EP0490040A2 - Liquid detergent - Google Patents
Liquid detergent Download PDFInfo
- Publication number
- EP0490040A2 EP0490040A2 EP91117180A EP91117180A EP0490040A2 EP 0490040 A2 EP0490040 A2 EP 0490040A2 EP 91117180 A EP91117180 A EP 91117180A EP 91117180 A EP91117180 A EP 91117180A EP 0490040 A2 EP0490040 A2 EP 0490040A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- liquid detergent
- fatty alcohol
- carbon atoms
- mixtures
- detergent according
- 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
- 239000003599 detergent Substances 0.000 title claims abstract description 28
- 239000007788 liquid Substances 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 25
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 14
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 10
- 239000000344 soap Substances 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- -1 alkylbenzene sulfonate Chemical class 0.000 claims description 11
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 239000007844 bleaching agent Substances 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 102000004190 Enzymes Human genes 0.000 claims description 3
- 108090000790 Enzymes Proteins 0.000 claims description 3
- 150000002402 hexoses Chemical class 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 150000002972 pentoses Chemical group 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 239000002304 perfume Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 231100000584 environmental toxicity Toxicity 0.000 abstract description 2
- 150000001298 alcohols Chemical class 0.000 description 8
- 239000004744 fabric Substances 0.000 description 7
- 238000005858 glycosidation reaction Methods 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000008121 dextrose Substances 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- 229920002774 Maltodextrin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004435 Oxo alcohol Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 210000004400 mucous membrane Anatomy 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 241000238578 Daphnia Species 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241000985284 Leuciscus idus Species 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- VJHCJDRQFCCTHL-UHFFFAOYSA-N acetic acid 2,3,4,5,6-pentahydroxyhexanal Chemical compound CC(O)=O.OCC(O)C(O)C(O)C(O)C=O VJHCJDRQFCCTHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 231100000460 acute oral toxicity Toxicity 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000002243 furanoses Chemical group 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003215 pyranoses Chemical class 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
-
- 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
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- 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
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- the present invention relates to liquid preparations for washing textiles.
- Liquid detergents today mainly consist of anionic surfactants, especially alkylbenzenesulfonate, fatty alcohol oxyethylate and soap. These surfactants, which are common in detergent formulations, are mainly based on petrochemicals. In view of the future raw material situation (oil shortage), this petrochemical basis is a considerable disadvantage. Another disadvantage is that the biodegradability and ecotoxicity of these surfactants often do not reach the corresponding level of surfactants on a native basis.
- the object of the invention was therefore to find a surfactant mixture for liquid detergents which contains a high proportion of surfactants which are obtained from renewable raw materials; In addition to excellent washing results, high biodegradability was required.
- This object was achieved by a mixture which, in addition to fatty alcohol oxyethylate and soap and small amounts of anionic surfactant, contains 3 to 30% alkyl polyglycoside.
- EP-0 075 994, EP-0 075 995 and EP-0 075 996 claim surfactant mixtures which, in addition to APG, contain anionic and nonionic surfactants, although the degree of glycosidation of the APG is ⁇ 1.5.
- DE-37 02 286 claims alkyl polyglycosides in addition to anionic and nonionic surfactants as detergents with the restrictions that the anionic content should be ⁇ 50% of that of the oxyethylate.
- EP-0 199 765 describes alkylpolyglycoside mixtures with anionic and nonionic surfactants, the content of nonionic surfactants should be ⁇ 10% and the degree of glycosidation of the alkylpolyglycoside ⁇ 1.4.
- the formulation according to the invention delivers excellent washing results with an extremely low anionic surfactant content.
- the alkyl polyglycosides used according to the invention can be produced by known processes based on renewable raw materials.
- dextrose is reacted with n-butanol to give butylpolyglycoside mixtures in the presence of an acidic catalyst, which are transglycosidated with long-chain alcohols in the presence of an acidic catalyst to give the desired alkylpolyglycoside mixtures.
- dextrose is immediately reacted with the desired long-chain alcohol.
- the structure of the products can be varied within certain limits.
- the alkyl radical R is determined by the choice of the long-chain alcohol.
- the industrially accessible alcohols with 8 to 18 carbon atoms, in particular native alcohols from the hydrogenation of carboxylic acids or carboxylic acid derivatives.
- Ziegler alcohols or oxo alcohols can also be used.
- the polyglycosyl radicals Z n are determined, on the one hand, by the selection of the carbohydrate and, on the other hand, by setting the average degree of polymerization n z. B. according to DE-OS 19 43 689.
- polysaccharides e.g. B. starch, maltodextrins, dextrose, galactose, mannose, xylose, etc.
- the industrially available carbohydrates starch, maltodextrins and especially dextrose are preferred.
- alkyl polyglycosides are always mixtures of oligomers, which in turn represent mixtures of different isomeric forms. They exist side by side with ⁇ - and ⁇ -glycosidic bonds in pyranose and furanose form. The junctions between two Saccachrid residues are also different.
- Alkyl polyglycosides used according to the invention can also be prepared by mixing alkyl polyglycosides with alkyl monoglycosides.
- the latter can e.g. B. according to EP-A 0 092 355 using polar solvents, such as acetone, from alkyl polyglycosides.
- the degree of glycosidation is advantageously determined by means of 1 H-NMR.
- the detergents according to the invention contain 3 to 30% alkyl polyglycoside, preferably 5-20%.
- the alkyl polyglycosides are considered to be extremely environmentally compatible.
- the degree of biodegradation for the alkyl polyglycosides according to the invention determined by means of a sewage treatment plant simulation model / DOC analysis, is 96 ⁇ 3%. This figure can be seen against the background that with this test method (total degradation) a degree of degradation ⁇ 70% already indicates the substance to be readily degradable.
