WO2003004593A1 - Multi-phase detergents - Google Patents
Multi-phase detergents Download PDFInfo
- Publication number
- WO2003004593A1 WO2003004593A1 PCT/EP2002/006889 EP0206889W WO03004593A1 WO 2003004593 A1 WO2003004593 A1 WO 2003004593A1 EP 0206889 W EP0206889 W EP 0206889W WO 03004593 A1 WO03004593 A1 WO 03004593A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- detergent
- cleaning
- hand dishwashing
- alkyl
- water
- Prior art date
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 126
- 238000004140 cleaning Methods 0.000 claims abstract description 77
- 239000000203 mixture Substances 0.000 claims abstract description 74
- 238000004851 dishwashing Methods 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011521 glass Substances 0.000 claims abstract description 29
- 239000004094 surface-active agent Substances 0.000 claims abstract description 24
- -1 alkane sulfonates Chemical group 0.000 claims description 140
- 239000003795 chemical substances by application Substances 0.000 claims description 43
- 239000012071 phase Substances 0.000 claims description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- 239000012459 cleaning agent Substances 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 25
- 238000000576 coating method Methods 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 21
- 239000000194 fatty acid Substances 0.000 claims description 21
- 229930195729 fatty acid Natural products 0.000 claims description 21
- 239000007791 liquid phase Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 238000000465 moulding Methods 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 16
- 150000004665 fatty acids Chemical class 0.000 claims description 16
- 150000002170 ethers Chemical class 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 239000002736 nonionic surfactant Substances 0.000 claims description 14
- 229920000151 polyglycol Polymers 0.000 claims description 14
- 239000010695 polyglycol Substances 0.000 claims description 14
- 230000002209 hydrophobic effect Effects 0.000 claims description 13
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 11
- 239000002562 thickening agent Substances 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 10
- 235000010443 alginic acid Nutrition 0.000 claims description 9
- 229920000615 alginic acid Polymers 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 7
- 239000003093 cationic surfactant Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- 229920001282 polysaccharide Polymers 0.000 claims description 6
- 239000005017 polysaccharide Substances 0.000 claims description 6
- 150000004804 polysaccharides Chemical class 0.000 claims description 6
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- 244000303965 Cyamopsis psoralioides Species 0.000 claims description 5
- 108010010803 Gelatin Proteins 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000008273 gelatin Substances 0.000 claims description 5
- 229920000159 gelatin Polymers 0.000 claims description 5
- 235000019322 gelatine Nutrition 0.000 claims description 5
- 235000011852 gelatine desserts Nutrition 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- 235000013312 flour Nutrition 0.000 claims description 4
- 239000004375 Dextrin Substances 0.000 claims description 3
- 229920001353 Dextrin Polymers 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920003086 cellulose ether Polymers 0.000 claims description 3
- 238000013270 controlled release Methods 0.000 claims description 3
- 235000019425 dextrin Nutrition 0.000 claims description 3
- 235000010987 pectin Nutrition 0.000 claims description 3
- 229920001277 pectin Polymers 0.000 claims description 3
- 239000001814 pectin Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000000783 alginic acid Substances 0.000 claims description 2
- 229960001126 alginic acid Drugs 0.000 claims description 2
- 150000004781 alginic acids Chemical class 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 229920000867 polyelectrolyte Polymers 0.000 claims description 2
- 229930014626 natural product Natural products 0.000 claims 1
- 229920000515 polycarbonate Polymers 0.000 claims 1
- 239000004417 polycarbonate Substances 0.000 claims 1
- 239000012487 rinsing solution Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002775 capsule Substances 0.000 description 35
- 239000001993 wax Substances 0.000 description 31
- 229920006395 saturated elastomer Polymers 0.000 description 27
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 24
- 239000011734 sodium Substances 0.000 description 24
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 23
- 229910052708 sodium Inorganic materials 0.000 description 23
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 22
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 150000002191 fatty alcohols Chemical class 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 235000001014 amino acid Nutrition 0.000 description 13
- 150000001413 amino acids Chemical class 0.000 description 13
- 229960003237 betaine Drugs 0.000 description 13
- 238000009472 formulation Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 150000001340 alkali metals Chemical class 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- 150000001298 alcohols Chemical class 0.000 description 11
- 229910052783 alkali metal Inorganic materials 0.000 description 11
- 230000000845 anti-microbial effect Effects 0.000 description 11
- 235000021186 dishes Nutrition 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- 229940123208 Biguanide Drugs 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 9
- 239000004599 antimicrobial Substances 0.000 description 9
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 9
- 239000002280 amphoteric surfactant Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 239000004480 active ingredient Substances 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 7
- 239000003760 tallow Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
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- 150000002430 hydrocarbons Chemical class 0.000 description 6
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- 239000002304 perfume Substances 0.000 description 6
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000001045 blue dye Substances 0.000 description 5
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- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 5
- 229940073507 cocamidopropyl betaine Drugs 0.000 description 5
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- 239000003205 fragrance Substances 0.000 description 5
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- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 4
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- 239000004166 Lanolin Substances 0.000 description 4
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
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- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
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- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 4
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- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
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- TYWMIZZBOVGFOV-UHFFFAOYSA-N tetracosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCO TYWMIZZBOVGFOV-UHFFFAOYSA-N 0.000 description 4
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 3
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
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- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 3
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- BUOSLGZEBFSUDD-BGPZCGNYSA-N bis[(1s,3s,4r,5r)-4-methoxycarbonyl-8-methyl-8-azabicyclo[3.2.1]octan-3-yl] 2,4-diphenylcyclobutane-1,3-dicarboxylate Chemical compound O([C@H]1C[C@@H]2CC[C@@H](N2C)[C@H]1C(=O)OC)C(=O)C1C(C=2C=CC=CC=2)C(C(=O)O[C@@H]2[C@@H]([C@H]3CC[C@H](N3C)C2)C(=O)OC)C1C1=CC=CC=C1 BUOSLGZEBFSUDD-BGPZCGNYSA-N 0.000 description 3
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- 229940091855 sodium lauraminopropionate Drugs 0.000 description 1
- 229940066718 sodium stearoamphoacetate Drugs 0.000 description 1
- UOZFSLAMWIZUEN-UHFFFAOYSA-M sodium;2-[2-(decanoylamino)ethyl-(2-hydroxyethyl)amino]acetate Chemical compound [Na+].CCCCCCCCCC(=O)NCCN(CCO)CC([O-])=O UOZFSLAMWIZUEN-UHFFFAOYSA-M 0.000 description 1
- BVAQZSBSTBYZPX-UHFFFAOYSA-M sodium;2-[2-(dodecanoylamino)ethyl-(2-hydroxyethyl)-[2-hydroxy-3-[hydroxy(oxido)phosphoryl]oxypropyl]azaniumyl]acetate Chemical compound [Na+].CCCCCCCCCCCC(=O)NCC[N+](CCO)(CC([O-])=O)CC(O)COP(O)([O-])=O BVAQZSBSTBYZPX-UHFFFAOYSA-M 0.000 description 1
- HVFAVOFILADWEZ-UHFFFAOYSA-M sodium;2-[2-(dodecanoylamino)ethyl-(2-hydroxyethyl)amino]acetate Chemical compound [Na+].CCCCCCCCCCCC(=O)NCCN(CCO)CC([O-])=O HVFAVOFILADWEZ-UHFFFAOYSA-M 0.000 description 1
- ZKBGPOVFSMIXBF-UHFFFAOYSA-M sodium;2-[2-hydroxyethyl-[2-(octadecanoylamino)ethyl]amino]acetate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC(=O)NCCN(CCO)CC([O-])=O ZKBGPOVFSMIXBF-UHFFFAOYSA-M 0.000 description 1
- YASOXPMFSCKYDU-UHFFFAOYSA-M sodium;2-[2-hydroxyethyl-[2-(octanoylamino)ethyl]amino]acetate Chemical compound [Na+].CCCCCCCC(=O)NCCN(CCO)CC([O-])=O YASOXPMFSCKYDU-UHFFFAOYSA-M 0.000 description 1
- IDXHDUOOTUFFOX-UHFFFAOYSA-M sodium;2-[2-hydroxyethyl-[2-(tetradecanoylamino)ethyl]amino]acetate Chemical compound [Na+].CCCCCCCCCCCCCC(=O)NCCN(CCO)CC([O-])=O IDXHDUOOTUFFOX-UHFFFAOYSA-M 0.000 description 1
- IPYKAMBNXWKFTC-KVVVOXFISA-M sodium;2-[2-hydroxyethyl-[2-[[(z)-octadec-9-enoyl]amino]ethyl]amino]acetate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC(=O)NCCN(CCO)CC([O-])=O IPYKAMBNXWKFTC-KVVVOXFISA-M 0.000 description 1
- HPHSQXYITTYVEY-KVVVOXFISA-M sodium;2-hydroxy-3-[2-hydroxyethyl-[2-[[(z)-octadec-9-enoyl]amino]ethyl]amino]propane-1-sulfonate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC(=O)NCCN(CCO)CC(O)CS([O-])(=O)=O HPHSQXYITTYVEY-KVVVOXFISA-M 0.000 description 1
- HWCHICTXVOMIIF-UHFFFAOYSA-M sodium;3-(dodecylamino)propanoate Chemical compound [Na+].CCCCCCCCCCCCNCCC([O-])=O HWCHICTXVOMIIF-UHFFFAOYSA-M 0.000 description 1
- LLKGTXLYJMUQJX-UHFFFAOYSA-M sodium;3-[2-carboxyethyl(dodecyl)amino]propanoate Chemical compound [Na+].CCCCCCCCCCCCN(CCC(O)=O)CCC([O-])=O LLKGTXLYJMUQJX-UHFFFAOYSA-M 0.000 description 1
- WMLIJOUAGPIENT-UHFFFAOYSA-M sodium;3-[2-hydroxyethyl-[2-(octanoylamino)ethyl]amino]propanoate Chemical compound [Na+].CCCCCCCC(=O)NCCN(CCO)CCC([O-])=O WMLIJOUAGPIENT-UHFFFAOYSA-M 0.000 description 1
- LOBXNKKFDKXXQW-UHFFFAOYSA-M sodium;3-[dodecanoyl(methyl)amino]propanoate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CCC([O-])=O LOBXNKKFDKXXQW-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-N sulfuric acid monooctyl ester Natural products CCCCCCCCOS(O)(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-N 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229960004559 theobromine Drugs 0.000 description 1
- 229960000278 theophylline Drugs 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FEFAREAYTNHYNP-UHFFFAOYSA-K tripotassium;[bis[[hydroxy(oxido)phosphoryl]methyl]-oxidoazaniumyl]methyl-hydroxyphosphinate Chemical compound [K+].[K+].[K+].OP([O-])(=O)C[N+]([O-])(CP(O)([O-])=O)CP(O)([O-])=O FEFAREAYTNHYNP-UHFFFAOYSA-K 0.000 description 1
- 229940057402 undecyl alcohol Drugs 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 235000019386 wax ester Nutrition 0.000 description 1
- 238000004018 waxing Methods 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0013—Liquid compositions with insoluble particles in suspension
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
Definitions
- the present invention relates to detergent-containing detergents, in particular hand dishwashing detergents.
- Conventional cleaning agents or hand dishwashing detergents are usually formulated as low-viscosity to viscous aqueous liquids. These practically exclusively single-phase formulated liquid cleaning or hand dishwashing detergents enable the user to easily produce the desired washing liquor or cleaning solution, which is also referred to as the application liquor, by diluting the cleaning or washing-up liquid concentrate without the user having to use the concentrated form of the agent comes into direct skin contact. Such skin contact is undesirable since the agents in concentrated form often have an irritating effect on the skin which the user perceives as unpleasant.
- Conventional single-phase hand dishwashing detergents and also cleaning agents usually contain water as the main constituent, in which the fat-dissolving and foam-active surfactants are dissolved.
- a serious disadvantage of conventional hand dishwashing detergents is that after the hand dishwashing detergent concentrate has been diluted with water, the user inevitably has a certain surfactant mixture or detergent component mixture in a certain concentration range, depending on the dishwashing detergent used. The resulting wash liquor is then used for manual cleaning of the entire wash ware.
- a specific hand dishwashing detergent composition or surfactant concentration which is matched to the respective wash ware, has or would have significantly better cleaning properties.
- the hand dishwashing detergent Since, for economic and ecological reasons, the user does not use a specifically designed hand dishwashing detergent for each special wash ware, the hand dishwashing detergent must inevitably contain all the components necessary for cleaning the respective wash ware. This has the consequence, for example, that when cleaning glass, which is usually carried out at the beginning of the washing process, with a universally applicable hand dishwashing detergent there is basically a strong foaming and a high fat-dissolving power, although, as stated above, this is undesirable or unnecessary ,
- any care products for the wash ware for example care components for glass and ceramic surfaces
- the wash liquor right from the start, namely with the addition of the hand dishwashing liquid.
- the care components were only added after the glasses had been cleaned.
- All previously known hand dishwashing detergents are not matched to the cleaning of the different items to be washed, which usually takes place in chronological phases or in steps, but rather represents a compromise in terms of Cleaning of, for example, glass, dishes with grease soiling, cutlery, etc. This applies both to the conventional single-phase and two-phase hand dishwashing detergents and, for example, to the previously described solid detergents and cleaning agents.
- cleaning agents such as floor cleaners.
- the user receives an appropriate cleaning solution or application liquor with a specific surfactant mixture or detergent component composition.
- the resulting cleaning solution thus contains, in addition to the dirt-dissolving substances, also appropriate care components which, for example, give the cleaned floor a glossy effect, provide the cleaned floor with a protective layer or are intended to prevent the cleaned surface from being soiled again quickly.
- all detergent components ie dirt-dissolving substances and care components, are forcibly applied to the surface to be cleaned when the agent is used. For understandable reasons, a gradual application of dirt-dissolving substances and care components would be advantageous, especially for heavily soiled surfaces, and would lead to a better cleaning result.
- DE 198 54 267 relates to a coated active substance for manual cleaning agents for hard surfaces, such as hand dishwashing liquid.
- the casing preferably consists of a material which contains at least one natural or synthetic polymer or a mixture thereof and which dissolves in water at about 35 ° C. within about 10 to 50 seconds, preferably about 20 to 40 seconds.
- the detergents or dishwashing detergents based on coated active substances according to DE 198 54 267 are distinguished by improved storage stability, but do not have a formulation which is coordinated with the chronological course of a cleaning process and therefore have the disadvantages described above.
- WO 94/14941 relates to aqueous neutral or slightly alkaline, automatic dishwashing detergents which are free from anionic and cationic surfactants.
- the Machine dishwashing detergents can be enclosed in water-soluble or water-dispersible containers, which consist, for example, of gelatin.
- the automatic dishwashing detergents described in WO 94/14941 which may include enclosed or encapsulated detergent components, are unsuitable as hand dishwashing detergents.
- the gelatin coating of the active ingredients described in the documents only serves to stabilize the components and to allow simple dosing.
- EP-A-9261754 relates to a foam bath in the form of a mixture of amine salts and long-chain alkyl ether sulfates and 25 to 35% by weight of liquid polyethylene glycols, encapsulated in an elastic gelatin capsule.
- EP-A-0533 239 relates to aqueous liquid detergent compositions which comprise enzymes and encapsulated bleach particles.
- the cleaning agents are particularly suitable for use as automatic dishwashing agents.
- the encapsulation of individual components, namely the bleaching agents, also serves to improve the shelf life or stability here, since interactions between the enzyme and the bleaching particles are to be avoided.
- the solution to the problems lies in the provision of a surfactant-containing detergent, in particular hand dishwashing detergent, the detergent being single-phase or multi-phase and wherein at least one phase has moldings which are suitable for releasing at least one detergent or detergent component when diluted with water with a time delay.
- Delayed for the purposes of the present invention means that the shaped bodies dissolve when diluted with water at a specific point in time or during a specific period of time.
- the terms “detergent component” and “detergent component” also include auxiliaries and additives, such as, for example, perfume or dyes, in addition to cleaning-active substances.
- the detergents or hand dishwashing detergents according to the invention are generally dissolved in water at a temperature of up to 50 ° C. and the resulting application liquor is then used, for example, for manual cleaning of hard surfaces and / or soft surfaces, in particular glasses, eating utensils and cookware etc. used.
- the term "manual cleaning" in the sense of the present invention naturally also includes a cleaning process which is carried out with the aid of mechanical aids, such as a brush, sponge or the like.
- the cleaning agent or hand dishwashing agent formulated according to the invention overcomes the disadvantages of the agents described in the prior art and enables an application liquor composition which is coordinated and optimized for the individual cleaning phases and rinsing phases.
- the cleaning agent in particular rinsing agent, has at least one, preferably liquid phase, which dissolves essentially without any time delay when diluted with water.
- this immediately soluble phase contains the detergent or detergent components that are particularly suitable for the rinse effect on glass, since glasses or glass objects are first cleaned in a conventional manual rinsing process.
- the liquid phase particularly preferably contains detergent components selected from the group comprising nonionic surfactants, in particular end-capped C ⁇ -C 22 alkyl alcohol polyglycol ethers, secondary alkane sulfonates, linear alkyl benzene sulfonates and alkyl polyglucosides.
- nonionic surfactants in particular end-capped C ⁇ -C 22 alkyl alcohol polyglycol ethers, secondary alkane sulfonates, linear alkyl benzene sulfonates and alkyl polyglucosides.
- the liquid phase of the cleaning agent according to the invention contains between 5 and 45% by weight of surfactants, based on the liquid phase, preferably selected from the group comprising nonionic surfactants, anionic surfactants, betaines, amine oxides and cationic surfactants, the proportion of cationic surfactants is preferably less than 5% by weight.
- the cleaning agent or hand dishwashing detergent according to the invention contains molded articles which contain the cleaning agents or detergents contained in the molded articles. Release detergent components with a time delay when diluted with water.
- the aforementioned “encapsulated” components are not released into water immediately after the addition of the agent, that is to say after the cleaning solution or rinsing liquor has been prepared, but only after a certain period of time.
- the shaped bodies are diluted with water at a temperature of about 40 ° C.
- a period of up to 10 min preferably within a period of 0.5 to 9 min, more preferably within 1 to 8 min, particularly preferably within 3 to 8 min at ⁇ 70% , preferably to ⁇ 80%, particularly preferably to> 90% and particularly preferably to 99 to 100% dissolved.
- the user has one for the second cleaning phase or Rinsing phase, which consists, for example, in the cleaning of plates and pots soiled with grease, etc., a detergent composition optimized for this specific cleaning process is available.
- the time-delayed dissolution process of the shaped bodies can be controlled using various mechanisms for releasing the active substances.
- the cleaning or rinsing agent components contained in the molded body for example surfactant components with strong fat-dissolving power, foam-forming components, etc., are preferably provided with suitable casing, coating and / or matrix materials.
- the coating or encapsulation while receiving, for example, capsule-like shaped bodies allows a particularly precise and precisely controllable release of the aforementioned components.
- the dissolving of the shaped bodies can take place, for example, in a time-controlled manner, in a pH-controlled manner, in a temperature-controlled manner or also in an electrolyte-controlled manner when diluted.
- a thickener is added to the liquid phase, so that a stabilization and uniform distribution of the shaped bodies, which particularly preferably have a spherical or capsule-like shape, is ensured in the aforementioned liquid phase.
- thickener is added to the liquid phase, so that the moldings “float” in the aforementioned liquid or gel-like phase. This ensures that the user actually produces the cleaning and The necessary proportions of detergent or rinsing agent components are added in the correct ratio
- a uniform distribution of the shaped bodies or a targeted addition can also be achieved by shaking vigorously immediately before preparing the cleaning solution or rinsing liquor.
- the moldings are particularly preferably present in the liquid phase at from 0.1 to 30% by weight, preferably from 0.2 to 10% by weight and particularly preferably from 0.5 to 3% by weight, based on the liquid phase ,
- the detergent in particular hand dishwashing detergent, contains moldings with the same or different detergent or dishwashing component composition, the components from the group comprising silver detergents, corrosion protection agents, hand or skin care agents, special care agents, preferably care agents for ceramics and / or glass, agents for removing special soiling, fat-dissolving substances or mixtures thereof are selected.
- Particularly preferred cleaning or rinsing agent components include betaines, fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkanesulfonates, linear alkylbenzenesulfonates, alkyl alcohol polyglycol ethers, alkyl polygucosides, fatty acid alkanolamides, amine oxides and mixtures thereof.
- “Fat-dissolving substances” in the sense of the present invention include, in addition to the aforementioned substances, also hydrophobic components.
- Suitable hydrophobic components include, for example, dialkyl ethers with identical or different C 4 - to Cu-alkyl radicals, in particular linear dioctyl ethers; hydrocarbons with a boiling range from 100 to 300 ° C. especially 140 to 280 ° C, especially aliphatic hydrocarbons with a boiling range of 145 to 200 ° C, isoparaffins with a boiling range of 200 to 260 ° C; essential oils, especially limonene and the pine oil extracted from pine roots and stumps and also mixtures of these hydrophobic components.
- Suitable cleaning and rinsing agent components are, for example, under the trade names Hostapur® SAS 60 (secondary alkane sulfonate from Clariant), Texapon® SPN 70 (fatty alcohol ether sulfate from Henkel KGaA, Düsseldorf), Empinin® KS8 (fatty alcohol ether sulfate from Albright & Wilson GmbH, Frankfurt), Ceraminox ® (amine oxide from Clariant), Sulfopon® 101 (C12-C14 lauryl sulfate from Henkel KGaA, Düsseldorf), Dehyton® (various betaines from Henkel KGaA, Düsseldorf).
- Hostapur® SAS 60 secondary alkane sulfonate from Clariant
- Texapon® SPN 70 fatty alcohol ether sulfate from Henkel KGaA, Düsseldorf
- Empinin® KS8 fatty alcohol ether sulfate from Albright & Wilson GmbH, Frankfurt
- Ceraminox ® amine
- substances selected from the group consisting of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used as silver protection agents.
- Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
- Zinc compounds can also be used to prevent corrosion on the wash ware.
- Other cleaning or rinsing agent components are gloss drying additives, cleaning enhancers, antimicrobial agents or disinfectants, antistatic agents, preservatives (eg glutaraldehyde), bleaching systems and dyes, and opacifiers or skin protection agents, as described in EP-A-522 556.
- the detergent in particular dishwashing detergent, comprises: a) shaped articles with a first detergent component composition comprising at least one component selected from the group consisting of silver detergents, corrosion inhibitors, hand and skin care agents, special care agents, preferably care agents for ceramics and / or glass, and / or means for removing special soiling; and b) moldings with a second detergent component composition comprising at least one fat-dissolving substance, preferably selected from the group consisting of betaines, fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkane sulfonates, linear alkylbenzenesulfonates, alkyl alcohol polyglycol ethers, alkyl polyglucosides, fatty acid alkanolamides, amine oxides and / or hydrophobic components Shaped body a) contained first detergent component composition when the detergent is diluted with water, preferably before the second detergent component composition contained in shaped body b) is released.
- a first detergent component composition compris
- molded bodies a) and b) differ from one another externally, for example in color.
- the release mechanism The components contained in molded body a) or b) can be based on the various possible parameters mentioned above. If a suitable shell or matrix material is used, the dissolution of the respective shaped bodies can be controlled almost at any time, pH-controlled, temperature-controlled or even electrolyte strength-controlled.
- the first cleaning or rinsing agent component composition contained in molded body a) is released upon dilution in water before the second cleaning or rinsing agent component composition contained in molded body b), i. H. that the materials or the release mechanism are selected so that the composition in the cleaning solution or rinsing liquor is matched or optimized to the respective cleaning or rinsing phase.
- the molded body b) preferably contains components which are particularly suitable for removing heavily greasy soiling, for example on plates.
- the cleaning agent according to the invention in particular hand dishwashing liquid, in a preferred embodiment comprises a liquid phase and moldings with the same or different composition.
- the shaped bodies can in principle have any shape, with shapes which can be produced economically and economically being preferred. These include, for example, all shapes which are rotationally symmetrical with respect to at least one axis, for example the spherical shape, elliptical shapes or cylindrical shapes, a capsule in the form of a cylinder closed at both ends being preferred.
- the matrix, coating and / or coating materials of the shaped bodies are selected such that they dissolve only slowly in water and the incorporated filler components are only incorporated into the application or at a specific point in time or during a specific period of time. Dispense wash liquor.
- the coating, coating and / or matrix material suitable according to the invention is preferably water-soluble, or at least water-dispersible, that is to say that the material at least partially dissolves after being introduced into water or at least a dispersion is formed, so that the covering, coating and / or matrix becomes permeable at a predetermined point in time or after a certain period of time and an exchange of substances between the water surrounding the shaped body and the enclosed cleaning agents or detergent components is made possible.
- Suitable coating, matrix and / or coating materials include polymers and / or copolymers which are suitable for the dissolution mechanism provided in each case.
- Suitable materials include alginic acid, alginates, pectins, guar flour, starch, dextrins, gelatin, organic modified natural substances, in particular carboxymethyl cellulose and cellulose ethers, hydroxyethyl and propyl cellulose and the like, polysaccharides, organic fully synthetic substances, in particular polyacrylic and polymethacrylic compounds, Vinyl polymers, in particular polyvinyl alcohols, polycarboxylic acids, polyethers, polyimines, polyamides, polyelectrolytes and, in principle, water-soluble or water-disintegrating polymers.
- the material from which the covering is made can contain additives which influence the elasticity and water solubility.
- Suitable plasticizers are, for example, glycol, sorbitol and glycerin.
- a time-controlled release of detergent components can be achieved, for example, by changing the pH of the cleaning solution or rinsing liquor. If you consider, for example, the process of manually cleaning dishes, the initial pH value of the washing liquor changes during the washing process. If one assumes that in the first rinsing phase, namely when cleaning the glasses, the object to be rinsed is first cleaned in the washing liquor and then rinsed with fresh water, the pH will drop due to the dilution with pH-neutral water -Values in the washing liquor. The resulting pH value depends on the volume and the detergent component concentration in the washing liquor and on the amount of fresh water added. This pH value change in the rinsing liquor can be used to control the dissolution process of the shaped bodies in a targeted manner. This effect or such a change in pH value is of course also the case with the dilution of cleaning and washing-up liquid concentrates and with diluted ones Observe cleaning agents and can also be used to control the dissolution process of the moldings.
- wrapping, matrix and / or coating materials which experience a change in the physicochemical properties when the pH of the application liquor changes. It is particularly preferred that such substances have an increased solubility in water and / or a decrease in the diffusion density when the pH changes.
- These substances include basic substances, in particular basic polymers and / or copolymers.
- the principle of pH-dependent water solubility is usually based on protonation or deprotonation of functional side groups of the polymers.
- Such polymers with pH-dependent solubility are also known, inter alia, from the pharmaceutical industry, for example in connection with enteric coatings on tablets.
- pH-sensitive coating, matrix and / or coating materials are (co) polymers which preferably have amino groups or aminoalkyl groups.
- Suitable comonomers are, for example, acrylates, methacrylates, maleinates or derivatives of these compounds.
- Polymaleimide copolymers, polyacrylamides, polyvinylpyrrolidone copolymers and / or polyurethanes are also suitable.
- the shaped bodies are dissolved under electrolyte control and / or the detergent components contained therein are released due to a change in the electrolyte concentration.
- the cleaning or rinsing agent components are released from the shaped bodies in a temperature-controlled manner.
- the moldings are produced, for example, from a melt dispersion or emulsion containing the detergent components, the melt suspension or emulsion essentially consisting of a coating substance which has a melting point above 30 ° C.
- the in the melt suspension Components or emulsion to be incorporated can be at the processing temperature both in solid and in liquid form.
- the coating substances which on the one hand relate to the melting or solidification behavior, but on the other hand also relate to the material properties of the coating in the solidified area at ambient temperature. Since the coating should only release the cleaning or rinsing agent components contained therein in the application liquor and not under thermal stress during transport or storage, the coating substances preferably have a melting point above 30 ° C.
- waxes are understood to mean a number of natural or artificially obtained substances which, as a rule, melt above 30 ° C. without decomposition and are relatively low-viscosity and not stringy even a little above the melting point. They have a strongly temperature-dependent consistency and solubility.
- the waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes.
- Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.
- vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax
- animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or
- the chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
- Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the stated requirements with regard to the softening point can also be used as covering materials. Suitable synthetic compounds have been found for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll 66 ® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ® ETLP (Condea). Conversely, synthetic or partially synthetic esters from lower alcohols with fatty acids from native sources can also be used.
- Tegin ® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances.
- Shellac for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used as a coating material according to the invention.
- wax alcohols are also included in the waxes in the context of the present invention, for example.
- Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms.
- the wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes.
- wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol.
- the coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ® (Pamentier & Co).
- wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ® (Pamentier & Co).
- fatty acid glycerol esters or fatty acid alkanolamides can also be used, at least in part, as a constituent of the casing, but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.
- suitable coating substances for the temperature-controlled release of the cleaning or rinsing agent components include polyethylene glycols, polyvinylpyrrolidones, polyethers, carboxymethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose and / or hydroxyethyl propyl cellulose.
- Another object of the present invention is the use of the cleaning agent according to the invention for cleaning hard surfaces and / or soft surfaces, preferably as an all-purpose cleaner, bathroom cleaner, floor cleaner, car cleaner, glass cleaner, furniture care agent, furniture cleaner, Facade cleaner, detergent and / or the like and particularly preferably for cleaning dishes.
- the present invention relates to a method for cleaning a hard and / or soft surface with an aqueous cleaning liquor, which is characterized in that the cleaning liquor is produced by dissolving or dispersing the cleaning agent according to the invention in water.
- the detergent and dishwashing detergent components of the detergent or hand dishwashing detergent according to the present invention include the following substances or groups of substances:
- the active cleaning phases according to the invention can contain anionic, nonionic, amphoteric or cationic surfactants or surfactant mixtures from one, several or all of these classes of surfactants as surfactant components.
- the detergents in particular hand dishwashing detergents, contain surfactants, distributed over the various phases, in amounts, based on the overall formulation, of 5 to 55% by weight, preferably 10 to 30% by weight.
- Anionic surfactants according to the present invention can be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates as well as aliphatic and aromatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates, lignin sulfonates, lignin sulfonates.
- Fatty acid cyanamides, sulfosuccinic acid esters, fatty acid isothionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates can also be used in the context of the present invention.
- alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half esters of the C 2 -C 8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C10- C 2 o-oxo alcohols and the half esters of secondary alcohols (secondary alkyl sulfates) of these chain lengths are preferred.
- alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
- the agent according to the invention as (hand) dishwashing detergent, the C 2 -C 6 alkyl sulfates and C 2 -C 15 alkyl sulfates and C 4 -Ci 5 alkyl sulfates are preferred.
- Suitable secondary alkyl sulfates contain 2- and / or 3-alkyl sulfates and optionally higher homologues (4-, 5-, 6-alkyl sulfates etc.), can be prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and are commercially available from Shell Oil Company at available under the name DAN ® , e.g. B. the products mentioned in US Pat. Nos.
- the fatty alcohol ether sulfates are particularly preferred in the context of the present invention.
- Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols.
- Suitable alkoxylated alcohols are obtained by reacting ethylene oxide with longer-chain alcohols, for example with straight-chain or branched alcohols with chain lengths of C to C 2 ⁇ such as 2-methyl-branched C 9 to Cn fatty alcohols.
- a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. Mixtures of ethylene oxide and propylene oxide can also be used in the ethoxylation reaction.
- Low-ethoxylated fatty alcohols 0.5 to 4 mol EO, preferably 1 to 2 mol EO) are very particularly preferred in the sense of the present invention.
- alkane in particular the secondary alkane sulfonates of unbranched paraffinic hydrocarbons, in particular C- ⁇ 2 _i 8 -alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization, be won.
- a preferred secondary alkane sulfonates is as Hostapur SAS ® 60, sold by Clariant secondary Ci-Na 3 -i 7 alkane.
- Suitable surfactants of the sulfonate type are alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, of the kind obtained, for example, from C 2 - 8 mono-olefins with terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products.
- Alkylbenzene sulfonates in the context of the teaching according to the invention are alkylbenzenesulfonates having a linear or branched, saturated or unsaturated C 6-22 alkyl, preferably C 8-18 alkyl, especially C 9 _i 4 alkyl, most preferably C ⁇ o- 13 alkyl radicals. They are used as alkali metal and / or alkaline earth metal salts, in particular sodium, potassium, magnesium and / or calcium salts, and also as ammonium salts or mono-, di- or trialkanolammonium salts, preferably mono-, di- or triethanol and / or -isopropanolammonium salts, especially mono-, di- or
- Triethanolammonium salts but also used as alkylbenzenesulfonic acid together with the corresponding alkali metal or alkaline earth metal hydroxide and / or ammonia or mono-, di- or trialkanolamine.
- esters of 2-sulfo fatty acids e.g. the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
- the anionic surfactants are in the form of their alkali metal and alkaline earth metal salts, in particular sodium, potassium and magnesium salts, as well as ammonium and mono-, di-, tri- or tetraalkylammonium salts and, in the case of the sulfonates, also in the form of the acid, for example dodecylbenzenesulfonic acid, C ⁇ 0 -C ⁇ 3 alkylbenzene and / or C ⁇ 0 -C ⁇ 4 alkylbenzene used.
- the cleaning agents according to the invention can also contain soaps, ie alkali metal or ammonium salts of saturated or unsaturated C6-C22 fatty acids.
- Nonionic surfactants in the context of the invention can be alkoxylates, such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end group-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters as well as alkyl polyglycosides or nitrogenous surfactants.
- alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end group-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters as well as alkyl polyglycosides or nitrogenous surfactants.
- Non-ionic surfactants which can preferably be used are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
- R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
- R3 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl -, 2-butyl or 2-methyl-2-butyl
- R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
- H, -CH3 or -CH 2 CH 3 are particularly preferred for the radical R 3 .
- Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
- the value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
- R 1 , R 2 and R 3 are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 1 and R 2 have 9 to 14 carbon atoms, R 3 represents H and x assumes values from 6 to 15.
- End group-capped fatty alcohol polyglycol ethers which are sold under the trade name Dehypon® by Henkel KGaA, Düsseldorf, are particularly preferably used in the context of the present invention.
- C 6 -C 22 alkyl alcohol polypropylene glycol / polyethylene glycol ethers are preferred known nonionic surfactants. They can be represented by the formula
- R 1 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 8 to 18, in particular 10 to 16, carbon atoms, p for 0 or numbers from 1 to 3 and e for numbers from 1 to 20.
- the C 6 -C 22 alkyl alcohol polyglycol ethers can be added to alkyl alcohols, preferably to oxo alcohols, by addition of propylene oxide and / or ethylene oxide branched chain primary alcohols obtainable by oxosynthesis or to fatty alcohols.
- Typical examples are polyglycol ethers in which R 1 is an alkyl radical having 8 to 18 carbon atoms, p is 0 to 2 and e is a number from 2 to 7.
- At least one alkyl alcohol polyglycol ether with a linear alkyl radical R 1 is combined with at least one alkyl alcohol polyglycol ether with a branched alkyl radical R 1 , for example C 2 -C 6 fatty alcohol + 5.5-EO and isodecanol + 6-EO. It is further preferred here that the linear alkyl radical comprises more carbon atoms than the branched alkyl radical.
- Fatty alcohol + 3 EO, and mixtures thereof - C ⁇ -fatty alcohol + 1.2PO + 8.4EO, C 8- ⁇ o-fatty alcohol + 5EO, C ⁇ 2- i4 fatty alcohol + 6 EO C 12 and 14 are particularly preferred.
- Preferred nonionic surfactants are furthermore alkyl polyglycosides (APG) of the formula R 2 0 [G] x , in which R 2 is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms, [G] is a glycosidically linked sugar radical and x is are a number from 1 to 10.
- APG are non-ionic surfactants and are known substances that can be obtained using the relevant methods of preparative organic chemistry.
- the index number x in the abovementioned general formula indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10.
- the value x for a certain alkyl glycoside is an analytically determined arithmetic parameter, which usually represents a fractional number.
- Alkyl glycosides with an average degree of oligomerization x of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl glycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6.
- Xylose, but especially glucose, is preferably used as the glycosidic sugar.
- the alkyl or alkenyl radical R 2 can be derived from primary alcohols having 8 to 22, preferably 8 to 14, carbon atoms.
- Typical examples are capronic alcohol, capryial alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from RoELEN's oxosynthesis.
- the alkyl or alkenyl radical R 2 is preferably derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol.
- Elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures should also be mentioned.
- Suitable nitrogen-containing nonionic surfactants are, for example, amine oxides, polyhydroxy fatty acid amides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxamides which have alkyl groups with 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
- the degree of ethoxylation of these compounds is generally between 1 and 20, preferably between 3 and 10.
- Ethanolamide derivatives of alkanoic acids with 8 to 22 C atoms, preferably 12 to 16 C atoms, are preferred.
- the particularly suitable compounds include the lauric acid, myristic acid and palmitic acid monoethanolamides.
- the amine oxides suitable according to the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides.
- Preferred amine oxides satisfy the formula R 1 R 2 R 3 N + -0 ⁇ , in which R 1 is a saturated or unsaturated C 6-22 alkyl radical, preferably Cs-is-alkyl radical, in particular a saturated C ⁇ o- 16 alkyl radical, for example a saturated C 2 _i 4 alkyl radical which in the alkylamidoamine oxides via a carbonylamidoalkylene group -CO-NH- (CH 2 ) z - and in the alkoxyalkylamine oxides via an oxaalkylene group -0- (CH 2 ) z - is bonded to the nitrogen atom N, where z in each case represents a number from 1 to 10, preferably 2 to 5, in particular 3, and R 2 and R 3 independently of one another are an optional
- Suitable amine oxides are the following compounds named in accordance with INCI: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide, Decyltetradecylamine Oxide, Diaminopyrimethyl Oxide Oxide, Dioxopoxymethyl Oxide Oxide, Diaminopyrimethyl Oxide Oxide, Diaminopyrimethyl Oxide Oxide, , Dihydroxyethyl C9-11 Alkoxypropylamine Oxide, Dihydroxyethyl C12-15 Alkoxypropylamine Oxide, Dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Tallowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallow
- Preferred amine oxide (s) are, for example, cocamine oxides (N-cocoalkyl-N, N-dimethylamine oxide), dihydroxyethyl tallowamine oxides (N-tallow alkyl-N, N-dihydroxyethylamine oxide) and / or cocamidopropylamine oxides (cocoamidopropylamine oxide), in particular Cocamidopropylamine oxides.
- Suitable surfactants are polyhydroxy fatty acid amides of the formula R 1 I
- RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
- R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
- [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- Suitable amphoteric surfactants are, for example, betaines.
- Suitable betaines are the alkyl betaines, the alkyl amido betaines, the imidazolinium betaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably satisfy the formula (R A ) (R B ) (R c ) N + CH 2 COO " , in which R A is one optionally interrupted by heteroatoms or heteroatom groups, alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms and R B and R c are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 1 -C 8 -alkyl-dimethylcarboxy-methylbetaines and Cn-C ⁇ 7- alkylamidopropyldimethylcarboxymethylbetaines, and betaines according to formula A,
- R 1 is a saturated or unsaturated C 6-22 alkyl radical, C 8-18 alkyl group, preferably, in particular a saturated C ⁇ 0-16 alkyl radical, for example a saturated C 2 -i 4 alkyl radical,
- n is a number from 1 to 10, preferably 2 to 5, in particular 3, x 0 or 1, preferably 1,
- R ", R '" independently of one another are a C 4 alkyl radical, optionally hydroxy-substituted, such as, for example, a hydroxyethyl radical, but in particular a methyl radical, m is a number from 1 to 4, in particular 1, 2 or 3, y 0 or 1 and
- Preferred amphoteric surfactants are the alkylbetaines of the formula A1, the alkylamido betaines of the formula A2, the sulfobetaines of the formula A3 and the amidosulfobetaines of the formula A4, R'-N + (CH 3 ) 2 -CH 2 COO- (A1) R 1 -CO- NH- (CH 2 ) 3 -N + (CH 3 ) 2 -CH 2 COO- (A2)
- amphoteric surfactants are the carbobetaines, in particular the carbobetaines of the formula A1 and A2, most preferably the alkylamidobetaines of the formula A2.
- betaines and sulfobetaines are the following compounds named according to INCI: Almondamidopropyl betaines, apricotamidopropyl betaines, avocadamidopropyl betaines, Babassuamidopropyl betaines, behenamidopropyl betaines, behenyl betaines, betaines, canolamidopropyl betaines, capryl / capramidopropyl betaine, betaine, carnitine, cocaine , Cocamidopropyl Betaine, Cocamidopropyl Hydroxysultaine, Coco-Betaine, Coco-Hydroxysultaine, Coco / Oleamidopropyl Betaine, Coco-Sultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glyc
- a preferred amphoteric surfactant is cocamidopropyl betaine (cocoamidopropyl betaine).
- Particularly preferred amphoteric surfactants are caprylic / capramidopropyl betaine (GAB), which is available, for example, from Th. Goldschmidt AG or Henkel KGaA under the trade names Tegotens® B 810, Tegobetain® F50 or Dehyton®.
- alkylamidoalkylamines are amphoteric surfactants of the formula B
- C 8-18 alkyl radical in particular a saturated C 0-16 alkyl radical, for example a saturated C ⁇ - alkyl radical
- R i is a hydrogen atom H or CH 2 COOM (to M su)
- j is a number from 1 to 4, preferably 1 or 2, in particular
- R 12 is a C ⁇ - alkyl group or M (see below), and M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine , for example protonated mono-, di- or
- Triethanolamine is.
- alkylamidoalkylamines are the following named according to INCI compounds: Cocoamphodipropionic Acid, Cocobetainamido amphopropionates, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropyl- sulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-lsodeceth-7 Carboxyamph
- Cocoamphohydroxypropylsulfonate Sodium Cocoamphopropionate, Sodium Comamphopropionate, Sodium Isostearoamphoacetate, Sodium Isostearoampho- propionate, Sodium lauroamphoacetate, sodium Lauroamphohydroxypropyl- sulfonate, Sodium Lauroampho PG-Acetate Phosphate, Sodium Lauroamphopropionate, Sodium Myristoamphoacetate, Sodium Oleoamphoacetate, Sodium Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate, Sodium Ricinoleoamphoacetate, Sodium Stearoamphoacetate, Sodium Stearoampho-hydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium Tallamphopropionate, Sodium Tallowamphoacetate, Sodium Undecylenoamphoacetate, Sodium Undecylenoamphoprop
- Alkyl-substituted amino acids preferred according to the invention are monoalkyl-substituted amino acids according to formula C,
- Cs- 18 alkyl radical in particular a saturated C ⁇ 0-16 alkyl radical, for example a saturated Ci 2 -i 4 alkyl radical
- R x is a hydrogen atom H or a C ⁇ - 4 alkyl radical, preferably H
- u is a number from 0 to 4 , preferably 0 or 1, in particular 1
- M ' is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or
- Triethanolamine is,
- R x ⁇ is a saturated or unsaturated C 6-22 -alkyl radical, preferably C ⁇ -is-alkyl radical, in particular a saturated C ⁇ o- 16 -alkyl radical, for example a saturated Ci 2 - 14 -alkyl radical
- v is a number from 1 to 5, preferably 2 or 3, in particular 2
- M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine, where M" in the two carboxy groups can have the same or two different meanings, for example hydrogen and sodium or twice sodium is
- Cs-is-alkyl radical in particular a saturated C ⁇ o- 16 alkyl radical, for example a saturated C ⁇ -u-alkyl radical
- R xl is a hydrogen atom or a optionally substituted by hydroxy or amine, for example a methyl, ethyl, hydroxyethyl or
- R x ⁇ v the rest of one of the 20 natural ⁇ -amino acids H 2 NCH (R xlv ) COOH, and M '"a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or
- Triethanolamine is.
- alkyl-substituted amino acids are the aminopropionates according to formula C1,
- alkyl-substituted amino acids are the following compounds named according to INCI: aminopropyl lauryl glutamine, cocaminobutyric acid, cocaminopropionic acid, DEA lauraminopropionate, disodium cocaminopropyl iminodiacetate, disodium dicarboxyethyl cocopropylenediamine, disodium laurododropropionate, disodium stiminaminodipionate, disodium steariminodiphenate Diethylenediaminoglycine, Myristaminopropionic Acid, Sodium C12-15 Alkoxypropyl Iminodipropionate, Sodium Cocaminopropionate, Sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA Lauraminopropionate and TEA Myristaminopropionate.
- Acylated amino acids are amino acids, especially the 20 natural ⁇ -amino acids, which contain the acyl residue R xv CO of a saturated or unsaturated fatty acid R COOH wear xv, where R xv a saturated or unsaturated C 6-22 alkyl, preferably Cs-is-alkyl radical, particularly a saturated Cio-i ⁇ alkyl group, for example a saturated C ⁇ - alkyl.
- the acylated amino acids can also be used as alkali metal salt, alkaline earth metal salt or alkanolammonium salt, for example mono-, di- or triethanolammonium salt.
- acylated amino acids are the acyl derivatives summarized according to INCI under amino acids, for example sodium cocoyl glutamate, lauroyl glutamic acid, capryloyl glycine or myristoyl methylalanine.
- Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R i ⁇ ) (R iv ) (R v ) (R vi ) N + X " , in which R ⁇ i to R vi represent four identical or different types, in particular two long and two short-chain, alkyl radicals and X "represent an anion, in particular a halide ion, for example didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
- the cleaning agents according to the invention contain one or more hydrophobic components.
- the hydrophobic components above all improve the cleaning effect against hydrophobic contaminants such as greasy dirt.
- Suitable hydrophobic components are, for example, dialkyl ethers with the same or different C 4 -C 6 -alkyl radicals, in particular linear dioctyl ether; Hydrocarbons with a boiling range of 100 to 300 ° C, especially 140 to 280 ° C, for. B.
- hydrophobic components are mixtures of various dialkyl ethers, of dialkyl ethers and hydrocarbons, of dialkyl ethers and essential oils, of hydrocarbons and essential oils, of dialkyl ethers and hydrocarbons and essential oils and of these mixtures.
- the cleaning agents according to the invention can contain one or more builders.
- Suitable builders are, for example, alkali metal citrates, gluconates, nitrilotriacetates, carbonates and bicarbonates, in particular sodium citrate, gluconate and nitrilotriacetate, as well as sodium and potassium carbonate and bicarbonate, and also alkali metal and alkaline earth metal hydroxides, in particular sodium and potassium hydroxide Amines, especially mono- and triethanolamine, or mixtures thereof.
- compositions contain builders in amounts, based on the composition, of 0 to 30% by weight, preferably 0.1 to 20% by weight, in particular 1 to 15% by weight, extremely preferably 2 to 10% by weight ,
- a preferred builder is citrate from the group of alkali metal, alkaline earth metal, ammonium and mono-, di- or trialkanolammonium citrates, preferably mono-, di- or triethanolammonium citrates, or mixtures thereof, in particular sodium citrate, extremely preferably potassium citrate.
- a particularly preferred alkaline builder is potassium hydroxide.
- the builder is also to act as a pH-stabilizing buffer, alkali metal and alkaline earth metal carbonates and bicarbonates, e.g. Soda, preferred.
- the cleaning agents according to the invention optionally contain at least one antimicrobial active ingredient, preferably selected from the groups of alcohols, amines, aldehydes, antimicrobial acids or their salts, Carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen acetals and formals, nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial quinoline compounds, amphoteric compounds 1, 2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and other halogens or halogen compounds as well as peroxides or perox
- guanidines including the biguanidines and polyguanidines are, for example, 1,6-bis- (2-ethylhexyl-biguanido-hexane) dihydrochloride, 1,6-di- (N ⁇ , N ⁇ , -phenyldiguanido-N 5 , N 5 l ) -hexane-tetrahydochloride, 1, 6-di- (Ni.Ni'-phenyl-Ni.Ni-methyldiguanido-Ns.Ns'J-hexane-dihydrochloride, 1,6-di- (N- ⁇ , N ⁇ '-chlorophenyldiguanido-N 5 , N 5 ') -hexane-dihydrochloride, 1,6-di- (N ⁇ , N ⁇ '-2,6-dichlorophenyldiguanido-N 5 , N 5 ') -hexane-
- antimicrobial agents see also International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997), published according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature, publisher: The Cosmetic, Toiletry, and Fragrance Association (CTFA), 1101 17th Street , NW, Suite 300, Washington, DC 20036, USA): Alcohol, Benzalkonium Chloride, Benzethonium Chloride, Camellia Sinensis Leaf Extract, Candida Bombicola / Glucose / Methyl, Rapeseedate Ferment, Hydrogen Peroxide, Methylbenzethonium Chloride, Phenol, Pinus Pinaster Bark Extract, Pinus Tabulaeformis Bark Extract, Poloxamer 188, PVP-lodine, Rosmarinus Officinalis (Rosemary), Leaf Extract and Vitis Vinifera (Grape) Seed Extract.
- CTFA Cosmetic, Toiletry, and Fragrance Association
- the agent according to the invention particularly preferably contains at least one quaternary ammonium compound (QAV) with an antimicobial action according to the general formula (R i ⁇ ) (R iv ) (R v ) (R vi ) N + X " in which R i ⁇ to R vi are identical or different C 1 -C 22 -alkyl radicals, C 7 -C 28 -aralkyl radicals or heterocyclic radicals, two or, in the case of an aromatic integration, such as in pyridine, even three radicals together with the nitrogen atom forming the heterocycle, for example a pyridinium or imidazolinium compound , represent and X "are halide ions, sulfate ions, hydroxide ions or similar anions.
- at least one of the residues preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
- QAV are by reacting tertiary amines with alkylating agents, such as. B. methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
- alkylating agents such as. B. methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
- the alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy, and the quaternization of tertiary amines with two long radicals and one methyl group can also be carried out using methyl chloride under mild conditions.
- Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are not very reactive and are preferably quaternized with dimethyl sulfate.
- Suitable QAC are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkon B (mp-dichlorobenzyldimethyl-C 12 -alkylammonium chloride, CAS No. 58390-78-6 ), Benzoxonium chloride (Benzyl dodecyl bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide
- benzetonium chloride N, N-dimethyl-N- [2- [2- [p- (1, 1, 3 , 3-tetramethylbutyl) phenoxy] ethoxy] ethyl] - benzylammonium chloride, CAS No. 121-54-0
- dialkyldimethylammonium chlorides such as di- ⁇ -decyl-dimethyl-ammonium chloride (CAS No. 7173-51-5-5), didecyldimethyl- ammonium bromide (CAS No.
- QAV benzalkonium chlorides with Cs-Cis-alkyl radicals, in particular C 12 -Ci 4 -Akly! -Benzyl-dimethylammonium chloride.
- Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ® ex Lonza, Marquat® ® ex Mason, Variquat ® ex Witco / Sherex and Hyamine ® ex Lonza and as Bardac ® ex Lonza.
- antimicrobial agents are N- (3-chloroallyl) - hexaminiumchlorid as Dowicide and Dowicil ® ® ex Dow, benzethonium chloride such as Hyamine ® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ® 10X ex Rohm & Haas, cetylpyridinium chloride such as Cepacol ex Merrell Labs ,
- the content of antimicrobial active ingredient, in particular surface-active quaternary compound, according to the invention is between 0 to 10% by weight, preferably 0.2 to 5% by weight, in particular 0.5 to 3% by weight, particularly preferably 1 to 2% by weight .-%, for example 1.5 wt .-%.
- the liquid phase used according to the invention can contain one or more thickeners, preferably in an amount of 0.01 to 5% by weight, in particular 0.05 to 2.5% by weight, particularly preferably 0.1 to 1 % By weight.
- Suitable thickeners are organic natural thickeners, such as agar agar, carrageenan, tragacanth, arabic gum, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin or Casein, organic modified natural substances such as carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and the like, gum flour, organic fully synthetic thickeners such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines or polyamides, and inorganic Thickeners such as polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas.
- organic natural thickeners such as agar agar, carrageenan, tragacanth, arabic gum, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, ge
- the polyacrylic and polymethacrylic compounds include, for example, the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (/ ⁇ / C / name according to the International Dictionary of Cosmetic Ingredients from The Cosmetic, Toiletry, and Fragrance Association (CTFA): Carbomer), also known as carboxyvinyl polymers.
- CFA Cosmetic, Toiletry, and Fragrance Association
- Such polyacrylic acids are available from BFGoodrich, among others, under the trade name CarbopoP, for example CarbopoP 940 (molecular weight approx. 4,000,000), CarbopoP 941 (molecular weight approx.
- acrylic acid copolymers (i) Copolymers of two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters (INCI acrylates copolymer), preferably formed with C 4 -alkanols, to which, for example, the copolymers of Methacrylic acid, butyl acrylate and methyl methacrylate (CAS name according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) belong and which, for example, from Rohm & Haas under the trade names Aculyn ® and Acusot ® are available, for example the anionic non-associative polymers Aculyn ® 33 (crosslinked), AcusoP 810 and AcusoP 830 (CAS 25852-37-3); (ii) Crosslinked high molecular acrylic acid, butyl acrylate and their simple esters (INCI acrylates copolymer), preferably formed with C 4
- Preferred thickeners are the polysaccharides and heteropolysaccharides, in particular the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guarane, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, for example propoxylated guar, and their mixtures.
- polysaccharide gums for example gum arabic, agar, alginates, carrageenans and their salts, guar, guarane, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, for example propoxylated guar, and their mixtures.
- polysaccharide thickeners such as starches or cellulose derivatives
- starches or cellulose derivatives can be used alternatively, but preferably in addition to a polysaccharide rubber, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
- starches of various origins and starch derivatives for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
- a particularly preferred polymer is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2 to 15 * 10 6 and is available, for example, from Kelco under the trade name KeltroP, for example as a cream-colored powder KeltroP T (Transparent) or as white granulate KeltroP RD (Readily Dispersable).
- KeltroP for example as a cream-colored powder KeltroP T (Transparent) or as white granulate KeltroP RD (Readily Dispersable).
- the agents according to the invention can contain further auxiliaries and additives as are customary in such agents.
- auxiliaries and additives include in particular perfume and fragrances, polymers, soil release agents, solvents, such as Ethanol, isopropanol and glycol ether, solubilizers, hydrotropes such as e.g. Cumene sulfonate, octyl sulfate, butyl glucoside and butyl glycol, cleaning enhancers, disinfectants, antistatic agents, preservatives, bleaching systems, enzymes and dyes as well as opacifiers or skin protection agents, as described in EP-A-522 556.
- Preferred auxiliaries and additives are perfume and fragrances and dyes.
- the cleaning or hand dishwashing detergents according to the invention in particular the moldings, can be produced in a manner known per se.
- the firm Phases or moldings can be obtained, for example, by coating in the immersion, fog or spray process.
- a capsule phase according to the invention that is to say a shaped body which contains suitable detergent components, by means of the so-called dropletization process, which is described, for example, in DE 2215441 Unilever.
- a clear, colorless hand dishwashing liquid was formulated with blue capsules.
- Capsules consisting of an aqueous solution of 40% C12-14 ether sulfate Na salt, 10% cocamidopropyl betaine, 10% C12-14 sulfate Na salt, 17% ethylene glycol and 0.1% base blue dye were encapsulated in polyvinyl alcohol gel, made from a solution of 10% polyvinyl alcohol (PVAI from Erkol), 0.0005% boric acid, balance water, using an extruder with a concentric outlet opening. The solution was dripped in the form of droplets in a collecting bath consisting of an aqueous solution of 0.5% NaOH and 20% Na 2 S0 4 .
- the capsule phase was added in a concentration of 5 - 30% in the basic rinsing solution. It was stable when stored. When it was diluted to the application concentration at a temperature of 40 ° C., it dissolved within 10 minutes and released the enclosed surfactant. The resulting diluted basic rinsing solution gently cleaned glasses. The blue capsules loosened sets off with a time delay and releases a surfactant mixture for the powerful cleaning of greasy, contaminated dishes.
- a clear hand dishwashing detergent was formulated with blue and green capsules.
- Capsules consisting of an aqueous solution of 40% C12-14 ether sulfate Na salt, 10% cocamidopropyl betaine, 10% C12-14 sulfate Na salt, 17% ethylene glycol and 0.1% base blue dye were encapsulated in polyvinyl alcohol gel, made from a solution of 10% polyvinyl alcohol (PVAI from Erkol), 0.0005% boric acid, balance water, using an extruder with a concentric outlet opening. The solution was dripped in the form of droplets into a collecting bath consisting of an aqueous solution of 0.5% NaOH and 20% Na 2 SO 4 .
- PVAI polyvinyl alcohol
- Capsules were produced, consisting of a core of 10 parts of TiO 2 powder and 6 parts of thiourea dispersed in 84 parts of liquid paraffin with the addition of 0.1% base green dye and a capsule wall made of carrageenan gum.
- the encapsulation was carried out using an aqueous solution of 1% Satiagel (K-carrageenan), 2% Aubygel (i-carrageenan), 0.25% Tragon (locust bean gum) and 2% glycerol and an extruder with a concentric outlet at 70 ° C ,
- the solution was dripped in the form of droplets into a collecting bath consisting of a solution of 5% KCI, 20% water and 75% alcohol.
- Both capsule phases were added in a concentration of 2.5 - 15% to the basic rinsing solution. It is stable when stored. The entire formulation was added to the water when dosing. The immediately rinsed basic rinsing solution cleaned the glasses very gently, after about 5 minutes the green capsules loosened. The released thiourea was particularly effective in cleaning silver cutlery stains. After another 5-10 minutes, the blue capsule phase dissolved and released the surfactant mixture, which effectively cleaned dishes contaminated with fat.
- a clear hand dishwashing detergent was formulated with blue and green capsules.
- the formulation corresponded to that described in Example 2. However, instead of the silver cleaner, the green phase contained aminopolysiloxane as a care component for glass and ceramics.
- the agent When dosing, the agent was placed in water. The immediately rinsed basic rinsing solution cleaned the glasses very gently, after about 5 minutes the green capsules came off. The released active ingredient is particularly suitable for the care of glass and ceramic surfaces. After another 5-10 minutes, the blue capsule phase dissolved and released a surfactant mixture for the powerful cleaning of greasy, contaminated dishes.
- a clear hand dishwashing detergent was formulated with blue and green capsules.
- the formulation corresponded to that described in Example 2. However, instead of the silver cleaner, the green phase contained jojoba oil as a skin care component.
- the formulation When dosing, the formulation was placed in water. The immediately rinsed basic rinsing solution cleaned the glasses very gently, after about 5 minutes the green capsules loosened. The released active ingredient is particularly suitable for skin care. After another 5-10 minutes, the blue capsule phase dissolved and released a surfactant mixture for the powerful cleaning of dishes contaminated with fat.
- a clear hand dishwashing detergent was formulated with blue capsules.
- the basic rinse solution corresponded to that described in Example 1.
- Example 2 The same basic rinsing solution as in Example 1 was used.
- Capsules were prepared by containing an aqueous emulsion containing 0.8% alginate, 1% polyvinyl alcohol, 40% C12-14 ether sulfate Na salt, 10% cocamido propyl betaine and 0.1% base blue dye in an aqueous precipitation bath 5% calcium chloride and 10% sodium sulfate dripped. The capsules obtained were filtered off, washed and added to the basic rinsing solution.
- composition of further basic rinse solutions A to E (external liquid phase) suitable according to the invention is shown in Table 1 below.
- Table 1 The composition of further basic rinse solutions A to E (external liquid phase) suitable according to the invention is shown in Table 1 below.
- a clear hand dishwashing detergent was formulated with blue capsules.
- the basic rinse solution corresponded to that described in Example 1.
- Example 2 The same basic rinsing solution as in Example 1 was used.
- Capsules were prepared by dropping an aqueous emulsion containing 0.8% alginate, 1% polyvinyl alcohol, 25% limonene oil and 0.1% base blue dye into an aqueous precipitation bath containing 5% calcium chloride and 10% sodium sulfate. The capsules obtained were filtered off, washed and added to the basic rinsing solution.
- a clear hand dishwashing liquid was formulated with blue capsules.
- the basic rinse solution corresponded to that described in Example 1.
- Example 2 The same basic rinsing solution as in Example 1 was used.
- Capsules were prepared by using an aqueous emulsion containing 0.8%
- the capsules obtained were filtered off, washed and added to the basic rinsing solution.
- the capsules which dissolve on dilution, released fragrances and skin care substances.
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Abstract
The invention relates to a single or multi-phase detergent containing a surfactant, in particular to a hand dishwashing detergent. At least one phase contains shaped bodies, which are suitable for dispensing at least one detergent component in a time-release manner by being dissolved in water. The inventive detergent contains shaped bodies, which dispense the detergent or rinsing components in a time-release manner by being dissolved in water. According to the invention, the aforementioned 'encapsulated' components are not dispensed immediately after their addition to the water, i.e. during the production of the detergent or rinsing solution, but only after a specific time period. After the first cleaning or rinsing phase, for example the cleaning of glass, the user is thus provided with a detergent composition for the second cleaning or rinsing phase, the latter for example consisting of the cleaning of crockery and saucepans that have greasy deposits, said composition being optimised for this specific cleaning operation.
