EP2787065A1 - Detergent composition for textiles comprising rhamnolipids having a predominant share of di-rhamnolipids - Google Patents
Detergent composition for textiles comprising rhamnolipids having a predominant share of di-rhamnolipids Download PDFInfo
- Publication number
- EP2787065A1 EP2787065A1 EP14158279.1A EP14158279A EP2787065A1 EP 2787065 A1 EP2787065 A1 EP 2787065A1 EP 14158279 A EP14158279 A EP 14158279A EP 2787065 A1 EP2787065 A1 EP 2787065A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- rhamnolipids
- detergent formulation
- gew
- rhamnolipid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 173
- 239000003599 detergent Substances 0.000 title claims abstract description 58
- 239000004753 textile Substances 0.000 title claims abstract description 18
- 238000009472 formulation Methods 0.000 claims abstract description 76
- 239000006260 foam Substances 0.000 claims abstract description 42
- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical compound CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)OC1OC(C)C(O)C(O)C1OC1C(O)C(O)C(O)C(C)O1 FCBUKWWQSZQDDI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000006641 stabilisation Effects 0.000 claims abstract description 11
- 238000011105 stabilization Methods 0.000 claims abstract description 11
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- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
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- PPMPLIBYTIWXPG-MSJADDGSSA-N L-rhamnosyl-3-hydroxydecanoyl-3-hydroxydecanoic acid Chemical compound CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)O[C@@H]1O[C@@H](C)[C@H](O)[C@@H](O)[C@H]1O PPMPLIBYTIWXPG-MSJADDGSSA-N 0.000 description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- 230000006820 DNA synthesis Effects 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 101150026476 PAO1 gene Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012753 anti-shrinkage agent Substances 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003876 biosurfactant Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 1
- 229940073507 cocamidopropyl betaine Drugs 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000003721 exogen phase Effects 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000007003 mineral medium Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000002018 overexpression Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000004962 physiological condition Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000010956 selective crystallization Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000003260 vortexing Methods 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/06—Ether- or thioether carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
Definitions
- the invention relates to detergent formulations for textiles containing rhamnolipids, wherein the content of di-rhamnolipids predominates, and the use of certain rhamnolipid mixture compositions and the aforementioned detergent formulations for accelerating foaming and / or foam stabilization and the use of rhamnolipids to prevent the graying of a textile.
- Aqueous surfactant solutions show, depending on their composition, different rapid foam buildup and different foam stability. Foaming and decay are affected by the presence of dirt. Foam stability is an important quality feature for the consumer, especially when washing laundry or fabrics. Desirable are detergent formulations with high foam stability.
- rhamnolipids (RL) with a high content of di-rhamnolipids in detergent formulations have a more stable foam and / or more foaming than surfactants according to the prior art, especially in the presence of high soil load.
- the present invention therefore provides laundry detergent formulations for textiles comprising a rhamnolipid blend composition having an increased proportion of di-rhamnolipids.
- Another object of the invention is the use of certain rhamnolipid blend compositions and the aforementioned detergent formulations to accelerate foaming and / or foam stabilization and the use of rhamnolipids to prevent the graying of a textile
- An advantage of the invention is that the surfactants used are biodegradable in the detergent formulation.
- An advantage of the formulations according to the invention is their outstanding foam stability in the aqueous.
- Another advantage of the formulations according to the invention is their outstanding foam volume in the aqueous.
- Another advantage of the formulations according to the invention is their excellent foaming behavior.
- Another advantage of the formulations according to the invention is their ease of formulation in any aqueous, surfactant systems.
- Another advantage of the formulations according to the invention is their good thickenability with conventional thickeners in formulations.
- Another advantage is their good washability of textiles.
- a further advantage of the formulations according to the invention is their mildness or good physiological compatibility, in particular characterized by a high value in the Red Blood Cell (RBC) test.
- Another advantage of the formulations according to the invention is that they leave a pleasant soft feel of the textile after washing.
- pH in the context of the present invention is defined as the value measured for corresponding substance at 25 ° C after five minutes of stirring with a pH electrode calibrated according to ISO 4319 (1977).
- aqueous in the context of the present invention is to be understood as meaning a composition which contains at least 5% by weight of water, based on the total composition under consideration.
- Claimed is thus a detergent formulation for textiles comprising a mono- and di-rhamnolipid mixture composition, characterized in that the weight ratio of di-rhamnolipids to mono-rhamnolipids greater than 51:49, preferably greater than 75:25, particularly preferably 97: 3, especially greater 98: 2.
- the blend composition according to the invention contains mono-rhamnolipids.
- the detergent formulation according to the invention is preferably liquid at room temperature.
- the rhamnolipid mixture composition contained in the formulation according to the invention contains rhamnolipids of the formula monoRL-CX or diRL-CX in only small amounts.
- the mixture composition according to the invention preferably contains 0 wt .-% to 5 wt .-%, preferably 0 wt .-% to 3 wt .-%, particularly preferably 0 wt .-% to 1 wt .-%, diRLC10, wherein the weight percent based on the sum of all Rhamnolipids, and the term "0 wt .-%" is no detectable amount to understand.
- the formulations of the invention are substantially free of fatty oil (at 20 ° C liquid acylglycerols) and thus in particular less than 0.5 wt .-%, in particular less than 0.1 wt .-%, particularly preferred no detectable levels of fatty oil based on the total blend composition.
- the mixture compositions contained in the formulations according to the invention can be prepared by mixing the pure substances, wherein the pure substances from conventionally prepared rhamnolipid mixtures can be purified.
- Corresponding purification methods are, for example, selective crystallizations and chromatographic methods.
- Corresponding methods are in Heyd et al., Development and trends of biosurfactant analysis and purification using rhamnolipids as an example, Anal. Bioanal Chem. 2008 Jul; 391 (5): 1579-90 described.
- Preferred formulations according to the invention comprise, in addition to the rhamnolipid mixture composition, at least one further surfactant, it being possible to use, for example, anionic, nonionic, cationic and / or amphoteric surfactants, with anionic surfactants being preferred.
- the total surfactant content of the formulation according to the invention is preferably from 5 to 40% by weight and more preferably from 9 to 35% by weight, based on the total formulation.
- 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 linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
- alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
- the preferred ethoxylated alcohols include, for example, C12-C14 alcohols with 3 EO, 4 EO or 7 EO, C9-C11 alcohol with 7 EO, C13-C15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12 C18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-C14 alcohol with 3 EO and C12-C18 alcohol with 7 EO.
- the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
- Preferred alcohol ethoxylates have a narrow homolog distribution.
- fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- Nonionic surfactants containing EO and PO (propylene oxide) groups together in the molecule can also be used.
- block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
- alkyl glycosides can also be used as further nonionic surfactants.
- Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants Surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fettsaurealkylester, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 are described or preferably according to the in the international patent application WO 90/13533 be prepared described methods.
- Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
- the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
- polyhydroxy fatty acid amides are 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 content of nonionic surfactants in the formulations according to the invention is preferably 5 to 30% by weight, preferably 7 to 20% by weight and in particular 9 to 15% by weight, based in each case on the entire formulation.
- anionic surfactants for example, those of the sulfonate type and sulfates are used.
- surfactants of the sulfonate type are preferably C9-C13-alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those of C12-C18 monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
- alkanesulfonates which are obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
- 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 in the preparation by esterification of a monoglycerol with 1 to 3 mol fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol Glycerol can be obtained.
- Preferred sulfated fatty acid glycerol esters are 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.
- Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C12-C18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C10-C20 oxo alcohols and those half esters secondary Alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
- C12-C16 alkyl sulfates and C12-C18 alkyl sulfates and C14-C18 alkyl sulfates are preferred.
- 2,3-alkyl sulfates which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 and can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.
- sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight or branched C7-C20 alcohols such as 2-methyl-branched C9-C11 alcohols having an average of 3.5 moles of ethylene oxide (EO) or C12-C18 fatty alcohols with 1 up to 4 EO, are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
- alkyl sulfosuccinic acid which are also known as sulfosuccinates or as Sulfosuccinic be called and represent the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C8-C18 fatty alcohol residues or mixtures of these.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols.
- 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.
- Particularly preferred anionic surfactants are soaps. Suitable are saturated and unsaturated 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, olive oil or tallow fatty acids.
- the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
- the content of anionic surfactants of the formulation according to the invention is preferably 2 to 30 wt .-%, preferably 4 to 25 wt .-% and in particular 5 to 22 wt .-% based on the total formulation.
- amphoteric surfactants such as surface-active compounds which carry at least one quaternary ammonium group and at least one -COO-- or -SO 3 - group in the molecule can be used as amphoteric surfactants.
- amphoteric surfactants in this context are betaine surfactants such as alkyl or alkylamidopropyl betaines.
- betaines such as the N-alkyl-N, N-dimethylammonium glycinate, z.
- cocoalkyl dimethylammoniumglycinat N-acyl-aminopropyl-N, N-dimethylammoniumglycinate, z.
- Cocoacylaminopropyldimethylammonium glycinate C12-C18-alkyl-dimethyl-acetobetaine, cocoamidopropyl-dimethyl-acetobetaine, 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines and sulfobetaines each having 8 to 18 carbon atoms in the alkyl or acyl group, as well as cocoacylaminoethylhydroxyethylcarboxymethylglycinate.
- a particularly preferred zwitterionic surfactant is the N, N-dimethyl-N- (lauroylamidopropyl) ammonium acetobetaine known by the INCI name Cocamidopropyl Betaine.
- amphoteric surfactants are the group of amphoacetates and amphodiacetates, in particular, for example, coconut or laurylamphoacetates or diacetates, the group of amphopropionates and amphodipropionates and the group of amino acid-based surfactants such as acylglutamates, in particular disodium cocoyl glutamates and sodium cocoyl glutamates, acylglycinates, in particular cocoyl Glycinates, and acyl sarcosinates, especially ammonium lauroyl sarcosinates and sodium cocoyl sarcosinates.
- acylglutamates in particular disodium cocoyl glutamates and sodium cocoyl glutamates
- acylglycinates in particular cocoyl Glycinates
- acyl sarcosinates especially ammonium lauroyl sarcosinates and sodium cocoyl sarcosinates.
- Particularly preferred detergent formulations according to the invention are characterized in that the surfactant is selected from the group of sulfonates and Sulfates, preferably of the linear alkyl-benzene sulfonates, in particular from the group of C 9 - C 13 alkyl benzene sulfonates, most preferably sodium (nC 10 -C 13 ) alkyl benzene sulfonate.
- the surfactant is selected from the group of sulfonates and Sulfates, preferably of the linear alkyl-benzene sulfonates, in particular from the group of C 9 - C 13 alkyl benzene sulfonates, most preferably sodium (nC 10 -C 13 ) alkyl benzene sulfonate.
- the detergent formulations may contain other ingredients which further enhance the performance and / or aesthetics of the detergent formulation.
- preferred detergent formulations additionally contain one or more substances from the group of builders, bleaches, bleach activators, enzymes, perfumes, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing auxiliaries, repellents and impregnating agents, swelling and anti-slip agents, neutral filler salts and UV absorbers.
- anti-wrinkling agents examples include anti-wrinkling agents, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, antistatic agents, ironing aids, UV absorbers.
- the detergent formulations may contain between 0.001 and 90, more preferably 0.01 to 45 wt .-% of one or more of the other ingredients mentioned herein, wherein the wt .-% refer to the total detergent formulation.
- the detergent formulations according to the invention can advantageously be used to accelerate foam formation and / or foam stabilization.
- the detergent formulations according to the invention are preferred for Foam stabilization used, this inventive use is carried out in particular in the presence of dirt.
- preference is given to using the detergent formulations which are mentioned above as preferred detergent formulations.
- the present invention is the use of the rhamnolipid mixture compositions contained in the detergent formulations according to the invention for accelerating foam formation and / or for foam stabilization.
- the rhamnolipid mixture compositions contained in the detergent formulations according to the invention are preferably used for foam stabilization, this use according to the invention being carried out in particular in the presence of dirt.
- Another object of the present invention is the use of a detergent formulation according to the invention for preventing the graying of a textile and / or as an anti-redeposition agent.
- a detergent formulation according to the invention for preventing the graying of a textile and / or as an anti-redeposition agent preference is given to using the detergent formulations which are mentioned above as preferred detergent formulations.