- the acute oral toxicity LD 50 (rat) with> 10,000 mg / kg as well as the aquatic toxicity LC 50 (gold orfe) with approx. 12 mg / l and EC 50 (daphnia) with 30 mg / l are by a factor of 3 to 5 cheaper than the corresponding values of today's most important surfactants. The same applies to skin and mucous membrane compatibility.
- Anionic surfactants used are alkylbenzene sulfate, alkane sulfonates, olefin sulfonates, fatty alcohol sulfates and fatty alcohol ether sulfates having 9 to 18 carbon atoms in the alkyl or alkylene group.
- Na, K, NH4, Mg and mixtures are the counterions.
- These anionic surfactants, which can be present in the mixtures according to the invention in amounts of 0 to 7% by weight, are not to be understood as soap. Quantities of 0 to 5% by weight are preferred.
- the fatty alcohol oxyethylates used according to the invention correspond to compounds of the formula II R '' - O- (CH2-CH2-O) x H II, in which R ′′ is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22, preferably 10 to 20 carbon atoms and x 2 to 20, preferably 3 to 15.
- the compounds are generally prepared by addition of ethylene oxide onto longer-chain alcohols in the presence of basic or acidic catalysts.
- basic or acidic catalysts For economic reasons, commercially available alcohols with 8 to 22 carbon atoms from the hydrogenation of carboxylic acids or carboxylic acid derivatives are favorable.
- Ziegler alcohols or oxo alcohols can also be used.
- the alcohol oxyethylates are known to be readily biodegradable; Their data are also favorable with regard to aquatoxicity, skin and mucous membrane compatibility.
- liquid detergents according to the invention contain 11 to 30% fatty alcohol oxyethylates, which can also be mixtures. Contents of 12 to 25% by weight are preferred.
- Fatty acid salts or their acids according to the invention correspond to formula III R '''COOP III, in which R '''is a saturated or unsaturated alkyl radical having 8 to 22 carbon atoms and P is hydrogen, alkali, ammonium or alkanolammonium.
- the detergents according to the invention contain 5 to 30% soap, which will usually be a mixture of different components. Contents of 7 to 25% are preferred.
- water-soluble builders such as different polyphosphates, phosphonates, carbonates, polycarboxylates, citronates, polyacetates such as NTA and EDTA, etc. or mixtures thereof are used. These compounds are usually used as alkali salts, preferably as sodium salts. Although not complex, too To mention sodium sulfate here.
- water-insoluble builders such as aluminosilicates of suitable particle size, is also according to the invention (cf. EP-A 0 075 994).
- concentration of the builders in the detergent is 0 to 70%, preferably 0 to 50%.
- Bleaching agents such as sodium perborate, optionally combined with bleach activators such as tetraacetylethylene diamine etc. or percarbonate, are also used according to the invention; Other bleaching agents are of course also possible (cf. K. Engel, Tenside Surfactants 25, S. (1988).
- concentration of the bleaching agents is 0 to 40%, preferably 0 to 30%.
- Adjusting agents such as low molecular weight mono- or dihydric alcohols, alkyl ethers of polyhydric alcohols, hydrotropics such as alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical, alkanolamines or urea, enzymes such as in particular proteases and enzyme stabilizers, corrosion inhibitors such as alkali silicates, optical, may be used according to the invention
- the total use concentration in the liquid detergents according to the invention is 0.3-20 g / l for the surfactant fraction according to the invention. 0.5-10 g / l are preferred.
- the invention is illustrated by the following examples.
- the liquid detergent formulations listed in Table 1 each contain 6% triethanolamine, 12% ethanol, 6% 1,2-propylene glycol and water ad 100% in addition to the surfactant components mentioned according to the invention.
- the viscosity of the cleaning liquid was measured in a rotary viscometer (Haake RV 20) at 25 ° C under shear rates of approx. 10 sec. ⁇ 1.
- the table shows the comparison of the properties of the detergents according to the invention as a liquid formulation with those of other known combinations and with a liquid brand detergent, in which one can presuppose a formulation optimization.
- the clear point, viscosity and foaming capacity correspond approximately to the standard customary for liquid detergents.
- the detergents according to the invention behave significantly superior in their washing activity.
- the results at low temperatures and problematic fabrics are almost outstanding like PE and MG: The tests show the superiority of the formulations according to the invention over the use of alkypolyglycosides with too high degrees of glycosidation or overly high levels of anionic surfactant at the expense of the oxyethylates.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft flüssige Zubereitungen zum Waschen von Textilien. Flüssige Waschmittel bestehen heute vor allem aus anionischen Tensiden, insbesondere Alkylbenzolsulfonat, Fettalkoholoxethylat und Seife. Diese in Waschmittelformulierungen üblichen Tenside basieren hauptsächlich auf petrochemischer Basis. Im Hinblick auf die zukünftige Rohstoffsituation (Erdölverknappung) ist diese petrochemische Basis ein erheblicher Nachteil. Ein weiterer Nachteil besteht darin, daß biologische Abbaubarkeit und Ökotoxizität dieser Tenside häufig nicht das entsprechende Niveau von Tensiden auf nativer Basis erreichen.The present invention relates to liquid preparations for washing textiles. Liquid detergents today mainly consist of anionic surfactants, especially alkylbenzenesulfonate, fatty alcohol oxyethylate and soap. These surfactants, which are common in detergent formulations, are mainly based on petrochemicals. In view of the future raw material situation (oil shortage), this petrochemical basis is a considerable disadvantage. Another disadvantage is that the biodegradability and ecotoxicity of these surfactants often do not reach the corresponding level of surfactants on a native basis.
Aufgabe der Erfindung war es daher, eine Tensidmischung für flüssige Waschmittel aufzufinden, die einen hohen Anteil an Tensiden enthält, die aus nachwachsenden Rohstoffen gewonnen werden; hierbei war neben hervorragenden Waschergebnissen hohe biologische Abbaubarkeit gefordert.The object of the invention was therefore to find a surfactant mixture for liquid detergents which contains a high proportion of surfactants which are obtained from renewable raw materials; In addition to excellent washing results, high biodegradability was required.