Description
Mehrphasen-Reinigungsmittel Multiphase detergent
Die vorliegende Erfindung betrifft tensidhaltige Reinigungsmittel, insbesondere Handgeschirrspülmittel.The present invention relates to detergent-containing detergents, in particular hand dishwashing detergents.
Herkömmliche Reinigungsmittel bzw. Handgeschirrspülmittel sind üblicherweise als dünnflüssige bis viskose wäßrige Flüssigkeiten formuliert. Diese praktisch ausschließlich einphasig formulierten flüssigen Reinigungs- bzw. Handgeschirrspülmittel ermöglichen es dem Anwender durch Verdünnung des Reinigungs- oder Spülmittelkonzentrats in Wasser die gewünschte Spülflotte oder Reinigungslösung, welche auch als Anwendungsflotte bezeichnet wird, auf einfache Weise herzustellen, ohne daß der Anwender mit der konzentrierten Form des Mittels in unmittelbaren Hautkontakt kommt. Ein solcher Hautkontakt ist unerwünscht, da die Mittel in konzentrierter Form oft eine irritierende Wirkung auf die Haut ausüben, die vom Anwender als unangenehm empfunden wird. Herkömmliche einphasige Handgeschirrspülmittel und auch Reinigungsmittel beinhalten üblicherweise als Hauptbestandteil Wasser, in welchem die fettlösenden und schaumaktiven Tenside gelöst sind.Conventional cleaning agents or hand dishwashing detergents are usually formulated as low-viscosity to viscous aqueous liquids. These practically exclusively single-phase formulated liquid cleaning or hand dishwashing detergents enable the user to easily produce the desired washing liquor or cleaning solution, which is also referred to as the application liquor, by diluting the cleaning or washing-up liquid concentrate without the user having to use the concentrated form of the agent comes into direct skin contact. Such skin contact is undesirable since the agents in concentrated form often have an irritating effect on the skin which the user perceives as unpleasant. Conventional single-phase hand dishwashing detergents and also cleaning agents usually contain water as the main constituent, in which the fat-dissolving and foam-active surfactants are dissolved.
Ein gravierender Nachteil herkömmlicher Handgeschirrspülmittel liegt darin, daß der Anwender nach der Verdünnung des Handgeschirrspülmittelkonzentrats mit Wasser in Abhängigkeit vom verwendeten Geschirrspülmittel zwangsläufig eine bestimmte Tensidmischung bzw. Spülmittelkomponentenmischung in einem bestimmten Konzentrationsbereich vorliegen hat. Die resultierende Spülflotte wird dann zur manuellen Reinigung des gesamten Spülguts verwendet. Es ist jedoch bekannt, daß eine spezifische, auf das jeweilige Spülgut abgestimmte Handgeschirrspülmittelzusammensetzung bzw. Tensidkonzentration deutlich bessere Reinigungseigenschaften aufweist bzw. aufweisen würde.A serious disadvantage of conventional hand dishwashing detergents is that after the hand dishwashing detergent concentrate has been diluted with water, the user inevitably has a certain surfactant mixture or detergent component mixture in a certain concentration range, depending on the dishwashing detergent used. The resulting wash liquor is then used for manual cleaning of the entire wash ware. However, it is known that a specific hand dishwashing detergent composition or surfactant concentration, which is matched to the respective wash ware, has or would have significantly better cleaning properties.
Beispielsweise ist es bei der Reinigung von Glas wünschenswert einen guten Klarspüleffekt zu erzielen, d. h., daß die Spülflüssigkeit abfließen sollte, ohne Spuren zu hinterlassen. Bei der Behandlung, Reinigung und Klarspülung von Gläsern ist eine große Schaumentwicklung daher unerwünscht. Darüber hinaus ist auch eine hohe Fettlösekraft im allgemeinen weder notwendig noch von Vorteil. Die beiden
vorgenannten Eigenschaften, nämlich starke Schaumentwicklung und hohe Fettlösekraft sind bei einem Handgeschirrspülmittel jedoch insbesondere dann absolut unentbehrlich, wenn fettige Anschmutzungen, beispielsweise auf Tellern und Töpfen, entfernt werden müssen. Ein bezüglich der Reinigung von Gläsern bzw. bezüglich des Klarspüleffektes optimiertes Handgeschirrspülmittel wäre somit für die Entfernung von fettigen Anschmutzungen weniger geeignet.For example, when cleaning glass, it is desirable to achieve a good rinse aid effect, that is to say that the rinsing liquid should drain off without leaving any traces. A large amount of foaming is therefore undesirable when treating, cleaning and rinsing glasses. In addition, a high fat-dissolving power is generally neither necessary nor advantageous. The two The aforementioned properties, namely strong foaming and high grease-dissolving power are absolutely indispensable in the case of a hand dishwashing detergent, in particular if greasy soiling, for example on plates and pots, has to be removed. A hand dishwashing detergent optimized with regard to the cleaning of glasses or with regard to the rinse aid effect would therefore be less suitable for the removal of greasy soiling.
Da der Anwender aus ökonomischen und ökologischen Erwägungen nicht für jedes spezielle Spülgut ein spezifisch zusammengesetztes Handgeschirrspülmittel verwendet, muß das Handgeschirrspülmittel zwangsweise sämtliche zur Reinigung der jeweiligen Spülgüter notwendigen Komponenten enthalten. Dies hat beispielsweise zur Folge, daß bei der Reinigung von Glas, welche üblicherweise am Anfang des Spülvorganges durchgeführt wird, mit einem universell anwendbaren Handgeschirrspülmittel grundsätzlich eine starke Schaumentwicklung und eine hohe Fettlösekraft gegeben ist, obwohl dies, wie oben ausgeführt, unerwünscht bzw. unnötig ist.Since, for economic and ecological reasons, the user does not use a specifically designed hand dishwashing detergent for each special wash ware, the hand dishwashing detergent must inevitably contain all the components necessary for cleaning the respective wash ware. This has the consequence, for example, that when cleaning glass, which is usually carried out at the beginning of the washing process, with a universally applicable hand dishwashing detergent there is basically a strong foaming and a high fat-dissolving power, although, as stated above, this is undesirable or unnecessary ,
Aus den oben genannten Gründen ist es ebenfalls von Nachteil, daß etwaige Pflegemittel für das Spülgut, beispielsweise Pflegekomponenten für Glas und Keramikoberflächen, bereits von Anfang an, nämlich mit Zugabe des Handgeschirrspülmittels, in der Spülflotte enthalten sind. Aus verständlichen Gründen wäre es von Vorteil, wenn die Pflegekomponenten erst nach der Reinigung der Gläser zugesetzt würden.For the reasons mentioned above, it is also disadvantageous that any care products for the wash ware, for example care components for glass and ceramic surfaces, are contained in the wash liquor right from the start, namely with the addition of the hand dishwashing liquid. For understandable reasons, it would be advantageous if the care components were only added after the glasses had been cleaned.
Aufgrund des üblichen zeitlichen Ablaufs würde man zur Erzielung eines optimalen Reinigungseffektes also zunächst ein Mittel zur manuellen Reinigung von Glas verwenden und anschließend Geschirr mit stark fetthaltigen Anschmutzungen mit Hilfe eines weiteren Mittels mit anderer Zusammensetzung säubern. Gegebenfalls würde man in einer weiteren Spülphase das Glas oder Geschirr noch mit einer Pflegekomponenten enthaltenden Spülflotte behandeln.Due to the usual schedule, one would first use a means for manual cleaning of glass to achieve an optimal cleaning effect and then clean dishes with heavily greasy soiling with the help of another agent with a different composition. In a further rinsing phase, the glass or dishes would possibly be treated with a rinsing liquor containing care components.
Alle bisher bekannten Handgeschirrspülmittel sind nicht auf die üblicherweise in zeitlichen Phasen bzw. schrittweise ablaufende Reinigung der verschiedenen Spülgüter abgestimmt, sondern stellen praktisch einen Kompromiß bezüglich der
Reinigung von beispielsweise Glas, mit Fettanschmutzung versehenem Geschirr, Besteck usw. dar. Dies gilt sowohl für die herkömmlichen einphasigen und zweiphasigen Handgeschirrspülmittel als auch beispielsweise für vorbeschriebene Spül- und Reinigungsmittel in fester Form.All previously known hand dishwashing detergents are not matched to the cleaning of the different items to be washed, which usually takes place in chronological phases or in steps, but rather represents a compromise in terms of Cleaning of, for example, glass, dishes with grease soiling, cutlery, etc. This applies both to the conventional single-phase and two-phase hand dishwashing detergents and, for example, to the previously described solid detergents and cleaning agents.
Ähnliche Nachteile sind auch im Zusammenhang mit Reinigungsmitteln, wie beispielsweise Fußbodenreinigern, zu beobachten. Der Anwender erhält durch Verdünnen des Reinigungsmittelkonzentrats eine entsprechende Reinigungslösung bzw. Anwendungsflotte mit einer bestimmten Tensidmischung bzw. Reinigungsmittelkomponenten-Zusammensetzung. Die resultierende Reinigungslösung enthält somit neben den schmutzlösenden Substanzen auch entsprechende Pflegekomponenten, die beispielsweise dem gereinigten Boden einen Glanzeffekt verleihen, den gesäuberten Boden mit einer Schutzschicht versehen oder aber die rasche Wiederanschmutzung der gereinigten Oberfläche verhindern sollen. Wie bereits ausgeführt, werden sämtliche Reinigungsmittelkomponenten, also schmutzlösende Substanzen und Pflegekomponenten, bei der Anwendung des Mittels zwangsweise gleichzeitig auf die zu reinigende Oberfläche aufgetragen. Aus nachvollziehbaren Gründen wäre insbesondere bei stark verschmutzen Oberflächen eine sukzessive Anwendung von schmutzlösenden Substanzen und Pflegekomponenten von Vorteil und würde zu einem besseren Reinigungsergebnis führen.Similar disadvantages can also be observed in connection with cleaning agents, such as floor cleaners. By diluting the detergent concentrate, the user receives an appropriate cleaning solution or application liquor with a specific surfactant mixture or detergent component composition. The resulting cleaning solution thus contains, in addition to the dirt-dissolving substances, also appropriate care components which, for example, give the cleaned floor a glossy effect, provide the cleaned floor with a protective layer or are intended to prevent the cleaned surface from being soiled again quickly. As already stated, all detergent components, ie dirt-dissolving substances and care components, are forcibly applied to the surface to be cleaned when the agent is used. For understandable reasons, a gradual application of dirt-dissolving substances and care components would be advantageous, especially for heavily soiled surfaces, and would lead to a better cleaning result.
Die DE 198 54 267 betrifft eine umhüllte Wirksubstanz für manuelle Reinigungsmittel für harte Oberflächen, wie etwa Handgeschirrspülmittel. Die Umhüllung besteht hierbei vorzugsweise aus einem Material, das mindestens ein natürliches oder synthetisches Polymer oder ein Gemisch davon enthält und sich in etwa 35°C warmem Wasser innerhalb von etwa 10 bis 50 Sekunden, vorzugsweise etwa 20 bis 40 Sekunden auflöst. Die auf umhüllten Wirksubstanzen basierenden Reinigungsmittel bzw. Geschirrspülmittel gemäß der DE 198 54 267 zeichnen sich durch eine verbesserte Lagerstabilität aus, weisen jedoch keine auf den zeitlichen Ablauf eines Reinigungsvorgangs abgestimmte Formulierung auf und haben daher die oben beschriebenen Nachteile.DE 198 54 267 relates to a coated active substance for manual cleaning agents for hard surfaces, such as hand dishwashing liquid. The casing preferably consists of a material which contains at least one natural or synthetic polymer or a mixture thereof and which dissolves in water at about 35 ° C. within about 10 to 50 seconds, preferably about 20 to 40 seconds. The detergents or dishwashing detergents based on coated active substances according to DE 198 54 267 are distinguished by improved storage stability, but do not have a formulation which is coordinated with the chronological course of a cleaning process and therefore have the disadvantages described above.
Die WO 94/14941 betrifft wäßrige neutrale oder leicht alkalische, maschinelle Geschirrspülmittel, die frei von anionischen und kationischen Tensiden sind. Die
maschinellen Geschirrspülmittel können in wasserlöslichen oder wasser- dispergierbaren Behältern eingeschlossen sein, die beispielsweise aus Gelatine bestehen.WO 94/14941 relates to aqueous neutral or slightly alkaline, automatic dishwashing detergents which are free from anionic and cationic surfactants. The Machine dishwashing detergents can be enclosed in water-soluble or water-dispersible containers, which consist, for example, of gelatin.
Die in WO 94/14941 beschriebenen maschinellen Geschirrspülmittel, welche eingeschlossene bzw. verkapselte Spülmittelkomponenten umfassen können, sind als Handgeschirrspülmittel ungeeignet. Die in den Dokumenten beschriebene Gelatine-Ummantelung der Wirkstoffe dient lediglich der Stabilisierung der Komponenten und einer einfachen Dosierung.The automatic dishwashing detergents described in WO 94/14941, which may include enclosed or encapsulated detergent components, are unsuitable as hand dishwashing detergents. The gelatin coating of the active ingredients described in the documents only serves to stabilize the components and to allow simple dosing.
Die EP-A-9261754 betrifft ein Schaumbad in Form eines Gemisches aus Aminsalzen und langkettigen Alkylethersulfaten und 25 bis 35 Gew.-% flüssigem Polyethylenglykolen, verkapselt in einer elastischen Gelatinekapsel.EP-A-9261754 relates to a foam bath in the form of a mixture of amine salts and long-chain alkyl ether sulfates and 25 to 35% by weight of liquid polyethylene glycols, encapsulated in an elastic gelatin capsule.
Die EP-A-0533 239 betrifft wäßrige flüssige Reinigungsmittelzusammensetzung, welche Enzyme und verkapselte Bleichpartikel umfassen. Die Reinigungsmittel eignen sich insbesondere zur Verwendung als maschinelle Geschirrspülmittel. Die Verkapselung einzelner Komponenten, nämlich der Bleichstoffe, dient auch hier der Verbesserung der Lagerfähigkeit, bzw. Stabilität, da Wechselwirkungen zwischen dem Enzym und den Bleichpartikeln vermieden werden sollen.EP-A-0533 239 relates to aqueous liquid detergent compositions which comprise enzymes and encapsulated bleach particles. The cleaning agents are particularly suitable for use as automatic dishwashing agents. The encapsulation of individual components, namely the bleaching agents, also serves to improve the shelf life or stability here, since interactions between the enzyme and the bleaching particles are to be avoided.
Es wäre daher sehr wünschenswert, ein einziges Reinigungsmittel, insbesondere Handgeschirrspülmittel zur Verfügung zu haben, welches hinsichtlich des üblichen manuellen Reinigungs- bzw. Spülablaufs in seiner Zusammensetzung und seiner Reinigungswirkung optimiert ist. Der übliche Spülablauf bei der Reinigung von Geschirr beinhaltet die manuelle Reinigung von Glas und anschließende Reinigung von Geschirr mit stark fetthaltigen Anschmutzungen.It would therefore be very desirable to have a single detergent, in particular hand dishwashing detergent, which is optimized in terms of its composition and its cleaning effect with regard to the usual manual cleaning or rinsing process. The usual rinsing process for cleaning dishes includes manual cleaning of glass and subsequent cleaning of dishes with heavily greasy soiling.
Eine Aufgabe der vorliegenden Erfindung ist es nunmehr, ein Reinigungsmittel, insbesondere Handgeschirrspülmittel bereitzustellen, welches die oben beschriebenen Nachteile herkömmlicher ein- und mehrphasiger Reinigungs- bzw. Handgeschirrspülmittel überwindet.
Es ist insbesondere eine Aufgabe der vorliegenden Erfindung, daß die Zusammensetzung des Reinigungs- bzw. Handgeschirrspülmittels im Hinblick auf den zeitlichen Ablauf des Reinigungsvorgangs und die zu reinigende Oberfläche bzw. das Spülgut abgestimmt und optimiert ist.It is now an object of the present invention to provide a cleaning agent, in particular hand dishwashing detergent, which overcomes the above-described disadvantages of conventional single- and multi-phase cleaning or hand dishwashing detergents. It is a particular object of the present invention that the composition of the cleaning or hand dishwashing detergent is coordinated and optimized with regard to the timing of the cleaning process and the surface to be cleaned or the items to be washed.
Weitere Aufgaben ergeben sich aus der nachfolgenden Beschreibung der Erfindung.Further objects result from the following description of the invention.
Die Lösung der Aufgaben liegt in der Bereitstellung eines tensidhaltigen Reinigungsmittels, insbesondere Handgeschirrspülmittels, wobei das Mittel ein- oder mehrphasig ist und wobei wenigstens eine Phase Formkörper aufweist, die geeignet sind, wenigstens eine Reinigungs- bzw. Spülmittelkomponente bei Verdünnung mit Wasser zeitlich verzögert freizusetzen.The solution to the problems lies in the provision of a surfactant-containing detergent, in particular hand dishwashing detergent, the detergent being single-phase or multi-phase and wherein at least one phase has moldings which are suitable for releasing at least one detergent or detergent component when diluted with water with a time delay.
Zeitlich verzögert im Sinne der vorliegenden Erfindung bedeutet, daß sich die Formkörper bei Verdünnung mit Wasser zu einem bestimmten Zeitpunkt oder während eines bestimmten Zeitraums lösen. Die Begriffe "Reinigungsmittelkomponente" und „Spülmittelkomponente" umfassen im Rahmen der Erfindung neben reinigungsaktiven Substanzen auch Hilfs- und Zusatzstoffe, wie beispielsweise Parfüm oder Farbstoffe.Delayed for the purposes of the present invention means that the shaped bodies dissolve when diluted with water at a specific point in time or during a specific period of time. In the context of the invention, the terms “detergent component” and “detergent component” also include auxiliaries and additives, such as, for example, perfume or dyes, in addition to cleaning-active substances.
Die erfindungsgemäßen Reinigungsmittel bzw. Handgeschirrspülmittel werden zum Gebrauch in der Regel in Wasser mit einer Temperatur von bis zu 50°C aufgelöst und die entstehende Anwendungsflotte wird dann beispielsweise zum manuellen Reinigen von harten Oberflächen und/oder weichen Oberflächen, insbesondere Gläsern, Eß- und Kochgeschirr etc. eingesetzt. Unter dem Begriff "manuelle Reinigung" im Sinne der vorliegenden Erfindung fällt selbstverständlich auch ein Reinigungsvorgang, der mit Hilfe mechanischer Hilfsmittel, wie etwa Bürste, Schwamm oder dergleichen, durchgeführt wird.The detergents or hand dishwashing detergents according to the invention are generally dissolved in water at a temperature of up to 50 ° C. and the resulting application liquor is then used, for example, for manual cleaning of hard surfaces and / or soft surfaces, in particular glasses, eating utensils and cookware etc. used. The term "manual cleaning" in the sense of the present invention naturally also includes a cleaning process which is carried out with the aid of mechanical aids, such as a brush, sponge or the like.
Es wurde gefunden, daß das erfindungsgemäß formulierte Reinigungsmittel bzw. Handgeschirrspülmittel die Nachteile der im Stand der Technik beschriebenen Mittel überwindet und eine auf die einzelnen Reinigungsphasen und Spülphasen abgestimmte und optimierte Anwendungsflottenzusammensetzung ermöglicht.
Es ist erfindungsgemäß vorgesehen, daß das Reinigungsmittel, insbesondere Spülmittel wenigstens eine, vorzugsweise flüssige Phase, aufweist, welche sich bei Verdünnung mit Wasser im wesentlichen ohne zeitliche Verzögerung löst. In einer bevorzugten Ausführungsform beinhaltet diese sofort lösliche Phase die für den Klarspüleffekt auf Glas besonders geeigneten Reinigungsmittel- bzw. Spülmittelkomponenten, da bei einem üblichen manuellen Spülvorgang zunächst Gläser bzw. gläserne Gegenstände gereinigt werden. Besonders bevorzugt enthält die flüssige Phase Reinigungsmittelkomponenten ausgewählt aus der Gruppe umfassend nichtionische Tenside, insbesondere endgruppenverschlossene Cβ-C22- Alkylalkoholpolyglykolether, sekundäre Alkansulfonate, lineare Alkylbenzolsulfonate und Alkylpolyglucoside.It has been found that the cleaning agent or hand dishwashing agent formulated according to the invention overcomes the disadvantages of the agents described in the prior art and enables an application liquor composition which is coordinated and optimized for the individual cleaning phases and rinsing phases. It is provided according to the invention that the cleaning agent, in particular rinsing agent, has at least one, preferably liquid phase, which dissolves essentially without any time delay when diluted with water. In a preferred embodiment, this immediately soluble phase contains the detergent or detergent components that are particularly suitable for the rinse effect on glass, since glasses or glass objects are first cleaned in a conventional manual rinsing process. The liquid phase particularly preferably contains detergent components selected from the group comprising nonionic surfactants, in particular end-capped Cβ-C 22 alkyl alcohol polyglycol ethers, secondary alkane sulfonates, linear alkyl benzene sulfonates and alkyl polyglucosides.
In einer weiteren bevorzugten Ausführungsform enthält die flüssige Phase des erfindungsgemäßen Reinigungsmittels zwischen 5 und 45 Gew.-% Tenside, bezogen auf die flüssige Phase, vorzugsweise ausgewählt aus der Gruppe umfassend nichtionische Tenside, anionische Tenside, Betaine, Aminoxide und kationische Tenside, wobei der Anteil an kationischen Tensiden vorzugsweise weniger als 5 Gew.-% beträgt.In a further preferred embodiment, the liquid phase of the cleaning agent according to the invention contains between 5 and 45% by weight of surfactants, based on the liquid phase, preferably selected from the group comprising nonionic surfactants, anionic surfactants, betaines, amine oxides and cationic surfactants, the proportion of cationic surfactants is preferably less than 5% by weight.
Weiterhin enthält das erfindungsgemäße Reinigungsmittel bzw. Handgeschirrspülmittel Formkörper, welche die in den Formkörpern enthaltenen Reinigungsmittelbzw. Spülmittelkomponenten bei Verdünnung mit Wasser zeitlich verzögert freisetzen. Gemäß der vorliegenden Erfindung werden vorgenannte „verkapselte" Komponenten nicht unmittelbar nach der Zugabe des Mittels in Wasser, also nach Herstellung der Reinigungslösung bzw. Spülflotte, freigesetzt, sondern erst nach einem bestimmten Zeitraum. In einer weiteren bevorzugten Ausführungsform werden die Formkörper bei Verdünnung mit Wasser bei einer Temperatur von etwa 40°C innerhalb eines Zeitraumes von bis zu 10 min, vorzugsweise innerhalb eines Zeitraums von 0,5 bis 9 min, mehr bevorzugt innerhalb von 1 bis 8 min, besonders bevorzugt innerhalb von 3 bis 8 min zu ≥ 70 %, vorzugsweise zu ≥ 80 %, besonders bevorzugt zu > 90 % und insbesondere bevorzugt zu 99 bis 100 % gelöst.Furthermore, the cleaning agent or hand dishwashing detergent according to the invention contains molded articles which contain the cleaning agents or detergents contained in the molded articles. Release detergent components with a time delay when diluted with water. According to the present invention, the aforementioned “encapsulated” components are not released into water immediately after the addition of the agent, that is to say after the cleaning solution or rinsing liquor has been prepared, but only after a certain period of time. In a further preferred embodiment, the shaped bodies are diluted with water at a temperature of about 40 ° C. within a period of up to 10 min, preferably within a period of 0.5 to 9 min, more preferably within 1 to 8 min, particularly preferably within 3 to 8 min at ≥ 70% , preferably to ≥ 80%, particularly preferably to> 90% and particularly preferably to 99 to 100% dissolved.
Auf diese Weise steht dem Anwender nach der ersten Reinigungsphase bzw. Spülphase (Reinigung der Gläser) eine für die zweite Reinigungsphase bzw.
Spülphase, welche beispielsweise in der Reinigung von mit Fettanschmutzungen versehenen Tellern und Töpfen etc. besteht, eine auf diesen spezifischen Reinigungsvorgang optimierte Reinigungsmittelzusammensetzung zur Verfügung.In this way, after the first cleaning phase or rinsing phase (cleaning the glasses), the user has one for the second cleaning phase or Rinsing phase, which consists, for example, in the cleaning of plates and pots soiled with grease, etc., a detergent composition optimized for this specific cleaning process is available.
Der zeitlich verzögerte Auflösevorgang der Formkörper kann erfindungsgemäß mit verschiedenen Mechanismen zur Freisetzung der Aktivsubstanzen gesteuert werden. Vorzugsweise werden die im Formkörper enthaltenen Reinigungs- bzw. Spülmittelkomponenten, beispielsweise Tensidkomponenten mit starker Fettlösekraft, schaumbildende Komponenten, etc., mit geeigneten Hüllen-, Beschichtungs- und/oder Matrixmaterialien versehen. Die Beschichtung bzw. Umhüllung unter Erhalt beispielsweise kapselartiger Formkörper erlaubt eine besonders präzise und zeitlich genau steuerbare Freisetzung der vorgenannten Komponenten.According to the invention, the time-delayed dissolution process of the shaped bodies can be controlled using various mechanisms for releasing the active substances. The cleaning or rinsing agent components contained in the molded body, for example surfactant components with strong fat-dissolving power, foam-forming components, etc., are preferably provided with suitable casing, coating and / or matrix materials. The coating or encapsulation while receiving, for example, capsule-like shaped bodies allows a particularly precise and precisely controllable release of the aforementioned components.
Erfindungsgemäß kann das Auflösen der Formkörper bei Verdünnung beispielsweise zeitlich gesteuert, pH-Wert-gesteuert, temperaturgesteuert oder auch Elektrolytstärke-gesteuert erfolgen .According to the invention, the dissolving of the shaped bodies can take place, for example, in a time-controlled manner, in a pH-controlled manner, in a temperature-controlled manner or also in an electrolyte-controlled manner when diluted.
Es ist in einer weiteren bevorzugten Ausführungsform vorgesehen, daß der flüssigen Phase ein Verdickungsmittel zugesetzt wird, so daß eine Stabilisierung und gleichmäßige Verteilung der Formkörper, welche besonders bevorzugt eine kugel- oder kapselartige Form aufweisen, in der vorgenannten flüssigen Phase gewährleistet ist. In einer bevorzugten Ausführungsform wird der flüssigen Phase Verdickungsmittel zugesetzt, so daß die Formkörper in der vorgenannten flüssigen bzw. gelartigen Phase „schweben". Auf diese Weise wird sichergestellt, daß der Anwender bei der Herstellung der Reinigungslösung oder Spülflotte tatsächlich die für die jeweiligen Reinigungs- oder Spülphasen erforderlichen Reinigungs- bzw. Spülmittelkomponenten im richtigen Verhältnis zudosiert. Eine gleichmäßige Verteilung der Formkörper bzw. eine gezielte Zudosierung kann auch durch kräftiges Schütteln unmittelbar vor Herstellung der Reinigungslösung oder Spülflotte erreicht werden.
Besonders bevorzugt sind die Formkörper mit 0,1 bis 30 Gew.-%, vorzugsweise mit 0,2 bis 10 Gew.-% und besonders bevorzugt 0,5 bis 3Gew.-%, bezogen auf die flüssige Phase, in der flüssigen Phase enthalten.In a further preferred embodiment it is provided that a thickener is added to the liquid phase, so that a stabilization and uniform distribution of the shaped bodies, which particularly preferably have a spherical or capsule-like shape, is ensured in the aforementioned liquid phase. In a preferred embodiment, thickener is added to the liquid phase, so that the moldings “float” in the aforementioned liquid or gel-like phase. This ensures that the user actually produces the cleaning and The necessary proportions of detergent or rinsing agent components are added in the correct ratio A uniform distribution of the shaped bodies or a targeted addition can also be achieved by shaking vigorously immediately before preparing the cleaning solution or rinsing liquor. The moldings are particularly preferably present in the liquid phase at from 0.1 to 30% by weight, preferably from 0.2 to 10% by weight and particularly preferably from 0.5 to 3% by weight, based on the liquid phase ,
In einer weiteren erfindungsgemäß bevorzugten Ausführungsform beinhaltet das Reinigungsmittel, insbesondere Handgeschirrspülmittel Formkörper mit gleicher oder unterschiedlicher Reinigungs- bzw. Spülmittelkomponenten-Zusammensetzung, wobei die Komponenten aus der Gruppe umfassend Silberreinigungsmittel, Korrosionsschutzmittel, Hand- bzw. Hautpflegemittel, spezielle Pflegemittel, vorzugsweise Pflegemittel für Keramik und/oder Glas, Mittel zur Entfernung spezieller Anschmutzungen, fettlösende Substanzen oder Mischungen davon ausgewählt sind.In a further preferred embodiment according to the invention, the detergent, in particular hand dishwashing detergent, contains moldings with the same or different detergent or dishwashing component composition, the components from the group comprising silver detergents, corrosion protection agents, hand or skin care agents, special care agents, preferably care agents for ceramics and / or glass, agents for removing special soiling, fat-dissolving substances or mixtures thereof are selected.
Besonders bevorzugte Reinigungs- bzw. Spülmittelkomponenten umfassen Betaine, Fettalkoholsulfate, Fettalkoholethersulfate, sekundäre Alkansulfonate, lineare Alkylbenzolsulfonate, Alkylalkoholpolyglykolether, Alkylpolygucoside, Fettsäure- alkanolamide, Aminoxide und Mischungen davon. „Fettlösende Substanzen" im Sinne der vorliegenden Erfindung umfassen neben den vorgenannten Substanzen auch hydrophobe Komponenten. Geeignete Hydrophobkomponenten umfassen beispielsweise Dialkylether mit gleichen oder verschiedenen C4- bis Cu-Alkylresten, insbesondere lineare Dioctylether; Kohlenwasserstoffe mit einem Siedebereich von 100 bis 300 °C, insbesondere 140 bis 280 °C, insbesondere aliphatische Kohlenwasserstoffe mit einem Siedebereich von 145 bis 200 °C, Isoparaffine mit einem Siedebereich von 200 bis 260 °C; etherische Öle, insbesondere Limonen und das aus Kiefern wurzeln und -stubben extrahierte Pine Oil und auch Mischungen dieser Hydrophobkomponenten.Particularly preferred cleaning or rinsing agent components include betaines, fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkanesulfonates, linear alkylbenzenesulfonates, alkyl alcohol polyglycol ethers, alkyl polygucosides, fatty acid alkanolamides, amine oxides and mixtures thereof. “Fat-dissolving substances” in the sense of the present invention include, in addition to the aforementioned substances, also hydrophobic components. Suitable hydrophobic components include, for example, dialkyl ethers with identical or different C 4 - to Cu-alkyl radicals, in particular linear dioctyl ethers; hydrocarbons with a boiling range from 100 to 300 ° C. especially 140 to 280 ° C, especially aliphatic hydrocarbons with a boiling range of 145 to 200 ° C, isoparaffins with a boiling range of 200 to 260 ° C; essential oils, especially limonene and the pine oil extracted from pine roots and stumps and also mixtures of these hydrophobic components.