- a further subject matter of the present invention is the use of at least one rhamnolipid for preventing the graying of a textile and / or as an anti-redeposition agent, preference being given to using the rhamnolipid mixture compositions contained in the detergent formulations according to the invention.
- the rhamnolipid mixture compositions which are contained in the detergent formulations mentioned above as being preferred are particularly preferably used
- Example 1 Production of rhamnolipids with rhIABC from P. aeruginosa PAO1 in P. putida, whereby the expression of the gene coding for the rhamnosyltransferase RHIC is in many cases stronger than that of the gene rnI6 coding for the rhamnosyltransferase RhIB
- aeruginosa PAO1 genes rhIA, rhIB and rhIC followed by a terminator, followed by the synthetic tac promoter, followed by the P. aeruginosa PAO1 gene rhIC and a terminator flanked by a Hind III - (5 'end) or Bsu 36I interface (3' end) ( SEQ ID NO: 2).
- the vectors supplied by the DNA synthesis provider, containing the synthesized DNA fragment are cut with Hind III and Bsu 36I and into the also with Hind III and Bsu 36I cut vector pBBR1 MCS-2 (Seq ID 3) by means of fast link ligation Kit (Epicenter Technologies, Madison, WI, USA).
- the obtained target vector pBBR1 MCS2-Plac-rhIABC-T-Ptac-rhIC-T (pBBR1 MCS-2 with synthesized fragment Seq ID No. 2) has a size of 9336 base pairs.
- the transformation of Pseudomonas putida KT2440 with the vector pBBR1 MCS2-Plac-rhIABC-T-Ptac-rhIC-T (Seq ID No. 1) is carried out as described above ( Iwasaki et al. Biosci. Biotech. Biochem. 1994. 58 (5): 851-854 ).
- the plasmid DNA of 10 clones each each is isolated and analyzed.
- the resulting plasmid-carrying strain is called P. putida KT2440 pBBR1 MCS2-Plac-rhIABC-T-Ptac-rhIC-T.
- Recombinant strain P. putida KT2440 pBBR1 MCS2-Plac-rhIABC-T-Ptac-rhIC-T is cultured on LB agar kanamycin (50 pg / ml) plates.
- M9 medium the medium referred to below as M9 medium is used.
- This medium consists of 2% (w / v) glucose, 0.3% (w / v) KH 2 PO 4 , 0.679% Na 2 HPO 4 , 0.05% (w / v) NaCl, 0.2% ( w / v) NH 4 Cl, 0.049% (w / v) MgSO 4 x 7 H 2 O and 0.1% (v / v) of a trace element solution.
- a preculture is first prepared. For this purpose, a colony of a strain freshly streaked out on an LB agar plate is used and 10 ml of LB medium are inoculated in a 100 ml Erlenmeyer flask. All recombinant P. putida strains are cultured in LB medium to which 50 ⁇ g / ml kanamycin is added. The cultivation of the P. putida strains are carried out at 30 ° C and 200 rpm overnight.
- the precultures are used to inoculate 50 ml of M9 medium (+ 50 ⁇ g / ml kanamycin) in the 250 ml Erlenmeyer flask (start OD 600 0.1).
- the cultures are cultured at 200 rpm and 30 ° C. After 24 h, a sample of 1 ml of culture broth is removed from the culture flask.
- a mineral medium (M9) is used for the main culture.
- the fermentation after inoculation with 10 vol. % Pre-culture and consumption of the glucose is carbon-limited by means of a glucose feed in a 2 liter fermenter with a working volume of 1.2 l.
- the glucose feed is based on the dissolved oxygen signal.
- the dissolved oxygen is regulated at 20% saturation above the stirrer speed.
- the pH is adjusted to 7 via a pH electrode and addition of NH 4 SO 4 .
- the fermentation is carried out over 4 days to a dry biomass of 15 g / l.
- the rhamnolipid concentration is determined by HPLC and is 9.8 g / l.
- the fermentation broth is adjusted to a pH of 4.0 by adding concentrated HCl.
- the mixture is then extracted with the same volume of ethyl acetate.
- the rhamnolipid Web organic phase is separated and on processed.
- KOH 50% strength by weight
- the pH of the solution is adjusted to pH 7. This leads to the formation of two liquid phases.
- the lower phase contains the liberated from lipophilic and hydrophilic impurities rhamnolipids in high purity.
- the composition of the rhamnolipid mixture is not affected by this.
- the lower phase is removed and the solvent removed as far as possible on a rotary evaporator.
- water is added again and the aqueous rhamnolipid solution is freeze-dried.
- the resulting powder is analyzed by means of HPLC and characterized by application technology.
- Sample preparation for the subsequent chromatographic analyzes is carried out as follows: 1 ml of acetone is introduced into a 2 ml reaction vessel using a displacement pipette (Combitip) and the reaction vessel is immediately closed to minimize evaporation. This is followed by the addition of 1 ml of culture broth. After vortexing the culture broth / acetone mixture, this is centrifuged off for 3 min at 13,000 rpm and 800 ⁇ l of the supernatant are transferred to an HPLC vessel. An Evaporative Light Scattering Detector (Sedex LT-ELSD Model 85LT) is used to detect and quantify rhamnolipids.
- the actual measurement is performed using Agilent Technologies 1200 Series (Santa Clara, California) and the Zorbax SB-C8 Rapid Resolution column (4.6 x 150 mm, 3.5 ⁇ m, Agilent).
- the injection volume is 5 ⁇ l and the runtime of the method is 20 min.
- the mobile phase used is aqueous 0.1% TFA (trifluoroacetic acid, solution A) and methanol (solution B).
- the column temperature is 40 ° C.
- the detectors used are the ELSD (detector temperature 60 ° C) and the DAD (diode array, 210 nm).
- the gradient used in the method is: t [min] Solution B vol .-% Flow [ml / min] 0.00 70% 1.00 15.00 100% 1.00 15,01 70% 1.00 20.00 70% 1.00
- the rhamnolipid composition of P. putida KT2440 pBBR1 MCS2-Plac-rhIABC-T-Ptac-rhIC-T obtained by the method described above contains: DIRL-C10C10 81% by weight DIRL-C10C12 10% by weight DIRL-C10C12: 1 8% by weight monoRL-C10C10 1% by weight resulting in a weight ratio of di-rhamnolipids to mono-rhamnolipids of 99: 1 results.
- the stirrer with a holder for 4 closable cylinders with a volume of 300 ml is placed at an angle of 90 °.
- the 300 ml measuring cylinder with closure are arranged so that the rotation of the cylinder is horizontal.
- the measuring cylinders are wetted with the surfactant solution. This solution is then discarded.
- 60 ml of surfactant solution to be tested are filled into each measuring cylinder as foam-free as possible.
- the sealed graduated cylinders are mounted in the appropriate holders and the mixer started at 20 rpm. At the same time a stopwatch is pressed. In order to measure the foam heights as a function of time, the mixer is stopped after appropriate time intervals, waited 30 seconds, and noted the foam height. If the foaming behavior is to be observed under dirt load, the dirt is added at defined times.
- the concentration of the surfactant is in all cases 0.4 g of active substance per liter of solution.
- the solution was shaken for 2 minutes without addition of dirt in the cylinder. Then the first portion of dirt was added, then shaken for a further 10 min. After reading the foam height, the second addition of a defined amount of dirt took place and it was shaken again for 10 minutes. After reading the foam height, the third addition of a defined amount of dirt took place and it was shaken again for 10 minutes and the foam height was measured.
- the measured foam heights represent mean values of 4 individual measurements.
- LAS MARLON ARL ⁇ Sasol, sodium (nC 10 -C 13) -alkylbenzolsulphonat with an active content of 80 wt .-%, is a known, high foaming anion surfactant, which finds wide use in detergent formulations.
- Jenil Commercial sample with a high mono-rhamnolipid content
- Example 1 shows a somewhat slower foaming behavior, but reaches a similar level after 10 minutes as the anionic surfactant LAS.
- Each with its high monoRL content and low diRL content exhibits a slower foaming behavior than Example 1, which has a low monoRL content and a high diRL content, and finally only achieves a significantly lower foam level than LAS or Example 1.
- Example 2 With three additions (see Example 2) of 76 mg of dirt into a cylinder, the composition of Example 1 shows a slightly higher foam formation than LAS after 15 minutes compared to LAS. After the third dirt addition (after 20 min), the foam height is still stable and significantly higher than in LAS.
- the reflectance of the test fabrics before and after washing is measured.
- the brightness L *, the value a * on the red-green color axis and the value b * on the yellow-blue color axis before and after washing are measured.
- the change in the color value ( ⁇ E value) is a measure of the achieved cleaning effect.
- ⁇ E value ie the better the soil removal, the larger the ⁇ E value becomes.
- AE value description > 2 Visually detectable reduction of contamination 4-10 Mediocre stain removal 10-20 Significant stain removal > 20 Complete stain removal
- wash liquor Composition cf. Table below
- Water hardness 16 ° dH
- Asset load per wash tank 500 ml
- Fabric load per wash tank 3 stains of a variety (10 x 10 cm) and 1 white cotton fabric (10 x 20 cm).
- the size of the lobules should be adjusted to weigh about 10g along with the white cotton fabric.
- Washing mechanics 10 steel balls ⁇ 6 mm Washing temperature: 25 ° C Washing time: 30 min Do the washing up: 3 x 30 s with tap water (about 5 ° dH)
- Detergent formulation A Concentration% by weight (100% active base)
- Example 1 37.60 glycerin 5 propylene glycol 9 triethanolamine 11.05 citric acid 1.71 water rest
- a detergent formulation containing as the effective surfactant excluding a composition of Example 1 is as effective in stain removal of soy, curry, carbon black and skin fat as a commercial liquid detergent based on an optimized surfactant ratio of LAS, other anionic surfactants and nonionic surfactants.
- rhamnolipids of the specific composition of Example 1 show a less graying effect on curry, soot, milk / cocoa than the commercial LAS-based liquid detergent and thus act as anti-redeposition agents.
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Abstract
Gegenstand der Erfindung sind Waschmittelformulierungen für Textilien enthaltend Rhamnolipide, wobei der Gehalt an di-Rhamnolipiden überwiegt, sowie die Verwendung von bestimmten Rhamnolipid-Mischungszusammensetzungen und der vorgenannten Waschmittelformulierungen zur Beschleunigung von Schaumentstehung und/oder zur Schaumstabilisierung sowie die Verwendung von Rhamnolipiden zur Verhinderung der Vergrauung eines Textils.The invention relates to detergent formulations for textiles containing rhamnolipids, wherein the content of di-rhamnolipids predominates, and the use of certain rhamnolipid mixture compositions and the aforementioned detergent formulations for accelerating foaming and / or foam stabilization and the use of rhamnolipids to prevent the graying of a textile.
Description
Gegenstand der Erfindung sind Waschmittelformulierungen für Textilien enthaltend Rhamnolipide, wobei der Gehalt an di-Rhamnolipiden überwiegt, sowie die Verwendung von bestimmten Rhamnolipid-Mischungszusammensetzungen und der vorgenannten Waschmittelformulierungen zur Beschleunigung von Schaumentstehung und/oder zur Schaumstabilisierung sowie die Verwendung von Rhamnolipiden zur Verhinderung der Vergrauung eines Textils.The invention relates to detergent formulations for textiles containing rhamnolipids, wherein the content of di-rhamnolipids predominates, and the use of certain rhamnolipid mixture compositions and the aforementioned detergent formulations for accelerating foaming and / or foam stabilization and the use of rhamnolipids to prevent the graying of a textile.
Wässrige Tensidlösungen zeigen in Abhängigkeit ihrer Zusammensetzung unterschiedlich schnellen Schaumaufbau und eine unterschiedliche Schaumstabilität. Schaumbildung und -zerfall werden durch die Anwesenheit von Schmutz beeinflusst. Schaumstabilität ist insbesondere beim Waschen von Wäsche bzw. Gewebe ein für den Verbraucher wichtiges Qualitätsmerkmal.
Wünschenswert sind Waschmittelformulierungen mit hoher Schaumstabilität.Aqueous surfactant solutions show, depending on their composition, different rapid foam buildup and different foam stability. Foaming and decay are affected by the presence of dirt. Foam stability is an important quality feature for the consumer, especially when washing laundry or fabrics.
Desirable are detergent formulations with high foam stability.