Diese Aufgabe wurde gelöst durch eine Mischung, die neben Fettalkoholoxethylat und Seife sowie geringen Mengen Aniontensid 3 bis 30 % Alkylpolyglycosid enthält.This object was achieved by a mixture which, in addition to fatty alcohol oxyethylate and soap and small amounts of anionic surfactant, contains 3 to 30% alkyl polyglycoside.
Gegenstand der Erfindung ist daher ein flüssiges Waschmittel enthaltend 3 - 30 Gew.-% Alkylpolyglycosid der Formel I
R-O-Zn I,
in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten aliphatischen Alkylrest mit 8 bis 18 Kohlenstoffatomen oder Gemische davon und Zn für einen Polyglycosylrest mit n = 1,0 bis 1,4 Hexose- oder Pentoseeinheiten oder Gemische davon stehen,
- 0 - 7 Gew.-%
- Aniontensid,
- 11 - 30 Gew.-%
- Fettalkoholoxethylat und
- 5 - 30 Gew.-%
- Seife.
RON n I,
in which R represents a linear or branched, saturated or unsaturated aliphatic alkyl radical having 8 to 18 carbon atoms or mixtures thereof and Z n represents a polyglycosyl radical with n = 1.0 to 1.4 hexose or pentose units or mixtures thereof,
- 0 - 7% by weight
- Anionic surfactant,
- 11-30% by weight
- Fatty alcohol oxyethylate and
- 5 - 30% by weight
- Soap.
In der EP-0 075 994, EP-0 075 995 und EP-0 075 996 werden Tensidmischungen beansprucht, die neben APG anionische und nichtionische Tenside enthalten, wobei allerdings der Glycosidierungsgrad des APG's ≧ 1,5 ist. Die DE-37 02 286 beansprucht Alkylpolyglycoside neben anionischen und nichtionischen Tensiden als Waschmittel mit den Einschränkungen, daß der anionische Anteil < 50 % der des Oxethylats sein soll. In der EP-0 199 765 werden Alkylpolyglycosidmischungen mit anionischen und nichtionischen Tensiden beschrieben, wobei der Gehalt an nichtionischen Tensiden ≦ 10 % betragen soll und der Glycosidierungsgrad des Alkylpolyglycosides ≦ 1,4 ist. Die Broschüre "Henkel APG, Alkylpolyglycoside" (1990) empfiehlt Rezepturen für flüssige Waschmittel die entsprechend der EP-0 199 765 Gehalte für Oxethylate ≦ 10 % enthalten, wohingegen der Gehalt an Alkylbenzolsulfonat jeweils 13 Gew.-% beträgt.EP-0 075 994, EP-0 075 995 and EP-0 075 996 claim surfactant mixtures which, in addition to APG, contain anionic and nonionic surfactants, although the degree of glycosidation of the APG is ≧ 1.5. DE-37 02 286 claims alkyl polyglycosides in addition to anionic and nonionic surfactants as detergents with the restrictions that the anionic content should be <50% of that of the oxyethylate. EP-0 199 765 describes alkylpolyglycoside mixtures with anionic and nonionic surfactants, the content of nonionic surfactants should be ≦ 10% and the degree of glycosidation of the alkylpolyglycoside ≦ 1.4. The brochure "Henkel APG, Alkylpolyglycoside" (1990) recommends recipes for liquid detergents which contain ≦ 10% according to EP-0 199 765, whereas the content of alkylbenzenesulfonate is 13% by weight.
Es wurde nun überraschend festgestellt, daß die erfindungsgemäße Formulierung bei äußerst geringem Aniontensidgehalt hervorragende Waschergebnisse liefert.It has now surprisingly been found that the formulation according to the invention delivers excellent washing results with an extremely low anionic surfactant content.
Erfindungsgemäß eingesetzte Alkylpolyglycoside genügen der Formel I,
R-O-Zn I
in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten aliphatischen Alkylrest mit 8 bis 18 Kohlenstoffatomen oder Gemische davon und Zn für einen Polyglycosylrest mit n = 1,0 bis 1,4 Hexose- oder Pentoseeinheiten oder Gemische davon stehen.Alkyl polyglycosides used according to the invention satisfy the formula I
RON n I
in which R stands for a linear or branched, saturated or unsaturated aliphatic alkyl radical with 8 to 18 carbon atoms or mixtures thereof and Z n for a polyglycosyl radical with n = 1.0 to 1.4 hexose or pentose units or mixtures thereof.
Bevorzugt werden Alkylpolyglycoside mit Alkylresten mit 9 bis 16 Kohlenstoffatomen sowie einem Polyglycosylrest von n = 1,1 bis 1,4. Besonders bevorzugt werden Alkylpolyglucoside.Alkyl polyglycosides with alkyl radicals with 9 to 16 carbon atoms and a polyglycosyl radical with n = 1.1 to 1.4 are preferred. Alkyl polyglucosides are particularly preferred.
Die erfindungsgemäß eingesetzten Alkylpolyglycoside können nach bekannten Verfahren auf Basis nachwachsender Rohstoffe hergestellt werden.The alkyl polyglycosides used according to the invention can be produced by known processes based on renewable raw materials.
Beispielsweise wird Dextrose in Gegenwart eines sauren Katalysators mit n-Butanol zu Butylpolyglycosidgemischen umgesetzt, welche mit langkettigen Alkoholen ebenfalls in Gegenwart eines sauren Katalysators zu den gewünschten Alkylpolyglycosidgemischen umglycosidiert werden. Oder Dextrose wird unmittelbar mit dem gewünschten langkettigen Alkohol umgesetzt.For example, dextrose is reacted with n-butanol to give butylpolyglycoside mixtures in the presence of an acidic catalyst, which are transglycosidated with long-chain alcohols in the presence of an acidic catalyst to give the desired alkylpolyglycoside mixtures. Or dextrose is immediately reacted with the desired long-chain alcohol.