Geeignete Reinigungs- bzw. Spülmittelkomponenten sind beispielsweise unter den Handelsnamen Hostapur® SAS 60 (sekundäres Alkansulfonat von Clariant), Texapon® SPN 70 (Fettalkoholethersulfat von Henkel KGaA, Düsseldorf), Empinin® KS8 (Fettalkoholethersulfat von Albright & Wilson GmbH, Frankfurt), Ceraminox® (Aminoxid von Clariant), Sulfopon® 101 (C12-C14-Laurylsulfat von Henkel KGaA, Düsseldorf), Dehyton® (verschiedene Betaine von Henkel KGaA, Düsseldorf) erhältlich.
Als Silberschutzmittel können beispielsweise Substanzen ausgewählt aus der Gruppe der Triazole, der Benzotriazole, der Bisbenzotriazole, der Aminotriazole, der Alkylaminotriazole und der Übergangsmetallsalze oder -komplexe eingesetzt werden. Besonders bevorzugt zu verwenden sind Benzotriazol und/oder Alkylaminotriazol. Ebenfalls können Zinkverbindungen zur Verhinderung der Korrosion am Spülgut eingesetzt werden. Weitere Reinigungs- bzw. Spülmittelkomponenten sind Glanztrocknungsadditive, Reinigungsverstärker, antimikrobielle Wirkstoffe bzw. Desinfektionsmittel, Antistatika, Konservierungsmittel (z.B. Glutaraldehyd), Bleichsysteme und Farbstoffe sowie Trübungsmittel oder auch Hautschutzmittel, wie sie in EP-A-522 556 beschrieben sind.Suitable cleaning and rinsing agent components are, for example, under the trade names Hostapur® SAS 60 (secondary alkane sulfonate from Clariant), Texapon® SPN 70 (fatty alcohol ether sulfate from Henkel KGaA, Düsseldorf), Empinin® KS8 (fatty alcohol ether sulfate from Albright & Wilson GmbH, Frankfurt), Ceraminox ® (amine oxide from Clariant), Sulfopon® 101 (C12-C14 lauryl sulfate from Henkel KGaA, Düsseldorf), Dehyton® (various betaines from Henkel KGaA, Düsseldorf). For example, substances selected from the group consisting of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used as silver protection agents. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. Zinc compounds can also be used to prevent corrosion on the wash ware. Other cleaning or rinsing agent components are gloss drying additives, cleaning enhancers, antimicrobial agents or disinfectants, antistatic agents, preservatives (eg glutaraldehyde), bleaching systems and dyes, and opacifiers or skin protection agents, as described in EP-A-522 556.
In einer insbesondere bevorzugten Ausführungsform umfaßt das Reinigungsmittel, insbesondere Spülmittel: a) Formkörper mit einer ersten Reinigungsmittelkomponenten- Zusammensetzung umfassend mindestens eine Komponente, die ausgewählt ist aus der Gruppe der Silberreinigungsmittel, Korrosionsschutzmittel, Hand- bzw. Hautpflegemittel, spezielle Pflegemittel, vorzugsweise Pflegemittel für Keramik und/oder Glas, und/oder Mittel zur Entfernung spezieller Anschmutzungen; und b) Formkörper mit einer zweiten Reinigungsmittelkomponenten- Zusammensetzung umfassend mindestens eine fettlösende Substanz, vorzugsweise ausgewählt aus der Gruppe der Betaine, Fettalkoholsulfate, Fettalkoholethersulfate, sekundäre Alkansulfonate, lineare Alkylbenzolsulfonate, Alkylalkoholpolyglykolether, Alkylpolyglucoside, Fettsäurealkanolamide, Aminoxide und/oder hydrophobe Komponenten, wobei die in Formkörper a) enthaltene erste Reinigungsmittelkomponenten- Zusammensetzung bei Verdünnung des Reinigungsmittels mit Wasser vorzugsweise vor der in Formkörper b) enthaltenen zweiten Reinigungsmittelkomponenten- Zusammensetzung freigesetzt wird.In a particularly preferred embodiment, the detergent, in particular dishwashing detergent, comprises: a) shaped articles with a first detergent component composition comprising at least one component selected from the group consisting of silver detergents, corrosion inhibitors, hand and skin care agents, special care agents, preferably care agents for ceramics and / or glass, and / or means for removing special soiling; and b) moldings with a second detergent component composition comprising at least one fat-dissolving substance, preferably selected from the group consisting of betaines, fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkane sulfonates, linear alkylbenzenesulfonates, alkyl alcohol polyglycol ethers, alkyl polyglucosides, fatty acid alkanolamides, amine oxides and / or hydrophobic components Shaped body a) contained first detergent component composition when the detergent is diluted with water, preferably before the second detergent component composition contained in shaped body b) is released.
In einer bevorzugten Ausführungsform unterscheiden sich Formkörper a) und b) äußerlich, beispielsweise farblich, voneinander. Der Mechanismus zur Freisetzung
der in Formkörper a) bzw. b) enthaltenen Komponenten kann auf den obengenannten, verschiedenen möglichen Parametern basieren. Bei Verwendung eines geeigneten Hüllen- oder Matrixmaterials kann die Auflösung der jeweiligen Formkörper nahezu beliebig zeitlich gesteuert, pH-Wert-gesteuert, temperaturgesteuert oder auch Elektrolytstärke-gesteuert erfolgen.In a preferred embodiment, molded bodies a) and b) differ from one another externally, for example in color. The release mechanism The components contained in molded body a) or b) can be based on the various possible parameters mentioned above. If a suitable shell or matrix material is used, the dissolution of the respective shaped bodies can be controlled almost at any time, pH-controlled, temperature-controlled or even electrolyte strength-controlled.
Gemäß der vorliegenden Erfindung ist es insbesondere bevorzugt, daß die in Formkörper a) enthaltene erste Reinigungs- bzw. Spülmittelkomponenten- Zusammensetzung bei Verdünnung in Wasser vor der in Formkörper b) enthaltenen zweiten Reinigungs- bzw. Spülmittelkomponenten-Zusammensetzung freigesetzt wird, d. h. daß die Materialien oder der Freisetzungsmechanismus so gewählt werden, daß die Zusammensetzung in der Reinigungslösung bzw. Spülflotte auf die jeweilige Reinigungs- oder Spülphase abgestimmt bzw. optimiert ist. Der Formkörper b) enthält vorzugsweise Komponenten, die sich insbesondere zur Entfernung von stark fetthaltigen Anschmutzungen, beispielsweise auf Tellern, eignen.According to the present invention, it is particularly preferred that the first cleaning or rinsing agent component composition contained in molded body a) is released upon dilution in water before the second cleaning or rinsing agent component composition contained in molded body b), i. H. that the materials or the release mechanism are selected so that the composition in the cleaning solution or rinsing liquor is matched or optimized to the respective cleaning or rinsing phase. The molded body b) preferably contains components which are particularly suitable for removing heavily greasy soiling, for example on plates.
Wie bereits ausgeführt, umfaßt das erfindungsgemäße Reinigungsmittel, insbesondere Handgeschirrspülmittel, in einer bevorzugten Ausführungsform eine flüssige Phase und Formkörper mit gleicher oder unterschiedlicher Zusammensetzung. Die Formkörper können grundsätzlich eine beliebige Form aufweisen, wobei rationell und kostengünstig herstellbare Formen in der Regel bevorzugt sind. Hierzu gehören beispielsweise alle in Bezug auf wenigstens eine Achse rotationssymmetrische Formen, beispielsweise die Kugelform, elliptische Formen oder zylindrische Formen, wobei eine Kapsel in Form eines an beiden Enden Halbkugelschalen verschlossenen Zylinders bevorzugt ist.As already stated, the cleaning agent according to the invention, in particular hand dishwashing liquid, in a preferred embodiment comprises a liquid phase and moldings with the same or different composition. The shaped bodies can in principle have any shape, with shapes which can be produced economically and economically being preferred. These include, for example, all shapes which are rotationally symmetrical with respect to at least one axis, for example the spherical shape, elliptical shapes or cylindrical shapes, a capsule in the form of a cylinder closed at both ends being preferred.
In einer weiteren besonders bevorzugten Ausführungsform sind die Matrix-, Umhüllungs- und/oder Beschichtungsmaterialien der Formkörper so gewählt, daß sie sich in Wasser nur langsam lösen und die inkorporierten Füllmittelkomponenten erst zu einem bestimmten Zeitpunkt oder während eines bestimmten Zeitraums in die Anwendungs- bzw. Spülflotte abgeben.In a further particularly preferred embodiment, the matrix, coating and / or coating materials of the shaped bodies are selected such that they dissolve only slowly in water and the incorporated filler components are only incorporated into the application or at a specific point in time or during a specific period of time. Dispense wash liquor.
Das erfindungsgemäß geeignete Umhüllungs-, Beschichtung und/oder Matrixmaterial ist vorzugsweise wasserlöslich, oder zumindest wasserdispergierbar, d. h., daß sich
das Material nach dem Einbringen in Wasser wenigstens teilweise auflöst oder zumindest eine Dispersion eingeht, so daß die Umhüllung, Beschichtung und/oder Matrix zu einem vorbestimmten Zeitpunkt oder nach einem bestimmten Zeitraum durchlässig wird und ein Stoffaustausch zwischen den Formkörper umgebenden Wasser und den eingeschlossenen Reinigungs- bzw. Spülmittelkomponenten ermöglicht wird.The coating, coating and / or matrix material suitable according to the invention is preferably water-soluble, or at least water-dispersible, that is to say that the material at least partially dissolves after being introduced into water or at least a dispersion is formed, so that the covering, coating and / or matrix becomes permeable at a predetermined point in time or after a certain period of time and an exchange of substances between the water surrounding the shaped body and the enclosed cleaning agents or detergent components is made possible.
Geeignete Umhüllungs-, Matrix- und/oder Beschichtungsmaterialien umfassen Polymere und/oder Co-Polymere, welche für den jeweils vorgesehenen Auflösungsmechanismus geeignet sind. Geeignete Materialien umfassen Alginsäure, Alginate, Pektine, Guar-Mehl, Stärke, Dextrine, Gelatine, organische abgewandelte Naturstoffe, insbesondere Carboxymethylcellulose und Celluloseether, Hydroxyethyl- und -propylcellulose und dergleichen, Polysaccharide, organische vollsynthetische Substanzen, insbesondere Polyacryl- und Polymethacryl-Verbindungen, Vinyl- polymere, insbesondere Polyvinylalkohole, Polycarbonsäuren, Polyether, Polyimine, Polyamide, Polyelektrolyte und grundsätzlich wasserlösliche oder in Wasser zerfallende Polymere. Weiterhin kann das Material, aus dem die Umhüllung besteht, Zusatzstoffe enthalten, welche die Elastizität und Wasserlöslichkeit beeinflussen. Geeignete Weichmacher sind beispielsweise Glykol, Sorbitol und Glycerin.Suitable coating, matrix and / or coating materials include polymers and / or copolymers which are suitable for the dissolution mechanism provided in each case. Suitable materials include alginic acid, alginates, pectins, guar flour, starch, dextrins, gelatin, organic modified natural substances, in particular carboxymethyl cellulose and cellulose ethers, hydroxyethyl and propyl cellulose and the like, polysaccharides, organic fully synthetic substances, in particular polyacrylic and polymethacrylic compounds, Vinyl polymers, in particular polyvinyl alcohols, polycarboxylic acids, polyethers, polyimines, polyamides, polyelectrolytes and, in principle, water-soluble or water-disintegrating polymers. Furthermore, the material from which the covering is made can contain additives which influence the elasticity and water solubility. Suitable plasticizers are, for example, glycol, sorbitol and glycerin.
Eine zeitlich kontrollierte Reinigungsmittelkomponentenfreisetzung kann beispielsweise durch eine pH-Wert-Änderung der Reinigungslösung bzw. Spülflotte erreicht werden. Betrachtet man beispielsweise den Vorgang des manuellen Reinigens von Geschirr, so verändert sich der anfängliche pH-Wert der Spülflotte während des Spülvorgangs. Geht man davon aus, daß in der ersten Spülphase, nämlich beim Reinigen der Gläser, das zu spülende Objekt zunächst in der Spülflotte gereinigt wird und anschließend mit Frischwasser nachgespült wird, so kommt es aufgrund der Verdünnung mit pH-neutralem Wasser zu einem Abfall des pH-Wertes in der Spülflotte. Der resultierende pH-Wert hängt hierbei vom Volumen und der Spülmittelkomponentenkonzentration in der Spülflotte sowie von der Menge an zugegebenem Frischwasser ab. Diese pH-Wert-Änderung in der Spülflotte kann dazu genutzt werden, den Auflösevorgang der Formkörper gezielt zu steuern. Dieser Effekt bzw. eine solche pH-Wert-Änderung ist selbstverständlich auch bei der Verdünnung von Reinigungs- und Spülmittelkonzentraten sowie bei verdünnten
Reinigungsmitteln zu beobachten und kann ebenfalls dazu genutzt werden, den Auflösevorgang der Formkörper gezielt zu steuern.A time-controlled release of detergent components can be achieved, for example, by changing the pH of the cleaning solution or rinsing liquor. If you consider, for example, the process of manually cleaning dishes, the initial pH value of the washing liquor changes during the washing process. If one assumes that in the first rinsing phase, namely when cleaning the glasses, the object to be rinsed is first cleaned in the washing liquor and then rinsed with fresh water, the pH will drop due to the dilution with pH-neutral water -Values in the washing liquor. The resulting pH value depends on the volume and the detergent component concentration in the washing liquor and on the amount of fresh water added. This pH value change in the rinsing liquor can be used to control the dissolution process of the shaped bodies in a targeted manner. This effect or such a change in pH value is of course also the case with the dilution of cleaning and washing-up liquid concentrates and with diluted ones Observe cleaning agents and can also be used to control the dissolution process of the moldings.
Es ist erfindungsgemäß bevorzugt, solche Umhüllungs-, Matrix- und/oder Beschichtungsmaterialien zu verwenden, welche bei einer Änderung des pH-Wertes der Anwendungsflotte eine Änderung der physikalisch-chemischen Eigenschaften erfahren. Es ist dabei insbesondere bevorzugt, daß solche Substanzen bei auftretender pH-Wert-Änderung eine erhöhte Löslichkeit in Wasser und/oder eine Abnahme der Diffusionsdichte aufweisen. Zu diesen Substanzen zählen basische Substanzen, insbesondere basische Polymere und/oder Copolymere. Das Prinzip der pH-abhängigen Wasserlöslichkeit beruht in der Regel auf einer Protonierung oder Deprotonierung funktioneller Seitengruppen der Polymere. Solche Polymere mit pH-abhängiger Löslichkeit sind unter anderem auch aus der Pharmazie bekannt, beispielsweise im Zusammenhang mit magensaftresistenten Überzügen auf Tabletten.According to the invention, it is preferred to use wrapping, matrix and / or coating materials which experience a change in the physicochemical properties when the pH of the application liquor changes. It is particularly preferred that such substances have an increased solubility in water and / or a decrease in the diffusion density when the pH changes. These substances include basic substances, in particular basic polymers and / or copolymers. The principle of pH-dependent water solubility is usually based on protonation or deprotonation of functional side groups of the polymers. Such polymers with pH-dependent solubility are also known, inter alia, from the pharmaceutical industry, for example in connection with enteric coatings on tablets.
Insbesondere geeignet als pH-sensitive Umhüllungs-, Matrix- und/oder Beschichtungsmaterialien sind im Rahmen der vorliegenden Erfindung (Co-)Polymere, welche vorzugsweise Aminogruppen bzw. Amonoalkylgruppen aufweisen. Geeignete Comonomere sind beispielsweise Acrylate, Methacrylate, Maleinate oder Derivate dieser Verbindungen. Weiterhin geeignet sind Polymaleinimid-Copolymere, Polyacrylamide, Polyvinylpyrrolidon- Copolymere und/oder Polyurethane.Particularly suitable as pH-sensitive coating, matrix and / or coating materials in the context of the present invention are (co) polymers which preferably have amino groups or aminoalkyl groups. Suitable comonomers are, for example, acrylates, methacrylates, maleinates or derivatives of these compounds. Polymaleimide copolymers, polyacrylamides, polyvinylpyrrolidone copolymers and / or polyurethanes are also suitable.
Des weiteren ist es erfindungsgemäß vorgesehen, daß die Formkörper elektrolytgesteuert gelöst und/oder die darin enthaltenen Spülmittelkomponenten aufgrund einer Änderung der Elektrolytkonzentration freigesetzt werden.Furthermore, it is provided according to the invention that the shaped bodies are dissolved under electrolyte control and / or the detergent components contained therein are released due to a change in the electrolyte concentration.
In einer besonders bevorzugten Ausführungsform werden die Reinigungs- bzw. Spülmittelkomponenten aus den Formkörpern temperaturgesteuert freigesetzt. Die Formkörper werden hierzu beispielsweise aus einer die Reinigungsmittelkomponenten enthaltenden Schmelzdispersion bzw. -emulsion hergestellt, wobei die Schmelzsuspension oder -emulsion im wesentlichen aus einer Hüllsubstanz besteht, die einen Schmelzpunkt oberhalb von 30°C aufweist. Die in die Schmelzsuspension
bzw. -emulsion einzuarbeitenden Komponenten können bei der Verarbeitungstemperatur sowohl in fester als aber auch in flüssiger Form vorliegen.In a particularly preferred embodiment, the cleaning or rinsing agent components are released from the shaped bodies in a temperature-controlled manner. For this purpose, the moldings are produced, for example, from a melt dispersion or emulsion containing the detergent components, the melt suspension or emulsion essentially consisting of a coating substance which has a melting point above 30 ° C. The in the melt suspension Components or emulsion to be incorporated can be at the processing temperature both in solid and in liquid form.
An die Hüllsubstanzen werden verschiedene Anforderungen gestellt, die zum einen das Schmelz- beziehungsweise Erstarrungsverhalten, zum anderen jedoch auch die Materialeigenschaften der Umhüllung im erstarrten Bereich bei Umgebungstemperatur betreffen. Da die Umhüllung die darin eingeschlossenen Reinigungs- bzw. Spülmittelkomponenten erst in der Anwendungsflotte freisetzen soll und nicht bei thermischer Belastung während Transport oder Lagerung, weisen die Hüllsubstanzen vorzugsweise einen Schmelzpunkt über 30°C auf.Various requirements are placed on the coating substances, which on the one hand relate to the melting or solidification behavior, but on the other hand also relate to the material properties of the coating in the solidified area at ambient temperature. Since the coating should only release the cleaning or rinsing agent components contained therein in the application liquor and not under thermal stress during transport or storage, the coating substances preferably have a melting point above 30 ° C.
Die oben genannten Eigenschaften werden in der Regel von sogenannten Wachsen erfüllt. Unter "Wachsen" wird eine Reihe natürlicher oder künstlich gewonnener Stoffe verstanden, die in der Regel über 30°C ohne Zersetzung schmelzen und schon wenig oberhalb des Schmelzpunktes verhältnismäßig niedrigviskos und nicht fadenziehend sind. Sie weisen eine stark temperaturabhängige Konsistenz und Löslichkeit auf.The properties mentioned above are usually fulfilled by so-called waxes. "Waxing" is understood to mean a number of natural or artificially obtained substances which, as a rule, melt above 30 ° C. without decomposition and are relatively low-viscosity and not stringy even a little above the melting point. They have a strongly temperature-dependent consistency and solubility.
Nach ihrer Herkunft teilt man die Wachse in drei Gruppen ein, die natürlichen Wachse, chemisch modifizierte Wachse und die synthetischen Wachse.The waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes.
Zu den natürlichen Wachsen zählen beispielsweise pflanzliche Wachse wie Candelillawachs, Carnaubawachs, Japanwachs, Espartograswachs, Korkwachs, Guarumawachs, Reiskeimölwachs, Zuckerrohrwachs, Ouricurywachs, oder Montanwachs, tierische Wachse wie Bienenwachs, Schellackwachs, Walrat, Lanolin (Wollwachs), oder Bürzelfett, Mineralwachse wie Ceresin oder Ozokerit (Erdwachs), oder petrochemische Wachse wie Petrolatum, Paraffinwachse oder Mikrowachse.Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.
Zu den chemisch modifizierten Wachsen zählen beispielsweise Hartwachse wie Montanesterwachse, Sassolwachse oder hydrierte Jojobawachse.The chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
Unter synthetischen Wachsen werden in der Regel Polyalkylenwachse oder Polyalkylenglycolwachse verstanden. Als Hüllmaterialien einsetzbar sind auch Verbindungen aus anderen Stoffklassen, die die genannten Erfordernisse hinsichtlich des Erweichungspunkts erfüllen. Als geeignete synthetische Verbindungen haben sich
beispielsweise höhere Ester der Phthalsäure, insbesondere Dicyclohexylphthalat, das kommerziell unter dem Namen Unimoll® 66 (Bayer AG) erhältlich ist, erwiesen. Geeignet sind auch synthetisch hergestellte Wachse aus niederen Carbonsäuren und Fettalkoholen, beispielsweise Dimyristyl Tartrat, das unter dem Namen Cosmacol® ETLP (Condea) erhältlich ist. Umgekehrt sind auch synthetische oder teilsynthetische Ester aus niederen Alkoholen mit Fettsäuren aus nativen Quellen einsetzbar. In diese Stoffklasse fällt beispielsweise das Tegin® 90 (Goldschmidt), ein Glycerinmonostearat- palmitat. Auch Schellack, beispielsweise Schellack-KPS-Dreiring-SP (Kalkhoff GmbH) ist erfindungsgemäß als Hüllmaterial einsetzbar.Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the stated requirements with regard to the softening point can also be used as covering materials. Suitable synthetic compounds have been found for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll 66 ® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ® ETLP (Condea). Conversely, synthetic or partially synthetic esters from lower alcohols with fatty acids from native sources can also be used. Tegin ® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances. Shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used as a coating material according to the invention.
Ebenfalls zu den Wachsen im Rahmen der vorliegenden Erfindung werden beispielsweise die sogenannten Wachsalkohole gerechnet. Wachsalkohole sind höhermolekulare, wasserunlösliche Fettalkohole mit in der Regel etwa 22 bis 40 Kohlenstoffatomen. Die Wachsalkohole kommen beispielsweise in Form von Wachsestern höhermolekularer Fettsäuren (Wachssäuren) als Hauptbestandteil vieler natürlicher Wachse vor. Beispiele für Wachsalkohole sind Lignocerylalkohol (1- Tetracosanol), Cetylalkohol, Myristylalkohol oder Melissylalkohol. Die Umhüllung der erfindungsgemäß umhüllten Feststoffpartikel kann gegebenenfalls auch Wollwachsalkohole enthalten, worunter man Triterpenoid- und Steroidalkohole, beispielsweise Lanolin, versteht, das beispielsweise unter der Handelsbezeichnung Argowax® (Pamentier & Co) erhältlich ist. Ebenfalls zumindest anteilig als Bestandteil der Umhüllung einsetzbar sind im Rahmen der vorliegenden Erfindung Fettsäureglycerinester oder Fettsäurealkanolamide aber gegebenenfalls auch wasserunlösliche oder nur wenig wasserlösliche Polyalkylenglycolverbindungen.The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ® (Pamentier & Co). In the context of the present invention, fatty acid glycerol esters or fatty acid alkanolamides can also be used, at least in part, as a constituent of the casing, but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.
Weiterhin geeignete Hüllsubstanzen zur temperaturgesteuerten Freisetzung der Reinigungs- bzw. Spülmittelkomponenten umfassen Polyethylenglykole, Polyvinylpyrrolidone, Polyether, Carboxymethylcellulose, Hydroxypropylcellulose, Hydroxyethylcellulose und/oder Hydroxyethylpropylcellulose.Further suitable coating substances for the temperature-controlled release of the cleaning or rinsing agent components include polyethylene glycols, polyvinylpyrrolidones, polyethers, carboxymethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose and / or hydroxyethyl propyl cellulose.
Ein weiterer Gegenstand der vorliegenden Erfindung liegt in der Verwendung des erfindungsgemäßen Reinigungsmittels zur Reinigung von harten Oberflächen und/oder weichen Oberflächen, vorzugsweise als Allzweckreiniger, Badreiniger, Fußbodenreiniger, Autoreiniger, Glasreiniger, Möbelpflegemittel, Möbelreiniger,
Fassadenreiniger, Waschmittel und/oder dergleichen und besonders bevorzugt zur Reinigung von Geschirr. Außerdem betrifft die vorliegende Erfindung ein Verfahren zur Reinigung einer harten und/oder weichen Oberfläche mit einer wäßrigen Reinigungsflotte, welches dadurch gekennzeichnet ist, daß die Reinigungsflotte durch Auflösen oder Dispergieren des erfindungsgemäßen Reinigungsmittels in Wasser hergestellt wird.Another object of the present invention is the use of the cleaning agent according to the invention for cleaning hard surfaces and / or soft surfaces, preferably as an all-purpose cleaner, bathroom cleaner, floor cleaner, car cleaner, glass cleaner, furniture care agent, furniture cleaner, Facade cleaner, detergent and / or the like and particularly preferably for cleaning dishes. In addition, the present invention relates to a method for cleaning a hard and / or soft surface with an aqueous cleaning liquor, which is characterized in that the cleaning liquor is produced by dissolving or dispersing the cleaning agent according to the invention in water.
Zu den erfindungsgemäß vorgesehenen Reinigungsmittel- und Spülmittelkomponenten des Reinigungs- bzw. Handgeschirrspülmittels gemäß der vorliegenden Erfindung zählen die folgenden Stoffe bzw. Stoffgruppen:The detergent and dishwashing detergent components of the detergent or hand dishwashing detergent according to the present invention include the following substances or groups of substances:
Tensidesurfactants
Die erfindungsgemäßen reinigungsaktiven Phasen können als Tensidkomponenten anionische, nichtionische, amphotere oder kationische Tenside bzw. Tensidgemische aus einer, mehreren oder allen diesen Tensidklassen enthalten. Die Reinigungsmittel, insbesondere Handgeschirrspülmittel enthalten auf die verschiedenen Phasen verteilt Tenside in Mengen, bezogen auf die Gesamtformulierung, von 5 bis 55 Gew.-%, vorzugsweise 10 bis 30 Gew.-%.The active cleaning phases according to the invention can contain anionic, nonionic, amphoteric or cationic surfactants or surfactant mixtures from one, several or all of these classes of surfactants as surfactant components. The detergents, in particular hand dishwashing detergents, contain surfactants, distributed over the various phases, in amounts, based on the overall formulation, of 5 to 55% by weight, preferably 10 to 30% by weight.
Anionische TensideAnionic surfactants
Anionische Tenside gemäß der vorliegenden Erfindung können aliphatische Sulfate wie Fettalkoholsulfate, Fettalkoholethersulfate, Dialkylethersulfate, Monoglycerid- sulfate sowie aliphatische und aromatische Sulfonate wie Alkansulfonate, Olefinsulfonate, Ethersulfonate, n-Alkylethersulfonate, Estersulfonate, Lignin- sulfonate und Alkylbenzolsulfonate sein. Ebenfalls im Rahmen der vorliegenden Erfindung verwendbar sind Fettsäurecyanamide, Sulfobemsteinsäureester, Fettsäure- isothionate, Acylaminoalkansulfonate (Fettsäuretauride), Fettsäuresarcosinate, Ethercarbonsäuren und Alkyl(ether)phosphate.Anionic surfactants according to the present invention can be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates as well as aliphatic and aromatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates, lignin sulfonates, lignin sulfonates. Fatty acid cyanamides, sulfosuccinic acid esters, fatty acid isothionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates can also be used in the context of the present invention.
Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der Cι2-Ci8-Fettalkohole, beispielsweise aus Kokosfettalkohol, Taigfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der C10-
C2o-Oxoalkohole und die Halbester sekundärer Alkohole (sekundäre Alkylsulfate) 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. Im Hinblick auf die Verwendung des erfindungsgemäßen Mittels als (Hand)geschirrspülmittel sind die Cι2-Cι6-Alkylsulfate und Cι2-C15-Alkylsulfate sowie Ci4-Ci5-Alkylsulfate bevorzugt. Geeignete sekundäre Alkylsulfate enthalten 2- und/oder 3-Alkylsulfate sowie gegebenenfalls höhere Homologe (4-, 5-, 6-Alkylsulfate etc.), sind beispielsweise gemäß den US-Patentschriften 3,234,258 oder 5,075,041 herstellbar und sind als Handelsprodukte der Shell Oil Company unter dem Namen DAN® erhältlich, z. B. die in den US-Patentschriften 5,529,724 und H 1 ,665 genannten Produkte DAN® 214, ein C14-SAS mit 99 % 2- und 3-Alkylsulfat, DAN® 216, ein C16-SAS mit 99 % 2- und 3-Alkylsulfat, und DAN® 100, ein SAS mit 62 % 2- und 3-Alkylsulfat.As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half esters of the C 2 -C 8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C10- C 2 o-oxo alcohols and the half esters of secondary alcohols (secondary alkyl sulfates) of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. With regard to the use of the agent according to the invention as (hand) dishwashing detergent, the C 2 -C 6 alkyl sulfates and C 2 -C 15 alkyl sulfates and C 4 -Ci 5 alkyl sulfates are preferred. Suitable secondary alkyl sulfates contain 2- and / or 3-alkyl sulfates and optionally higher homologues (4-, 5-, 6-alkyl sulfates etc.), can be prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and are commercially available from Shell Oil Company at available under the name DAN ® , e.g. B. the products mentioned in US Pat. Nos. 5,529,724 and H 1,665 DAN® 214, a C 14 -SAS with 99% 2- and 3-alkyl sulfate, DAN® 216, a C 16 -SAS with 99% 2- and 3-alkyl sulfate, and DAN® 100, a SAS with 62% 2- and 3-alkyl sulfate.
