekennzeichnet, dass es sich bei den Alkylgruppen in den Al- kylammoniumionen um solche mit jeweils 1 bis 4 C-Atomen und deren Mischungen, und bei den Alkylgruppen in den Hydroxyalkylammoniumionen um solche mit jeweils 2 bis 4 C-Atomen und deren Mischungen handelt. 2. Composition according to claim 1, characterized in that it is the alkyl groups in the alkyl kylammoniumionen to those having in each case 1 to 4 carbon atoms and mixtures thereof, and in the alkyl groups in the hydroxyalkylammonium to those with 2 to 4 C respectively And their mixtures.
3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass es 0,000001 Gew.-% bis 50 Gew.- %, insbesondere 0, 1 Gew.-% bis 20 Gew.-% des Rhamnolipidgemischs enthält. 3. Composition according to claim 1 or 2, characterized in that it contains 0.000001 wt .-% to 50 wt .-%, in particular 0, 1 wt .-% to 20 wt .-% of the Rhamnolipidgemischs.
4. Verwendung eines Rhamnolipidgemischs aus 35 Gew.-% bis 45 Gew.-% 3-({3-[(6-deoxy-ol_- mannopyranosyl)oxy]decanoyl}oxy)decansäure und/oder deren Natrium-, Kalium-, Ammonium-, Alkylammonium- und/oder Hydroxyalkylammoniumsalz und 55 Gew.-% bis 65 Gew.-% 3-[(3-{[6- deoxy-2-0-(6-deoxy-a-L-mannopyranosyl)-a-L-mannopyranosyl]oxy}decanoyl)oxy]decansäure und/oder deren Natrium-, Kalium-, Ammonium-, Alkylammonium- und/oder Hydroxyalkylammoniumsalz zur Erhöhung der Wasch- oder Reinigungsleistung von Wasch- oder Reinigungsmitteln. 4. Use of a rhamnolipid mixture of 35% by weight to 45% by weight of 3 - ({3 - [(6-deoxy-ol-mannopyranosyl) oxy] decanoyl} oxy) decanoic acid and / or its sodium, potassium, Ammonium, alkylammonium and / or hydroxyalkylammonium salt and 55% to 65% by weight of 3 - [(3 - {[6-deoxy-2-0- (6-deoxy-aL-mannopyranosyl) -al-mannopyranosyl ] oxy} decanoyl) oxy] decanoic acid and / or its sodium, potassium, ammonium, alkylammonium and / or hydroxyalkylammonium salt for increasing the washing or cleaning performance of detergents or cleaners.
5. Verwendung nach Anspruch 4, dadurch gekennzeichnet, dass es sich bei den Alkylgruppen in den Alkylammoniumionen um solche mit jeweils 1 bis 4 C-Atomen und deren Mischungen, und bei den Alkylgruppen in den Hydroxyalkylammoniumionen um solche mit jeweils 2 bis 4 C-Atomen und deren Mischungen handelt. 5. Use according to claim 4, characterized in that the alkyl groups in the alkylammonium ions are those having in each case 1 to 4 C atoms and mixtures thereof, and the alkyl groups in the hydroxyalkylammonium ions are those having in each case 2 to 4 C atoms and mixtures thereof.
6. Verwendung nach Anspruch 4 oder 5, dadurch gekennzeichnet, dass man das Rhamnolipidgemisch einer wasch- oder reinigungsmittelhaltigen wässrigen Flotte zusetzt oder es als Bestandteil eines Wasch- oder Reinigungsmittels in die wässrige Flotte einbringt, und zu waschende oder reinigende Gegenstände mit der Flotte in Kontakt bringt. 6. Use according to claim 4 or 5, characterized in that one adds the rhamnolipid mixture of a washing or cleaning agent-containing aqueous liquor or introduces it as a constituent of a washing or cleaning agent in the aqueous liquor, and to washing or cleaning articles in contact with the liquor brings.
7. Verwendung nach Anspruch 6, dadurch gekennzeichnet, dass man zu waschende oder reinigende Gegenstände bei Temperaturen von 10 °C bis 60 °C, insbesondere 20 °C bis 40 °C mit der Flotte in Kontakt bringt. 7. Use according to claim 6, characterized in that one brings to washing or cleaning articles at temperatures of 10 ° C to 60 ° C, in particular 20 ° C to 40 ° C in contact with the liquor.
8. Mittel nach einem der Ansprüche 1 bis 3 oder Verwendung nach einem der Ansprüche 4 bis 7, dadurch gekennzeichnet, dass das Mittel neben dem Rhamnolipidgemisch mindestens 3, insbesondere mindestens 4 weitere Tenside enthält. 8. Composition according to one of claims 1 to 3 or use according to one of claims 4 to 7, characterized in that the means in addition to the rhamnolipid mixture contains at least 3, in particular at least 4 other surfactants.
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EP0499434A1 (en) * 1991-02-12 1992-08-19 Unilever Plc Detergent compositions
EP0605308A1 (en) 1992-12-30 1994-07-06 Institut Francais Du Petrole Composition containing a surfactant and glycolipids for decontaminating a polluted medium
EP1445302B1 (en) 2003-01-28 2006-06-07 Ecover Belgium Detergent compositions
EP2410039A1 (en) 2010-07-22 2012-01-25 Unilever PLC Rhamnolipids with improved cleaning
WO2012010407A1 (en) 2010-07-22 2012-01-26 Unilever Plc Detergent compositions comprising biosurfactant and lipase
WO2012010406A1 (en) 2010-07-22 2012-01-26 Unilever Plc Combinations of rhamnolipids and enzymes for improved cleaning
WO2012010405A1 (en) 2010-07-22 2012-01-26 Unilever Plc Detergent compositions comprising biosurfactant and enzyme
EP2787065A1 (en) 2013-04-02 2014-10-08 Evonik Industries AG Detergent composition for textiles comprising rhamnolipids having a predominant share of di-rhamnolipids
EP2786743A1 (en) 2013-04-02 2014-10-08 Evonik Industries AG Mixture composition containing rhamnolipids

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0499434A1 (en) * 1991-02-12 1992-08-19 Unilever Plc Detergent compositions
EP0499434B1 (en) 1991-02-12 1995-07-19 Unilever Plc Detergent compositions
EP0605308A1 (en) 1992-12-30 1994-07-06 Institut Francais Du Petrole Composition containing a surfactant and glycolipids for decontaminating a polluted medium
EP1445302B1 (en) 2003-01-28 2006-06-07 Ecover Belgium Detergent compositions
EP2410039A1 (en) 2010-07-22 2012-01-25 Unilever PLC Rhamnolipids with improved cleaning
WO2012010407A1 (en) 2010-07-22 2012-01-26 Unilever Plc Detergent compositions comprising biosurfactant and lipase
WO2012010406A1 (en) 2010-07-22 2012-01-26 Unilever Plc Combinations of rhamnolipids and enzymes for improved cleaning
WO2012010405A1 (en) 2010-07-22 2012-01-26 Unilever Plc Detergent compositions comprising biosurfactant and enzyme
EP2787065A1 (en) 2013-04-02 2014-10-08 Evonik Industries AG Detergent composition for textiles comprising rhamnolipids having a predominant share of di-rhamnolipids
EP2786743A1 (en) 2013-04-02 2014-10-08 Evonik Industries AG Mixture composition containing rhamnolipids

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