Die Struktur der Produkte ist in bestimmten Grenzen variierbar. Der Alkylrest R wird durch die Auswahl des langkettigen Alkohols festgelegt. Günstig aus wirtschaftlichen Gründen sind die großtechnisch zugänglichen Alkohole mit 8 bis 18 C-Atomen insbesondere native Alkohole aus der Hydrierung von Carbonsäuren bzw. Carbonsäurederivaten. Verwendbar sind auch Ziegleralkohole oder Oxoalkohole.The structure of the products can be varied within certain limits. The alkyl radical R is determined by the choice of the long-chain alcohol. Favorable for economic reasons are the industrially accessible alcohols with 8 to 18 carbon atoms, in particular native alcohols from the hydrogenation of carboxylic acids or carboxylic acid derivatives. Ziegler alcohols or oxo alcohols can also be used.
Die Polyglycosylreste Zn werden einerseits durch die Auswahl des Kohlenhydrats und andererseits durch die Einstellung des mittleren Polymerisationsgrads n z. B. nach DE-OS 19 43 689 festgelegt. Im Prinzip können bekanntlich Polysaccharide, z. B. Stärke, Maltodextrine, Dextrose, Galaktose, Mannose, Xylose, etc. eingesetzt werden. Bevorzugt sind die großtechnisch verfügbaren Kohlenhydrate Stärke, Maltodextrine und besonders Dextrose. Da die wirtschaftlich interessanten Alkylpolyglycosidsynthesen nicht regio- und stereoselektiv verlaufen, sind die Alkylpolyglycoside stets Gemische von Oligomeren, die ihrerseits Gemische verschiedener isomerer Formen darstellen. Sie liegen nebeneinander mit α- und β-glycosidischen Bindungen in Pyranose- und Furanoseform vor. Auch die Verknüpfungsstellen zwischen zwei Saccachridresten sind unterschiedlich.The polyglycosyl radicals Z n are determined, on the one hand, by the selection of the carbohydrate and, on the other hand, by setting the average degree of polymerization n z. B. according to DE-OS 19 43 689. In principle, it is known that polysaccharides, e.g. B. starch, maltodextrins, dextrose, galactose, mannose, xylose, etc. can be used. The industrially available carbohydrates starch, maltodextrins and especially dextrose are preferred. Since the economically interesting alkyl polyglycoside syntheses are not regio- and stereoselective, the alkyl polyglycosides are always mixtures of oligomers, which in turn represent mixtures of different isomeric forms. They exist side by side with α- and β-glycosidic bonds in pyranose and furanose form. The junctions between two Saccachrid residues are also different.
Erfindungsgemäß eingesetzte Alkylpolyglycoside lassen sich auch durch Abmischen von Alkylpolyglycosiden mit Alkylmonoglycosiden herstellen. Letztere kann man z. B. nach EP-A 0 092 355 mittels polarer Lösemittel, wie Aceton, aus Alkylpolyglycosiden gewinnen bzw. anreichern.Alkyl polyglycosides used according to the invention can also be prepared by mixing alkyl polyglycosides with alkyl monoglycosides. The latter can e.g. B. according to EP-A 0 092 355 using polar solvents, such as acetone, from alkyl polyglycosides.
Der Glycosidierungsgrad wird zweckmäßigerweise mittels ¹H-NMR bestimmt.The degree of glycosidation is advantageously determined by means of 1 H-NMR.
Die erfindungsgemäßen Waschmittel enthalten 3 bis 30 % Alkylpolyglycosid, vorzugsweise 5 - 20 %.The detergents according to the invention contain 3 to 30% alkyl polyglycoside, preferably 5-20%.
Im Vergleich zu fast allen anderen in Waschmitteln eingesetzten Tensiden gelten die Alkylpolyglycoside als überaus umweltverträglich. So liegt der mittels Kläranlagen-Simulationsmodell/DOC-Analyse bestimmte biologische Abbaugrad für die erfindungsgemäßen Alkylpolyglycoside bei 96 ± 3 %. Diese Zahl ist vor dem Hintergrund zu sehen, daß bei diesem Testverfahren (Totalabbau) bereits ein Abbaugrad ≧ 70 % die Substanz als gut abbaubar indiziert.Compared to almost all other surfactants used in detergents, the alkyl polyglycosides are considered to be extremely environmentally compatible. The degree of biodegradation for the alkyl polyglycosides according to the invention, determined by means of a sewage treatment plant simulation model / DOC analysis, is 96 ± 3%. This figure can be seen against the background that with this test method (total degradation) a degree of degradation ≧ 70% already indicates the substance to be readily degradable.
Auch die akute orale Toxizität LD 50 (Ratte) mit > 10 000 mg/kg sowie die aquatische Toxizität LC 50 (Goldorfe) mit ca. 12 mg/l und EC 50 (Daphnien) mit 30 mg/l liegen um den Faktor 3 bis 5 günstiger als die entsprechenden Werte der heute wichtigsten Tenside. Ähnliches gilt für die Haut- und Schleimhautverträglichkeit.The acute oral toxicity LD 50 (rat) with> 10,000 mg / kg as well as the aquatic toxicity LC 50 (gold orfe) with approx. 12 mg / l and EC 50 (daphnia) with 30 mg / l are by a factor of 3 to 5 cheaper than the corresponding values of today's most important surfactants. The same applies to skin and mucous membrane compatibility.