Besonders bevorzugt im Rahmen der vorliegenden Erfindung sind die Fettalkoholethersulfate. Fettalkoholethersulfate sind Produkte von Sulfatierreaktionen an alkoxylierten Alkoholen. Durch Reaktion von Ethylenoxid mit längerkettigen Alkohole, beispielsweise mit geradkettigen oder verzweigten Alkoholen mit Kettenlängen von C bis C2ι wie etwa 2-Methyl-verzweigte C9- bis Cn- Fettalkohole werden geeignete alkoxylierte Alkohole erhalten. In der Regel entsteht aus n Molen Ethylenoxid und einem Mol Alkohol abhängig von den Reaktionsbedingungen ein komplexes Gemisch von Additionsprodukten unterschiedlichen Ethoxylierungs- grades. Bei der Ethoxylierungsreaktion können auch Gemische von Ethylenoxid und Propylenoxid eingesetzt werden. Ganz besonders bevorzugt im Sinne der vorliegenden Erfindung sind niederethoxylierte Fettalkohole (0,5 bis 4 Mol EO, bevorzugt 1 bis 2 Mol EO).The fatty alcohol ether sulfates are particularly preferred in the context of the present invention. Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. Suitable alkoxylated alcohols are obtained by reacting ethylene oxide with longer-chain alcohols, for example with straight-chain or branched alcohols with chain lengths of C to C 2 ι such as 2-methyl-branched C 9 to Cn fatty alcohols. As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. Mixtures of ethylene oxide and propylene oxide can also be used in the ethoxylation reaction. Low-ethoxylated fatty alcohols (0.5 to 4 mol EO, preferably 1 to 2 mol EO) are very particularly preferred in the sense of the present invention.
Besonders bevorzugt im Rahmen der vorliegenden Erfindung sind weiterhin die Alkansulfonate, insbesondere die sekundären Alkansulfonate, die aus unverzweigten Paraffinkohlenwasserstoffen, insbesondere C-ι2_i8-Alkanen, beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation
gewonnen werden. Ein bevorzugtes sekundäres Alkansulfonate ist das als Hostapur® SAS 60 von Clariant vertriebene sekundäre Na-Ci3-i7-Alkansulfonat.Particularly preferred within the scope of the present invention further provides the alkane, in particular the secondary alkane sulfonates of unbranched paraffinic hydrocarbons, in particular C-ι 2 _i 8 -alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization, be won. A preferred secondary alkane sulfonates is as Hostapur SAS ® 60, sold by Clariant secondary Ci-Na 3 -i 7 alkane.
Als weitere Tenside vom Sulfonat-Typ kommen Alkylbenzolsulfonate, Olefin- sulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, in Betracht, wie man sie beispielsweise aus Cι2_i8-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält. Alkylbenzolsulfonate im Sinne der erfindungsgemäßen Lehre sind Alkylbenzolsulfonate mit geradkettigen oder verzweigten, gesättigten oder ungesättigten C6-22-Alkylresten, bevorzugt C8-18-Alkylresten, insbesondere C9_i4-Alkylresten, äußerst bevorzugt Cιo-13-Alkylresten. Sie werden als Alkalimetall- und/oder Erdalkalimetallsalze, insbesondere Natrium-, Kalium-, Magnesium- und/oder Calciumsalze, wie auch als Ammoniumsalze bzw. Mono-, Di- oder Trialkanolammoniumsalze, vorzugsweise Mono-, Di- oder Triethanol- und/oder -isopropanolammoniumsalze, insbesondere Mono-, Di- bzw.Other suitable surfactants of the sulfonate type are alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, of the kind obtained, for example, from C 2 - 8 mono-olefins with terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products. Alkylbenzene sulfonates in the context of the teaching according to the invention are alkylbenzenesulfonates having a linear or branched, saturated or unsaturated C 6-22 alkyl, preferably C 8-18 alkyl, especially C 9 _i 4 alkyl, most preferably Cιo- 13 alkyl radicals. They are used as alkali metal and / or alkaline earth metal salts, in particular sodium, potassium, magnesium and / or calcium salts, and also as ammonium salts or mono-, di- or trialkanolammonium salts, preferably mono-, di- or triethanol and / or -isopropanolammonium salts, especially mono-, di- or
Triethanolammoniumsalze, aber genauso als Alkylbenzolsulfonsäure zusammen mit dem entsprechenden Alkalimetall- bzw. Erdalkalimetallhydroxid und/oder Ammoniak bzw. Mono-, Di- oder Trialkanolamin eingesetzt. Ebenso sind auch die Ester von 2- Sulfofettsäuren (Estersulfonate), z.B. die 2-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Taigfettsäuren geeignet.Triethanolammonium salts, but also used as alkylbenzenesulfonic acid together with the corresponding alkali metal or alkaline earth metal hydroxide and / or ammonia or mono-, di- or trialkanolamine. Likewise, the esters of 2-sulfo fatty acids (ester sulfonates), e.g. the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
Die Aniontenside werden in Form ihrer Alkalimetall- und Erdalkalimetallsalze, insbesondere Natrium-, Kalium- und Magnesiumsalze, wie auch Ammonium- und Mono-, Di-, Tri- bzw. Tetraalkylammoniumsalze sowie im Falle der Sulfonate auch in Form der Säure, z.B. Dodecylbenzolsulfonsäure, Cι0-Cι3-Alkylbenzolsulfonsäure und/oder Cι0-Cι4-Alkylbenzolsulfonsäure, eingesetzt. Beim Einsatz von Sulfonsäure wird diese üblicherweise in situ mit einer oder mehreren entsprechenden Basen, z.B. Alkalimetall- und Erdalkalimetallhydroxide, insbesondere Natrium-, Kalium- und Magnesiumhydroxid, sowie Ammoniak oder Mono-, Di-, Tri- bzw. Tetraalkylamin, - je nach einzustellendem pH-Wert des Mittels teilweise oder vollständig - zu den vorgenannten Salzen neutralisiert.
Wegen ihrer schaumdämpfenden und verdickenden Eigenschaften können die erfindungsgemäßen Reinigungsmittel auch Seifen, d.h. Alkali- oder Ammoniumsalze gesättigter oder ungesättigter C6-C22-Fettsäuren, enthalten.The anionic surfactants are in the form of their alkali metal and alkaline earth metal salts, in particular sodium, potassium and magnesium salts, as well as ammonium and mono-, di-, tri- or tetraalkylammonium salts and, in the case of the sulfonates, also in the form of the acid, for example dodecylbenzenesulfonic acid, Cι 0 -Cι 3 alkylbenzene and / or Cι 0 -Cι 4 alkylbenzene used. When sulfonic acid is used, it is usually mixed in situ with one or more corresponding bases, for example alkali metal and alkaline earth metal hydroxides, in particular sodium, potassium and magnesium hydroxide, and ammonia or mono-, di-, tri- or tetraalkylamine, depending on what is to be set pH of the agent partially or completely - neutralized to the aforementioned salts. Because of their foam-suppressing and thickening properties, the cleaning agents according to the invention can also contain soaps, ie alkali metal or ammonium salts of saturated or unsaturated C6-C22 fatty acids.
Nichtionische TensideNonionic surfactants
Nichtionische Tenside im Rahmen der Erfindung können Alkoxylate sein, wie Polyglycolether, Fettalkoholpolyglycolether, Alkylphenolpolyglycolether, endgruppen- verschlossene Polyglycolether, Mischether und Hydroxymischether und Fettsäure- polyglycolester sowie Alkylpolyglykoside oder auch stickstoffhaltige Tenside.Nonionic surfactants in the context of the invention can be alkoxylates, such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end group-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters as well as alkyl polyglycosides or nitrogenous surfactants.
Bevorzugt einsetzbare nichtionische Tenside sind die endgruppenverschlossenen Poly(oxyalkylierten) Niotenside der FormelNon-ionic surfactants which can preferably be used are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
R10[CH2CH(R3)0]χ[CH2]kCH(OH)[CH2]jOR2 R 1 0 [CH 2 CH (R 3 ) 0] χ [CH 2 ] k CH (OH) [CH 2 ] j OR 2
in der R1 und R2 für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 1 bis 30 Kohlenstoffatomen stehen, R3 für H oder einen Methyl-, Ethyl-, n-Propyl-, iso-Propyl, n-Butyl-, 2-Butyl- oder 2-Methyl-2-Butylrest steht, x für Werte zwischen 1 und 30, k und j für Werte zwischen 1 und 12, vorzugsweise zwischen 1 und 5 stehen. Wenn der Wert x = 2 ist, kann jedes R3 in der obenstehenden Formel unterschiedlich sein. R1 und R2 sind vorzugsweise lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 6 bis 22 Kohlenstoffatomen, wobei Reste mit 8 bis 18 C-Atomen besonders bevorzugt sind. Für den Rest R3 sind H, -CH3 oder -CH2CH3 besonders bevorzugt. Besonders bevorzugte Werte für x liegen im Bereich von 1 bis 20, insbesondere von 6 bis 15.in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R3 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl -, 2-butyl or 2-methyl-2-butyl, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x = 2, each R 3 in the above formula can be different. R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH3 or -CH 2 CH 3 are particularly preferred for the radical R 3 . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
Wie vorstehend beschrieben, kann jedes R3 in der obenstehenden Formel unterschiedlich sein, falls x = 2 ist. Hierdurch kann die Alkylenoxideinheit in der eckigen Klammer variiert werden. Steht x beispielsweise für 3, kann der Rest R3 ausgewählt werden, um Ethylenoxid (EO)-(R3 = H) oder Propylenoxid (PO)- (R3 = CH3) Einheiten zu bilden, die in jedweder Reihenfolge aneinandergefügt sein können, beispielsweise (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO),
(PO)(PO)(EO) und (PO)(PO)(PO). Der Wert 3 für x ist hierbei beispielhaft gewählt worden und kann durchaus größer sein, wobei die Variationsbreite mit steigenden x-Werten zunimmt und beispielsweise eine große Anzahl (EO)-Gruppen, kombiniert mit einer geringen Anzahl (PO)-Gruppen einschließt, oder umgekehrt.As described above, each R 3 in the above formula can be different if x = 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if x stands for 3, the radical R 3 can be selected to form ethylene oxide (EO) - (R 3 = H) or propylene oxide (PO) - (R 3 = CH3) units which can be joined together in any order, for example (EO) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (PO). The value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
Insbesondere bevorzugte endgruppenverschlossenen Poly(oxyalkylierte) Alkohole der obenstehenden Formel weisen Werte von k = 1 und j = 1 auf, so daß sich die vorstehende Formel zuParticularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula can be used
R10[CH2CH(R3)0]xCH2CH(OH)CH2OR2 R 1 0 [CH 2 CH (R 3 ) 0] x CH 2 CH (OH) CH 2 OR 2
vereinfacht. In der letztgenannten Formel sind R1, R2 und R3 wie oben definiert und x steht für Zahlen von 1 bis 30, vorzugsweise von 1 bis 20 und insbesondere von 6 bis 18. Besonders bevorzugt sind Tenside, bei denen die Reste R1 und R2 9 bis 14 C-Atome aufweisen, R3 für H steht und x Werte von 6 bis 15 annimmt.simplified. In the last-mentioned formula, R 1 , R 2 and R 3 are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 1 and R 2 have 9 to 14 carbon atoms, R 3 represents H and x assumes values from 6 to 15.
Insbesondere bevorzugt werden im Rahmen der vorliegenden Erfindung endgruppenverschlossene Fettalkoholpolyglykolether verwendet, die unter dem Handelsnamen Dehypon® von der Henkel KGaA, Düsseldorf, vertrieben werden.End group-capped fatty alcohol polyglycol ethers, which are sold under the trade name Dehypon® by Henkel KGaA, Düsseldorf, are particularly preferably used in the context of the present invention.
Alkylalkoholpolyglykoletheralkyl alcohol
C6-C22-AlkyIalkoholpolypropylenglykol/polyethylenglykolether stellen bevorzugte bekannte nichtionische Tenside dar. Sie können durch die FormelC 6 -C 22 alkyl alcohol polypropylene glycol / polyethylene glycol ethers are preferred known nonionic surfactants. They can be represented by the formula
R10-(CH2CH(CH3)0)p(CH2CH20)e-HR 1 0- (CH 2 CH (CH 3 ) 0) p (CH 2 CH 2 0) e -H
beschrieben werden, in der R1 für einen linearen oder verzweigten, aliphatischen Alkyl- und/oder Alkenylrest mit 6 bis 22, vorzugsweise 8 bis 18, insbesondere 10 bis 16, Kohlenstoffatomen, p für 0 oder Zahlen von 1 bis 3 und e für Zahlen von 1 bis 20 steht.are described in which R 1 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 8 to 18, in particular 10 to 16, carbon atoms, p for 0 or numbers from 1 to 3 and e for numbers from 1 to 20.
Die C6-C22-Alkylalkoholpolyglykolether kann man durch Anlagerung von Propylenoxid und/oder Ethylenoxid an Alkylalkohole, vorzugsweise an Oxoalkohole, an
verzweigtkettige durch Oxosynthese erhältliche primäre Alkohole oder an Fettalkohole erhalten. Typische Beispiele sind Polyglykolether, bei denen R1 für einen Alkylrest mit 8 bis 18 Kohlenstoffatomen, p für 0 bis 2 und e für Zahlen von 2 bis 7 steht. Bevorzugte Vertreter sind beispielsweise Cι0-Cι -Fettalkohol+1 PO+6EO-ether (p = 1 , e = 6), C12-Ci6-Fettalkohol+5.5-EO (p = 0, e = 5,5), Cι2-Cι8-Fettalkohol+7EO- ether (p = 0, e = 7) und lsodecanol+6-EO (R1 = Isomerengemisch von C-io- Oxoalkoholresten, p = 0, e = 6) sowie deren Mischungen. In besonderen Mischungen ist mindestens ein Alkylalkoholpolyglykolether mit einem linearen Alkylrest R1 mit mindestens einem Alkylalkoholpolyglykolether mit einem verzweigten Alkylrest R1 kombiniert, beispielsweise Cι2-Ci6-Fettalkohol+5.5-EO und lsodecanol+6-EO. Hierbei ist es weiterhin bevorzugt, daß der lineare Alkylrest mehr Kohlenstoffatome als der verzweigte Alkylrest umfaßt. Besonders bevorzugt sind Cβ-Fett- alkohol+1.2PO+8.4EO, C8-ιo-Fettalkohol+5EO, Cι2-i4-Fettalkohol+6EO und C12-14- Fettalkohol+3EO sowie deren Mischungen.The C 6 -C 22 alkyl alcohol polyglycol ethers can be added to alkyl alcohols, preferably to oxo alcohols, by addition of propylene oxide and / or ethylene oxide branched chain primary alcohols obtainable by oxosynthesis or to fatty alcohols. Typical examples are polyglycol ethers in which R 1 is an alkyl radical having 8 to 18 carbon atoms, p is 0 to 2 and e is a number from 2 to 7. Preferred representatives are, for example, -C 0 -C 1 fatty alcohol + 1 PO + 6EO ether (p = 1, e = 6), C 12 -Ci 6 fatty alcohol + 5.5-EO (p = 0, e = 5.5), Cι 2 -Cι 8 fatty alcohol + 7EO ether (p = 0, e = 7) and isodecanol + 6-EO (R 1 = isomer mixture of C-io-oxo alcohol residues, p = 0, e = 6) and mixtures thereof. In special mixtures, at least one alkyl alcohol polyglycol ether with a linear alkyl radical R 1 is combined with at least one alkyl alcohol polyglycol ether with a branched alkyl radical R 1 , for example C 2 -C 6 fatty alcohol + 5.5-EO and isodecanol + 6-EO. It is further preferred here that the linear alkyl radical comprises more carbon atoms than the branched alkyl radical. Fatty alcohol + 3 EO, and mixtures thereof - Cβ-fatty alcohol + 1.2PO + 8.4EO, C 8- ιo-fatty alcohol + 5EO, Cι 2- i4 fatty alcohol + 6 EO C 12 and 14 are particularly preferred.
AlkylpolyglykosideAlkylpolyglykoside
Bevorzugte nichtionische Tenside sind weiterhin Alkylpolyglykoside (APG) der Formel R20[G]x, in der R2 für einen linearen oder verzweigten, gesättigten oder ungesättigten Alkylrest mit 8 bis 22 Kohlenstoffatomen, [G] für einen glykosidisch verknüpften Zuckerrest und x für eine Zahl von 1 bis 10 stehen. APG sind nichtionische Tenside und stellen bekannte Stoffe dar, die nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden können. Die Indexzahl x in der vorgenannten allgemeinen Formel gibt den Oligomerisierungsgrad (DP-Grad) an, d.h. die Verteilung von Mono- und Oligoglykosiden, und steht für eine Zahl zwischen 1 und 10. Während x in einer gegebenen Verbindung stets ganzzahlig sein muß und hier vor allem die Werte x = 1 bis 6 annehmen kann, ist der Wert x für ein bestimmtes Alkylglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkylglykoside mit einem mittleren Oligomerisierungsgrad x von 1 ,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkylglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1 ,7 ist und insbesondere zwischen 1 ,2 und 1 ,6 liegt. Als glykosidische Zucker wird vorzugsweise Xylose, insbesondere aber Glucose verwendet.
Der Alkyl- bzw. Alkenylrest R2 kann sich von primären Alkoholen mit 8 bis 22, vorzugsweise 8 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Capronalkohol, Capryialkohol, Caprinalkohol und Undecylalkohol sowie deren technische Gemische, wie sie beispielsweise im Verlauf der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der RoELENschen Oxosynthese anfallen.Preferred nonionic surfactants are furthermore alkyl polyglycosides (APG) of the formula R 2 0 [G] x , in which R 2 is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms, [G] is a glycosidically linked sugar radical and x is are a number from 1 to 10. APG are non-ionic surfactants and are known substances that can be obtained using the relevant methods of preparative organic chemistry. The index number x in the abovementioned general formula indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While x must always be an integer in a given compound and here before can assume all the values x = 1 to 6, the value x for a certain alkyl glycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl glycosides with an average degree of oligomerization x of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl glycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6. Xylose, but especially glucose, is preferably used as the glycosidic sugar. The alkyl or alkenyl radical R 2 can be derived from primary alcohols having 8 to 22, preferably 8 to 14, carbon atoms. Typical examples are capronic alcohol, capryial alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from RoELEN's oxosynthesis.
Vorzugsweise leitet sich der Alkyl- bzw. Alkenylrest R2 aber von Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol oder Oleylalkohol ab. Weiterhin sind Elaidylalkohol, Petroselinylalkohol, Arachidylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol sowie deren technische Gemische zu nennen.However, the alkyl or alkenyl radical R 2 is preferably derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol. Elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures should also be mentioned.
Stickstoffhaltige nichtionische TensideNitrogen-containing non-ionic surfactants
Geeignete Stickstoff enthaltende nichtionische Tenside sind beispielsweise Aminoxide, Polyhydroxyfettsäureamide, beispielsweise Glucamide, und Ethoxylate von Alkylaminen, vicinalen Diolen und/oder Carbonsäureamiden, die Alkylgruppen mit 10 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen, besitzen. Der Ethoxylierungsgrad dieser Verbindungen liegt dabei in der Regel zwischen 1 und 20, vorzugsweise zwischen 3 und 10. Bevorzugt sind Ethanolamid-Derivate von Alkansäuren mit 8 bis 22 C-Atomen, vorzugsweise 12 bis 16 C-Atomen. Zu den besonders geeigneten Verbindungen gehören die Laurinsäure-, Myristinsäure- und Palmitinsäuremonoethanolamide.Suitable nitrogen-containing nonionic surfactants are, for example, amine oxides, polyhydroxy fatty acid amides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxamides which have alkyl groups with 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The degree of ethoxylation of these compounds is generally between 1 and 20, preferably between 3 and 10. Ethanolamide derivatives of alkanoic acids with 8 to 22 C atoms, preferably 12 to 16 C atoms, are preferred. The particularly suitable compounds include the lauric acid, myristic acid and palmitic acid monoethanolamides.
Aminoxideamine oxides
Zu den erfindungsgemäß geeigneten Aminoxiden gehören Alkylaminoxide, insbesondere Alkyldimethylaminoxide, Alkylamidoaminoxide und Alkoxyalkylamin- oxide. Bevorzugte Aminoxide genügen der Formel R1 R2R3N+-0~, in der R1 ein gesättiger oder ungesättigter C6-22-Alkylrest ist, vorzugsweise Cs-is-Alkylrest, insbesondere ein gesättigter Cιo-16-Alkylrest, beispielsweise ein gesättigter C 2_i4-Alkylrest, der in den Alkylamidoaminoxiden über eine Carbonylamidoalkylen- gruppe -CO-NH-(CH2)z- und in den Alkoxyalkylaminoxiden über eine Oxaalkylen-
gruppe -0-(CH2)z- an das Stickstoffatom N gebunden ist, wobei z jeweils für eine Zahl von 1 bis 10 steht, vorzugsweise 2 bis 5, insbesondere 3, und R2 und R3 unabhängig voneinander ein gegebenenfalls hydroxysubstituierter Cι-4-Alkylrest wie z.B. ein Hydroxyethylrest, insbesondere ein Methylrest, ist.The amine oxides suitable according to the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides. Preferred amine oxides satisfy the formula R 1 R 2 R 3 N + -0 ~ , in which R 1 is a saturated or unsaturated C 6-22 alkyl radical, preferably Cs-is-alkyl radical, in particular a saturated Cιo- 16 alkyl radical, for example a saturated C 2 _i 4 alkyl radical which in the alkylamidoamine oxides via a carbonylamidoalkylene group -CO-NH- (CH 2 ) z - and in the alkoxyalkylamine oxides via an oxaalkylene group -0- (CH 2 ) z - is bonded to the nitrogen atom N, where z in each case represents a number from 1 to 10, preferably 2 to 5, in particular 3, and R 2 and R 3 independently of one another are an optionally hydroxy-substituted C 1 - 4 -alkyl radical such as a hydroxyethyl radical, in particular a methyl radical.
Beispiele geeigneter Aminoxide sind die folgenden gemäß INCI benannten Verbindungen: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide, Decyltetradecylamine Oxide, Diaminopyrimidine Oxide, Dihydroxyethyl C8-10 Alkoxypropylamine Oxide, Dihydroxyethyl C9-11 Alkoxypropylamine Oxide, Dihydroxyethyl C12-15 Alkoxypropylamine Oxide, Dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Tallowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallowamine Oxide, Hydroxyethyl Hydroxypropyl C12-15 Alkoxypropylamine Oxide, Isostearamidopropyl- amine Oxide, Isostearamidopropyl Morpholine Oxide, Lauramidopropylamine Oxide, Lauramine Oxide, Methyl Morpholine Oxide, Milkamidopropyl Amine Oxide, Minkamidopropylamine Oxide, Myristamidopropylamine Oxide, Myristamine Oxide, Myristyl/Cetyl Amine Oxide, Oleamidopropylamine Oxide, Oleamine Oxide, Olivamidopropylamine Oxide, Palmitamidopropylamine Oxide, Palmitamine Oxide, PEG-3 Lauramine Oxide, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Trisphosphonomethylamine Oxide, Sesamidopropylamine Oxide, Soyamidopropylamine Oxide, Stearamidopropylamine Oxide, Stearamine Oxide, Tallowamidopropylamine Oxide, Tallowamine Oxide, Undecylenamidopropylamine Oxide und Wheat Germamidopropylamine Oxide. Bevorzugte(s) Aminoxid(e) ist/sind beispielsweise Cocamine Oxide (N-Kokosalkyl-N,N-dimethylaminoxid), Dihydroxyethyl Tallowamine Oxide (N-Talgalkyl-N,N-dihydroxyethylaminoxid) und/oder Cocamidopropylamine Oxide (Cocoamidopropylaminoxid), insbesondere Cocamidopropylamine Oxide.Examples of suitable amine oxides are the following compounds named in accordance with INCI: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide, Decyltetradecylamine Oxide, Diaminopyrimethyl Oxide Oxide, Dioxopoxymethyl Oxide Oxide, Diaminopyrimethyl Oxide Oxide, Diaminopyrimethyl Oxide Oxide, , Dihydroxyethyl C9-11 Alkoxypropylamine Oxide, Dihydroxyethyl C12-15 Alkoxypropylamine Oxide, Dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Tallowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallowamine Oxide, Hydroxyethyl Hydroxide Oxypropyl Cycle - amine oxides, isostearamidopropyl morpholine oxides, lauramidopropylamine oxides, lauramine oxides, methyl morpholine oxides, milkamidopropyl amine oxides, minkamidopropylamine oxides, myristamidopropylamine oxides, myristamine oxides, myristyl / cetyl amine ox ide, Oleamidopropylamine Oxide, Oleamine Oxide, Olivamidopropylamine Oxide, Palmitamidopropylamine Oxide, Palmitamine Oxide, PEG-3 Lauramine Oxide, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Trisphosphonomethylamine Oxide, Sesamidopropylamine Oxide, Soyamidopropylamine Oxide Oxide, Stearamidideoxamine, Stearamidopropyl Oxamine, Stearamidopropyl Oxamine, Stearamidopropyl Oxamine, Stearamidopropyl Oxamine, Stearamidopropyl Oxamine, Stearamidopropyl Oxamine, Stearamidopropyl Oxamine, Stearamidopropyl Oxamine, Stearamide Propamine , Undecylenamidopropylamine Oxide and Wheat Germamidopropylamine Oxide. Preferred amine oxide (s) are, for example, cocamine oxides (N-cocoalkyl-N, N-dimethylamine oxide), dihydroxyethyl tallowamine oxides (N-tallow alkyl-N, N-dihydroxyethylamine oxide) and / or cocamidopropylamine oxides (cocoamidopropylamine oxide), in particular Cocamidopropylamine oxides.
Polyhydroxyfettsäureamidepolyhydroxy
Weitere geeignete Tenside sind Polyhydroxyfettsäureamide der Formel,
R1 IOther suitable surfactants are polyhydroxy fatty acid amides of the formula R 1 I
R-CO-N-[Z]R-CO-N- [Z]
in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R1 für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkyl- ester oder einem Fettsäurechlorid erhalten werden können.in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
Amphotere TensideAmphoteric surfactants
Geeignete Amphotenside sind beispielsweise Betaine. Geeignete Betaine sind die Alkylbetaine, die Alkylamidobetaine, die Imidazoliniumbetaine, die Sulfobetaine (INCI Sultaines) sowie die Phosphobetaine und genügen vorzugsweise der Formel (RA)(RB)(Rc)N+CH2COO", in der RA einen gegebenenfalls durch Heteroatome oder Heteroatomgruppen unterbrochenen Alkylrest mit 8 bis 25, vorzugsweise 10 bis 21 Kohlenstoffatomen und RB sowie Rc gleichartige oder verschiedene Alkylreste mit 1 bis 3 Kohlenstoffatomen bedeuten, insbesondere Cι0-Ci8-Alkyl-dimethylcarboxy- methylbetaine und Cn-Cι7-Alkylamidopropyl-dimethylcarboxymethylbetaine, und Betaine gemäß Formel A,Suitable amphoteric surfactants are, for example, betaines. Suitable betaines are the alkyl betaines, the alkyl amido betaines, the imidazolinium betaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably satisfy the formula (R A ) (R B ) (R c ) N + CH 2 COO " , in which R A is one optionally interrupted by heteroatoms or heteroatom groups, alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms and R B and R c are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 1 -C 8 -alkyl-dimethylcarboxy-methylbetaines and Cn-Cι 7- alkylamidopropyldimethylcarboxymethylbetaines, and betaines according to formula A,
Rl-[CO-X-(CH2)n]^N+(Rll)(R,l,)-(CH2)m-[CH(OH)-CH2]y-Y- (A)R l - [CO-X- (CH 2 ) n] ^ N + (R ll ) (R , l, ) - (CH2) m - [CH (OH) -CH 2 ] y -Y- (A)
in der R1 ein gesättiger oder ungesättigter C6-22-Alkylrest, vorzugsweise C8-18-Alkylrest, insbesondere ein gesättigter Cι0-16-Alkylrest, beispielsweise ein gesättigter C-i2-i4-Alkylrest,in which R 1 is a saturated or unsaturated C 6-22 alkyl radical, C 8-18 alkyl group, preferably, in particular a saturated Cι 0-16 alkyl radical, for example a saturated C 2 -i 4 alkyl radical,
X NH, NRIV mit dem Cι- -Alkylrest Rlv, O oder S, n eine Zahl von 1 bis 10, vorzugsweise 2 bis 5, insbesondere 3, x 0 oder 1 , vorzugsweise 1 ,X NH, NR IV with the -CC alkyl radical R lv , O or S, n is a number from 1 to 10, preferably 2 to 5, in particular 3, x 0 or 1, preferably 1,
R", R'"unabhängig voneinander ein Cι-4-Alkylrest, ggf. hydroxysubstituiert wie z.B. ein Hydroxyethylrest, insbesondere aber ein Methylrest,
m eine Zahl von 1 bis 4, insbesondere 1 , 2 oder 3, y 0 oder 1 undR ", R '" independently of one another are a C 4 alkyl radical, optionally hydroxy-substituted, such as, for example, a hydroxyethyl radical, but in particular a methyl radical, m is a number from 1 to 4, in particular 1, 2 or 3, y 0 or 1 and
Y COO, S03, OPO(ORv)0 oder P(0)(ORv)0, wobei Rv ein Wasserstoff
Y COO, S0 3 , OPO (OR v ) 0 or P (0) (OR v ) 0, where R v is a hydrogen
Die Alkyl- und Alkylamidobetaine, Betaine der Formel A mit einer Carboxylatgruppe (Y~ = COO~), heißen auch Carbobetaine. Bevorzugte Amphotenside sind die Alkylbetaine der Formel A1 , die Alkylamidobetaine der Formel A2, die Sulfobetaine der Formel A3 und die Amidosulfobetaine der Formel A4, R'-N+(CH3)2-CH2COO- (A1) Rl-CO-NH-(CH2)3-N+(CH3)2-CH2COO- (A2)The alkyl and alkyl amido betaines, betaines of formula A with a carboxylate group (Y ~ = COO ~ ), are also called carbobetaines. Preferred amphoteric surfactants are the alkylbetaines of the formula A1, the alkylamido betaines of the formula A2, the sulfobetaines of the formula A3 and the amidosulfobetaines of the formula A4, R'-N + (CH 3 ) 2 -CH 2 COO- (A1) R 1 -CO- NH- (CH 2 ) 3 -N + (CH 3 ) 2 -CH 2 COO- (A2)
Rl-N+(CH3)2-CH2CH(OH)CH2Sθ3~ (A3) Rl-CO-NH-(CH2)3-N+(CH3)2-CH2CH(OH)CH2S03- (A4) in denen R1 die gleiche Bedeutung wie in Formel A hat.R l -N + (CH 3 ) 2-CH2CH (OH) CH 2 Sθ3 ~ (A3) R l -CO-NH- (CH 2 ) 3 -N + (CH 3 ) 2 -CH 2 CH (OH) CH 2 S0 3 - (A4) in which R 1 has the same meaning as in formula A.