Überraschend wurde gefunden, dass Rhamnolipide (RL) mit einem hohen Gehalt an di- Rhamnolipiden in Waschmittelformulierungen einen stabileren Schaum und/oder mehr Schaumbildung zeigen als Tenside nach dem Stand der Technik, insbesondere in Gegenwart von hoher Schmutzlast.Surprisingly, it has been found that rhamnolipids (RL) with a high content of di-rhamnolipids in detergent formulations have a more stable foam and / or more foaming than surfactants according to the prior art, especially in the presence of high soil load.
Überraschenderweise wurde gefunden, dass die im Folgenden beschriebenen Formulierungen die der Erfindung gestellt Aufgabe zu lösen vermögen.Surprisingly, it has been found that the formulations described below are capable of solving the problem set by the invention.
Gegenstand der vorliegenden Erfindung sind daher Waschmittelformulierungen für Textilien enthaltend eine Rhamnolipid-Mischungszusammensetzung mit einem erhöhten Anteil an di-Rhamnolipiden.The present invention therefore provides laundry detergent formulations for textiles comprising a rhamnolipid blend composition having an increased proportion of di-rhamnolipids.
Ein weiterer Gegenstand der Erfindung ist die Verwendung von bestimmten Rhamnolipid-Mischungszusammensetzungen und der vorgenannten Waschmittelformulierungen zur Beschleunigung von Schaumentstehung und/oder zur Schaumstabilisierung sowie die Verwendung von Rhamnolipiden zur Verhinderung der Vergrauung eines TextilsAnother object of the invention is the use of certain rhamnolipid blend compositions and the aforementioned detergent formulations to accelerate foaming and / or foam stabilization and the use of rhamnolipids to prevent the graying of a textile
Ein Vorteil der Erfindung ist es, dass die eingesetzten Tenside in der Waschmittelformulierung biologisch abbaubar sind.
Ein Vorteil der erfindungsgemäßen Formulierungen ist deren überragende Schaumstabilität im Wässrigen.
Noch ein Vorteil der erfindungsgemäßen Formulierungen ist deren überragendes Schaumvolumen im Wässrigen.
Ein weiterer Vorteil der erfindungsgemäßen Formulierungen ist deren hervorragendes Anschäumverhalten.
Noch ein Vorteil der erfindungsgemäßen Formulierungen ist deren einfache Formulierbarkeit in beliebigen wässrigen, tensidischen Systemen.
Ein weiterer Vorteil der erfindungsgemäßen Formulierungen ist deren gute Verdickbarkeit mit konventionellen Verdickern in Formulierungen.
Noch ein Vorteil ist ihre gute Auswaschbarkeit von Textilien.
Ein weiterer Vorteil der erfindungsgemäßen Formulierungen ist ihre Mildheit bzw. gute physiologische Verträglichkeit, insbesondere charakterisiert durch einen hohen Wert im Red Blood-Cell (RBC) Test.
Ein weiterer Vorteil der erfindungsgemäßen Formulierungen ist, dass sie einen angenehmen Weichgriff des Textils nach dem Waschen hinterlassen.An advantage of the invention is that the surfactants used are biodegradable in the detergent formulation.
An advantage of the formulations according to the invention is their outstanding foam stability in the aqueous.
Another advantage of the formulations according to the invention is their outstanding foam volume in the aqueous.
Another advantage of the formulations according to the invention is their excellent foaming behavior.
Another advantage of the formulations according to the invention is their ease of formulation in any aqueous, surfactant systems.
Another advantage of the formulations according to the invention is their good thickenability with conventional thickeners in formulations.
Another advantage is their good washability of textiles.
A further advantage of the formulations according to the invention is their mildness or good physiological compatibility, in particular characterized by a high value in the Red Blood Cell (RBC) test.
Another advantage of the formulations according to the invention is that they leave a pleasant soft feel of the textile after washing.
Unter dem Begriff "Rhamnolipid" im Zusammenhang mit der vorliegenden Erfindung werden insbesondere Verbindungen der allgemeinen Formel (I) oder deren Salze verstanden,
- m = 2, 1 oder 0,
- n = 1 oder 0,
- R1 und R2 = unabhängig voneinander gleicher oder verschiedener organischer Rest mit 2 bis 24, bevorzugt 5 bis 13 Kohlenstoffatomen, insbesondere gegebenenfalls verzweigter, gegebenenfalls substituierter, insbesondere hydroxy-substituierter, gegebenenfalls ungesättigter, insbesondere gegebenenfalls einfach, zweifach oder dreifach ungesättigter, Alkylrest, bevorzugt solcher ausgewählt aus der Gruppe bestehend aus Pentenyl, Heptenyl, Nonenyl, Undecenyl und Tridecenyl und (CH2)o-CH3 mit O = 1 bis 23, bevorzugt 4 bis 12.
Unter dem Begriff "mono-Rhamnolipid" im Zusammenhang mit der vorliegenden Erfindung werden Verbindungen der allgemeinen Formel (I) oder deren Salze verstanden, bei denen n =0.
Distinkte Rhamnolipide werden gemäß folgender Nomenklatur abgekürzt:
Unter "diRL-CXCY" werden di-Rhamnolipide der allgemeinen Formel (I) verstanden, bei denen einer der Reste R1 und R2 = (CH2)o-CH3 mit o = X-4 und der verbleibende Rest R1 oder R2 = (CH2)o-CH3 mit o = Y-4.
Unter "monoRL-CXCY" werden mono-Rhamnolipide der allgemeinen Formel (I) verstanden, bei denen einer der Reste R1 und R2 = (CH2)o-CH3 mit o = X-4 und der verbleibende Rest R1 oder R2 = (CH2)o-CH3 mit o = Y-4.The term "rhamnolipid" in connection with the present invention is understood in particular to mean compounds of the general formula (I) or their salts,
- m = 2, 1 or 0,
- n = 1 or 0,
- R 1 and R 2 = independently of one another the same or different organic radical having 2 to 24, preferably 5 to 13 carbon atoms, in particular optionally branched, optionally substituted, in particular hydroxy-substituted, optionally unsaturated, in particular optionally mono-, di- or triunsaturated, alkyl radical, preferably those selected from the group consisting of pentenyl, heptenyl, nonenyl, undecenyl and tridecenyl and (CH 2 ) o -CH 3 where O = 1 to 23, preferably 4 to 12.
The term "mono-rhamnolipid" in connection with the present invention means compounds of the general formula (I) or their salts in which n = 0.
Distinct rhamnolipids are abbreviated according to the following nomenclature:
By "diRL-CXCY" di-rhamnolipids of the general formula (I) are understood, in which one of the radicals R 1 and R 2 = (CH 2 ) o -CH 3 with o = X-4 and the remaining radical R 1 or R 2 = (CH 2 ) o -CH 3 with o = Y-4.
"Mono R-CXCY" is understood as meaning mono rhamnolipids of the general formula (I) in which one of the radicals R 1 and R 2 = (CH 2 ) o -CH 3 with o = X-4 and the remainder R 1 or R 2 = (CH 2 ) o -CH 3 with o = Y-4.
Die verwendete Nomenklatur unterscheidet somit nicht zwischen "CXCY" und "CYCX". Für Rhamnolipide mit m=0 wird entsprechend monoRL-CX bzw. diRL-CX verwendet. Ist einer der oben genannten Indices X und/oder Y mit ,,:Z" versehen, so bedeutet dies, dass der jeweilige Rest R1 und/oder R2 = ein unverzweigter, unsubstituierter Kohlenwasserstoffrest mit X-3 bzw. Y-3 Kohlenstoffatomen aufweisend Z Doppelbindungen darstellt.The nomenclature used does not distinguish between "CXCY" and "CYCX". For rhamnolipids with m = 0, correspondingly monoRL-CX or diRL-CX is used. If one of the abovementioned indices X and / or Y is provided with ": Z", this means that the respective radical R 1 and / or R 2 = an unbranched, unsubstituted hydrocarbon radical with X-3 or Y-3 carbon atoms having Z represents double bonds.
Der "pH-Wert" im Zusammenhang mit der vorliegenden Erfindung ist definiert als der Wert, welcher für entsprechenden Stoff bei 25 °C nach fünf Minuten Rühren mit einer gemäß ISO 4319 (1977) kalibrierten pH-Elektrode gemessen wird.
Unter dem Begriff "wässriges" im Zusammenhang mit der vorliegenden Erfindung ist eine Zusammensetzung zu verstehen, die mindestens 5 Gew.-% Wasser, bezogen auf die betrachtete Gesamtzusammensetzung enthält.The "pH" in the context of the present invention is defined as the value measured for corresponding substance at 25 ° C after five minutes of stirring with a pH electrode calibrated according to ISO 4319 (1977).
The term "aqueous" in the context of the present invention is to be understood as meaning a composition which contains at least 5% by weight of water, based on the total composition under consideration.
Alle angegebenen Prozent (%) sind, wenn nicht anders angegeben, Massenprozent. Beansprucht wird somit eine Waschmittelformulierung für Textilien enthaltend eine mono- und di-Rhamnolipid-Mischungszusammensetzung, dadurch gekennzeichnet, dass das Gewichtsverhältnis von di-Rhamnolipiden zu mono-Rhamnolipiden größer als 51:49, bevorzugt größer 75:25, besonders bevorzugt 97:3, insbesondere größer 98:2 ist.
Durch den Begriff "mono- und di-Rhamnolipid-Mischungszusammensetzung" im Zusammenhang mit der vorliegenden Erfindung ist herausgestellt, dass die erfindungsgemäße Mischungszusammensetzung mono-Rhamnolipide enthält. Bevorzugt ist die erfindungsgemäße Waschmittelformulierung bei Raumtemperatur flüssig.All percentages (%) are by mass unless otherwise specified. Claimed is thus a detergent formulation for textiles comprising a mono- and di-rhamnolipid mixture composition, characterized in that the weight ratio of di-rhamnolipids to mono-rhamnolipids greater than 51:49, preferably greater than 75:25, particularly preferably 97: 3, especially greater 98: 2.
By the term "mono- and di-rhamnolipid blend composition" in the context of the present invention, it is pointed out that the blend composition according to the invention contains mono-rhamnolipids. The detergent formulation according to the invention is preferably liquid at room temperature.
Erfindungsgemäß bevorzugte Waschmittelformulierung ist dadurch gekennzeichnet, dass die Rhamnolipid-Mischungszusammensetzung
- 51 Gew.-% bis 95 Gew.-%, bevorzugt 70 Gew.-% bis 90 Gew.-%, besonders bevorzugt
- 75 Gew.-% bis 85 Gew.-%, diRL-C10C10 und
- 0,5 Gew.-% bis 9 Gew.-%, bevorzugt 0,5 Gew.-% bis 3 Gew.-%, besonders bevorzugt
- 0,5 Gew.-% bis 2 Gew.-%, monoRL-C10C10
wobei sich die Gewichtsprozente auf die Summe aller enthaltenen Rhamnolipide beziehen,The detergent formulation preferred according to the invention is characterized in that the rhamnolipid mixture composition
- 51 wt .-% to 95 wt .-%, preferably 70 wt .-% to 90 wt .-%, particularly preferably
- 75 wt .-% to 85 wt .-%, diRL-C10C10 and
- 0.5% by weight to 9% by weight, preferably 0.5% by weight to 3% by weight, more preferably
- From 0.5% to 2% by weight, mono-C10C10
wherein the percentages by weight refer to the sum of all contained rhamnolipids,
Erfindungsgemäß bevorzugte Waschmittelformulierung ist dadurch gekennzeichnet, dass die Rhamnolipid-Mischungszusammensetzung neben den oben genannten diRL-C10C10- und monoRL-C10C10 Gehalten
- 0,5 Gew.-% bis 15 Gew.-%, bevorzugt 3 Gew.-% bis 12 Gew.-%, besonders bevorzugt
- 5 Gew.-% bis 10 Gew.-%, diRL-C10C12:1
wobei sich die Gewichtsprozente auf die Summe aller enthaltenen Rhamnolipide beziehen.A detergent formulation preferred according to the invention is characterized in that the rhamnolipid mixture composition contains, in addition to the abovementioned diRL-C10C10 and monoRL-C10C10 contents
- From 0.5% to 15% by weight, preferably from 3% to 12% by weight, more preferably
- From 5% to 10% by weight, diRL-C10C12: 1
wherein the percentages by weight refer to the sum of all contained rhamnolipids.