Als Aniontenside finden Alkylbenzolsulfat, Alkansulfonate, Olefinsulfonate, Fettalkoholsulfate und Fettalkoholethersulfate mit 9 bis 18 C-Atomen in der Alkyl- bzw. Alkylengruppe Verwendung. Na, K, NH₄, Mg sowie Gemische sind die Gegenionen. Unter diesen Aniontensiden, die in Mengen von 0 bis 7 Gew.% in den erfindungsgemäßen Mischungen anwesend sein können, wird keine Seife verstanden. Bevorzugt sind Mengen von 0 bis 5 Gew.-%.Anionic surfactants used are alkylbenzene sulfate, alkane sulfonates, olefin sulfonates, fatty alcohol sulfates and fatty alcohol ether sulfates having 9 to 18 carbon atoms in the alkyl or alkylene group. Na, K, NH₄, Mg and mixtures are the counterions. These anionic surfactants, which can be present in the mixtures according to the invention in amounts of 0 to 7% by weight, are not to be understood as soap. Quantities of 0 to 5% by weight are preferred.
FettalkoholoxethylateFatty alcohol oxyethylates
Die erfindungsgemäß eingesetzten Fettalkoholoxethylate entsprechen Verbindungen der Formel II
R''-O-(CH₂-CH₂-O)xH II,
in der R'' ein linearer oder verzweigter, gesättigter oder ungesättigter Alkylrest mit 8 bis 22, vorzugsweise 10 - 20 Kohlenstoffatomen und x 2 bis 20, vorzugsweise 3 bis 15 bedeuten.The fatty alcohol oxyethylates used according to the invention correspond to compounds of the formula II
R '' - O- (CH₂-CH₂-O) x H II,
in which R ″ is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22, preferably 10 to 20 carbon atoms and x 2 to 20, preferably 3 to 15.
Die Verbindungen werden im allgemeinen durch Anlagerung von Ethylenoxid an längerkettige Alkohole in Gegenwart von basischen oder sauren Katalysatoren hergestellt. Günstig aus wirtschaftlichen Gründen sind großtechnisch zugängliche Alkohole mit 8 bis 22 C-Atomen aus der Hydrierung von Carbonsäuren bzw. Carbonsäurederivaten. Verwendbar sind aber auch Ziegleralkohole oder Oxoalkohole.The compounds are generally prepared by addition of ethylene oxide onto longer-chain alcohols in the presence of basic or acidic catalysts. For economic reasons, commercially available alcohols with 8 to 22 carbon atoms from the hydrogenation of carboxylic acids or carboxylic acid derivatives are favorable. Ziegler alcohols or oxo alcohols can also be used.
Die Alkoholoxethylate sind bekanntlich biologisch sehr gut abbaubar; günstig ebenfalls sind ihre Daten hinsichtlich Aquatoxizität, Haut- und Schleimhautverträglichkeit.The alcohol oxyethylates are known to be readily biodegradable; Their data are also favorable with regard to aquatoxicity, skin and mucous membrane compatibility.
Die erfindungsgemäßen flüssigen Waschmittel enthalten 11 bis 30 % Fettalkoholoxethylate, die auch Gemische sein können. Bevorzugt sind Gehalte von 12 bis 25 Gew.-%.The liquid detergents according to the invention contain 11 to 30% fatty alcohol oxyethylates, which can also be mixtures. Contents of 12 to 25% by weight are preferred.
Erfindungsgemäße fettsaure Salze bzw. ihre Säuren entsprechen der Formel III
R'''COOP III,
in der R''' ein gesättigter oder ungesättigter Alkylrest mit 8 bis 22 C-Atomen und P Wasserstoff, Alkali, Ammonium oder Alkanolammonium bedeuten.Fatty acid salts or their acids according to the invention correspond to formula III
R '''COOP III,
in which R '''is a saturated or unsaturated alkyl radical having 8 to 22 carbon atoms and P is hydrogen, alkali, ammonium or alkanolammonium.
Die erfindungsgemäßen Waschmittel enthalten 5 bis 30 % Seife, die meist ein Gemisch von verschiedenen Komponenten sein wird. Bevorzugt werden Gehalte von 7 bis 25 %.The detergents according to the invention contain 5 to 30% soap, which will usually be a mixture of different components. Contents of 7 to 25% are preferred.
Als nicht-tensidische Bestandteile sind in erster Linie Builder zu nennen. Erfindungsgemäß verwendet werden wasserlösliche Builder wie unterschiedliche Polyphosphate, Phosphonate, Carbonate, Polycarboxylate, Citronate, Polyacetate wie NTA und EDTA, etc. bzw. deren Gemische. Diese Verbindungen werden gewöhnlich als Alkalisalze, vorzugsweise als Natriumsalze eingesetzt. Obwohl nicht komplexierend ist auch Natriumsulfat hier zu nennen. Ebenfalls erfindungsgemäß ist die Verwendung von wasserunlöslichen Buildern, wie Alumosilikaten geeigneter Teilchengröße (vgl. EP-A 0 075 994). Die Konzentration der Builder im Waschmittel beträgt 0 bis 70 %, vorzugsweise 0 bis 50 %.First of all, builders should be mentioned as non-surfactant components. According to the invention, water-soluble builders such as different polyphosphates, phosphonates, carbonates, polycarboxylates, citronates, polyacetates such as NTA and EDTA, etc. or mixtures thereof are used. These compounds are usually used as alkali salts, preferably as sodium salts. Although not complex, too To mention sodium sulfate here. The use of water-insoluble builders, such as aluminosilicates of suitable particle size, is also according to the invention (cf. EP-A 0 075 994). The concentration of the builders in the detergent is 0 to 70%, preferably 0 to 50%.
Erfindungsgemäß eingesetzt werden ferner Bleichmittel wie Natriumperborat gegebenenfalls kombiniert mit Bleichaktivatoren wie Tetraacetylethylendiamin etc. oder Percarbonat; in Frage kommen natürlich auch andere Bleichmittel (vgl. K. Engel, Tenside Surfactants 25, S. (1988). Die Konzentration der Bleichmittel beträgt 0 bis 40 %, vorzugsweise 0 - 30 %.Bleaching agents such as sodium perborate, optionally combined with bleach activators such as tetraacetylethylene diamine etc. or percarbonate, are also used according to the invention; Other bleaching agents are of course also possible (cf. K. Engel, Tenside Surfactants 25, S. (1988). The concentration of the bleaching agents is 0 to 40%, preferably 0 to 30%.