Besonders bevorzugte Amphotenside sind die Carbobetaine, insbesondere die Carbobetaine der Formel A1 und A2, äußerst bevorzugt die Alkylamidobetaine der Formel A2.Particularly preferred amphoteric surfactants are the carbobetaines, in particular the carbobetaines of the formula A1 and A2, most preferably the alkylamidobetaines of the formula A2.
Beispiele geeigneter Betaine und Sulfobetaine sind die folgenden gemäß INCI benannten Verbindungen: Almondamidopropyl Betaine, Apricotamidopropyl Betaine, Avocadamidopropyl Betaine, Babassuamidopropyl Betaine, Behenamidopropyl Betaine, Behenyl Betaine, Betaine, Canolamidopropyl Betaine, Capryl/Capramido- propyl Betaine, Carnitine, Cetyl Betaine, Cocamidoethyl Betaine, Cocamidopropyl Betaine, Cocamidopropyl Hydroxysultaine, Coco-Betaine, Coco-Hydroxysultaine, Coco/Oleamidopropyl Betaine, Coco-Sultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl PG-Betaine, Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow Betaine, Isostearamidopropyl Betaine, Lauramidopropyl Betaine, Lauryl Betaine, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaine, Minkamidopropyl Betaine, Myristamidopropyl Betaine, Myristyl Betaine, Oleamidopropyl Betaine, Oleamidopropyl Hydroxysultaine, Oleyl Betaine, Olivamidopropyl Betaine, Palmamidopropyl Betaine, Palmitamidopropyl Betaine, Palmitoyl Carnitine, Palm Kernelamidopropyl Betaine,
Polytetrafluoroethylene Acetoxypropyl Betaine, Ricinoleamidopropyl Betaine, Sesamidopropyl Betaine, Soyamidopropyl Betaine, Stearamidopropyl Betaine, Stearyl Betaine, Tallowamidopropyl Betaine, Tallowamidopropyl Hydroxysultaine, Tallow Betaine, Tallow Dihydroxyethyl Betaine, Undecylenamidopropyl Betaine und Wheat Germamidopropyl Betaine. Ein bevorzugtes Amphotensid ist Cocamidopropyl Betaine (Cocoamidopropylbetain). Besonders bevorzugte Amphotenside sind Capryl/Capramidopropyl Betaine (GAB), welche beispielsweise unter dem Handelsnamen Tegotens® B 810, Tegobetain® F50 bzw. Dehyton® von der Th. Goldschmidt AG bzw. Henkel KGaA erhältlich ist.Examples of suitable betaines and sulfobetaines are the following compounds named according to INCI: Almondamidopropyl betaines, apricotamidopropyl betaines, avocadamidopropyl betaines, Babassuamidopropyl betaines, behenamidopropyl betaines, behenyl betaines, betaines, canolamidopropyl betaines, capryl / capramidopropyl betaine, betaine, carnitine, cocaine , Cocamidopropyl Betaine, Cocamidopropyl Hydroxysultaine, Coco-Betaine, Coco-Hydroxysultaine, Coco / Oleamidopropyl Betaine, Coco-Sultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, PG-Beta-Ethyline Glycinate, PG-Beta-Methylate Hydroxysultaine, Hydrogenated Tallow Betaine, Isostearamidopropyl Betaine, Lauramidopropyl Betaine, Lauryl Betaine, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaine, Minkamidopropyl Betaine, Myristamidopropyl Betaine, Myristyl Betaine, Oleamidopropyl Betaine, Oleamidopropyl Hydroxysu ltaine, oleyl betaine, olivamidopropyl betaine, palmamidopropyl betaine, palmitamidopropyl betaine, palmitoyl carnitine, palm kernelamidopropyl betaine, Polytetrafluoroethylene Acetoxypropyl Betaine, Ricinoleamidopropyl Betaine, Sesamidopropyl Betaine, Soyamidopropyl Betaine, Stearamidopropyl Betaine, Stearyl Betaine, Tallowamidopropyl Betaine, Tallowamidopropyl Hydroxysultaine, Tallow Betaine, Tallow Dihydroxyethyl Betaine, Undecylenamidopropyl Betaine and Wheat. A preferred amphoteric surfactant is cocamidopropyl betaine (cocoamidopropyl betaine). Particularly preferred amphoteric surfactants are caprylic / capramidopropyl betaine (GAB), which is available, for example, from Th. Goldschmidt AG or Henkel KGaA under the trade names Tegotens® B 810, Tegobetain® F50 or Dehyton®.
Alkylamidoalkylaminealkylamidoalkylamines
Die Alkylamidoalkylamine (INCI Alkylamido Alkylamines) sind Amphotenside der Formel B,The alkylamidoalkylamines (INCI alkylamido alkylamines) are amphoteric surfactants of the formula B
Rvl-CO-NRvll-(CH2)i-N(Rvlll)-(CH2CH2θ)r(CH2)k-[CH(OH)]ι-CH2-Z-OM (B)R vl -CO-NR vll - (CH 2 ) iN (R vlll ) - (CH 2 CH 2 θ) r (CH 2 ) k - [CH (OH)] ι-CH 2 -Z-OM (B)
in der Rvι ein gesättiger oder ungesättigter
vorzugsweisein the R vι a saturated or unsaturated preferably
C8-18-Alkylrest, insbesondere ein gesättigter Cι0-16-Alkylrest, beispielsweise ein gesättigter C^- -Alkylrest, Rv" ein Wasserstoffatom H oder ein Cι- -Alkylrest, vorzugsweise H, i eine Zahl von 1 bis 10, vorzugsweise 2 bis 5, insbesondere 2 oder 3,C 8-18 alkyl radical, in particular a saturated C 0-16 alkyl radical, for example a saturated C ^ - alkyl radical, R v "is a hydrogen atom H or a C 1 -C alkyl radical, preferably H, i is a number from 1 to 10, preferably 2 to 5, in particular 2 or 3,
R i" ein Wasserstoffatom H oder CH2COOM (zu M s.u.), j eine Zahl von 1 bis 4, vorzugsweise 1 oder 2, insbesondere 1, k eine Zahl von 0 bis 4, vorzugsweise 0 oder 1 , I 0 oder 1 , wobei k = 1 ist, wenn I = 1 ist,R i "is a hydrogen atom H or CH 2 COOM (to M su), j is a number from 1 to 4, preferably 1 or 2, in particular 1, k is a number from 0 to 4, preferably 0 or 1, I 0 or 1, where k = 1 if I = 1,
Z CO, S02, OPO(OR12) oder P(0)(OR12), wobei R12 ein Cι- -Alkylrest oder M (s.u.) ist, und M ein Wasserstoff, ein Alkalimetall, ein Erdalkalimetall oder ein protoniertes Alkanolamin, z.B. protoniertes Mono-, Di- oderZ CO, S0 2 , OPO (OR 12 ) or P (0) (OR 12 ), where R 12 is a Cι- alkyl group or M (see below), and M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine , for example protonated mono-, di- or
Triethanolamin, ist.Triethanolamine, is.
Bevorzugte Vertreter genügen den Formeln B1 bis B4, Rvl-CO-NH-(CH2)2-N(R lll)-CH2CH2θ-CH2-COOM (B1 )
RvLcθ-NH-(CH2)2-N(R l")-CH2CH2θ-CH2CH2-COOM (B2)Preferred representatives satisfy the formulas B1 to B4, R vl -CO-NH- (CH 2 ) 2-N (R III ) -CH 2 CH 2 θ-CH 2 -COOM (B1) R v Lcθ-NH- (CH 2 ) 2 -N (R l ") -CH 2 CH 2 θ-CH 2 CH 2 -COOM (B2)
RvLcθ-NH-(CH2)2-N(RViil)-CH2CH2θ-CH2CH(OH)CH2-Sθ3M (B3)R v Lcθ-NH- (CH 2 ) 2 -N (R Viil ) -CH 2 CH 2 θ-CH 2 CH (OH) CH 2 -Sθ 3 M (B3)
Rvl-CO-NH-(CH2)2-N(Rvlll)-CH2CH2θ-CH2CH(OH)CH2-OPθ3HM (B4) in denen Rvι, Rvι" und M die gleiche Bedeutung wie in Formel B haben.R vl -CO-NH- (CH 2 ) 2 -N (R vlll ) -CH 2 CH 2 θ-CH 2 CH (OH) CH 2 -OPθ 3 HM (B4) in which R vι , R vι "and M have the same meaning as in formula B.
Beispielhafte Alkylamidoalkylamine sind die folgenden gemäß INCI benannten Verbindungen: Cocoamphodipropionic Acid, Cocobetainamido Amphopropionate, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropyl- sulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-lsodeceth-7 Carboxyamphodiacetate, Disodium Stearoamphodiacetate, Disodium Tallowamphodiacetate, Disodium Wheatgermamphodiacetate, Lauroamphodipropionic Acid, Quaternium-85, Sodium Caproamphoacetate, Sodium Caproamphohydroxypropylsulfonate, Sodium Caproamphopropionate, Sodium Capryloamphoacetate, Sodium Capryloamphohydroxypropylsulfonate, Sodium Capryloamphopropionate, Sodium Cocoamphoacetate, SodiumExemplary alkylamidoalkylamines are the following named according to INCI compounds: Cocoamphodipropionic Acid, Cocobetainamido amphopropionates, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropyl- sulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-lsodeceth-7 Carboxyamphodiacetate, Disodium Stearoamphodiacetate, Disodium Tallowamphodiacetate, Disodium Wheatgermamphodiacetate, Lauroamphodipropionic Acid, Quaternium-85, Sodium Caproamphoacetate, Sodium Caproamphohydroxypropylsulfonate, Sodium Caproamphopropionate, Sodium Capryloamphoacetate, Sodium Capryloamphohydroxypropylsulfonate, Sodium Capr yloamphopropionate, sodium cocoamphoacetate, sodium
Cocoamphohydroxypropylsulfonate, Sodium Cocoamphopropionate, Sodium Comamphopropionate, Sodium Isostearoamphoacetate, Sodium Isostearoampho- propionate, Sodium Lauroamphoacetate, Sodium Lauroamphohydroxypropyl- sulfonate, Sodium Lauroampho PG-Acetate Phosphate, Sodium Lauroamphopropionate, Sodium Myristoamphoacetate, Sodium Oleoamphoacetate, Sodium Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate, Sodium Ricinoleoamphoacetate, Sodium Stearoamphoacetate, Sodium Stearoampho- hydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium Tallampho- propionate, Sodium Tallowamphoacetate, Sodium Undecylenoamphoacetate, Sodium Undecylenoamphopropionate, Sodium Wheat Germamphoacetate und Trisodium Lauroampho PG-Acetate Chloride Phosphate.
Alkylsubstituierte AminosäurenCocoamphohydroxypropylsulfonate, Sodium Cocoamphopropionate, Sodium Comamphopropionate, Sodium Isostearoamphoacetate, Sodium Isostearoampho- propionate, Sodium lauroamphoacetate, sodium Lauroamphohydroxypropyl- sulfonate, Sodium Lauroampho PG-Acetate Phosphate, Sodium Lauroamphopropionate, Sodium Myristoamphoacetate, Sodium Oleoamphoacetate, Sodium Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate, Sodium Ricinoleoamphoacetate, Sodium Stearoamphoacetate, Sodium Stearoampho-hydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium Tallamphopropionate, Sodium Tallowamphoacetate, Sodium Undecylenoamphoacetate, Sodium Undecylenoamphopropionate, Sodium Wheat Germamphoacetamate Phosphate Acid and Chloride. Alkyl substituted amino acids
Erfindungsgemäß bevorzugte alkylsubstituierte Aminosäuren (INCI Alkyl-Substituted Amino Acids) sind monoalkylsubstituierte Aminosäuren gemäß Formel C,Alkyl-substituted amino acids preferred according to the invention (INCI alkyl-substituted amino acids) are monoalkyl-substituted amino acids according to formula C,
Rlx-NH-CH(Rx)-(CΗ2)u-COOM' (C)R lx -NH-CH (R x ) - (CΗ 2 ) u-COOM '(C)
in der Rlx ein gesättiger oder ungesättigter C6-22-Alkylrest, vorzugsweisein the R lx a saturated or unsaturated C 6-22 alkyl radical, preferably
Cs-18-Alkylrest, insbesondere ein gesättigter Cι0-16-Alkylrest, beispielsweise ein gesättigter C-i2-i4-Alkylrest, Rx ein Wasserstoffatom H oder ein Cι-4-Alkylrest, vorzugsweise H, u eine Zahl von 0 bis 4, vorzugsweise 0 oder 1 , insbesondere 1 , und M' ein Wasserstoff, ein Alkalimetall, ein Erdalkalimetall oder ein protoniertes Alkanolamin, z.B. protoniertes Mono-, Di- oderCs- 18 alkyl radical, in particular a saturated Cι 0-16 alkyl radical, for example a saturated Ci 2 -i 4 alkyl radical, R x is a hydrogen atom H or a Cι- 4 alkyl radical, preferably H, u is a number from 0 to 4 , preferably 0 or 1, in particular 1, and M 'is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or
Triethanolamin, ist,Triethanolamine, is,
alkylsubstituierte Iminosäuren gemäß Formel D,alkyl-substituted imino acids according to formula D,
Rxl-N-[(CH2)v-COOM"]2 (D)R xl -N - [(CH 2 ) v-COOM "] 2 (D)
in der Rxι ein gesättiger oder ungesättigter C6-22-Alkylrest, vorzugsweise Cδ-is-Alkylrest, insbesondere ein gesättigter Cιo-16-Alkylrest, beispielsweise ein gesättigter Ci2-14-Alkylrest, v eine Zahl von 1 bis 5, vorzugsweise 2 oder 3, insbesondere 2, und M" ein Wasserstoff, ein Alkalimetall, ein Erdalkalimetall oder ein protoniertes Alkanolamin, z.B. protoniertes Mono-, Di- oder Triethanolamin, wobei M" in den beiden Carboxygruppen die gleiche oder zwei verschiedene Bedeutungen haben kann, z.B. Wasserstoff und Natrium oder zweimal Natrium sein kann, ist,in which R xι is a saturated or unsaturated C 6-22 -alkyl radical, preferably C δ -is-alkyl radical, in particular a saturated Cιo- 16 -alkyl radical, for example a saturated Ci 2 - 14 -alkyl radical, v is a number from 1 to 5, preferably 2 or 3, in particular 2, and M "is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine, where M" in the two carboxy groups can have the same or two different meanings, for example hydrogen and sodium or twice sodium is
und mono- oder dialkylsubstituierte natürliche Aminosäuren gemäß Formel E,and mono- or dialkyl-substituted natural amino acids according to formula E,
Rx"-N(Rxlll)-CH(Rxlv)-COOMm (E)
in der Rx" ein gesättiger oder ungesättigter C6-22-Alkylrest, vorzugsweiseR x "-N (R xlll ) -CH (R xlv ) -COOM m (E) in which R x "is a saturated or unsaturated C 6-22 alkyl radical, preferably
Cs-is-Alkylrest, insbesondere ein gesättigter Cιo-16-Alkylrest, beispielsweise ein gesättigter C^-u-Alkylrest, Rxl" ein Wasserstoffatom oder ein
ggf. hydroxy- oder aminsubstituiert, z.B. ein Methyl-, Ethyl-, Hydroxyethyl- oderCs-is-alkyl radical, in particular a saturated Cιo- 16 alkyl radical, for example a saturated C ^ -u-alkyl radical, R xl "is a hydrogen atom or a optionally substituted by hydroxy or amine, for example a methyl, ethyl, hydroxyethyl or
Aminpropylrest, Rxιv den Rest einer der 20 natürlichen α-Aminosäuren H2NCH(Rxlv)COOH, und M'" ein Wasserstoff, ein Alkalimetall, ein Erdalkalimetall oder ein protoniertes Alkanolamin, z.B. protoniertes Mono-, Di- oderAminpropylrest, R xιv the rest of one of the 20 natural α-amino acids H 2 NCH (R xlv ) COOH, and M '"a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or
Triethanolamin, ist.Triethanolamine, is.
Besonders bevorzugte alkylsubstituierte Aminosäuren sind die Aminopropionate gemäß Formel C1 ,Particularly preferred alkyl-substituted amino acids are the aminopropionates according to formula C1,
Rlx-NH-CH2CH2COOM' (C1)R lx -NH-CH 2 CH 2 COOM '(C1)
in der Rlx und M' die gleiche Bedeutung wie in Formel C haben.in which R lx and M 'have the same meaning as in formula C.
Beispielhafte alkylsubstituierte Aminosäuren sind die folgenden gemäß INCI benannten Verbindungen: Aminopropyl Laurylglutamine, Cocaminobutyric Acid, Cocaminopropionic Acid, DEA-Lauraminopropionate, Disodium Cocaminopropyl Iminodiacetate, Disodium Dicarboxyethyl Cocopropylenediamine, Disodium Lauriminodipropionate, Disodium Steariminodipropionate, Disodium Tallowiminodi- propionate, Lauraminopropionic Acid, Lauryl Aminopropylglycine, Lauryl Diethylenediaminoglycine, Myristaminopropionic Acid, Sodium C12-15 Alkoxypropyl Iminodipropionate, Sodium Cocaminopropionate, Sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA- Lauraminopropionate und TEA-Myristaminopropionate.Exemplary alkyl-substituted amino acids are the following compounds named according to INCI: aminopropyl lauryl glutamine, cocaminobutyric acid, cocaminopropionic acid, DEA lauraminopropionate, disodium cocaminopropyl iminodiacetate, disodium dicarboxyethyl cocopropylenediamine, disodium laurododropropionate, disodium stiminaminodipionate, disodium steariminodiphenate Diethylenediaminoglycine, Myristaminopropionic Acid, Sodium C12-15 Alkoxypropyl Iminodipropionate, Sodium Cocaminopropionate, Sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA Lauraminopropionate and TEA Myristaminopropionate.
Acylierte AminosäurenAcylated amino acids
Acylierte Aminosäuren sind Aminosäuren, insbesondere die 20 natürlichen α-Aminosäuren, die am Aminostickstoffatom den Acylrest RxvCO einer gesättigten oder
ungesättigen Fettsäure RxvCOOH tragen, wobei Rxv ein gesättiger oder ungesättigter C6-22-Alkylrest, vorzugsweise Cs-is-Alkylrest, insbesondere ein gesättigter Cio-iβ-Alkylrest, beispielsweise ein gesättigter C^- -Alkylrest ist. Die acylierten Aminosäuren können auch als Alkalimetallsalz, Erdalkalimetallsalz oder Alkanolammoniumsalz, z.B. Mono-, Di- oder Triethanolammoniumsalz, eingesetzt werden. Beispielhafte acylierte Aminosäuren sind die gemäß INCI unter Amino Acids zusammengefaßten Acylderivate, z.B. Sodium Cocoyl Glutamate, Lauroyl Glutamic Acid, Capryloyl Glycine oder Myristoyl Methylalanine.Acylated amino acids are amino acids, especially the 20 natural α-amino acids, which contain the acyl residue R xv CO of a saturated or unsaturated fatty acid R COOH wear xv, where R xv a saturated or unsaturated C 6-22 alkyl, preferably Cs-is-alkyl radical, particularly a saturated Cio-iβ alkyl group, for example a saturated C ^ - alkyl. The acylated amino acids can also be used as alkali metal salt, alkaline earth metal salt or alkanolammonium salt, for example mono-, di- or triethanolammonium salt. Exemplary acylated amino acids are the acyl derivatives summarized according to INCI under amino acids, for example sodium cocoyl glutamate, lauroyl glutamic acid, capryloyl glycine or myristoyl methylalanine.
Kationische TensideCationic surfactants
Geeignete Kationtenside sind u.a. die quartären Ammoniumverbindungen der Formel (Riπ)(Riv)(Rv)(Rvi)N+ X", in der Rπi bis Rvi für vier gleich- oder verschiedenartige, insbesondere zwei lang- und zwei kurzkettige, Alkylreste und X" für ein Anion, insbesondere ein Halogenidion, stehen, beispielsweise Didecyl-dimethyl-ammonium- chlorid, Alkyl-benzyl-didecyl-ammoniumchlorid und deren Mischungen.Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R iπ ) (R iv ) (R v ) (R vi ) N + X " , in which R πi to R vi represent four identical or different types, in particular two long and two short-chain, alkyl radicals and X "represent an anion, in particular a halide ion, for example didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
Hydrophobkomponentenhydrophobic components
In einer besonders vorteilhaften Ausführungsform der Erfindung enthalten die erfindungsgemäßen Reinigungsmittel, insbesondere Handgeschirrspülmittel eine oder mehrere hydrophobe Komponenten. Die Hydrophobkomponenten verbessern vor allem die Reinigungswirkung gegenüber hydrophoben Verunreinigungen wie Fettschmutz. Geeignete Hydrophobkomponenten sind beispielsweise Dialkylether mit gleichen oder verschiedenen C4- bis Cu-Alkylresten, insbesondere linearer Dioctylether; Kohlenwasserstoffe mit einem Siedebereich von 100 bis 300 °C, insbesondere 140 bis 280 °C, z. B. aliphatische Kohlenwasserstoffe mit einem Siedebereich von 145 bis 200 °C, Isoparaffine mit einem Siedebereich von 200 bis 260 °C; etherische Öle, insbesondere Limonen und das aus Kiefernwurzeln und -stubben extrahierte Pine Oil; und auch Mischungen dieser Hydrophobkomponenten, insbesondere Mischungen von zwei oder drei der genannten Hydrophobkomponenten. Bevorzugte Gemische von Hydrophobkomponenten sind Gemische von verschiedenen Dialkylethern, von Dialkylethern und Kohlenwasserstoffen, von Dialkylethern und etherischen Ölen, von Kohlenwasserstoffen und etherischen Ölen,
von Dialkylethern und Kohlenwasserstoffen und etherischen Ölen und von diesen Gemischen.In a particularly advantageous embodiment of the invention, the cleaning agents according to the invention, in particular hand dishwashing agents, contain one or more hydrophobic components. The hydrophobic components above all improve the cleaning effect against hydrophobic contaminants such as greasy dirt. Suitable hydrophobic components are, for example, dialkyl ethers with the same or different C 4 -C 6 -alkyl radicals, in particular linear dioctyl ether; Hydrocarbons with a boiling range of 100 to 300 ° C, especially 140 to 280 ° C, for. B. aliphatic hydrocarbons with a boiling range of 145 to 200 ° C, isoparaffins with a boiling range of 200 to 260 ° C; essential oils, in particular limonene and pine oil extracted from pine roots and stumps; and also mixtures of these hydrophobic components, in particular mixtures of two or three of the hydrophobic components mentioned. Preferred mixtures of hydrophobic components are mixtures of various dialkyl ethers, of dialkyl ethers and hydrocarbons, of dialkyl ethers and essential oils, of hydrocarbons and essential oils, of dialkyl ethers and hydrocarbons and essential oils and of these mixtures.
BuilderBuilder
Weiterhin können die erfindungsgemäßen Reinigungsmittel ein oder mehrere Builder enthalten. Geeignete Builder sind beispielsweise Alkalimetallcitrate, -gluconate, -nitrilotriacetate, -carbonate und -bicarbonate, insbesondere Natriumeitrat, -gluconat, und -nitrilotriacetat sowie Natrium- und Kaliumcarbonat und -bicarbonat, sowie Alkalimetall- und Erdalkalimetallhydroxide, insbesondere Natrium- und Kaliumhydroxid, Ammoniak und Amine, insbesondere Mono- und Triethanolamin, bzw. deren Mischungen. Hierzu zählen auch die Salze der Glutarsäure, Bernsteinsäure, Adipinsäure, Weinsäure und Benzolhexacarbonsäure sowie Phosphonate und Phosphate, beispielsweise Natriumhexametaphosphat wie etwa eine Mischung kondensierter Orthophosphate der Formel I, in der n für einen Mittelwert von etwa 12 steht. Die Mittel enthalten Builder in Mengen, bezogen auf die Zusammensetzung, von 0 bis 30 Gew.-%, vorzugsweise 0,1 bis 20 Gew.-%, insbesondere 1 bis 15 Gew.-%, äußerst bevorzugt 2 bis 10 Gew.-%.Furthermore, the cleaning agents according to the invention can contain one or more builders. Suitable builders are, for example, alkali metal citrates, gluconates, nitrilotriacetates, carbonates and bicarbonates, in particular sodium citrate, gluconate and nitrilotriacetate, as well as sodium and potassium carbonate and bicarbonate, and also alkali metal and alkaline earth metal hydroxides, in particular sodium and potassium hydroxide Amines, especially mono- and triethanolamine, or mixtures thereof. These also include the salts of glutaric acid, succinic acid, adipic acid, tartaric acid and benzene hexacarboxylic acid as well as phosphonates and phosphates, for example sodium hexametaphosphate such as a mixture of condensed orthophosphates of the formula I, in which n stands for an average of about 12. The compositions contain builders in amounts, based on the composition, of 0 to 30% by weight, preferably 0.1 to 20% by weight, in particular 1 to 15% by weight, extremely preferably 2 to 10% by weight ,
Ein bevorzugter Builder ist Citrat aus der Gruppe der Alkalimetall-, Erdalkalimetall-, Ammonium- sowie Mono-, Di- bzw. Trialkanolammoniumcitrate, vorzugsweise Mono-, Di- bzw. Triethanolammoniumcitrate, oder deren Mischungen, insbesondere Natriumeitrat, äußerst bevorzugt Kaliumeitrat.A preferred builder is citrate from the group of alkali metal, alkaline earth metal, ammonium and mono-, di- or trialkanolammonium citrates, preferably mono-, di- or triethanolammonium citrates, or mixtures thereof, in particular sodium citrate, extremely preferably potassium citrate.
Ein besonders bevorzugter alkalischer Builder ist Kaliumhydroxid.A particularly preferred alkaline builder is potassium hydroxide.
Soll der Builder zudem als pH-stabilisierender Puffer wirken, so werden Alkalimetall- und Erdalkalimetallcarbonate und -bicarbonate, z.B. Soda, bevorzugt.If the builder is also to act as a pH-stabilizing buffer, alkali metal and alkaline earth metal carbonates and bicarbonates, e.g. Soda, preferred.
Antimikrobieller WirkstoffAntimicrobial agent
Die erfindungsgemäßen Reinigungsmittel, insbesondere Handgeschirrspülmittel enthalten für die antimikrobielle/desinfizierende Wirkung gegebenenfalls mindestens einen antimikrobiellen Wirkstoff, vorzugsweise ausgewählt aus den Gruppen der Alkohole, Amine, Aldehyde, antimikrobiellen Säuren bzw. deren Salze,
Carbonsäureester, Säureamide, Phenole, Phenolderivate, Diphenyle, Diphenyl- alkane, Harnstoffderivate, Sauerstoff-Acetale sowie -Formale, Stickstoff-Acetale sowie -Formale, Benzamidine, Isothiazoline, Phthalimidderivate, Pyridinderivate, antimikrobiellen oberflächenaktiven Verbindungen, Guanidine, antimikrobiellen amphoteren Verbindungen, Chinoline, 1 ,2-Dibrom-2,4-dicyanobutan, lodo-2- propynyl-butyl-carbamat, lod, lodophore und anderer Halogene bzw. Halogenverbindungen sowie Peroxide bzw. Peroxoverbindungen, insbesondere ausgewählt aus Ethanol, n-Propanol, i-Propanol, 1,3-Butandiol, Phenoxyethanol, 1 ,2-Propylen- glykol, Glycerin, Undecylensäure, Zitronensäure, Milchsäure, Benzoesäure, Salicyl- säure, Dihydracetsäure, o-Phenylphenol, N-Methylmorpholin-acetonitril (MMA), 2- Benzyl-4-chlorphenol, 2,2'-Methylen-bis-(6-brom-4-chlorphenol), 4,4'-Dichlor-2'-hy- droxydiphenylether (Dichlosan), 2,4,4'-Trichlor-2'-hydroxydiphenylether (Trichlosan), Chlorhexidin, N-(4-Chlorphenyl)-N-(3,4-dichlorphenyl)-harnstoff, N,N'-(1,10-decan- diyldi-1-pyridinyl-4-yliden)-bis-(1-octanamin)-dihydrochlorid, N,N'-Bis-(4-chlorphenyl)- 3, 12-diimino-2,4, 11 ,13-tetraaza-tetradecandiimidamid, Glucoprotaminen, antimikrobiellen oberflächenaktiven quaternären Verbindungen, Guanidinen einschließlich den Bi- und Polyguanidinen, Peroxoverbindungen, Chlorverbindungen, Amphoteren sowie natürlichen antimikrobiellen Wirkstoffen pflanzlicher Herkunft (z.B. aus Gewürzen oder Kräutern) oder tierischer Herkunft, besonders bevorzugt mindestens eine antimikrobiell wirkende oberflächenaktive quatemäre Verbindung, eine Peroxoverbindung, ein halogenierf.es Xylol- und Kresolderivat, wie p-Chlor-m-kresol oder p-Chlor-m-xylol, ein natürlicher antimikrobieller Wirkstoff pflanzlicher Herkunft, ein natürlicher antimikrobieller Wirkstoff tierischer Herkunft und/oder antimikrobieller Wirkstoff mikrobieller Herkunft (sogenannte Bakteriozine), äußerst bevorzugt mindestens ein natürlicher antimikrobieller Wirkstoff pflanzlicher Herkunft aus der Gruppe, umfassend Coffein, Theobromin und Theophyllin sowie etherische Öle wie Eugenol, Thymol und Geraniol, und/oder mindestens ein natürlicher antimikrobieller Wirkstoff tierischer Herkunft aus der Gruppe, umfassend Enzyme wie Eiweiß aus Milch, Lysozym und Lactoperoxidase, und/oder mindestens eine antimikrobiell wirkende oberflächenaktive quatemäre Verbindung mit einer Ammonium-, Sulfonium-, Phosphonium-, lodonium- oder Arsoniumgruppe, wie sie beispielsweise K. H. Wallhäußer in "Praxis der Sterilisation, Desinfektion - Konservierung: Keimidentifizierung - Betriebshygiene" (5. Aufl. - Stuttgart ; New York : Thieme, 1995) beschreibt.