Erfindungsgemäß bevorzugte Waschmittelformulierung ist dadurch gekennzeichnet, dass die Rhamnolipid-Mischungszusammensetzung neben den oben genannten diRL-C10C10- und monoRL-C10C10 Gehalten
- 0,5 bis 25 Gew.-%, bevorzugt 5 Gew.-% bis 15 Gew.-%, besonders bevorzugt 7 Gew.-% bis 12 Gew.-%, diRL-C10C12
wobei sich die Gewichtsprozente auf die Summe aller enthaltenen Rhamnolipide beziehen.A detergent formulation preferred according to the invention is characterized in that the rhamnolipid mixture composition contains, in addition to the abovementioned diRL-C10C10 and monoRL-C10C10 contents
- 0.5 to 25 wt .-%, preferably 5 wt .-% to 15 wt .-%, particularly preferably 7 wt .-% to 12 wt .-%, diRL-C10C12
wherein the percentages by weight refer to the sum of all contained rhamnolipids.
Erfindungsgemäß bevorzugte Waschmittelformulierung ist dadurch gekennzeichnet, dass die Rhamnolipid-Mischungszusammensetzung neben den oben genannten diRL-C10C10- und monoRL-C10C10 Gehalten
- 0,1 Gew.-% bis 5 Gew.-%, bevorzugt 0,5 Gew.-% bis 3 Gew.-%, besonders bevorzugt
- 0,5 Gew.-% bis 2 Gew.-%, monoRL-C10C12 und/oder, bevorzugt und
- 0,1 Gew.-% bis 5 Gew.-%, bevorzugt 0,5 Gew.-% bis 3 Gew.-%, besonders bevorzugt
- 0,5 Gew.-% bis 2 Gew.-%, monoRL-C10C12:1,
wobei sich die Gewichtsprozente auf die Summe aller enthaltenen Rhamnolipide beziehen.A detergent formulation preferred according to the invention is characterized in that the rhamnolipid mixture composition contains, in addition to the abovementioned diRL-C10C10 and monoRL-C10C10 contents
- 0.1 wt .-% to 5 wt .-%, preferably 0.5 wt .-% to 3 wt .-%, particularly preferably
- 0.5 wt .-% to 2 wt .-%, monoRL-C10C12 and / or, preferably and
- 0.1 wt .-% to 5 wt .-%, preferably 0.5 wt .-% to 3 wt .-%, particularly preferably
- From 0.5% to 2% by weight, mono-C-C10C12: 1,
wherein the percentages by weight refer to the sum of all contained rhamnolipids.
Es kann vorteilhaft sein und ist daher bevorzugt, wenn die in der erfindungsgemäßen Formulierung enthaltene Rhamnolipid-Mischungszusammensetzung neben den oben genannten diRL-C10C10- und monoRL-C10C10 Gehalten
- 0,1 Gew.-% bis 25 Gew.-%, bevorzugt 2 Gew.-% bis 10 Gew.-%, besonders bevorzugt
- 4 Gew.-% bis 8 Gew.-%, diRL-C8C10,
wobei sich die Gewichtsprozente auf die Summe aller enthaltenen Rhamnolipide beziehen.It may be advantageous, and is therefore preferred, for the rhamnolipid mixture composition contained in the formulation according to the invention to contain, in addition to the abovementioned diRL-C10C10 and monoRL-C10C10 contents
- 0.1 wt .-% to 25 wt .-%, preferably 2 wt .-% to 10 wt .-%, more preferably
- From 4% to 8% by weight, diRL-C8C10,
wherein the percentages by weight refer to the sum of all contained rhamnolipids.
Erfindungsgemäß besonders bevorzugte Waschmittelformulierung ist dadurch gekennzeichnet, dass die Rhamnolipid-Mischungszusammensetzung neben den oben genannten diRL-C10C10- und monoRL-C10C10 Gehalten
- 0,5 Gew.-% bis 15 Gew.-%, bevorzugt 3 Gew.-% bis 12 Gew.-%, besonders bevorzugt
- 5 Gew.-% bis 10 Gew.-%, diRL-C10C12:1,
- 0,5 bis 25 Gew.-%, bevorzugt 5 Gew.-% bis 15 Gew.-%, besonders bevorzugt 7 Gew.-% bis 12 Gew.-%, diRL-C10C12,
- 0,1 Gew.-% bis 5 Gew.-%, bevorzugt 0,5 Gew.-% bis 3 Gew.-%, besonders bevorzugt
- 0,5 Gew.-% bis 2 Gew.-%, monoRL-C10C12 und
- 0,1 Gew.-% bis 5 Gew.-%, bevorzugt 0,5 Gew.-% bis 3 Gew.-%, besonders bevorzugt
- 0,5 Gew.-% bis 2 Gew.-%, monoRL-C10C12:1,
wobei sich die Gewichtsprozente auf die Summe aller enthaltenen Rhamnolipide beziehen.A particularly preferred detergent formulation according to the invention is characterized in that the rhamnolipid mixture composition contains, in addition to the abovementioned diRL-C10C10 and monoRL-C10C10 contents
- From 0.5% to 15% by weight, preferably from 3% to 12% by weight, more preferably
- From 5% to 10% by weight, diRL-C10C12: 1,
- From 0.5% to 25% by weight, preferably from 5% by weight to 15% by weight, particularly preferably from 7% by weight to 12% by weight, of diRL-C10C12,
- 0.1 wt .-% to 5 wt .-%, preferably 0.5 wt .-% to 3 wt .-%, particularly preferably
- 0.5 wt .-% to 2 wt .-%, monoRL-C10C12 and
- 0.1 wt .-% to 5 wt .-%, preferably 0.5 wt .-% to 3 wt .-%, particularly preferably
- From 0.5% to 2% by weight, mono-C-C10C12: 1,
wherein the percentages by weight refer to the sum of all contained rhamnolipids.
Es ist überdies hinaus bevorzugt, wenn die in der erfindungsgemäßen Formulierung enthaltene Rhamnolipid-Mischungszusammensetzung Rhamnolipide der Formel monoRL-CX bzw. diRL-CX in nur kleinen Mengen enthält. Insbesondere enthält die erfindungsgemäße Mischungszusammensetzung bevorzugt
0 Gew.-% bis 5 Gew.-%, bevorzugt 0 Gew.-% bis 3 Gew.-%, besonders bevorzugt 0 Gew.-% bis 1 Gew.-%, diRLC10, wobei sich die Gewichtsprozente auf die Summe aller enthaltenen Rhamnolipide beziehen, und unter dem Begriff "0 Gew.-%" keine nachweisbare Menge zu verstehen ist.Furthermore, it is preferred if the rhamnolipid mixture composition contained in the formulation according to the invention contains rhamnolipids of the formula monoRL-CX or diRL-CX in only small amounts. In particular, the mixture composition according to the invention preferably contains
0 wt .-% to 5 wt .-%, preferably 0 wt .-% to 3 wt .-%, particularly preferably 0 wt .-% to 1 wt .-%, diRLC10, wherein the weight percent based on the sum of all Rhamnolipids, and the term "0 wt .-%" is no detectable amount to understand.
Es ist erfindungsgemäß bevorzugt, dass die erfindungsgemäßen Formulierungen im Wesentlichen frei von fettem Öl (bei 20 °C flüssigen Acylglycerolen) sind und somit insbesondere weniger als 0,5 Gew.-%, insbesondere weniger als 0,1 Gew.-%, besonders bevorzugt keine nachweisbaren Mengen fettes Öl bezogen auf die gesamte Mischungszusammensetzung enthalten.It is inventively preferred that the formulations of the invention are substantially free of fatty oil (at 20 ° C liquid acylglycerols) and thus in particular less than 0.5 wt .-%, in particular less than 0.1 wt .-%, particularly preferred no detectable levels of fatty oil based on the total blend composition.
Die in den erfindungsgemäßen Formulierungen enthaltenen Mischungszusammensetzungen lassen sich durch Abmischen der Reinsubstanzen herstellen, wobei die Reinsubstanzen aus herkömmlich hergestellten Rhamnolipid-Mischungen aufgereinigt werden können. Entsprechende Aufreinigungsverfahren sind beispielsweise selektive Kristallisationen und chromatographische Methoden. Entsprechende Verfahren sind in
Insbesondere die im Folgenden beschriebenen Verfahren eignen sich zur Herstellung von den in den erfindungsgemäßen Formulierungen enthaltenen Mischungszusammensetzungen.
Ein erstes Verfahren umfasst die Verfahrensschritte:
- Ia) Bereitstellen einer Pseudomonas putida Zelle, die derart gentechnisch verändert wurde, dass sie jeweils mindestens ein Gen der Gruppe rhIA, rhIB und rhIC überexprimiert,
- IIa) in Kontakt Bringen der erfindungsgemäßen Zelle mit einem Medium beinhaltend mindestens eine Kohlenstoffquelle
- IIIa) Kultivieren der Zelle unter Bedingungen, die es der Zelle ermöglichen, aus der Kohlenstoffquelle Rhamnolipid zu bilden und
- IVa) gegebenenfalls Isolierung der gebildeten Rhamnolipide,
Die relative Stärke der oben beschriebenen Überexpression lässt sich beispielsweise mit Hilfe von RT-PCR bestimmen, bei der die Menge an gebildeter mRNA für das jeweilige Gen bestimmt wird.
Eine Regulierung der Stärke der Expression kann der Fachmann gezielt beispielsweise durch die Wahl von Promotoren oder durch den Einsatz induzierbarer Promotoren in Kombination mit Menge an Induktor erreichen oder auch durch Genvervielfachungen. Ein alternatives Verfahren umfasst die Verfahrensschritte:
- Ib) Bereitstellen einer Pseudomonas putida Zelle, die derart gentechnisch verändert wurde, dass sie jeweils mindestens ein exogenes Gen der Gruppe rhIA, rhIB und rhIC, von denen mindestens eines unter der Kontrolle eines induzierbaren Promotors steht, aufweist,
- IIb) in Kontakt Bringen und Kultivieren der erfindungsgemäßen Zelle mit einem Medium beinhaltend mindestens eine Kohlenstoffquelle unter Erreichung einer Zelldichte von 1-30 g Zelltrockenmasse pro L Fermentationsbrühe, bevorzugt 2-20 g Zelltrockenmasse pro L Fermentationsbrühe, besonders bevorzugt 5-15 g Zelltrockenmasse pro L Fermentationsbrühe,
- IIIb) Induzieren des mindestens einen induzierbaren Promotors und Kultivieren der Zelle unter Bedingungen, die es der Zelle ermöglichen, aus der Kohlenstoffquelle Rhamnolipid zu bilden und
- IVb) gegebenenfalls Isolierung der gebildeten Rhamnolipide.
Unter dem Begriff "Induzieren des mindestens einen induzierbaren Promotors" ist im Zusammenhang mit der vorliegenden Erfindung zu verstehen, dass die Aktivität des induzierbaren Promotors durch eine Veränderung des die Zelle umgebenden Mediums erhöht wird.
Geeignete induzierbare Promotoren im Zusammenhang mit der vorliegenden Erfindung sind beispielsweise Promotoren, die durch Zugabe chemischer Induktoren (etwa Laktose, IPTG, Dicyclopropylketon, Tetracyclin, Doxycyclin, Propionat, Cumat, Benzoat, Arabinose, Rhamnose, Nikotinsäure, etc.) induziert werden, die durch veränderte Umweltbedingungen (etwa auftretender Phosphat- oder Schwefelmangel, veränderte Temperaturen oder pH, etc.) induziert werden, oder die durch bestimmte physiologische Zustände (etwa bestimmte Zelldichten oder Wachstumsraten bzw. - phasen) induziert werden.
Insbesondere bevorzugt in dem Verfahren eingesetzte induzierbare Promotoren sind ausgewählt aus der Gruppe der durch Dicyclopropylketon, Tetracyclin, Doxycyclin, Propionat, Cumat, Benzoat, Phosphatmangel, Schwefelmangel oder eine verminderte Wachstumsrate induzierbaren Promotoren.
Die Gene rhIA, rhIB und rhIC sind in beiden oben beschriebenen Verfahren bevorzugt ausgewählt aus denen aus P. aeruginosa. In particular, the processes described below are suitable for the preparation of the mixture compositions contained in the formulations according to the invention.
A first method comprises the method steps:
- Ia) providing a Pseudomonas putida cell genetically engineered to overexpress at least one of the groups rhIA, rhIB and rhIC,
- IIa) contacting the cell of the invention with a medium containing at least one carbon source
- IIIa) culturing the cell under conditions that allow the cell to form rhamnolipid from the carbon source and
- IVa) if appropriate, isolation of the rhamnolipids formed,
The relative strength of the overexpression described above can be determined, for example, by means of RT-PCR, in which the amount of mRNA formed for the respective gene is determined.