Erfindungsgemäß einzusetzen sind ggf. Stellmittel wie niedermolekulare 1- oder 2-wertige Alkohole, Alkylether von mehrwertigen Alkoholen, Hydrotropica wie Alkylbenzolsulfonate mit 1 bis 3 C-Atomen im Alkylrest, Alkanolamine oder Harnstoff, Enzyme wie insbesondere Proteasen sowie Enzymstabilisatoren, Korrosionsinhibitoren wie Alkalisilikate, optische Aufheller insbesondere auf Stilben- und Pyrazolinbasis, Schaumregulatoren, Vergrauungsinhibitoren wie z. B. Carboxymethylcellulose, Parfümöle, Farbstoffe und weitere für flüssige bzw. pulverförmige Waschmittel übliche Inhaltsstoffe.Adjusting agents such as low molecular weight mono- or dihydric alcohols, alkyl ethers of polyhydric alcohols, hydrotropics such as alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical, alkanolamines or urea, enzymes such as in particular proteases and enzyme stabilizers, corrosion inhibitors such as alkali silicates, optical, may be used according to the invention Brighteners based in particular on stilbene and pyrazoline, foam regulators, graying inhibitors such as, for. B. carboxymethyl cellulose, perfume oils, dyes and other ingredients customary for liquid or powder detergents.
Die Gesamteinsatzkonzentration in den erfindungsgemäßen flüssige Waschmitteln beträgt für den erfindungsgemäßen tensidischen Anteil 0,3 - 20 g/l. Bevorzugt werden 0,5 - 10 g/l.The total use concentration in the liquid detergents according to the invention is 0.3-20 g / l for the surfactant fraction according to the invention. 0.5-10 g / l are preferred.
Durch die nachfolgenden Beispiele wird die Erfindung erläutert. Die in Tabelle 1 aufgeführten Flüssigwaschmittelformulierungen enthalten außer den genannten, erfindungsgemäß verwendeten tensidischen Bestandteilen jeweils 6 % Triethanolamin, 12 % Ethanol, 6 % 1,2-Propylenglycol und Wasser ad 100 %.The invention is illustrated by the following examples. The liquid detergent formulations listed in Table 1 each contain 6% triethanolamine, 12% ethanol, 6% 1,2-propylene glycol and water ad 100% in addition to the surfactant components mentioned according to the invention.
Zur Charakterisierung der Reinigungsflüssigkeit wurde der Klarpunkt und die Viskosität bestimmt.The clear point and the viscosity were determined to characterize the cleaning liquid.
Zur Klarpunktbestimmung wurden 10 g Reinigungsflüssigkeit in einem Shukoffkolben auf -20 °C abgekühlt und sodann erwärmt. Gemessen wird die Temperatur bei völliger Klärung.To determine the clear point, 10 g of cleaning liquid were cooled to -20 ° C. in a Shukoff flask and then heated. The temperature is measured with complete clarification.
Die Viskosität der Reinigungsflüssigkeit wurde in einem Rotationsviskosimeter (Haake RV 20) bei 25 °C unter Scherraten von ca. 10 sec.⁻¹ gemessen.The viscosity of the cleaning liquid was measured in a rotary viscometer (Haake RV 20) at 25 ° C under shear rates of approx. 10 sec.⁻¹.
Das Waschvermögen wurde in einer normalen Haushaltsmaschine bestimmt, hierbei wurde ebenfalls die Schaumentwicklung geprüft.The washability was determined in a normal household machine, and the foam development was also checked here.
Als Modellgewebe dienten 11 x 18 cm große Lappen aus WFK-Testgewebe mit Hautfett-Pigmentanschmutzung: Polyester (PE), Mischgewebe (MG) und Baumwolle (BW), die auf Baumwollhandtücher aufgenäht sind. Gleichzeitig wird die Waschmaschine mit 4 kg Ballastgewebe beschickt. Als Wasser dient Trinkwasser (13 °dH), die Wirkstoffkonzentration beträgt 5 g/l, der pH-Wert jeweils 8, das Flottenverhältnis 1 : 4 und die Waschzeit etwa 80 Minuten. Die Waschwerte nach dem Trocknen der Gewebe wurden - wie üblich - spektralphotometrisch relativ zu einem Weißstandard (Datacolor, 560 nm) gemessen.11 x 18 cm rags made of WFK test fabric with skin fat pigment soiling served as model fabric: polyester (PE), mixed fabric (MG) and cotton (BW), which are sewn onto cotton towels. At the same time, the washing machine is loaded with 4 kg of ballast fabric. Drinking water (13 ° dH) serves as water, the active ingredient concentration is 5 g / l, the pH value is 8, the liquor ratio is 1: 4 and the washing time is about 80 minutes. The washing values after drying the fabrics were - as usual - measured spectrophotometrically relative to a white standard (Datacolor, 560 nm).
Die Tabelle zeigt den Vergleich der Eigenschaften der erfindunsgemäßen Waschmittel als Flüssigformulierung mit denen anderer bekannten Kombinationen sowie mit einem flüssigen Markenwaschmittel, bei dem man eine Rezepturoptimierung voraussetzen kann. Klarpunkt, Viskosität und Schaumvermögen entsprechen in etwa dem für flüssige Waschmittel marktüblichen Standard.The table shows the comparison of the properties of the detergents according to the invention as a liquid formulation with those of other known combinations and with a liquid brand detergent, in which one can presuppose a formulation optimization. The clear point, viscosity and foaming capacity correspond approximately to the standard customary for liquid detergents.