Geeignete Vertreter aus der Gruppe der Guanidine einschließlich der Biguanidine und Polyguanidine sind beispielsweise 1 ,6-Bis-(2-ethylhexyl-biguanido-hexan)- dihydrochlorid, 1 ,6-Di-(Nι,Nι,-phenyldiguanido-N5,N5 l)-hexan-tetrahydochlorid, 1 ,6-Di- (Ni.Ni'-phenyl-Ni.Ni-methyldiguanido-Ns.Ns'J-hexan-dihydrochlorid, 1,6-Di-(N-ι,Nι'-o- chlorophenyldiguanido-N5,N5')-hexan-dihydrochlorid, 1 ,6-Di-(Nι ,Nι'-2,6-dichloro- phenyldiguanido-Ns.Nδ'J-hexan-dihydrochlorid, 1,6-Di-[Nι,Nι'-ß-(p-methoxyphenyl)- diguanido-Nδ.Nδ'j-hexan-dihydrochlorid, 1 ,6-Di-(Nι ,Nι'-alpha-methyl-ß-phenyldi- guanido-N5,N5')-hexan-dihydrochlorid, l ^-D Ni.Ni'-p-nitrophenyldiguanido-Ns.Ns')- hexan-dihydrochlorid, ω:ω-Di-(Nι,Nι'-phenyldiguanido-N5,N5')-di-n-propylether-di- hydrochlorid, ω:ω,-Di-(N1,Nι'-p-chlorophenyldiguanido-N5,N5 ,)-di-n-propylether-tetra- hydrochlorid, 1 ,6-Di-(Nι,Nι'-2,4-dichlorophenyldiguanido-N5,N5 hexan-tetrahydro- chlorid, 1 ,6-Di-(Nι,Nι'-p-methylphenyldiguanido-N5,N5')-hexan-dihydrochlorid, 1 ,6-Di- (Nι,Nι'-2,4,5-trichlorophenyldiguanido-N5,N5 -hexan-tetrahydrochlorid, 1 ,6-Di-[Nι,Nι'- alpha-(p-chlorophenyl)-ethyldiguanido-N5,N5']-hexan-dihydrochlorid, ω:ω-Di-(N-ι,Nι'- p-chlorophenyldiguanido-N5,N5')-m-xylene-dihydrochlorid, 1,12-Di-(Nι,Nι'-p-chloro- phenyldiguanido-Ns.NsΗodecan-dihydrochlorid, lO-DKNi.N-i'-phenyldiguanido- N5,N5')-decan-tetrahydrochlorid, l .^-D Ni.Ni'-phenyldiguanido-Ns.Ns^-dodecan- tetrahydrochlorid, 1 ,6-Di-(Nι,Nι,-o-chlorophenyldiguanido-N5,N5 ,)-hexan-dihydro- chlorid, 1 ,6-Di-(Nι,Nι'-o-chlorophenyldiguanido-N5,N5')-hexan-tetrahydrochlorid,For the antimicrobial / disinfectant effect, the cleaning agents according to the invention, in particular hand dishwashing detergents, optionally contain at least one antimicrobial active ingredient, preferably selected from the groups of alcohols, amines, aldehydes, antimicrobial acids or their salts, Carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen acetals and formals, nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial quinoline compounds, amphoteric compounds 1, 2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and other halogens or halogen compounds as well as peroxides or peroxo compounds, especially selected from ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1, 2-propylene glycol, glycerin, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholine acetonitrile (MMA), 2-benzyl-4 -chlorophenol, 2,2'-methylene-bis- (6-bromo-4-chlorophenol), 4,4'-dichloro-2'-hydroxydiphenyl ether (dichlosan), 2,4,4'-trichloro-2 ' -hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis- (4-chlorophenyl) - 3, 12-diimino-2,4, 11, 13-tetraaza-tetradecanediimidamide, glucoprotamines, antimicrobial surface-active quaternary compounds, guanidines including the bi- and polyguanidines, peroxo compounds, chlorine compounds, amphoterics and natural antimicrobial agents of plant origin (eg from spices or herbs) or of animal origin, particularly preferably at least one antimicrobial surface-active quaternary compound, a peroxo compound, a halogenated xylene and cresol derivative, such as p-chloro-m-cresol or p-chloro-m-xylene, a natural antimicrobial agent of plant origin, a natural antimicrobial agent of animal origin and / or antimicrobial agent of microbial origin (so-called bacteriocins), extremely preferably at least one natural antimicrobial agent All active ingredient of plant origin from the group, including caffeine, theobromine and theophylline as well as essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial active ingredient of animal origin from the group, including enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound with an ammonium, sulfonium, phosphonium, iodonium or arsonium group, as described, for example, by KH Wallhäußer in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene" (5. Ed. - Stuttgart; New York: Thieme, 1995). Suitable representatives from the group of guanidines including the biguanidines and polyguanidines are, for example, 1,6-bis- (2-ethylhexyl-biguanido-hexane) dihydrochloride, 1,6-di- (Nι, Nι , -phenyldiguanido-N 5 , N 5 l ) -hexane-tetrahydochloride, 1, 6-di- (Ni.Ni'-phenyl-Ni.Ni-methyldiguanido-Ns.Ns'J-hexane-dihydrochloride, 1,6-di- (N-ι, Nι '-chlorophenyldiguanido-N 5 , N 5 ') -hexane-dihydrochloride, 1,6-di- (Nι, Nι'-2,6-dichlorophenyldiguanido-Ns.N δ 'J-hexane-dihydrochloride, 1 , 6-Di- [Nι, Nι'-ß- (p-methoxyphenyl) - diguanido-N δ .N δ 'j-hexane-dihydrochloride, 1, 6-di- (Nι, Nι'-alpha-methyl-ß -phenyldi- guanido-N5, N 5 ') -hexane-dihydrochloride, l ^ -D Ni.Ni'-p-nitrophenyldiguanido-Ns.Ns') - hexane-dihydrochloride, ω: ω-di- (Nι, Nι' -phenyldiguanido-N 5 , N 5 ') -di-n-propylether-di-hydrochloride, ω: ω , -Di- (N 1 , Nι'-p-chlorophenyldiguanido-N 5 , N 5 , ) -di-n -propylether-tetra-hydrochloride, 1, 6-di- (Nι, Nι'-2,4-dichlorophenyldiguanido-N 5 , N 5 hexane-tetrahydrochloride, 1, 6-di- (Nι, Nι ' -p-methylphenyldiguanido-N 5 , N 5 ') -hexane-dihydrochloride, 1, 6-di- (Nι, Nι'-2,4,5-trichlorophenyldiguanido-N 5 , N 5 -hexane-tetrahydrochloride, 1, 6th -Di- [Nι, Nι'- alpha- (p-chlorophenyl) -ethyldiguanido-N 5 , N 5 '] -hexane-dihydrochloride, ω: ω-Di- (N-ι, Nι'- p-chlorophenyldiguanido-N 5 , N 5 ') -m-xylene-dihydrochloride, 1,12-di- (Nι, Nι'-p-chlorophenyldiguanido-Ns.NsΗodecan-dihydrochloride, 10-DKNi.N-i'-phenyldiguanido-N 5 , N 5 ') -decane-tetrahydrochloride, l. ^ - D Ni.Ni'-phenyldiguanido-Ns.Ns ^ -dodecane tetrahydrochloride, 1, 6-di- (Nι, Nι , -o-chlorophenyldiguanido-N 5 , N 5 , ) -hexane-dihydrochloride, 1, 6-di- (Nι, Nι'-o-chlorophenyldiguanido-N 5 , N 5 ') -hexane-tetrahydrochloride,
Ethylen-bis-(l-tolylbiguanid), Ethylen-bis-(p-tolylbiguanide), Ethylen-bis-(3,5-di- methylphenylbiguanid), Ethylen-bis-(p-tert-amylphenylbiguanid), Ethylen-bis- (nonylphenylbiguanid), Ethylen-bis-(phenylbiguanid), Ethylen-bis-(N-butylphenyl- biguanid), Ethylen-bis-(2,5-diethoxyphenylbiguanid), Ethylen-bis-(2,4-dimethylphenyl- biguanid), Ethylen-bis-(o-diphenylbiguanid), Ethylen-bis-(mixed-amyl-naphthyl- biguanid), N-Butyl-ethylen-bis-(phenylbiguanid), Trimethylen-bis-(o-tolylbiguanid), N- Butyl-trimethylen-bis-(phenylbiguanide) und die entsprechenden Salze wie Acetate, Gluconate, Hydrochloride, Hydrobromide, Citrate, Bisulfite, Fluoride, Polymaleate, N- Cocosalkylsarcosinate, Phosphite, Hypophosphite, Perfluorooctanoate, Silicate, Sorbate, Salicylate, Maleate, Tartrate, Fumarate, Ethylendiamintetraacetate, Imino- diacetate, Cinnamate, Thiocyanate, Arginate, Pyromellitate, Tetracarboxybutyrate, Benzoate, Glutarate, Monofluorphosphate, Perfluorpropionate sowie beliebige Mischungen davon.
Weiterhin geeignet sind folgende gemäß der International Nomenclature Cosmetic Ingredient (INCI)-Nomenklatur bezeichnete antimikrobielle Wirkstoffe (s. a. International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997), Herausgeber: The Cosmetic, Toiletry, and Fragrance Association (CTFA), 1101 17th Street, NW, Suite 300, Washington, DC 20036, USA): Alcohol, Benzalkonium Chloride, Benzethonium Chloride, Camellia Sinensis Leaf Extract, Candida Bombicola/Glucose/Methyl, Rapeseedate Ferment, Hydrogen Peroxide, Methyl- benzethonium Chloride, Phenol, Pinus Pinaster Bark Extract, Pinus Tabulaeformis Bark Extract, Poloxamer 188, PVP-lodine, Rosmarinus Officinalis (Rosemary), Leaf Extract und Vitis Vinifera (Grape) Seed Extract.Ethylene bis (l-tolyl biguanide), ethylene bis (p-tolyl biguanide), ethylene bis (3,5-dimethylphenyl biguanide), ethylene bis (p-tert-amylphenyl biguanide), ethylene bis- (nonylphenyl biguanide), ethylene bis (phenyl biguanide), ethylene bis (N-butylphenyl biguanide), ethylene bis (2,5-diethoxyphenyl biguanide), ethylene bis (2,4-dimethylphenyl biguanide), Ethylene bis (o-diphenyl biguanide), ethylene bis (mixed amyl naphthyl biguanide), N-butyl ethylene bis (phenyl biguanide), trimethylene bis (o-tolyl biguanide), N-butyl trimethylene-bis- (phenylbiguanide) and the corresponding salts such as acetates, gluconates, hydrochlorides, hydrobromides, citrates, bisulfites, fluorides, polymaleates, N-cocoalkylsarcosinates, phosphites, hypophosphites, perfluorooctanoates, silicates, sorbates, salicylates, maleates, maleates, tareates Ethylene diamine tetraacetates, imino diacetates, cinnamates, thiocyanates, arginates, pyromellitates, tetracarboxybutyrates, benzoates, glutarates, monofluorophosphates, perfluoropropionates and any mixtures thereof. Also suitable are the following antimicrobial agents (see also International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997), published according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature, publisher: The Cosmetic, Toiletry, and Fragrance Association (CTFA), 1101 17th Street , NW, Suite 300, Washington, DC 20036, USA): Alcohol, Benzalkonium Chloride, Benzethonium Chloride, Camellia Sinensis Leaf Extract, Candida Bombicola / Glucose / Methyl, Rapeseedate Ferment, Hydrogen Peroxide, Methylbenzethonium Chloride, Phenol, Pinus Pinaster Bark Extract, Pinus Tabulaeformis Bark Extract, Poloxamer 188, PVP-lodine, Rosmarinus Officinalis (Rosemary), Leaf Extract and Vitis Vinifera (Grape) Seed Extract.
Besonders bevorzugt enthält das erfindungsgemäße Mittel mindestens eine quatemäre Ammoniumverbindung (QAV) mit antimikobieller Wirkung gemäß der allgemeinen Formel (Riπ)(Riv)(Rv)(Rvi)N+ X" in der Riπ bis Rvi gleiche oder verschiedene Cι-C22-Alkylreste, C7-C28-Aralkylreste oder heterozyklische Reste, wobei zwei oder im Falle einer aromatischen Einbindung wie im Pyridin sogar drei Reste gemeinsam mit dem Stickstoffatom den Heterozyklus, z. B. eine Pyridinium- oder Imidazoliniumverbindung, bilden, darstellen und X" Halogenidionen, Sulfationen, Hydroxidionen oder ähnliche Anionen sind. Für eine optimale antimikrobielle Wirkung weist vorzugsweise wenigstens einer der Reste eine Kettenlänge von 8 bis 18, insbesondere12 bis 16, C-Atomen auf.The agent according to the invention particularly preferably contains at least one quaternary ammonium compound (QAV) with an antimicobial action according to the general formula (R iπ ) (R iv ) (R v ) (R vi ) N + X " in which R iπ to R vi are identical or different C 1 -C 22 -alkyl radicals, C 7 -C 28 -aralkyl radicals or heterocyclic radicals, two or, in the case of an aromatic integration, such as in pyridine, even three radicals together with the nitrogen atom forming the heterocycle, for example a pyridinium or imidazolinium compound , represent and X "are halide ions, sulfate ions, hydroxide ions or similar anions. For an optimal antimicrobial effect, at least one of the residues preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
QAV sind durch Umsetzung tertiärer Amine mit Alkylierungsmitteln, wie z. B. Methylchlorid, Benzylchlorid, Dimethylsulfat, Dodecylbromid, aber auch Ethylenoxid herstellbar. Die Alkylierung von tertiären Aminen mit einem langen Alkyl-Rest und zwei Methyl-Gruppen gelingt besonders leicht, auch die Quaternierung von tertiären Aminen mit zwei langen Resten und einer Methyl-Gruppe kann mit Hilfe von Methylchlorid unter milden Bedingungen durchgeführt werden. Amine, die über drei lange Alkyl-Reste oder Hydroxy-substituierte Alkyl-Reste verfügen, sind wenig reaktiv und werden bevorzugt mit Dimethylsulfat quaterniert.QAV are by reacting tertiary amines with alkylating agents, such as. B. methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide. The alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy, and the quaternization of tertiary amines with two long radicals and one methyl group can also be carried out using methyl chloride under mild conditions. Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are not very reactive and are preferably quaternized with dimethyl sulfate.
Geeignete QAV sind beispielweise Benzalkoniumchlorid (N-Alkyl-N,N-dimethyl- benzylammoniumchlorid, CAS No. 8001-54-5), Benzalkon B (m.p-Dichlorbenzyl- dimethyl-C12-alkylammoniumchlorid, CAS No. 58390-78-6), Benzoxoniumchlorid
(Benzyl-dodecyl-bis-(2-hydroxyethyl)-ammoniumchlorid), CetrimoniumbromidSuitable QAC are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkon B (mp-dichlorobenzyldimethyl-C 12 -alkylammonium chloride, CAS No. 58390-78-6 ), Benzoxonium chloride (Benzyl dodecyl bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide
(N-Hexadecyl-N,N-trimethyl-ammoniumbromid, CAS No. 57-09-0), Benzetonium- chlorid (N,N-Dimethyl-N-[2-[2-[p-(1 ,1 ,3,3-tetramethylbutyl)phenoxy]ethoxy]ethyl]- benzylammoniumchlorid, CAS No. 121-54-0), Dialkyldimethylammoniumchloride wie Di-π-decyl-dimethyl-ammoniumchlorid (CAS No. 7173-51-5-5), Didecyldimethyl- ammoniumbromid (CAS No. 2390-68-3), Dioctyl-dimethyl-ammoniumchloric, 1-Cetylpyridiniumchlorid (CAS No. 123-03-5) und Thiazolinjodid (CAS No. 15764-48-1) sowie deren Mischungen. Besonders bevorzugte QAV sind die Benzalkoniumchloride mit Cs-Cis-Alkylresten, insbesondere C12-Ci4-Akly!-benzyl- dimethylammoniumchlorid.(N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No. 57-09-0), benzetonium chloride (N, N-dimethyl-N- [2- [2- [p- (1, 1, 3 , 3-tetramethylbutyl) phenoxy] ethoxy] ethyl] - benzylammonium chloride, CAS No. 121-54-0), dialkyldimethylammonium chlorides such as di-π-decyl-dimethyl-ammonium chloride (CAS No. 7173-51-5-5), didecyldimethyl- ammonium bromide (CAS No. 2390-68-3), dioctyl-dimethyl-ammoniumchloric, 1-cetylpyridinium chloride (CAS No. 123-03-5) and thiazoline iodide (CAS No. 15764-48-1) and their mixtures. Particularly preferred QAV are the benzalkonium chlorides with Cs-Cis-alkyl radicals, in particular C 12 -Ci 4 -Akly! -Benzyl-dimethylammonium chloride.
Benzalkoniumhalogenide und/oder substituierte Benzalkoniumhalogenide sind beispielsweise kommerziell erhältlich als Barquat® ex Lonza, Marquat® ex Mason, Variquat® ex Witco/Sherex und Hyamine® ex Lonza, sowie Bardac® ex Lonza. Weitere kommerziell erhältliche antimikrobielle Wirkstoffe sind N-(3-Chlorallyl)- hexaminiumchlorid wie Dowicide® und Dowicil® ex Dow, Benzethoniumchlorid wie Hyamine® 1622 ex Rohm & Haas, Methylbenzethoniumchlorid wie Hyamine® 10X ex Rohm & Haas, Cetylpyridiniumchlorid wie Cepacolchlorid ex Merrell Labs.Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ® ex Lonza, Marquat® ® ex Mason, Variquat ® ex Witco / Sherex and Hyamine ® ex Lonza and as Bardac ® ex Lonza. Other commercially obtainable antimicrobial agents are N- (3-chloroallyl) - hexaminiumchlorid as Dowicide and Dowicil ® ® ex Dow, benzethonium chloride such as Hyamine ® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ® 10X ex Rohm & Haas, cetylpyridinium chloride such as Cepacol ex Merrell Labs ,
Der Gehalt an antimikrobiellem Wirkstoff, insbesondere oberflächenaktiver quaternärer Verbindung, beträgt erfindungsgemäß zwischen 0 bis 10 Gew.-%, vorzugsweise 0,2 bis 5 Gew.-%, insbesondere 0,5 bis 3 Gew.-%, besonders bevorzugt 1 bis 2 Gew.-%, beispielsweise 1,5 Gew.-%.The content of antimicrobial active ingredient, in particular surface-active quaternary compound, according to the invention is between 0 to 10% by weight, preferably 0.2 to 5% by weight, in particular 0.5 to 3% by weight, particularly preferably 1 to 2% by weight .-%, for example 1.5 wt .-%.
Verdickungsmittelthickener
Zur Einstellung der Viskosität kann die erfindungsgemäß verwendete flüssige Phase ein oder mehrere Verdickungsmittel, vorzugsweise in einer Menge von 0,01 bis 5 Gew.-%, insbesondere 0,05 bis 2,5 Gew.-%, besonders bevorzugt 0,1 bis 1 Gew.- %, enthalten.To adjust the viscosity, the liquid phase used according to the invention can contain one or more thickeners, preferably in an amount of 0.01 to 5% by weight, in particular 0.05 to 2.5% by weight, particularly preferably 0.1 to 1 % By weight.
Geeignete Verdickungsmittel sind organische natürliche Verdickungsmittel, wie beispielsweise Agar-Agar, Carrageen, Tragant, Gummi arabicum, Alginate, Pektine, Polyosen, Guar-Mehl, Johannisbrotbaumkernmehl, Stärke, Dextrine, Gelatine oder
Casein, organische abgewandelte Naturstoffe, wie beispielsweise Carboxymethyl- cellulose und andere Celluloseether, Hydroxyethyl- und -propylcellulose und dergleichen, Kemmehlether, organische vollsynthetische Verdickungsmittel, wie etwa Polyacryl- und Polymethacryl-Verbindungen, Vinylpolymere, Polycarbonsäuren, Polyether, Polyimine oder Polyamide, und anorganisch Verdickungsmittel, wie etwa Polykieselsäuren, Tonmineralien wie Montmorillonite, Zeolithe, Kieselsäuren.Suitable thickeners are organic natural thickeners, such as agar agar, carrageenan, tragacanth, arabic gum, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin or Casein, organic modified natural substances such as carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and the like, gum flour, organic fully synthetic thickeners such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines or polyamides, and inorganic Thickeners such as polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas.
Zu den Polyacryl- und Polymethacryl-Verbindungen zählen beispielsweise die hochmolekulare mit einem Polyalkenylpolyether, insbesondere einem Allylether von Saccharose, Pentaerythrit oder Propylen, vernetzten Homopolymere der Acrylsäure (/Λ/C/-Bezeichnung gemäß International Dictionary of Cosmetic Ingredients der The Cosmetic, Toiletry, and Fragrance Association (CTFA): Carbomer), die auch als Carboxyvinylpolymere bezeichnet werden. Solche Polyacrylsäuren sind u.a. von der Fa. BFGoodrich unter dem Handelsnamen CarbopoP erhältlich, z.B. CarbopoP 940 (Molekulargewicht ca. 4.000.000), CarbopoP 941 (Molekulargewicht ca. 1.250.000) oder CarbopoP 934 (Molekulargewicht ca. 3.000.000). Weiterhin fallen darunter folgende Acrylsäure-Copolymere: (i) Copolymere von zwei oder mehr Monomeren aus der Gruppe der Acrylsäure, Methacrylsäure und ihrer einfachen, vorzugsweise mit C -4-Alkanolen gebildeten, Ester (INCI Acrylates Copolymer), zu denen etwa die Copolymere von Methacrylsäure, Butylacrylat und Methylmethacrylat (CAS- Bezeichnung gemäß Chemical Abstracts Service: 25035-69-2) oder von Butylacrylat und Methylmethacrylat (CAS 25852-37-3) gehören und die beispielsweise von der Fa. Rohm & Haas unter den Handelsnamen Aculyn® und Acusot® erhältlich sind, z.B. die anionischen nicht-assoziativen Polymere Aculyn® 33 (vernetzt), AcusoP 810 und AcusoP 830 (CAS 25852-37-3); (ii) vernetzte hochmolekulare Acrylsäurecopolymere, zu denen etwa die mit einem Allylether der Saccharose oder des Pentaerythrits vernetzten Copolymere von Cιo-30-Alkylacrylaten mit einem oder mehreren Monomeren aus der Gruppe der Acrylsäure, Methacrylsäure und ihrer einfachen, vorzugsweise mit Cι-4-Alkanolen gebildeten, Ester (INCI Acrylat.es/C10-30 Alkyl Acrylate Crosspolymer) gehören und die beispielsweise von der Fa. BFGoodrich unter dem Handelsnamen Carbopoi® erhältlich sind, z.B. das hydrophobierte CarbopoP ETD 2623 und CarbopoP 1382 (INCI Acrylates/C 10-30 Alkyl Acrylate Crosspolymer) sowie CarbopoP AQUA 30 (früher CarbopoP EX 473).
Bevorzugte Verdickungsmittel sind die Polysaccharide und Heteropolysaccharide, insbesondere die Polysaccharidgummen, beispielsweise Gummi arabicum, Agar, Alginate, Carrageene und ihre Salze, Guar, Guaran, Tragacant, Gellan, Ramsan, Dextran oder Xanthan und ihre Derivate, z.B. propoxyliertes Guar, sowie ihre Mischungen. Andere Polysaccharidverdicker, wie Stärken oder Cellulosederivate, können alternativ, vorzugsweise aber zusätzlich zu einem Polysaccharidgummi eingesetzt werden, beispielsweise Stärken verschiedensten Ursprungs und Stärkederivate, z.B. Hydroxyethylstärke, Stärkephosphatester oder Stärkeacetate, oder Carboxymethylcellulose bzw. ihr Natriumsalz, Methyl-, Ethyl-, Hydroxyethyl-, Hydroxypropyl-, Hydroxypropyl-methyl- oder Hydroxyethyl-methyl-cellulose oder Celluloseacetat.The polyacrylic and polymethacrylic compounds include, for example, the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (/ Λ / C / name according to the International Dictionary of Cosmetic Ingredients from The Cosmetic, Toiletry, and Fragrance Association (CTFA): Carbomer), also known as carboxyvinyl polymers. Such polyacrylic acids are available from BFGoodrich, among others, under the trade name CarbopoP, for example CarbopoP 940 (molecular weight approx. 4,000,000), CarbopoP 941 (molecular weight approx. 1,250,000) or CarbopoP 934 (molecular weight approx. 3,000,000). The following also include the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters (INCI acrylates copolymer), preferably formed with C 4 -alkanols, to which, for example, the copolymers of Methacrylic acid, butyl acrylate and methyl methacrylate (CAS name according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) belong and which, for example, from Rohm & Haas under the trade names Aculyn ® and Acusot ® are available, for example the anionic non-associative polymers Aculyn ® 33 (crosslinked), AcusoP 810 and AcusoP 830 (CAS 25852-37-3); (ii) Crosslinked high molecular acrylic copolymers, for example the copolymers crosslinked with an allyl ether of sucrose or pentaerythritol of Cιo- 30- alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with Cι -4 -alkanols formed esters (INCI Acrylat.es/C10-30 alkyl acrylate crosspolymer) and which are available, for example, from BFGoodrich under the trade name Carbopoi ® , for example the hydrophobized CarbopoP ETD 2623 and CarbopoP 1382 (INCI Acrylates / C 10-30 Alkyl Acrylate Crosspolymer) and CarbopoP AQUA 30 (formerly CarbopoP EX 473). Preferred thickeners are the polysaccharides and heteropolysaccharides, in particular the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guarane, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, for example propoxylated guar, and their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, can be used alternatively, but preferably in addition to a polysaccharide rubber, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
Ein besonders bevorzugtes Polymer ist das mikrobielle anionische Heteropolysaccharid Xanthan Gum, das von Xanthomonas campestris und einigen anderen Species unter aeroben Bedingungen mit einem Molekulargewicht von 2 bis 15*106 produziert wird und beispielsweise von der Fa. Kelco unter dem Handelsnamen KeltroP erhältlich ist, z.B. als cremefarbenes Pulver KeltroP T (Transparent) oder als weißes Granulat KeltroP RD (Readily Dispersable).A particularly preferred polymer is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2 to 15 * 10 6 and is available, for example, from Kelco under the trade name KeltroP, for example as a cream-colored powder KeltroP T (Transparent) or as white granulate KeltroP RD (Readily Dispersable).
Hilfs- und ZusatzstoffeAuxiliaries and additives
Neben den genannten Komponenten können die erfindungsgemäßen Mittel weitere Hilfs- und Zusatzstoffe enthalten, wie sie in derartigen Mitteln üblich sind. Hierzu zählen insbesondere Parfüm und Duftstoffe, Polymere, Soil-Release-Wirkstoffe, Lösungsmittel, wie z.B. Ethanol, Isopropanol und Glykolether, Lösungsvermittler, Hydrotrope, wie z.B. Cumolsulfonat, Octylsulfat, Butylglucosid und Butylglykol, Reinigungsverstärker, Desinfektionsmittel, Antistatika, Konservierungsmittel, Bleichsysteme, Enzyme und Farbstoffe sowie Trübungsmittel oder auch Hautschutzmittel, wie sie in EP-A-522 556 beschrieben sind. Bevorzugte Hilfs- und Zusatzstoffe sind Parfüm und Duftstoffe sowie Farbstoffe.In addition to the components mentioned, the agents according to the invention can contain further auxiliaries and additives as are customary in such agents. These include in particular perfume and fragrances, polymers, soil release agents, solvents, such as Ethanol, isopropanol and glycol ether, solubilizers, hydrotropes such as e.g. Cumene sulfonate, octyl sulfate, butyl glucoside and butyl glycol, cleaning enhancers, disinfectants, antistatic agents, preservatives, bleaching systems, enzymes and dyes as well as opacifiers or skin protection agents, as described in EP-A-522 556. Preferred auxiliaries and additives are perfume and fragrances and dyes.
Die Herstellung der erfindungsgemäßen Reinigungs- bzw. Handgeschirrspülmittel, insbesondere der Formkörper kann in an sich bekannter Weise erfolgen. Die festen
Phasen bzw. Formkörper können beispielsweise durch Beschichtung im Tauch-, Schleier-, oder Sprühverfahren erhalten werden.The cleaning or hand dishwashing detergents according to the invention, in particular the moldings, can be produced in a manner known per se. The firm Phases or moldings can be obtained, for example, by coating in the immersion, fog or spray process.
Die Herstellung einer erfindungsgemäßen Kapselphase, also eines Formkörpers, welcher geeignete Spülmittelkomponenten enthält, ist auch über das sogenannte Vertropfungsverfahren, welches beispielsweise in der DE 2215441 Unilever beschrieben wird, möglich.It is also possible to produce a capsule phase according to the invention, that is to say a shaped body which contains suitable detergent components, by means of the so-called dropletization process, which is described, for example, in DE 2215441 Unilever.
Die nachfolgenden Beispiele dienen der Veranschaulichung der vorliegenden Erfindung und sind nicht als eine Beschränkung auf die nachfolgend beschriebenen Ausführungsformen zu verstehen.
The following examples serve to illustrate the present invention and are not to be understood as a limitation to the embodiments described below.
Ausführungsbeispieleembodiments
Beispiel 1:Example 1:
Es wurde ein klares, farbloses Handgeschirrspülmittel formuliert, das blaue Kapseln aufweist.A clear, colorless hand dishwashing liquid was formulated with blue capsules.