Regulation of the level of expression can be achieved by a person skilled in the art, for example, by the choice of promoters or by the use of inducible promoters in combination with the amount of inducer or by gene multiplication. An alternative method comprises the method steps:
- Ib) providing a Pseudomonas putida cell genetically engineered to each have at least one exogenous gene of group rhIA, rhIB and rhIC, at least one of which is under the control of an inducible promoter,
- IIb) bringing into contact and cultivating the cell according to the invention with a medium containing at least one carbon source to reach a cell density of 1-30 g of cell dry matter per L of fermentation broth, preferably 2-20 g Dry cell mass per L of fermentation broth, more preferably 5-15 g of cell dry mass per L of fermentation broth,
- IIIb) inducing the at least one inducible promoter and culturing the cell under conditions that allow the cell to form rhamnolipid from the carbon source and
- IVb) if appropriate, isolation of the rhamnolipids formed.
The term "inducing the at least one inducible promoter" in the context of the present invention means that the activity of the inducible promoter is increased by a change in the medium surrounding the cell.
Suitable inducible promoters in the context of the present invention are, for example, promoters which are induced by the addition of chemical inducers (such as lactose, IPTG, dicyclopropyl ketone, tetracycline, doxycycline, propionate, cumate, benzoate, arabinose, rhamnose, nicotinic acid, etc.) altered environmental conditions (such as occurring phosphate or sulfur deficiency, altered temperatures or pH, etc.) are induced, or induced by certain physiological conditions (such as certain cell densities or growth rates or - phases).
Particularly preferred inducible promoters used in the method are selected from the group of promoters inducible by dicyclopropyl ketone, tetracycline, doxycycline, propionate, cumate, benzoate, phosphate deficiency, sulfur deficiency or a reduced growth rate.
The genes rhIA, rhIB and rhIC are preferably selected in both of the methods described above from those from P. aeruginosa.
Bevorzugte erfindungsgemäße Formulierungen enthalten neben der Rhamnolipid-Mischungszusammensetzung mindestens ein weiteres Tensid, wobei beispielsweise anionische, nichtionische, kationische und/oder amphotere Tenside eingesetzt werden können, wobei anionische Tenside bevorzugt sind.Preferred formulations according to the invention comprise, in addition to the rhamnolipid mixture composition, at least one further surfactant, it being possible to use, for example, anionic, nonionic, cationic and / or amphoteric surfactants, with anionic surfactants being preferred.
Bevorzugt sind aus anwendungstechnischer Sicht Mischungen aus anionischen und nichtionischen Tensiden in den erfindungsgemäßen Formulierungen enthalten.
Der Gesamttensidgehalt der erfindungsgemäßen Formulierung beträgt vorzugsweise 5 bis 40 Gew.-% und besonders bevorzugt 9 bis 35 Gew.-%, bezogen auf die gesamte Formulierung.From an application point of view, preference is given to mixtures of anionic and nonionic surfactants in the formulations according to the invention.
The total surfactant content of the formulation according to the invention is preferably from 5 to 40% by weight and more preferably from 9 to 35% by weight, based on the total formulation.
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 bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, zum Beispiel aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-C14-Alkohole mit 3 EO, 4 EO oder 7 EO, C9-C11-Alkohol mit 7 EO, C13-C15- Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-C18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-C14-Alkohol mit 3 EO und C12-C18-Alkohol mit 7 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf. 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. Auch nichtionische Tenside, die EO- und PO(Propylenoxid)-Gruppen zusammen im Molekül enthalten, sind einsetzbar. Hierbei können Blockcopolymere mit EO-PO-Blockeinheiten bzw. PO-EO-Blockeinheiten eingesetzt werden, aber auch EO-PO-EO-Copolymere bzw. PO-EO-PO-Copolymere.
Selbstverständlich sind auch gemischt alkoxylierte nichtionische Tenside einsetzbar, in denen EO-und PO-Einheiten nicht blockweise, sondern statistisch verteilt sind. Solche Produkte sind durch gleichzeitige Einwirkung von Ethylen- und Propylenoxid auf Fettalkohole erhältlich.
Außerdem können als weitere nichtionische Tenside auch Alkylglykoside eingesetzt werden.
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 Fettsaurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester, wie sie beispielsweise in der japanischen Patentanmeldung
Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.
Weitere geeignete Tenside sind Polyhydroxyfettsäureamide; bei den Polyhydroxyfettsäureamiden handelt es sich um Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.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 linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C12-C14 alcohols with 3 EO, 4 EO or 7 EO, C9-C11 alcohol with 7 EO, C13-C15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12 C18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-C14 alcohol with 3 EO and C12-C18 alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution. In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO (propylene oxide) groups together in the molecule can also be used. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
Of course, it is also possible to use mixed alkoxylated nonionic surfactants in which EO and PO units are not distributed in blocks, but randomly. Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.
In addition, alkyl glycosides can also be used as further nonionic surfactants.
Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants Surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fettsaurealkylester, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese Patent Application
Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
Further suitable surfactants are polyhydroxy fatty acid amides; the polyhydroxy fatty acid amides are 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.
Der Gehalt an nichtionischen Tensiden beträgt in den erfindungsgemäßen Formulierungen bevorzugt 5 bis 30 Gew.-%, vorzugsweise 7 bis 20 Gew.-% und insbesondere 9 bis 15 Gew.-%, jeweils bezogen auf die gesamte Formulierung.The content of nonionic surfactants in the formulations according to the invention is preferably 5 to 30% by weight, preferably 7 to 20% by weight and in particular 9 to 15% by weight, based in each case on the entire formulation.
Als anionische Tenside werden beispielsweise solche vom Typ der Sulfonate und Sulfate eingesetzt. Als Tenside vom Sulfonat-Typ kommen dabei vorzugsweise C9-C13-Alkylbenzolsulfonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C12-C18-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Alkansulfonate, die aus C12-C18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. 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.
Weitere geeignete anionische Tenside sind sulfierte Fettsäureglycerinester. Unter Fettsäureglycerinestern sind die Mono-, Di- und Triester sowie deren Gemische zu verstehen, wie sie bei der Herstellung durch Veresterung von einem Monoglycerin 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.
Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettalkohole, beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der C10-C20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlängen bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate 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. Aus waschtechnischem Interesse sind die C12-C16-Alkylsulfate und C12-C18-Alkylsulfate sowie C14-C18-Alkylsulfate bevorzugt. Auch 2,3-Alkylsulfate, welche beispielsweise gemäß den
Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-C20-Alkohole, wie 2-Methyl-verzweigte C9-C11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12-C18-Fettalkohole mit 1 bis 4 EO, sind geeignet. Sie werden in Reinigungsmitteln aufgrund ihres hohen Schaumverhaltens nur in relativ geringen Mengen, beispielsweise in Mengen von 1 bis 5 Gew.-%, eingesetzt.
Weitere geeignete anionische Tenside 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 C8-C18-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet. Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit enger 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. Insbesondere bevorzugte anionische Tenside sind Seifen. Geeignet sind gesättigte und ungesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, (hydrierten) Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, zum Beispiel Kokos-, Palmkern-, Olivenöl- 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 anionic surfactants, for example, those of the sulfonate type and sulfates are used. As surfactants of the sulfonate type are preferably C9-C13-alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those of C12-C18 monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also 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.
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 in the preparation by esterification of a monoglycerol with 1 to 3 mol fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol Glycerol can be obtained. Preferred sulfated fatty acid glycerol esters are 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.
Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C12-C18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C10-C20 oxo alcohols and those half esters secondary Alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C12-C16 alkyl sulfates and C12-C18 alkyl sulfates and C14-C18 alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which, for example, according to the
Also, the sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight or branched C7-C20 alcohols, such as 2-methyl-branched C9-C11 alcohols having an average of 3.5 moles of ethylene oxide (EO) or C12-C18 fatty alcohols with 1 up to 4 EO, are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
Further suitable anionic surfactants are also the salts of alkyl sulfosuccinic acid, which are also known as sulfosuccinates or as
Sulfosuccinic be called and represent the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C8-C18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols. 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. Particularly preferred anionic surfactants are soaps. Suitable are saturated and unsaturated 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, olive oil 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.
Der Gehalt an anionischen Tensiden der erfindungsgemäßen Formulierung beträgt vorzugsweise 2 bis 30 Gew.-%, vorzugsweise 4 bis 25 Gew.-% und insbesondere 5 bis 22 Gew.-% bezogen auf die gesamte Formulierung.The content of anionic surfactants of the formulation according to the invention is preferably 2 to 30 wt .-%, preferably 4 to 25 wt .-% and in particular 5 to 22 wt .-% based on the total formulation.
Als amhpotere Tenside können erfindungsgemäß solche oberflächenaktiven Verbindungen eingesetzt werden, die im Molekül mindestens eine quartäre Ammoniumgruppe und mindestens eine -COO-- oder -SO3 - -Gruppe tragen. Besonders bevorzugte amphotere Tenside sind in diesem Zusammenhang Betain-Tenside wie Alkyl- oder Alkylamidopropylbetaine. Insbesondere sind hier Betaine wie die N-Alkyl-N,N-dimethylammonium-glycinate, z. B. das Kokosalkyl-dimethylammoniumglycinat, N-Acyl-aminopropyl-N,N-dimethylammoniumglycinate, z. B. das Kokosacylaminopropyldimethylammoniumglycinat, das C12-C18-Alkyl-dimethyl-acetobetain, das Kokosamidopropyl-dimethyl-acetobetain, 2-Alkyl-3-carboxymethyl-3-hydroxyethyl-imidazoline und Sulfobetaine mit jeweils 8 bis 18 C-Atomen in der Alkyl-oder Acylgruppe sowie das Kokosacylaminoethylhydroxyethylcarboxymethylglycinat bevorzugt. Ein besonders bevorzugtes zwitterionisches Tensid ist das unter der INCI-Bezeichnung Cocamidopropyl Betaine bekannte N,N-Dimethyl-N-(lauroylamidopropyl)ammoniumacetobetain.
Weitere geeignete amphotere Tenside bildet die Gruppe der Amphoacetate und Amphodiacetate, insbesondere beispielsweise Kokos- oder Laurylamphoacetate oder-diacetate, die Gruppe der Amphopropionate und Amphodipropionate sowie die Gruppe der aminosäurebasierten Tenside wie Acylglutamate, insbesondere Disodium Cocoyl Glutamate und Sodium Cocoyl Glutamate, Acylglycinate, insbesondere Cocoyl Glycinate, und Acylsarcosinate, insbesondere Ammonium Lauroyl Sarcosinate und Sodium Cocoyl Sarcosinate.According to the invention, such surface-active compounds which carry at least one quaternary ammonium group and at least one -COO-- or -SO 3 - group in the molecule can be used as amphoteric surfactants. Particularly preferred amphoteric surfactants in this context are betaine surfactants such as alkyl or alkylamidopropyl betaines. In particular, here are betaines such as the N-alkyl-N, N-dimethylammonium glycinate, z. As the cocoalkyl dimethylammoniumglycinat, N-acyl-aminopropyl-N, N-dimethylammoniumglycinate, z. Cocoacylaminopropyldimethylammonium glycinate, C12-C18-alkyl-dimethyl-acetobetaine, cocoamidopropyl-dimethyl-acetobetaine, 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines and sulfobetaines each having 8 to 18 carbon atoms in the alkyl or acyl group, as well as cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A particularly preferred zwitterionic surfactant is the N, N-dimethyl-N- (lauroylamidopropyl) ammonium acetobetaine known by the INCI name Cocamidopropyl Betaine.
Further suitable amphoteric surfactants are the group of amphoacetates and amphodiacetates, in particular, for example, coconut or laurylamphoacetates or diacetates, the group of amphopropionates and amphodipropionates and the group of amino acid-based surfactants such as acylglutamates, in particular disodium cocoyl glutamates and sodium cocoyl glutamates, acylglycinates, in particular cocoyl Glycinates, and acyl sarcosinates, especially ammonium lauroyl sarcosinates and sodium cocoyl sarcosinates.