Im Vergleich mit dem Markenwaschmittel (Beispiel 9 (V) und selbst auch mit den alkylpolyglycosidhaltigen Formulierungen (Beispiel 1(V) bis 3(V) verhalten sich die erfindungsgemäßen Waschmittel in ihrer Waschaktivität deutlich überlegen. Geradezu hervorragend sind die Ergebnisse bei tiefen Temperaturen und Problemgeweben wie PE und MG: Die Versuche zeigen die Überlegenheit der erfindunsgemäßen Formulierungen gegenüber dem Einsatz von Alkypolyglycosiden mit zu hohen Glycosidierungsgraden bzw. gegenüber zu hohen Gehalten an anionischem Tensid auf Kosten der Oxethylate.In comparison with the branded detergent (Example 9 (V) and even with the alkyl polyglycoside-containing formulations (Examples 1 (V) to 3 (V)), the detergents according to the invention behave significantly superior in their washing activity. The results at low temperatures and problematic fabrics are almost outstanding like PE and MG: The tests show the superiority of the formulations according to the invention over the use of alkypolyglycosides with too high degrees of glycosidation or overly high levels of anionic surfactant at the expense of the oxyethylates.
Folgende Abkürzungen wurden in der Tabelle verwendet:
- C₁₂C₁₄ [G 1.2]
- - C12/14-Alkylpolyglycosid mit einem Glycosidierungsgrad von 1.2
- C₁₂C₁₄ [G 1.4]
- - C12/14-Alkylpolyglycosid mit einem Glycosidierungsgrad von 1.4
- C₁₂C₁₄ [G 1.6]
- - C12/14-Alkylpolyglycosid mit einem Glycosidierungsgrad von 1.6
- MARLIPAL(R) 24/60
- - C12/14-Alkanoloxethylat mit 6 mol EO/mol
- MARLON(R) A
- - C₁₀C₁₃-Alkylbenzolsulfonat
- MARLINAT(R) DFK 30
- - C₁₂C₁₈-Alkylsulfat
- Seife
- - Kokosfettsäure
- PE
- - Polyester
- MG
- - Mischgewebe
- BW
- - Baumwolle
- C₁₂C₁₄ [G 1.2]
- - C 12/14 alkyl polyglycoside with a degree of glycosidation of 1.2
- C₁₂C₁₄ [G 1.4]
- - C 12/14 alkyl polyglycoside with a degree of glycosidation of 1.4
- C₁₂C₁₄ [G 1.6]
- - C 12/14 alkyl polyglycoside with a degree of glycosidation of 1.6
- MARLIPAL (R) 24/60
- - C 12/14 alkanol oxyethylate with 6 mol EO / mol
- MARLON (R) A
- - C₁₀C₁₃ alkylbenzenesulfonate
- MARLINAT (R) DFK 30
- - C₁₂C₁₈ alkyl sulfate
- Soap
- - coconut fatty acid
- PE
- - polyester
- MG
- - blended fabrics
- BW
- - cotton
Claims (6)
R-O-Zn I,
in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten aliphatischen Alkylrest mit 8 bis 18 Kohlenstoffatomen oder Gemische davon und Zn für einen Polyglycosylrest mit n = 1,0 bis 1,4 Hexose- oder Pentoseeinheiten oder Gemische davon stehen,
RON n I,
in which R represents a linear or branched, saturated or unsaturated aliphatic alkyl radical having 8 to 18 carbon atoms or mixtures thereof and Z n represents a polyglycosyl radical with n = 1.0 to 1.4 hexose or pentose units or mixtures thereof,
dadurch gekennzeichnet,
daß das Aniontensid Alkylbenzolsulfonat, Alkansulfonat, Olefinsulfonat, Fettalkoholsulfat und/oder Fettalkoholethersulfat bedeutet, wobei jeweils die Alkyl- bzw. Alkylengruppe g - 18 C-Atome enthält und Na, K, NH₄, Mg sowie ihre Gemische die Gegenionen sind.Liquid detergent according to claim 1 or 2,
characterized,
that the anionic surfactant means alkylbenzene sulfonate, alkane sulfonate, olefin sulfonate, fatty alcohol sulfate and / or fatty alcohol ether sulfate, where the alkyl or alkylene group contains g - 18 carbon atoms and Na, K, NH₄, Mg and their mixtures are the counterions.
dadurch gekennzeichnet,
daß das Fettalkoholoxethylat der Formel II
R''-O-(CH₂-CH₂-O)xH II,
entspricht, in der R'' ein linearer oder verzweigter, gesättigter oder ungesättigter Alkylrest mit 8 bis 22 Kohlenstoffatomen und x = 2 bis 20 bedeuten.Liquid detergent according to claims 1 to 3,
characterized,
that the fatty alcohol oxyethylate of the formula II
R '' - O- (CH₂-CH₂-O) x H II,
in which R ″ is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms and x = 2 to 20.
dadurch gekennzeichnet,
daß die Seife der Formel III
R'''COOP III
entspricht, in der R''' ein gesättigter und/oder ungesättigter Alkylrest mit 8 bis 22 Kohlenstoffatomen und P Wasserstoff, Alkali, Ammonium oder Alkanolammonium bedeuten.Liquid detergent according to claims 1 to 4,
characterized,
that the soap of formula III
R '''COOP III
in which R '''is a saturated and / or unsaturated alkyl radical having 8 to 22 carbon atoms and P is hydrogen, alkali, ammonium or alkanolammonium.
dadurch gekennzeichnet,
daß als nichttensidische Bestandteile Builder, Bleichmittel, Stellmittel, Enzyme, Stabilisatoren, Vergrauungsinhibitoren, Korrosionsinhibitoren, optische Aufheller, Farbstoffe, Parfümöle und ggf. weitere Additive enthalten sind.Liquid detergent according to claims 1 to 5,
characterized,
that builders, bleaching agents, adjusting agents, enzymes, stabilizers, graying inhibitors, corrosion inhibitors, optical brighteners, dyes, perfume oils and possibly other additives are contained as non-surfactant constituents.