Formulierung:Formulation:
Basisspüllösung (externe flüssige Phase):Basic rinsing solution (external liquid phase):
1 % Ethylenoxid-Propylenoxid-Ethylenoxid-Blockcopolymer (Pluronic® F 108)1% ethylene oxide-propylene oxide-ethylene oxide block copolymer (Pluronic® F 108)
4 % C12-14-Sulfat, Na-Salz4% C12-14 sulfate, Na salt
4 % Fettalkohol C12-18 + 5 EO, n-butylverschlossen (z. B. Dehypon LT 054)4% fatty alcohol C12-18 + 5 EO, n-butyl sealed (e.g. Dehypon LT 054)
10 % Na2SO410% Na 2 SO4
10 % Ethanol10% ethanol
0,5 % Parfümöl ad 100 Wasser0.5% perfume oil ad 100 water
Blaue Kapselphase:Blue capsule phase:
Hergestellt durch Vertropfungsverfahren gemäß im Stand der Technik bekanntemManufactured by dripping methods according to what is known in the art
Verfahren, z.B. analog der DE 2215441 von Unilever.Methods, e.g. analogous to DE 2215441 from Unilever.
Es wurden Kapseln, bestehend aus einer wäßrigen Lösung von 40 % C12-14- Ethersulfat-Na-Salz, 10 % Cocamidopropylbetain, 10 % C12-14-Sulfat-Na-Salz, 17 % Ethylenglycol und 0,1 % Farbstoff Basisblau, eingekapselt in Polyvinylalkoholgel, aus einer Lösung von 10 % Polyvinylalkohol (PVAI von Erkol), 0,0005 % Borsäure, Rest Wasser, mit Hilfe eines Extruders mit konzentrischer Austrittsöffnung hergestellt. Die Lösung wurde in Form von Tröpfchen in ein Sammelbad, das aus einer wäßrigen Lösung von 0,5 % NaOH und 20 % Na2S04 besteht, vertropft.Capsules consisting of an aqueous solution of 40% C12-14 ether sulfate Na salt, 10% cocamidopropyl betaine, 10% C12-14 sulfate Na salt, 17% ethylene glycol and 0.1% base blue dye were encapsulated in polyvinyl alcohol gel, made from a solution of 10% polyvinyl alcohol (PVAI from Erkol), 0.0005% boric acid, balance water, using an extruder with a concentric outlet opening. The solution was dripped in the form of droplets in a collecting bath consisting of an aqueous solution of 0.5% NaOH and 20% Na 2 S0 4 .
Die Kapselphase wurde in einer Konzentration von 5 - 30 % in die Basisspüllösung gegeben. Sie war bei Lagerung stabil. Sie löste sich beim Verdünnen auf Anwendungskonzentration bei einer Temperatur von 40°C innerhalb von 10 Minuten auf und setzte das eingeschlossene Tensid frei. Die resultierende verdünnte Basisspüllösung reinigte Gläser besonders schonend. Die blauen Kapseln lösten
sich zeitverzögert auf und setzen eine Tensidmischung zur kraftvollen Reinigung fettigen, belasteten Geschirrs frei.The capsule phase was added in a concentration of 5 - 30% in the basic rinsing solution. It was stable when stored. When it was diluted to the application concentration at a temperature of 40 ° C., it dissolved within 10 minutes and released the enclosed surfactant. The resulting diluted basic rinsing solution gently cleaned glasses. The blue capsules loosened sets off with a time delay and releases a surfactant mixture for the powerful cleaning of greasy, contaminated dishes.
Beispiel 2:Example 2:
Es wurde ein klares Handgeschirrspülmittel formuliert, das blaue und grüne Kapseln aufweist.A clear hand dishwashing detergent was formulated with blue and green capsules.
Formulierung:Formulation:
Basisspüllösung (externe flüssige Phase):Basic rinsing solution (external liquid phase):
1 % Ethylenoxid-Propylenoxid-Ethylenoxid-Blockcopolymer (Pluronic® F 108)1% ethylene oxide-propylene oxide-ethylene oxide block copolymer (Pluronic® F 108)
4 % C12-14-Sulfat, Na-Salz4% C12-14 sulfate, Na salt
4 % Fettalkohol C12-18 + 5 EO, n-butylverschlossen (z. B. Dehypon LT 054)4% fatty alcohol C12-18 + 5 EO, n-butyl sealed (e.g. Dehypon LT 054)
10 % Na2SO4 10% Na 2 SO 4
10 % Ethanol10% ethanol
0,5 % Parfümöl ad 100 Wasser0.5% perfume oil ad 100 water
Blaue Kapselphase:Blue capsule phase:
Es wurden Kapseln, bestehend aus einer wäßrigen Lösung von 40 % C12-14- Ethersulfat-Na-Salz, 10 % Cocamidopropylbetain, 10% C12-14-Sulfat-Na-Salz, 17 % Ethylenglycol und 0,1 % Farbstoff Basisblau, eingekapselt in Polyvinylalkoholgel, aus einer Lösung von 10 % Polyvinylalkohol (PVAI von Erkol), 0,0005 % Borsäure, Rest Wasser, mit Hilfe eines Extruders mit konzentrischer Austrittsöffnung hergestellt. Die Lösung wurde in Form von Tröpfchen in ein Sammelbad, das aus einer wäßrigen Lösung von 0,5 % NaOH und 20 % Na2SO4 besteht, vertropft.Capsules consisting of an aqueous solution of 40% C12-14 ether sulfate Na salt, 10% cocamidopropyl betaine, 10% C12-14 sulfate Na salt, 17% ethylene glycol and 0.1% base blue dye were encapsulated in polyvinyl alcohol gel, made from a solution of 10% polyvinyl alcohol (PVAI from Erkol), 0.0005% boric acid, balance water, using an extruder with a concentric outlet opening. The solution was dripped in the form of droplets into a collecting bath consisting of an aqueous solution of 0.5% NaOH and 20% Na 2 SO 4 .
Grüne Kapselphase:Green capsule phase:
Es wurden Kapseln hergestellt, bestehend aus einem Kern aus 10 Teilen Tiθ2-Pulver und 6 Teilen Thioharnstoff dispergiert in 84 Teilen flüssigem Paraffin unter Zusatz von 0,1 % Farbstoff Basisgrün sowie einer Kapselwand aus Carrageenan-Gummi. Die Verkapselung erfolgte mittels einer wäßrigen Lösung von 1 % Satiagel (K- Carrageenan), 2 % Aubygel (i-Carrageenan), 0,25 % Tragon (Johannisbrot-Gummi) und 2 % Glycerin und eines Extruders mit konzentrischer Austrittsöffnung bei 70°C.
Die Lösung wurde in Form von Tröpfchen in ein Sammelbad, das aus einer Lösung von 5 % KCI, 20 % Wasser und 75 % Alkohol besteht, vertropft.Capsules were produced, consisting of a core of 10 parts of TiO 2 powder and 6 parts of thiourea dispersed in 84 parts of liquid paraffin with the addition of 0.1% base green dye and a capsule wall made of carrageenan gum. The encapsulation was carried out using an aqueous solution of 1% Satiagel (K-carrageenan), 2% Aubygel (i-carrageenan), 0.25% Tragon (locust bean gum) and 2% glycerol and an extruder with a concentric outlet at 70 ° C , The solution was dripped in the form of droplets into a collecting bath consisting of a solution of 5% KCI, 20% water and 75% alcohol.
Beide Kapselphasen wurden in einer Konzentration von jeweils 2,5 - 15 % in die Basisspüllösung gegeben. Sie ist bei Lagerung stabil. Beim Dosieren wurde die Gesamtformulierung in das Wasser gegeben. Die sofort gelöste Basisspüllösung reinigte Gläser besonders schonend, nach ca. 5 min lösten sich die grünen Kapseln. Der freigesetzte Thioharnstoff reinigte besonders wirksam Silberbesteck- Anschmutzungen. Nach weiteren 5-10 min löste sich die blaue Kapselphase und setzte die Tensidmischung frei, welche fettbelastetes Geschirr wirksam reinigte.Both capsule phases were added in a concentration of 2.5 - 15% to the basic rinsing solution. It is stable when stored. The entire formulation was added to the water when dosing. The immediately rinsed basic rinsing solution cleaned the glasses very gently, after about 5 minutes the green capsules loosened. The released thiourea was particularly effective in cleaning silver cutlery stains. After another 5-10 minutes, the blue capsule phase dissolved and released the surfactant mixture, which effectively cleaned dishes contaminated with fat.
Beispiel 3:Example 3:
Es wurde ein klares Handgeschirrspülmittel formuliert, das blaue und grüne Kapseln aufweist.A clear hand dishwashing detergent was formulated with blue and green capsules.
Formulierung:Formulation:
Die Formulierung entsprach der in Beispiel 2 beschriebenen. Jedoch enthielt die grüne Phase statt des Silberreinigers Aminopolysiloxan als Pflegekomponente für Glas und Keramik.The formulation corresponded to that described in Example 2. However, instead of the silver cleaner, the green phase contained aminopolysiloxane as a care component for glass and ceramics.
Beim Dosieren wurde das Mittel in Wasser gegeben. Die sofort gelöste Basisspüllösung reinigte Gläser besonders schonend, nach ca. 5 min lösten sich die grünen Kapseln. Der freigesetzte Wirkstoff ist besonders geeignet für die Pflege von Glas- und Keramikoberflächen. Nach weiteren 5-10 min löste sich die blaue Kapselphase und setzte eine Tensidmischung frei zur kraftvollen Reinigung fettigen, belasteten Geschirrs.When dosing, the agent was placed in water. The immediately rinsed basic rinsing solution cleaned the glasses very gently, after about 5 minutes the green capsules came off. The released active ingredient is particularly suitable for the care of glass and ceramic surfaces. After another 5-10 minutes, the blue capsule phase dissolved and released a surfactant mixture for the powerful cleaning of greasy, contaminated dishes.
Beispiel 4:Example 4:
Es wurde ein klares Handgeschirrspülmittel formuliert, das blaue und grüne Kapseln aufweist.
Formulierung:A clear hand dishwashing detergent was formulated with blue and green capsules. Formulation:
Die Formulierung entsprach der in Beispiel 2 beschriebenen. Jedoch enthielt die grüne Phase statt des Silberreinigers Jojobaöl als Pflegekomponente für die Haut.The formulation corresponded to that described in Example 2. However, instead of the silver cleaner, the green phase contained jojoba oil as a skin care component.
Beim Dosieren wurde die Formulierung in Wasser gegeben. Die sofort gelöste Basisspüllösung reinigte Gläser besonders schonend, nach ca. 5 min lösten sich die grünen Kapseln. Der freigesetzte Wirkstoff ist besonders geeignet für die Pflege der Haut. Nach weiteren 5-10 min löste sich die blaue Kapselphase und setzte eine Tensidmischung frei zur kraftvollen Reinigung von mit Fett belasteten Geschirrs.When dosing, the formulation was placed in water. The immediately rinsed basic rinsing solution cleaned the glasses very gently, after about 5 minutes the green capsules loosened. The released active ingredient is particularly suitable for skin care. After another 5-10 minutes, the blue capsule phase dissolved and released a surfactant mixture for the powerful cleaning of dishes contaminated with fat.
Beispiel 5:Example 5:
Es wurde ein klares Handgeschirrspülmittel formuliert, das blaue Kapseln aufwies. Die Basispüllösung entsprach der in Beispiel 1 beschriebenen.A clear hand dishwashing detergent was formulated with blue capsules. The basic rinse solution corresponded to that described in Example 1.
Formulierung:Formulation:
Es wurde die gleiche Basisspüllösung wie im Beispiel 1 eingesetzt.The same basic rinsing solution as in Example 1 was used.
Blaue KapselphaseBlue capsule phase
Es wurden Kapseln hergestellt, indem man eine wäßrige Emulsion enthaltend 0,8 % Alginat, 1 % Polyvinylalkohol, 40 % C12-14-Ethersulfat-Na-Salz, 10 % Cocamido- propylbetain und 0,1 % Farbstoff Basisblau in ein wäßriges Fällbad enthaltend 5 % Calciumchlorid und 10 % Natriumsulfat vertropfte. Die erhaltenen Kapseln wurden abfiltriert, gewaschen und in die Basisspüllösung gegeben.Capsules were prepared by containing an aqueous emulsion containing 0.8% alginate, 1% polyvinyl alcohol, 40% C12-14 ether sulfate Na salt, 10% cocamido propyl betaine and 0.1% base blue dye in an aqueous precipitation bath 5% calcium chloride and 10% sodium sulfate dripped. The capsules obtained were filtered off, washed and added to the basic rinsing solution.
Beispiel 6:Example 6:
Die Zusammensetzung weiterer erfindungsgemäß geeigneter Basisspüllösungen A bis E (externe flüssige Phase) ist in nachfolgender Tabelle 1 dargestellt.
Tabelle 1The composition of further basic rinse solutions A to E (external liquid phase) suitable according to the invention is shown in Table 1 below. Table 1
Beispiel 7:Example 7:
Es wurde ein klares Handgeschirrspülmittel formuliert, das blaue Kapseln aufwies. Die Basispüllösung entsprach der in Beispiel 1 beschriebenen.A clear hand dishwashing detergent was formulated with blue capsules. The basic rinse solution corresponded to that described in Example 1.
Formulierung:Formulation:
Es wurde die gleiche Basisspüllösung wie im Beispiel 1 eingesetzt.The same basic rinsing solution as in Example 1 was used.
Blaue KapselphaseBlue capsule phase
Es wurden Kapseln hergestellt, indem man eine wäßrige Emulsion enthaltend 0,8 % Alginat, 1 % Polyvinylalkohol, 25 % Limonenöl und 0,1 % Farbstoff Basisblau in ein wäßriges Fällbad enthaltend 5 % Caiciumchlorid und 10 % Natriumsulfat vertropfte.
Die erhaltenen Kapseln wurden abfiltriert, gewaschen und in die Basisspüllösung gegeben.Capsules were prepared by dropping an aqueous emulsion containing 0.8% alginate, 1% polyvinyl alcohol, 25% limonene oil and 0.1% base blue dye into an aqueous precipitation bath containing 5% calcium chloride and 10% sodium sulfate. The capsules obtained were filtered off, washed and added to the basic rinsing solution.
Beispiel 8:Example 8:
Es wurde ein klares Handgeschirrspülmittel formuliert, das blaue Kapseln aufweist. Die Basisspüllösung entsprach der in Beispiel 1 beschriebenen.A clear hand dishwashing liquid was formulated with blue capsules. The basic rinse solution corresponded to that described in Example 1.
Formulierung:Formulation:
Es wurde die gleiche Basisspüllösung wie im Beispiel 1 eingesetzt.The same basic rinsing solution as in Example 1 was used.
Blaue KapselphaseBlue capsule phase
Es wurden Kapseln hergestellt, indem man eine wässrige Emulsion enthaltend 0,8 %Capsules were prepared by using an aqueous emulsion containing 0.8%
Alginat, 0,5 % Xanthan, 6 % Parfümöl, 6 % Polyethylenglycol (PEG 400), 2%Alginate, 0.5% xanthan, 6% perfume oil, 6% polyethylene glycol (PEG 400), 2%
Citronensäure und 0,1 % Farbstoff Basisblau in ein wäßriges Fällbad enthaltend 1 %Citric acid and 0.1% base blue dye in an aqueous precipitation bath containing 1%
Polydiallyldimethylammoniumchlorid (p-DADMAC) und 2 % Citronensäure vertropfte.Polydiallyldimethylammonium chloride (p-DADMAC) and 2% citric acid dripped.
Die erhaltenen Kapseln wurden abfiltriert, gewaschen und in die Basisspüllösung gegeben.The capsules obtained were filtered off, washed and added to the basic rinsing solution.
Die sich bei Verdünnung lösenden Kapseln gaben Duftstoffe und Hautpflegestoffe ab.
The capsules, which dissolve on dilution, released fragrances and skin care substances.
Claims
1. Tensidhaltiges Reinigungsmittel, insbesondere Handgeschirrspülmittel, dadurch gekennzeichnet, daß es ein- oder mehrphasig ist, wobei wenigstens eine Phase Formkörper aufweist, die geeignet sind wenigstens eine Reinigungsmittelkomponente bei Verdünnung in Wasser zeitlich verzögert freizusetzen.1. surfactant-containing detergent, in particular hand dishwashing detergent, characterized in that it is single or multi-phase, at least one phase having moldings which are suitable for releasing at least one detergent component with a time delay when diluted in water.
2. Reinigungsmittel, insbesondere Handgeschirrspülmittel nach Anspruch 1 , dadurch gekennzeichnet, daß das Mittel wenigstens eine flüssige Phase umfaßt, welche sich bei Verdünnung in Wasser im wesentlichen ohne zeitliche Verzögerung löst.2. Detergent, in particular hand dishwashing detergent according to claim 1, characterized in that the agent comprises at least one liquid phase, which dissolves in water substantially without any delay when diluted.
3. Reinigungsmittel, insbesondere Handgeschirrspülmittel nach Anspruch 2, dadurch gekennzeichnet, daß die flüssige Phase Reinigungsmittelkomponenten umfaßt, vorzugsweise ausgewählt aus der Gruppe umfassend nichtionische Tenside, insbesondere endgruppenverschlossene C6-C22-Alkylalkoholpolyglykol- ether, sekundäre Alkansulfonate, lineare Alkylbenzolsulfonate und Alkylpolyglucoside.3. Detergent, in particular hand dishwashing detergent according to claim 2, characterized in that the liquid phase comprises detergent components, preferably selected from the group comprising nonionic surfactants, in particular end-capped C 6 -C 22 alkyl alcohol polyglycol ethers, secondary alkane sulfonates, linear alkyl benzene sulfonates and alkyl polyglucosides.
4. Reinigungsmittel, insbesondere Handgeschirrspülmittel nach einem der Ansprüche 2 oder 3, dadurch gekennzeichnet, daß die flüssige Phase zwischen 5 und 45 Gew.-% Tenside, bezogen auf die flüssige Phase, umfaßt, vorzugsweise ausgewählt aus der Gruppe umfassend nichtionische Tenside, anionische Tenside, Betaine, Aminoxide und kationische Tenside.4. Detergent, in particular hand dishwashing detergent according to one of claims 2 or 3, characterized in that the liquid phase comprises between 5 and 45% by weight of surfactants, based on the liquid phase, preferably selected from the group comprising nonionic surfactants, anionic surfactants , Betaines, amine oxides and cationic surfactants.
5. Reinigungsmittel, insbesondere Handgeschirrspülmittel nach einem der Ansprüche 2 bis 4, dadurch gekennzeichnet, daß die flüssige Phase ein Verdickungsmittel aufweist.5. Detergent, in particular hand dishwashing detergent according to one of claims 2 to 4, characterized in that the liquid phase has a thickener.
6. Reinigungsmittel, insbesondere Handgeschirrspülmittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Formkörper eine vorzugsweise wasserlösliche oder wasserdispergierbare Beschichtung, Matrix und/oder Umhüllung zur gesteuerten Freisetzung der in den Formkörpern enthaltenen Reinigungsmittelkomponente(n) aufweisen. 6. Detergent, in particular hand dishwashing detergent according to one of claims 1 to 5, characterized in that the moldings have a preferably water-soluble or water-dispersible coating, matrix and / or covering for the controlled release of the detergent component (s) contained in the moldings.
7. Reinigungsmittel, insbesondere Handgeschirrspülmittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Beschichtung, Matrix und/oder Umhüllung wasserlösliche und/oder wasserdispergierbare Materialien aufweist, wobei die Materialien vorzugsweise ausgewählt sind aus der Gruppe umfassend Alginsäure, Alginate, Pektine, Guar-Mehl, Stärke, Dextrine, Gelatine, organische abgewandelte Naturstoffe, insbesondere Carboxymethylcellulose, Celluloseether, Hydroxyethyl- und -propylcellulose, Polysaccharide, organische vollsynthetische Substanzen, insbesondere Polyacryl- und Polymethacryl- Verbindungen, Vinylpolymere, insbesondere Polyvinylalkohole, Polycarbon- säuren, Polyether, Polyimine, Polyamide und Polyelektrolyte.7. Detergent, in particular hand dishwashing detergent according to one of claims 1 to 6, characterized in that the coating, matrix and / or coating comprises water-soluble and / or water-dispersible materials, the materials preferably being selected from the group comprising alginic acid, alginates, pectins, Guar flour, starch, dextrins, gelatin, organic modified natural products, especially carboxymethyl cellulose, cellulose ethers, hydroxyethyl and propyl cellulose, polysaccharides, organic fully synthetic substances, especially polyacrylic and polymethacrylic compounds, vinyl polymers, especially polyvinyl alcohols, polycarbonates, polyethers, Polyimines, polyamides and polyelectrolytes.
8. Reinigungsmittel, insbesondere Handgeschirrspülmittel nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Freisetzung der in den Formkörpern enthaltenen Reinigungsmittelkomponenten zeitlich gesteuert, pH- Wert gesteuert, temperaturgesteuert und/oder elektrolytstärkegesteuert erfolgt.8. Detergent, in particular hand dishwashing detergent according to one of claims 1 to 7, characterized in that the release of the detergent components contained in the moldings is time-controlled, pH-controlled, temperature-controlled and / or controlled by electrolyte strength.
9. Reinigungsmittel, insbesondere Handgeschirrspülmittel nach einem der Ansprüche 2 bis 8, dadurch gekennzeichnet, daß die Formkörper mit 0,1 bis 30 Gew.-%, vorzugsweise mit 0,2 bis 10 Gew.-%, besonders bevorzugt 0,5 - 3 Gew.-%, bezogen auf die flüssige Phase, in der flüssigen Phase enthalten sind.9. Detergent, in particular hand dishwashing detergent according to one of claims 2 to 8, characterized in that the shaped body with 0.1 to 30 wt .-%, preferably with 0.2 to 10 wt .-%, particularly preferably 0.5-3 % By weight, based on the liquid phase, is contained in the liquid phase.
10. Reinigungsmittel, insbesondere Handgeschirrspülmittel nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß das Mittel Formkörper mit gleicher oder unterschiedlicher Reinigungsmittelkomponenten-Zusammensetzung enthält, wobei die Reinigungsmittelkomponenten aus der Gruppe umfassend Silberreinigungsmittel, Korrosionsschutzmittel, Hand- bzw. Hautpflegemittel, spezielle Pflegemittel, vorzugsweise Pflegemittel für Keramik und/oder Glas, Mittel zur Entfernung spezieller Anschmutzungen, und fettlösende Substanzen ausgewählt sind.10. cleaning agent, in particular hand dishwashing agent according to one of claims 1 to 9, characterized in that the agent contains moldings with the same or different cleaning agent component composition, the cleaning agent components from the group comprising silver cleaning agents, anti-corrosion agents, hand or skin care products, special care products, preferably cleaning agents for ceramics and / or glass, agents for removing special soiling, and fat-dissolving substances are selected.
11. Reinigungsmittel, insbesondere Handgeschirrspülmittel nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß sich die Formkörper bei Verdünnung des Mittels mit Wasser bei einer Temperatur von etwa 40°C innerhalb eines Zeitraumes von bis zu 10 min, vorzugsweise innerhalb eines Zeitraums von 1 bis 8 min, besonders bevorzugt innerhalb von 3 bis 8 min zu ≥ 70 %, vorzugsweise zu > 80 %, besonders bevorzugt zu > 90 % und insbesondere bevorzugt zu 99 bis 100 % auflösen.11. Detergent, in particular hand dishwashing detergent according to one of claims 1 to 10, characterized in that the moldings are diluted with water at a temperature of about 40 ° C within a period of up to 10 min, preferably within a period of 1 to 8 min, particularly preferably within 3 to 8 min to ≥70%, preferably to> 80%, particularly preferably to> 90% and particularly preferably to 99 to Dissolve 100%.
12. Reinigungsmittel, insbesondere Handgeschirrspülmittel nach einem der Ansprüche 1 bis 11 dadurch gekennzeichnet, daß das Mittel umfaßt: a) Formkörper mit einer ersten Reinigungsmittelkomponenten-Zusammensetzung b) umfassend mindestens eine Komponente, die ausgewählt ist aus der Gruppe der Silberreinigungsmittel, Korrosionsschutzmittel, Hand- bzw. Hautpflegemittel, spezielle Pflegemittel, vorzugsweise Pflegemittel für Keramik und/oder Glas, und/oder Mittel zur Entfernung spezieller Anschmutzungen; und c) Formkörper mit einer zweiten Reinigungsmittelkomponenten-Zusammensetzung umfassend mindestens eine fettlösende Substanz, vorzugsweise ausgewählt aus der Gruuppe der Betaine, Fettalkoholsulfate, Fettalkoholethersulfate, sekundäre Alkansulfonate, lineare Alkylbenzolsulfonate, Alkylalkoholpolyglykolether, Alkylpolyglucoside, Fettsäurealkanolamide, Aminoxide und/oder hydrophobe Komponenten, d) wobei die in Formkörper a) enthaltene erste Reinigungsmittelkomponenten- Zusammensetzung bei Verdünnung des Reinigungsmittels mit Wasser vorzugsweise vor der in Formkörper b) enthaltenen zweiten Reinigungsmittelkomponenten-Zusammensetzung freigesetzt wird.12. Detergent, in particular hand dishwashing detergent according to one of claims 1 to 11, characterized in that the agent comprises: a) moldings with a first detergent component composition b) comprising at least one component which is selected from the group of silver detergents, corrosion inhibitors, hand or skin care products, special care products, preferably care products for ceramics and / or glass, and / or products for removing special soiling; and c) moldings with a second detergent component composition comprising at least one fat-dissolving substance, preferably selected from the group of betaines, fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkane sulfonates, linear alkylbenzenesulfonates, alkyl alcohol polyglycol ethers, alkyl polyglucosides, fatty acid alkanolamides, amine oxides, and / or hydrophobic the first detergent component composition contained in molded article a) is preferably released upon dilution of the detergent with water before the second detergent component composition contained in molded article b).
13. Verwendung des Reinigungsmittels gemäß einem der vorhergehenden Ansprüche zur Reinigung von harten Oberflächen und/oder weichen Oberflächen, vorzugsweise als Allzweckreiniger, Badreiniger, Fußbodenreiniger, Autoreiniger, Glasreiniger, Möbelpflegemittel, Möbelreiniger, Fassadenreiniger, Waschmittel und/oder dergleichen und besonders bevorzugt zur Reinigung von Geschirr.13. Use of the cleaning agent according to one of the preceding claims for cleaning hard surfaces and / or soft surfaces, preferably as an all-purpose cleaner, bathroom cleaner, floor cleaner, car cleaner, glass cleaner, furniture care agent, furniture cleaner, facade cleaner, detergent and / or the like and particularly preferably for cleaning Dishes.
14. Verfahren zur Reinigung einer harten und/oder weichen Oberfläche mit einer wäßrigen Reinigungsflotte, dadurch gekennzeichnet, daß die Reinigungsflotte durch Auflösen oder Dispergieren des Reinigungsmittels nach einem der Ansprüche 1 bis 12 in Wasser hergestellt wird. 14. A method for cleaning a hard and / or soft surface with an aqueous cleaning liquor, characterized in that the cleaning liquor is prepared by dissolving or dispersing the cleaning agent according to one of claims 1 to 12 in water.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10131722A DE10131722A1 (en) | 2001-06-30 | 2001-06-30 | Multiphase detergent |
DE10131722.0 | 2001-06-30 |
Publications (1)
Publication Number | Publication Date |
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WO2003004593A1 true WO2003004593A1 (en) | 2003-01-16 |
Family
ID=7690131
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2002/006889 WO2003004593A1 (en) | 2001-06-30 | 2002-06-21 | Multi-phase detergents |
Country Status (2)
Country | Link |
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DE (1) | DE10131722A1 (en) |
WO (1) | WO2003004593A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003054125A1 (en) * | 2001-12-20 | 2003-07-03 | Henkel Kommanditgesellschaft Auf Aktien | Cleaning agent comprising microcapsules |
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US3708429A (en) * | 1970-03-06 | 1973-01-02 | Lever Brothers Ltd | Cleaning compositions |
DE19817964A1 (en) * | 1998-04-22 | 1999-10-28 | Henkel Kgaa | Production of encapsulated solid particles (especially nonionic surfactants) for use in detergents for hard surfaces or for machine or manual washing-up or dishwashing liquids |
WO2000006688A1 (en) * | 1998-07-29 | 2000-02-10 | Reckitt Benckiser N.V. | Composition for use in a dishwashing machine |
WO2000046337A1 (en) * | 1999-02-02 | 2000-08-10 | Quest International B.V. | Detergent composition |
DE19918265A1 (en) * | 1999-04-22 | 2000-10-26 | Henkel Kgaa | Abrasive-containing aqueous liquid cleaning or scouring agent for hard surfaces contains microcapsules containing an ingredient to be protected e.g. a perfume |
DE19932144A1 (en) * | 1999-07-09 | 2001-01-11 | Basf Ag | Microcapsule preparations and washing and cleaning agents containing microcapsules |
US6242405B1 (en) * | 1995-12-29 | 2001-06-05 | Novo Nordisk A/S | Enzyme-containing particles and liquid detergent concentrate |
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GB1390503A (en) * | 1971-03-30 | 1975-04-16 | Unilever Ltd | Liquid detergent compositions |
DE19721708A1 (en) * | 1997-05-23 | 1998-11-26 | Henkel Kgaa | Encapsulated detergent |
-
2001
- 2001-06-30 DE DE10131722A patent/DE10131722A1/en not_active Ceased
-
2002
- 2002-06-21 WO PCT/EP2002/006889 patent/WO2003004593A1/en not_active Application Discontinuation
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US3708429A (en) * | 1970-03-06 | 1973-01-02 | Lever Brothers Ltd | Cleaning compositions |
US6242405B1 (en) * | 1995-12-29 | 2001-06-05 | Novo Nordisk A/S | Enzyme-containing particles and liquid detergent concentrate |
DE19817964A1 (en) * | 1998-04-22 | 1999-10-28 | Henkel Kgaa | Production of encapsulated solid particles (especially nonionic surfactants) for use in detergents for hard surfaces or for machine or manual washing-up or dishwashing liquids |
WO2000006688A1 (en) * | 1998-07-29 | 2000-02-10 | Reckitt Benckiser N.V. | Composition for use in a dishwashing machine |
WO2000046337A1 (en) * | 1999-02-02 | 2000-08-10 | Quest International B.V. | Detergent composition |
DE19918265A1 (en) * | 1999-04-22 | 2000-10-26 | Henkel Kgaa | Abrasive-containing aqueous liquid cleaning or scouring agent for hard surfaces contains microcapsules containing an ingredient to be protected e.g. a perfume |
DE19932144A1 (en) * | 1999-07-09 | 2001-01-11 | Basf Ag | Microcapsule preparations and washing and cleaning agents containing microcapsules |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2003054125A1 (en) * | 2001-12-20 | 2003-07-03 | Henkel Kommanditgesellschaft Auf Aktien | Cleaning agent comprising microcapsules |
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