Besonders bevorzugte erfindungsgemäße Waschmittelformulierungen sind dadurch gekennzeichnet, dass das Tensid ausgewählt ist aus der Gruppe der Sulfonate und Sulfate, bevorzugt der linearen Alkyl-Benzol-Sulfonate, insbesondere aus der Gruppe der C9 - C13 Alkyl-Benzol-Sulfonate, ganz besonders bevorzugt Natrium-(n-C10-C13)-Alkyl-Benzol-Sulfonat.Particularly preferred detergent formulations according to the invention are characterized in that the surfactant is selected from the group of sulfonates and Sulfates, preferably of the linear alkyl-benzene sulfonates, in particular from the group of C 9 - C 13 alkyl benzene sulfonates, most preferably sodium (nC 10 -C 13 ) alkyl benzene sulfonate.
Zusätzlich zu den Tensiden können die Waschmittelformulierungen weitere Inhaltsstoffe enthalten, die die anwendungstechnischen und/oder ästhetischen Eigenschaften der Waschmittelformulierung weiter verbessern. Im Rahmen der vorliegenden Erfindung enthalten bevorzugte Waschmittelformulierungen zusätzlich einen oder mehrere Stoffe aus der Gruppe der Gerüststoffe, Bleichmittel, Bleichaktivatoren, Enzyme, Parfüme, Parfümträger, Fluoreszenzmittel, Farbstoffe, Schauminhibitoren, Silikonöle, Antiredepositionsmittel, optischen Aufheller, Vergrauungsinhibitoren, Einlaufverhinderer, Knitterschutzmittel, Farbübertragungsinhibitoren, antimikrobiellen Wirkstoffe, Germizide, Fungizide, Antioxidantien, Konservierungsmittel, Korrosionsinhibitoren, Antistatika, Bittermittel, Bügelhilfsmittel, Phobier- und Imprägniermittel, Quell-und Schiebefestmittel, neutrale Füllsalze sowie UV-Absorber.In addition to the surfactants, the detergent formulations may contain other ingredients which further enhance the performance and / or aesthetics of the detergent formulation. In the context of the present invention, preferred detergent formulations additionally contain one or more substances from the group of builders, bleaches, bleach activators, enzymes, perfumes, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing auxiliaries, repellents and impregnating agents, swelling and anti-slip agents, neutral filler salts and UV absorbers.
Beispiele für Gerüststoffe, Builder, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren und Enzymen werden in der
Insbesondere können die Waschmittelformulierungen zwischen 0,001 und 90, besonders bevorzugt 0,01 bis 45 Gew.-% eines oder mehrerer der hier genannten weiteren Inhaltsstoffe enthalten, wobei sich die Gew.-% auf die gesamte Waschmittelformulierung beziehen.In particular, the detergent formulations may contain between 0.001 and 90, more preferably 0.01 to 45 wt .-% of one or more of the other ingredients mentioned herein, wherein the wt .-% refer to the total detergent formulation.
Die erfindungsgemäßen Waschmittelformulierungen lassen sich vorteilhaft zur Beschleunigung von Schaumentstehung und/oder zur Schaumstabilisierung verwenden. Bevorzugt werden die erfindungsgemäßen Waschmittelformulierungen zur Schaumstabilisierung verwendet, wobei diese erfindungsgemäße Verwendung insbesondere in Gegenwart von Schmutz durchgeführt wird.
Im Rahmen der vorgenannten erfindungsgemäßen Verwendung zur Beschleunigung von Schaumentstehung und/oder zur Schaumstabilisierung werden bevorzugt die Waschmittelformulierungen verwendet, die oben als bevorzugte Waschmittelformulierungen genannt sind.The detergent formulations according to the invention can advantageously be used to accelerate foam formation and / or foam stabilization. The detergent formulations according to the invention are preferred for Foam stabilization used, this inventive use is carried out in particular in the presence of dirt.
In the context of the abovementioned use according to the invention for accelerating foam formation and / or for foam stabilization, preference is given to using the detergent formulations which are mentioned above as preferred detergent formulations.
Ebenfalls Gegenstand der vorliegenden Erfindung ist die Verwendung der in den erfindungsgemäßen Waschmittelformulierungen enthaltenen Rhamnolipid-Mischungszusammensetzungen zur Beschleunigung von Schaumentstehung und/oder zur Schaumstabilisierung. Bevorzugt werden die in den erfindungsgemäßen Waschmittelformulierungen enthaltenen Rhamnolipid-Mischungszusammensetzungen zur Schaumstabilisierung verwendet, wobei diese erfindungsgemäße Verwendung insbesondere in Gegenwart von Schmutz durchgeführt wird.
Im Rahmen der vorgenannten erfindungsgemäßen Verwendung zur Beschleunigung von Schaumentstehung und/oder zur Schaumstabilisierung werden bevorzugt die Rhamnolipid-Mischungszusammensetzungen verwendet, die in den oben als bevorzugt genannten Waschmittelformulierungen enthalten sind.Likewise provided by the present invention is the use of the rhamnolipid mixture compositions contained in the detergent formulations according to the invention for accelerating foam formation and / or for foam stabilization. The rhamnolipid mixture compositions contained in the detergent formulations according to the invention are preferably used for foam stabilization, this use according to the invention being carried out in particular in the presence of dirt.
Within the scope of the abovementioned use according to the invention for accelerating foam formation and / or for foam stabilization, preference is given to using the rhamnolipid mixture compositions which are present in the detergent formulations mentioned above as being preferred.
Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung einer erfindungsgemäßen Waschmittelformulierung zur Verhinderung der Vergrauung eines Textils und/oder als Antiredepositionsmittel.
Im Rahmen der vorgenannten erfindungsgemäßen Verwendung zur Verhinderung der Vergrauung eines Textils und/oder als Antiredepositionsmittel werden bevorzugt die Waschmittelformulierungen verwendet, die oben als bevorzugte Waschmittelformulierungen genannt sind.Another object of the present invention is the use of a detergent formulation according to the invention for preventing the graying of a textile and / or as an anti-redeposition agent.
In the context of the abovementioned use according to the invention for preventing the graying of a textile and / or as an anti-redeposition agent, preference is given to using the detergent formulations which are mentioned above as preferred detergent formulations.
Noch ein Gegenstand der vorliegenden Erfindung ist die Verwendung mindestens eines Rhamnolipides zur Verhinderung der Vergrauung eines Textils und/oder als Antiredepositionsmittel, wobei bevorzugt die in den erfindungsgemäßen Waschmittelformulierungen enthaltenen Rhamnolipid-Mischungszusammensetzungen verwendet werden. Besonders bevorzugt werden im Rahmen der vorgenannten erfindungsgemäßen Verwendung zur Verhinderung der Vergrauung eines Textils und/oder als Antiredepositionsmittel bevorzugt die Rhamnolipid-Mischungszusammensetzungen verwendet, die in den oben als bevorzugt genannten Waschmittelformulierungen enthalten sindA further subject matter of the present invention is the use of at least one rhamnolipid for preventing the graying of a textile and / or as an anti-redeposition agent, preference being given to using the rhamnolipid mixture compositions contained in the detergent formulations according to the invention. In the context of the abovementioned use according to the invention for preventing the graying of a textile and / or as antiredeposition agent, the rhamnolipid mixture compositions which are contained in the detergent formulations mentioned above as being preferred are particularly preferably used
In den nachfolgend aufgeführten Beispielen wird die vorliegende Erfindung beispielhaft beschrieben, ohne dass die Erfindung, deren Anwendungsbreite sich aus der gesamten Beschreibung und den Ansprüchen ergibt, auf die in den Beispielen genannten Ausführungsformen beschränkt sein soll.In the examples given below, the present invention is described by way of example, without the invention, the scope of application of which is apparent from the entire description and the claims, to be limited to the embodiments mentioned in the examples.
Um Rhamnolipide mit rhIABC aus P. aeruginosa PAO1 in einem P. putida-Stamm herzustellen, in dem die Expression des für die Rhamnosyltransferase RHIC kodierenden Gens vielfach stärker erfolgt, als die des für die Rhamnosyltransferase RhIB kodierenden Gens rhIB, wird das Plasmid pBBR1 MCS2-Plac-rhIABC-T-Ptac-rhIC-T (Seq ID Nr. 1) konstruiert. Dazu wurden folgende DNA-Fragmente synthetisiert: P. aeruginosa PAO1-Gene rhIA, rhIB und rhIC, gefolgt von einem Terminator, gefolgt vom synthetischen tac-Promoter, gefolgt vom P. aeruginosa PAO1-Gene rhIC und einem Terminator, flankiert von einer HindIII- (5'-Ende) bzw. Bsu36I-Schnittstelle (3'-Ende) (Seq ID Nr. 2).
Die vom DNA-Synthese-Provider gelieferten Vektoren, die das synthetisierte DNA Fragment enthalten, werden mit HindIII und Bsu36I geschnitten und in den ebenfalls mit HindIII und Bsu36I geschnittenen Vektor pBBR1 MCS-2 (Seq ID 3) mittels Fast Link Ligation Kit (Epicentre Technologies; Madison, WI, USA) ligiert. Der erhaltene Zielvektor pBBR1 MCS2-Plac-rhIABC-T-Ptac-rhIC-T (pBBR1 MCS-2 mit synthetisiertem Fragment Seq ID Nr. 2) hat eine Größe von 9336 Basenpaaren.
Die Transformation von Pseudomonas putida KT2440 mit dem Vektor pBBR1 MCS2-Plac-rhIABC-T-Ptac-rhIC-T (Seq ID Nr. 1) erfolgt wie vorbeschrieben (
The vectors supplied by the DNA synthesis provider, containing the synthesized DNA fragment, are cut with Hind III and Bsu 36I and into the also with Hind III and Bsu 36I cut vector pBBR1 MCS-2 (Seq ID 3) by means of fast link ligation Kit (Epicenter Technologies, Madison, WI, USA). The obtained target vector pBBR1 MCS2-Plac-rhIABC-T-Ptac-rhIC-T (pBBR1 MCS-2 with synthesized fragment Seq ID No. 2) has a size of 9336 base pairs.
The transformation of Pseudomonas putida KT2440 with the vector pBBR1 MCS2-Plac-rhIABC-T-Ptac-rhIC-T (Seq ID No. 1) is carried out as described above (
Der rekombinante Stamm P. putida KT2440 pBBR1 MCS2-Plac-rhIABC-T-Ptac-rhIC-T wird auf LB-Agar-Kanamycin (50 pg/ml)-Platten kultiviert.
Zur Produktion der Rhamnolipide wird das im Folgenden als M9-Medium bezeichnete Medium verwendet. Dieses Medium besteht aus 2 % (w/v) Glukose, 0,3 % (w/v) KH2PO4, 0,679 % Na2HPO4, 0,05 % (w/v) NaCl, 0,2 % (w/v) NH4Cl, 0,049 % (w/v) MgSO4 x 7 H2O und 0,1 % (v/v) einer Spurenelementlösung. Diese besteht aus 1,78 % (w/v) FeSO4 x 7 H2O, 0,191 % (w/v) MnCl2 x 7 H2O, 3,65 % (w/v) HCl, 0,187 % (w/v) ZnSO4 x 7 H2O, 0,084 % (v/v) Na-EDTA x 2 H2O, 0,03 % (v/v) H3BO3, 0,025 % (w/v) Na2MoO4 x 2 H2O und 0,47 % (w/v) CaCl2 x 2 H2O. Der pH-Wert des Mediums wird mit NH4OH auf 7,4 eingestellt und das Medium folgend mittels Autoklav (121 °C, 20 min) sterilisiert. Ein Einstellen des pH-Wertes während der Kultivierung ist nicht nötig.Recombinant strain P. putida KT2440 pBBR1 MCS2-Plac-rhIABC-T-Ptac-rhIC-T is cultured on LB agar kanamycin (50 pg / ml) plates.
For the production of rhamnolipids, the medium referred to below as M9 medium is used. This medium consists of 2% (w / v) glucose, 0.3% (w / v) KH 2 PO 4 , 0.679% Na 2 HPO 4 , 0.05% (w / v) NaCl, 0.2% ( w / v) NH 4 Cl, 0.049% (w / v) MgSO 4 x 7 H 2 O and 0.1% (v / v) of a trace element solution. This consists of 1.78% (w / v) FeSO 4 .7H 2 O, 0.191% (w / v) MnCl 2 .7H 2 O, 3.65% (w / v) HCl, 0.187% (w / v) / v) ZnSO 4 .7H 2 O, 0.084% (v / v) Na-EDTA x 2H 2 O, 0.03% (v / v) H 3 BO 3 , 0.025% (w / v) Na 2 MoO 4 × 2 H 2 O and 0.47% (w / v) CaCl 2 × 2 H 2 O. The pH of the medium is adjusted to 7.4 with NH 4 OH and the medium is subsequently autoclave (121 ° C, 20 min). It is not necessary to adjust the pH during the cultivation.