dadurch gekennzeichnet,
daß die Einsatzkonzentration des tensidischen Anteils 0,3 bis 20 g/l beträgt.Liquid detergent according to claims 1 to 6,
characterized,
that the use concentration of the surfactant portion is 0.3 to 20 g / l.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4039223A DE4039223A1 (en) | 1990-12-08 | 1990-12-08 | LIQUID DETERGENT |
| DE4039223 | 1990-12-08 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0490040A2 true EP0490040A2 (en) | 1992-06-17 |
| EP0490040A3 EP0490040A3 (en) | 1992-10-21 |
| EP0490040B1 EP0490040B1 (en) | 1997-08-13 |
Family
ID=6419889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91117180A Expired - Lifetime EP0490040B1 (en) | 1990-12-08 | 1991-10-09 | Liquid detergent |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0490040B1 (en) |
| AT (1) | ATE156855T1 (en) |
| DE (2) | DE4039223A1 (en) |
| ES (1) | ES2106043T3 (en) |
| NO (1) | NO178267C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0592947A1 (en) * | 1992-10-12 | 1994-04-20 | ALBRIGHT & WILSON UK LIMITED | Cleaning preparations |
| EP0634480A1 (en) * | 1993-07-14 | 1995-01-18 | The Procter & Gamble Company | Detergent compositions |
| US5866530A (en) * | 1995-11-25 | 1999-02-02 | Henkel Kommanditgesellschaft Auf Aktien | Non-aqueous liquid mixtures of alkyl polyglycoside and alkyl polyalkylene glycol ether useful in various detergent applications |
| US6384010B1 (en) | 2000-06-15 | 2002-05-07 | S.C. Johnson & Son, Inc. | All purpose cleaner with low organic solvent content |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4236506A1 (en) * | 1992-10-29 | 1994-05-05 | Henkel Kgaa | Process for the preparation of aqueous solutions of anionic surfactants with improved low-temperature stability |
| US5759979A (en) * | 1993-04-05 | 1998-06-02 | Henkel Kommanditgesellschaft Auf Aktien | Detergent mixtures comprising APG and fatty alcohol polyglycol ether |
| DE19844004A1 (en) * | 1998-09-25 | 2000-03-30 | Cognis Deutschland Gmbh | Surfactant mixtures |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0075995A2 (en) * | 1981-09-28 | 1983-04-06 | THE PROCTER & GAMBLE COMPANY | Detergent compositions containing mixtures of alkylpolysaccharide and nonionic surfactants |
| WO1990015855A1 (en) * | 1989-06-22 | 1990-12-27 | Henkel Kommanditgesellschaft Auf Aktien | Liquid detergents |
| WO1992002607A1 (en) * | 1990-07-27 | 1992-02-20 | Henkel Kommanditgesellschaft Auf Aktien | Liquid washing agent with bleaching action |
| WO1992003527A1 (en) * | 1990-08-22 | 1992-03-05 | Henkel Kommanditgesellschaft Auf Aktien | Liquid washing agent with increased viscosity |
-
1990
- 1990-12-08 DE DE4039223A patent/DE4039223A1/en not_active Withdrawn
-
1991
- 1991-10-09 ES ES91117180T patent/ES2106043T3/en not_active Expired - Lifetime
- 1991-10-09 EP EP91117180A patent/EP0490040B1/en not_active Expired - Lifetime
- 1991-10-09 AT AT91117180T patent/ATE156855T1/en not_active IP Right Cessation
- 1991-10-09 DE DE59108822T patent/DE59108822D1/en not_active Expired - Fee Related
- 1991-12-06 NO NO914816A patent/NO178267C/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0075995A2 (en) * | 1981-09-28 | 1983-04-06 | THE PROCTER & GAMBLE COMPANY | Detergent compositions containing mixtures of alkylpolysaccharide and nonionic surfactants |
| WO1990015855A1 (en) * | 1989-06-22 | 1990-12-27 | Henkel Kommanditgesellschaft Auf Aktien | Liquid detergents |
| WO1992002607A1 (en) * | 1990-07-27 | 1992-02-20 | Henkel Kommanditgesellschaft Auf Aktien | Liquid washing agent with bleaching action |
| WO1992003527A1 (en) * | 1990-08-22 | 1992-03-05 | Henkel Kommanditgesellschaft Auf Aktien | Liquid washing agent with increased viscosity |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0592947A1 (en) * | 1992-10-12 | 1994-04-20 | ALBRIGHT & WILSON UK LIMITED | Cleaning preparations |
| EP0634480A1 (en) * | 1993-07-14 | 1995-01-18 | The Procter & Gamble Company | Detergent compositions |
| US5866530A (en) * | 1995-11-25 | 1999-02-02 | Henkel Kommanditgesellschaft Auf Aktien | Non-aqueous liquid mixtures of alkyl polyglycoside and alkyl polyalkylene glycol ether useful in various detergent applications |
| US6384010B1 (en) | 2000-06-15 | 2002-05-07 | S.C. Johnson & Son, Inc. | All purpose cleaner with low organic solvent content |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2106043T3 (en) | 1997-11-01 |
| ATE156855T1 (en) | 1997-08-15 |
| NO914816L (en) | 1992-06-09 |
| NO914816D0 (en) | 1991-12-06 |
| DE4039223A1 (en) | 1992-06-11 |
| EP0490040A3 (en) | 1992-10-21 |
| DE59108822D1 (en) | 1997-09-18 |
| EP0490040B1 (en) | 1997-08-13 |
| NO178267C (en) | 1996-02-21 |
| NO178267B (en) | 1995-11-13 |
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