Zur Untersuchung der Rhamnolipidproduktion im Schüttelkolben wird zunächst eine Vorkultur angesetzt. Hierzu wird eine Kolonie eines frisch auf LB-Agar-Platte ausgestrichenen Stammes verwendet und 10 ml LB-Medium in einem 100 ml Erlenmeyerkolben beimpft. Alle rekombinanten P. putida-Stämme werden im LB-Medium, dem 50 µg/ml Kanamycin zugesetzt wird, kultiviert. Die Kultivierung der P. putida-Stämme erfolgt bei 30 °C und 200 rpm über Nacht.
Die Vorkulturen werden verwendet, um 50 ml M9-Medium (+ 50 µg/ml Kanamycin) im 250 ml Erlenmeyerkolben zu beimpfen (Start-OD600 0,1). Die Kulturen werden bei 200 rpm und 30 °C kultiviert. Nach 24 h wird eine Probe von 1 ml Kulturbrühe dem Kulturkolben entnommen.To study the production of rhamnolipids in a shake flask, a preculture is first prepared. For this purpose, a colony of a strain freshly streaked out on an LB agar plate is used and 10 ml of LB medium are inoculated in a 100 ml Erlenmeyer flask. All recombinant P. putida strains are cultured in LB medium to which 50 μg / ml kanamycin is added. The cultivation of the P. putida strains are carried out at 30 ° C and 200 rpm overnight.
The precultures are used to inoculate 50 ml of M9 medium (+ 50 μg / ml kanamycin) in the 250 ml Erlenmeyer flask (start OD 600 0.1). The cultures are cultured at 200 rpm and 30 ° C. After 24 h, a sample of 1 ml of culture broth is removed from the culture flask.
Für die Hauptkultur kommt ebenfalls ein Mineralmedium (M9) zum Einsatz. Die Fermentation nach Animpfen mit 10 vol. % Vorkultur und Verbrauch der vorgelegten Glucose erfolgt kohlenstofflimitiert über eine Glukosezufütterung in einem 2 Liter Fermenter mit einem Arbeitsvolumen von 1,2 L . Die Glukosezufütterung erfolgt anhand des Gelöstsauerstoffsignals. Der Gelöstsauerstoff wird bei 20 % Sättigung über die Rührerdrehzahl reguliert. Der pH Wert wird über eine pH Elektrode und Zugabe von NH4SO4 auf 7 reguliert. Die Fermentation wird über 4 Tage bis zu einer Biotrockenmasse von 15 g/l geführt. Die Rhamnolipidkonzentration wird über HPLC ermittelt und beträgt 9,8 g/l. Nach Abtrennen der Zellen mittels Zentrifugation bei 10.000 g wird die Fermentationsbrühe durch Zugabe konzentrierter HCl auf einen pH-Wert von 4,0 eingestellt. Anschließend wird mit gleichem Volumen Ethylacetat extrahiert. Die rhamnolipidhaltige organische Phase wird abgetrennt und weiter verarbeitet. Durch Zugabe von 50 Gew %iger KOH (aq) wird der pH-Wert der Lösung auf pH 7 eingestellt. Hierbei kommt es zur Bildung zweier flüssiger Phasen. Die untere Phase enthält die von lipophilen und hydrophilen Verunreinigungen befreiten Rhamnolipide in hoher Reinheit. Die Zusammensetzung der Rhamnolipid-Mischung wird hierdurch nicht beeinflusst. Die untere Phase wird abgenommen und das Lösungsmittel am Rotationsverdampfer weitestgehend entfernt. Dann wird erneut Wasser zugegeben und die wässrige Rhamnolipid Lösung gefriergetrocknet. Das erhaltene Pulver wird mittels HPLC analysiert und anwendungstechnisch charakterisiert.For the main culture also a mineral medium (M9) is used. The fermentation after inoculation with 10 vol. % Pre-culture and consumption of the glucose is carbon-limited by means of a glucose feed in a 2 liter fermenter with a working volume of 1.2 l. The glucose feed is based on the dissolved oxygen signal. The dissolved oxygen is regulated at 20% saturation above the stirrer speed. The pH is adjusted to 7 via a pH electrode and addition of NH 4 SO 4 . The fermentation is carried out over 4 days to a dry biomass of 15 g / l. The rhamnolipid concentration is determined by HPLC and is 9.8 g / l. After separating the cells by centrifugation at 10,000 g, the fermentation broth is adjusted to a pH of 4.0 by adding concentrated HCl. The mixture is then extracted with the same volume of ethyl acetate. The rhamnolipidhaltige organic phase is separated and on processed. By adding 50% strength by weight KOH (aq), the pH of the solution is adjusted to pH 7. This leads to the formation of two liquid phases. The lower phase contains the liberated from lipophilic and hydrophilic impurities rhamnolipids in high purity. The composition of the rhamnolipid mixture is not affected by this. The lower phase is removed and the solvent removed as far as possible on a rotary evaporator. Then water is added again and the aqueous rhamnolipid solution is freeze-dried. The resulting powder is analyzed by means of HPLC and characterized by application technology.
Die Probenvorbereitung für die nachfolgenden chromatographischen Analysen erfolgt folgendermaßen Mit einer Verdrängerpipette (Combitip) wird in einem 2 ml-Reaktionsgefäß 1 ml Aceton vorgelegt und das Reaktionsgefäß zur Minimierung von Verdunstung unmittelbar verschlossen. Es folgt die Zugabe von 1 ml Kulturbrühe. Nach Vortexen des Kulturbrühe/Acetongemisches wird dieses für 3 min bei 13.000 rpm abzentrifugiert, und 800 µl des Überstands in ein HPLC-Gefäß überführt.
Zum Nachweis und zur Quantifizierung von Rhamnolipiden wird ein Evaporative Light Scattering Detektor (Sedex LT-ELSD Model 85LT) benutzt. Die eigentliche Messung wird mittels Agilent Technologies 1200 Series (Santa Clara, Kalifornien) und der Zorbax SB-C8 Rapid Resolution Säule (4,6 x 150 mm, 3,5 µm, Agilent) durchgeführt. Das Injektionsvolumen beträgt 5 µl und die Laufzeit der Methode 20 min. Als mobile Phase wird wässrige 0,1 % TFA (Trifluor-Essigsäure, Lösung A) und Methanol (Lösung B) verwendet. Die Säulentemperatur beträgt 40 °C. Als Detektoren dienen der ELSD (Detektortemperatur 60 °C) und der DAD (Diodenarray, 210 nm). Der in der Methode verwendete Gradient ist:
An Evaporative Light Scattering Detector (Sedex LT-ELSD Model 85LT) is used to detect and quantify rhamnolipids. The actual measurement is performed using Agilent Technologies 1200 Series (Santa Clara, California) and the Zorbax SB-C8 Rapid Resolution column (4.6 x 150 mm, 3.5 μm, Agilent). The injection volume is 5 μl and the runtime of the method is 20 min. The mobile phase used is aqueous 0.1% TFA (trifluoroacetic acid, solution A) and methanol (solution B). The column temperature is 40 ° C. The detectors used are the ELSD (detector temperature 60 ° C) and the DAD (diode array, 210 nm). The gradient used in the method is:
Die mit oben beschriebenem Verfahren erhaltene Rhamnolipidzusammensetzung aus P. putida KT2440 pBBR1 MCS2-Plac-rhIABC-T-Ptac-rhIC-T enthält:
Das Rührwerk mit einer Halterung für 4 verschließbare Zylinder mit einem Volumen von 300 ml wird im Winkel von 90° platziert. Die 300 ml Messzylinder mit Verschluss sind so angeordnet, dass die Drehung der Zylinder horizontal erfolgt. Vor der eigentlichen Messung werden die Messzylinder mit der Tensidlösung benetzt. Diese Lösung wird anschließend verworfen.
In jeden Messzylinder werden möglichst schaumfrei je 60 ml zu prüfende Tensidlösung eingefüllt. Die verschlossenen Messzylinder werden in den entsprechenden Halterungen befestigt und das Mischgerät mit 20 U/min gestartet. Zeitgleich wird eine Stoppuhr betätigt. Um die Schaumhöhen in Abhängigkeit der Zeit zu messen wird nach entsprechenden Zeitabständen das Mischwerk angehalten, 30 Sekunden gewartet, und die Schaumhöhe notiert.
Soll das Schaumverhalten unter Schmutzbelastung beobachtet werden, so erfolgt die Schmutzzugabe zu definierten Zeitpunkten.The stirrer with a holder for 4 closable cylinders with a volume of 300 ml is placed at an angle of 90 °. The 300 ml measuring cylinder with closure are arranged so that the rotation of the cylinder is horizontal. Before the actual measurement, the measuring cylinders are wetted with the surfactant solution. This solution is then discarded.
60 ml of surfactant solution to be tested are filled into each measuring cylinder as foam-free as possible. The sealed graduated cylinders are mounted in the appropriate holders and the mixer started at 20 rpm. At the same time a stopwatch is pressed. In order to measure the foam heights as a function of time, the mixer is stopped after appropriate time intervals, waited 30 seconds, and noted the foam height.
If the foaming behavior is to be observed under dirt load, the dirt is added at defined times.
Die Konzentration des Tensids beträgt in allen Fällen 0,4 g Aktivsubstanz pro Liter Lösung.
Die Lösung wurde jeweils 2 min ohne Zugabe von Schmutz im Zylinder geschüttelt. Anschließend erfolgte die Zugabe der ersten Portion Schmutz, dann wurde weitere 10 min geschüttelt. Nach dem Ablesen der Schaumhöhe erfolgte die zweite Zugabe einer definierten Schmutzmenge und es wurden nochmals 10 min geschüttelt. Nach dem Ablesen der Schaumhöhe erfolgte die dritte Zugabe einer definierten Schmutzmenge und es wurde nochmals 10 min geschüttelt und die Schaumhöhe gemessen.The concentration of the surfactant is in all cases 0.4 g of active substance per liter of solution.
The solution was shaken for 2 minutes without addition of dirt in the cylinder. Then the first portion of dirt was added, then shaken for a further 10 min. After reading the foam height, the second addition of a defined amount of dirt took place and it was shaken again for 10 minutes. After reading the foam height, the third addition of a defined amount of dirt took place and it was shaken again for 10 minutes and the foam height was measured.
Die gemessenen Schaumhöhen stellen Mittelwerte aus 4 Einzelmessungen dar.The measured foam heights represent mean values of 4 individual measurements.
Als Schmutz wurde Standardschmutzgewebe SBL 2004 der Firma wfk Testgewebe GmbH aus Krefeld benutzt. Die Schmutzbeladung des Gewebes beträgt 8g Schmutz pro Gewebestück (zertifiziert von der Firma wfk Testgewebe GmbH aus Krefeld). SBL 2004 ist ein weit verbreiteter Industrieschmutzstanddard, um die Waschleitung von Waschmitteln in Gegenwart von Schmutz zu untersuchen.
Die typische Zusammensetzung des Standardschmutze ist nach Angaben der Firma wfk Testgewebe GmbH wie folgt:
- 18,4 % Olivenöl (Olio Extra Vergine di Oliva)
- 18,4 % Synthetisches Sebum nach Bey
- 9,4 % Kaolin
- 9,2 % Protein (aus Eiweißpulver)
- 8,0 % Bleach consuming agent
- 6,9 % Stärke
- 6,9 % Salz
- 6,9 % Mineralöl
- 6,9 % Lanolin
- 2,8 % Emulgator (Uniperol ® Dispergiermittel Handelsname der, BASF SE)
- 2,3 % Harnstoff (synthetic)
- 2,0 % Quartz
- 1,8 % Calciumchlorid
- 0,075 % Ruß
- 0,025 % Eisenoxid
The typical composition of the Standardschmutze is according to the company wfk Testgewebe GmbH as follows:
- 18.4% olive oil (Olio Extra Vergine di Oliva)
- 18.4% Synthetic Sebum after Bey
- 9.4% kaolin
- 9.2% protein (from protein powder)
- 8.0% Bleach consuming agent
- 6.9% strength
- 6.9% salt
- 6.9% mineral oil
- 6.9% lanolin
- 2.8% emulsifier (Uniperol® dispersant trade name of, BASF SE)
- 2.3% urea (synthetic)
- 2.0% quartz
- 1.8% calcium chloride
- 0.075% carbon black
- 0.025% iron oxide
- Wasserhärte: Gemessen in Grad deutscher Härte °dH, Verhältnis von Ca und Mg = 2:1 molarMWater hardness: Measured in degrees German hardness ° dH, ratio of Ca and Mg = 2: 1 molarM
- Wasser 5° dH,Water 5 ° dH,
- 0,4 g/L Aktivkonzentration an Tensid.0.4 g / L active concentration of surfactant.
LAS = MARLON ARL© der Firma Sasol, Natrium-(n-C10-C13)-alkylbenzolsulphonat mit einem Aktivgehalt von 80 Gew.-%, ist ein bekanntes, stark schäumendes Anionentensid, welches breite Verwendung in Waschmittelformulierungen findet.
Jeneil: Kommerzielle Probe mit einem hohen mono-Rhamnolipid-AnteilLAS = MARLON ARL © Sasol, sodium (nC 10 -C 13) -alkylbenzolsulphonat with an active content of 80 wt .-%, is a known, high foaming anion surfactant, which finds wide use in detergent formulations.
Jenil: Commercial sample with a high mono-rhamnolipid content
Die Zusammensetzung des Beispiels 1 zeigt ein etwas langsameres Anschäumverhalten, erreicht aber nach 10 min ein ähnlich gutes Niveau, wie das Aniontensid LAS. Jeneil mit seinem hohen monoRL Anteil und geringem diRL Anteil zeigt ein langsameres Anschäumverhalten als Beispiel 1, welches einen geringen monoRL Anteil und einen hohen diRL Anteil aufweist, und erreicht am Ende auch nur ein deutlich kleineres Schaumniveau als LAS oder das Beispiel 1.The composition of Example 1 shows a somewhat slower foaming behavior, but reaches a similar level after 10 minutes as the anionic surfactant LAS. Each with its high monoRL content and low diRL content exhibits a slower foaming behavior than Example 1, which has a low monoRL content and a high diRL content, and finally only achieves a significantly lower foam level than LAS or Example 1.
Bei dreimaliger Zugabe (vgl. Beispiel 2) von je 76 mg Schmutz in einen Zylinder zeigt die Zusammensetzung des Beispiels 1 im Vergleich zu LAS nach 15 min eine etwas höhere Schaumbildung als LAS. Nach der dritten Schmutzzugabe (nach 20 min) ist die Schaumhöhe immer noch stabil und deutlich höher als bei LAS. Die kommerzielle Probe von Jeneil zeigt bereits ohne Schmutzzugabe eine verringertes Anschäumverhalten als LAS oder die Zusammensetzung des Beispiels 1 (= Schaumhöhe bei 2 min)
Schmutzbelastung: 3 x 76 mg bei 0,4 g/L Aktivsubstanz Tensid. Es wurden Mischungen von LAS und Zusammensetzung des Beispiels 1 in den angegebenen Gewichtsverhältnissen eingesetzt.
Ohne Schmutzzugabe im Anschäumverhalten, d. h. im Aufbau von Schaum, zeigen Mischungen von LAS und der Zusammensetzung des Beispiels 1 eine deutlich höheres Schaumvolumen als die jeweilige Komponente alleine. Nach der ersten Schmutzzugabe (bei t = 2 min) zeigen die Mischungen von LAS und der Zusammensetzung des Beispiels 1 im Verhältnis 50:50 (w/w) und 25:75 (w/w) ein deutlich höheres Schaumvolumen und eine verstärkt Schaumstabilität als die jeweilige Komponente alleine.
Es konnte damit gezeigt werden, dass Mischungen von LAS und Rhamnolipiden sich im Schaumverhalten positiv synergistisch verhalten.Without dirt added in the foaming behavior, ie in the structure of foam, mixtures of LAS and the composition of Example 1 show a significantly higher foam volume than the respective component alone. After the first addition of dirt (at t = 2 min), the mixtures of LAS and the composition of Example 1 in a ratio of 50:50 (w / w) and 25:75 (w / w) show a significantly higher foam volume and increased foam stability than the respective component alone.
It could thus be shown that mixtures of LAS and rhamnolipids behave positively synergistically in the foaming behavior.
Die Wirksamkeit der Fleckentfernung wird in einem Liniwaschgerät (Prinzip: geschlossene Metallgefäße, die in einem temperierten Wasserbad um eine horizontale Achse bewegt werden) an verschiedenen, künstlich angeschmutzten Testgeweben ermittelt.
EMPA = Eidgenössische Materialprüfanstalt
EMPA = Federal Material Testing Institute
Mit einem Spektralphotometer der Marke Datacolor Elrepho SF450 mit Auswertesoftware ColorTools wird die Reflexion der Testgewebe vor und nach dem Waschen gemessen. Dabei werden unter Zuhilfenahme der CIE-Lab Farbraumklassifikation die Helligkeit L*, der Wert a* auf der rot - grün Farbachse und der Wert b* auf der gelb- blau Farbachse vor und nach dem Waschen gemessen. Die Änderung des Farbwertes (ΔE-Wert) ist dabei ein Maß für den erzielten Reinigungseffekt.
Der ΔE-Wert ist definiert als und wird errechnet, wobei die Errechnung automatisch über die Auswertesoftware ColorTools erfolgt, über folgende Formel 
The ΔE value is defined as and is calculated, the calculation being carried out automatically using the ColorTools evaluation software, using the following formula
d.h. je besser die Schmutzentfernung ist, desto größer wird der ΔE-Wert.
Für die Effizienz der Fleckentfernung kann folgende Einteilung verwendet werden:
For stain removal efficiency, the following division can be used:
Die Bedingungen der Waschversuche waren wie folgt:
Um gesicherte Messergebnisse zu erhalten, werden die Waschgänge mit jeder Waschmittelformulierung an jeder Anschmutzung 3x durchgeführt. D.h. es werden pro Waschmittelformulierung 9 Testgewebe jeder Schmutz-Sorte gewaschen.
Die Waschmittelformulierungen wurden mit Natronlauge auf pH 8.2 eingestellt.
Als Vergleich wurde ein käufliches Persil© Universal Gel der Firma Henkel verwendet. Persil Universal Gel wurde nach Dosierungsempfehlung 40 ml/ 10L eingesetzt. Bei der Waschmittelformulierung A betrug die Gesamttensidkonzentration in der Waschflotte 0,5 g/L.
As a comparison, a commercially available Persil © Universal Gel from Henkel was used. Persil Universal Gel was used according to the recommended dose of 40 ml / 10L. In the detergent formulation A, the total surfactant concentration in the wash liquor was 0.5 g / L.
Eine Waschmittelformulierung enthaltend als wirksames Tensid ausschließlich eine Zusammensetzung des Beispiels 1 ist in Bezug auf die Fleckentfernung von Soja, Curry, Ruß und Hautfett genau so effektiv wie ein kommerzielles Flüssigwaschmittel auf der Basis eines optimierten Tensid-Verhältnisses von LAS, weiteren Anionentensiden und nichtionischen Tensiden.A detergent formulation containing as the effective surfactant excluding a composition of Example 1 is as effective in stain removal of soy, curry, carbon black and skin fat as a commercial liquid detergent based on an optimized surfactant ratio of LAS, other anionic surfactants and nonionic surfactants.
Ein weiterer wichtiger Aspekt bei der Reinigung von Textilien ist, dass einmal in der Waschflotte dispergierter, gelöster oder emulgierter Schmutz sich nicht wieder auf sauberes Gewebe ablagert. Dieser unerwünschte Ablagerungseffekt ist als Vergrauung bekannt.
Um diesen Effekt messen zu können, wurde bei allen Waschversuchen ein sauberer weißer Baumwolllappen mitgewaschen (s.o.) und anschließend ebenfalls der ΔE-Wert von diesem gemessen. In diesem Fall liefert der reziproke ΔE-Wert ein Maß für die Vergrauung; je niedriger der reziproke ΔE-Wert desto geringer die Vergrauung.
In order to be able to measure this effect, a clean white cotton cloth was washed in all washing tests (see above) and subsequently also the ΔE value of this was measured. In this case, the reciprocal ΔE value provides a measure of graying; the lower the reciprocal ΔE value, the lower the graying.
Es ist deutlich zu sehen, dass Rhamnolipide der spezifischen Zusammensetzung des Beispiels 1 einen geringeren Vergrauungseffekt zeigen bei Curry, Ruß, Milch/Kakao als das kommerzielle, auf LAS-Basis aufgebaute Flüssigwaschmittel und somit als Antiredepositionsmittel wirken.It can clearly be seen that rhamnolipids of the specific composition of Example 1 show a less graying effect on curry, soot, milk / cocoa than the commercial LAS-based liquid detergent and thus act as anti-redeposition agents.
Claims (14)
wobei sich die Gewichtsprozente auf die Summe aller enthaltenen Rhamnolipide beziehen,Detergent formulation according to claim 1, characterized in that the rhamnolipid mixture composition
wherein the percentages by weight refer to the sum of all contained rhamnolipids,
wobei sich die Gewichtsprozente auf die Summe aller enthaltenen Rhamnolipide beziehen.Detergent formulation according to claim 2, characterized in that the rhamnolipid mixture composition
wherein the percentages by weight refer to the sum of all contained rhamnolipids.
wobei sich die Gewichtsprozente auf die Summe aller enthaltenen Rhamnolipide beziehen.Detergent formulation according to claim 2 or 3, characterized in that the rhamnolipid mixture composition
wherein the percentages by weight refer to the sum of all contained rhamnolipids.
wobei sich die Gewichtsprozente auf die Summe aller enthaltenen Rhamnolipide beziehen.Detergent formulation according to at least one of claims 2 to 4, characterized in that the rhamnolipid mixture composition
wherein the percentages by weight refer to the sum of all contained rhamnolipids.
wobei sich die Gewichtsprozente auf die Summe aller enthaltenen Rhamnolipide beziehen.Detergent formulation according to at least one of claims 2 to 5, characterized in that the rhamnolipid mixture composition
wherein the percentages by weight refer to the sum of all contained rhamnolipids.
wobei sich die Gewichtsprozente auf die Summe aller enthaltenen Rhamnolipide beziehen.Detergent formulation according to at least one of claims 2 to 6, characterized in that the rhamnolipid mixture composition
wherein the percentages by weight refer to the sum of all contained rhamnolipids.
Applications Claiming Priority (1)
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|---|---|---|---|
| DE102013205755.5A DE102013205755A1 (en) | 2013-04-02 | 2013-04-02 | Detergent formulation for textiles containing rhamnolipids with a predominant content of di-rhamnolipids |
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| EP (1) | EP2787065B1 (en) |
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| CN (1) | CN104099190B (en) |
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| WO2024002738A1 (en) | 2022-06-28 | 2024-01-04 | Evonik Operations Gmbh | Composition comprising biosurfactant and persicomycin |
| EP4155371A1 (en) | 2022-08-29 | 2023-03-29 | Evonik Operations GmbH | Composition rich in mono-rhamnolipids |
| WO2024068270A1 (en) | 2022-09-26 | 2024-04-04 | Evonik Operations Gmbh | Compositions comprising sophorolipids and lactic acid |
| EP4353806A1 (en) | 2022-10-14 | 2024-04-17 | Henkel AG & Co. KGaA | Surfactant mixtures |
| DE102022210879A1 (en) | 2022-10-14 | 2024-04-25 | Henkel Ag & Co. Kgaa | Surfactant mixtures |
Also Published As
| Publication number | Publication date |
|---|---|
| BR102014007949B1 (en) | 2022-03-03 |
| CA2847909C (en) | 2021-03-02 |
| DE102013205755A1 (en) | 2014-10-02 |
| CA2847909A1 (en) | 2014-10-02 |
| BR102014007949A2 (en) | 2015-12-08 |
| EP2787065B1 (en) | 2017-07-19 |
| CN104099190B (en) | 2018-09-25 |
| US20140296125A1 (en) | 2014-10-02 |
| CN104099190A (en) | 2014-10-15 |
| JP2014201745A (en) | 2014-10-27 |
| US9243212B2 (en) | 2016-01-26 |
| BR102014007949A8 (en) | 2021-08-31 |
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