EP0846758A2 - Detergent additive - Google Patents
Detergent additive Download PDFInfo
- Publication number
- EP0846758A2 EP0846758A2 EP97121101A EP97121101A EP0846758A2 EP 0846758 A2 EP0846758 A2 EP 0846758A2 EP 97121101 A EP97121101 A EP 97121101A EP 97121101 A EP97121101 A EP 97121101A EP 0846758 A2 EP0846758 A2 EP 0846758A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- additives
- additive
- acid
- zeolite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000654 additive Substances 0.000 title claims abstract description 92
- 239000003599 detergent Substances 0.000 title claims abstract description 34
- 230000000996 additive effect Effects 0.000 title claims abstract description 31
- 239000012459 cleaning agent Substances 0.000 claims abstract description 45
- 239000000126 substance Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 25
- 239000010457 zeolite Substances 0.000 claims abstract description 24
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000003287 optical effect Effects 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000005469 granulation Methods 0.000 claims abstract description 12
- 230000003179 granulation Effects 0.000 claims abstract description 12
- 239000013543 active substance Substances 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 32
- 150000003839 salts Chemical class 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 22
- 239000004615 ingredient Substances 0.000 claims description 21
- 239000000344 soap Substances 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003112 inhibitor Substances 0.000 claims description 13
- 229920005646 polycarboxylate Polymers 0.000 claims description 12
- 238000001694 spray drying Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000006260 foam Substances 0.000 claims description 9
- 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 claims description 8
- 239000003352 sequestering agent Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000000969 carrier Substances 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 36
- 238000002360 preparation method Methods 0.000 abstract description 7
- 150000004996 alkyl benzenes Chemical class 0.000 abstract description 3
- -1 polyol carboxylic acids Chemical class 0.000 description 53
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 30
- 235000014113 dietary fatty acids Nutrition 0.000 description 23
- 239000000194 fatty acid Substances 0.000 description 23
- 229930195729 fatty acid Natural products 0.000 description 23
- 239000003945 anionic surfactant Substances 0.000 description 20
- 150000002191 fatty alcohols Chemical class 0.000 description 19
- 239000002253 acid Substances 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- 150000004665 fatty acids Chemical class 0.000 description 17
- 239000008187 granular material Substances 0.000 description 14
- 102000004190 Enzymes Human genes 0.000 description 13
- 108090000790 Enzymes Proteins 0.000 description 13
- 229940088598 enzyme Drugs 0.000 description 13
- 150000004760 silicates Chemical class 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000007844 bleaching agent Substances 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 150000007513 acids Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 108091005804 Peptidases Proteins 0.000 description 9
- 239000004365 Protease Substances 0.000 description 9
- 150000001298 alcohols Chemical class 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000012190 activator Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 229920002245 Dextrose equivalent Polymers 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 7
- 239000003760 tallow Substances 0.000 description 7
- 239000004375 Dextrin Substances 0.000 description 6
- 229920001353 Dextrin Polymers 0.000 description 6
- 108090001060 Lipase Proteins 0.000 description 6
- 102000004882 Lipase Human genes 0.000 description 6
- 239000004367 Lipase Substances 0.000 description 6
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 6
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 235000019425 dextrin Nutrition 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 235000019421 lipase Nutrition 0.000 description 6
- 230000002366 lipolytic effect Effects 0.000 description 6
- 235000019419 proteases Nutrition 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- 235000000346 sugar Nutrition 0.000 description 6
- 108010059892 Cellulase Proteins 0.000 description 5
- 108010084185 Cellulases Proteins 0.000 description 5
- 102000005575 Cellulases Human genes 0.000 description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Chemical class 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- 108010065511 Amylases Proteins 0.000 description 4
- 102000013142 Amylases Human genes 0.000 description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 235000019418 amylase Nutrition 0.000 description 4
- 229940106157 cellulase Drugs 0.000 description 4
- 230000003111 delayed effect Effects 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 229930182470 glycoside Natural products 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 3
- 239000004435 Oxo alcohol Substances 0.000 description 3
- 102000035195 Peptidases Human genes 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
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- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
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- 125000006850 spacer group Chemical group 0.000 description 2
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- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical group OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 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 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/02—Preparation in the form of powder by spray drying
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
-
- 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
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0063—Photo- activating compounds
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
Definitions
- the invention relates to an additive for use in detergents or cleaning agents, a method for its manufacture as well as detergents or cleaning agents containing these additives contain.
- Modern powdery to granular detergents or cleaning agents are used today, for example by mixing and / or granulating additives and / or raw materials produced, with certain proportions of additives and raw materials also liquid, for example can be present as an aqueous solution or aqueous dispersion.
- the solid additives can by spray drying, granulation, roller compaction, extrusion or other compaction measures have been produced.
- liquid organic substances for example nonionic surfactants, or aqueous Solutions or aqueous dispersions have been used.
- surfactants especially anionic surfactants, are known to be both in aqueous form (as a paste) as well as in solid form (as a powder or additive).
- anionic surfactants Alkyl benzene sulfonates and alkyl sulfates.
- Alkylbenzenesulfonates in particular are important Anionic surfactants with excellent washing performance, but which have the disadvantage that they have very sticky properties, so that additives or detergents or cleaning agents with relatively high concentrations of alkylbenzenesulfonates, for example additives with Held above 30 wt .-% alkylbenzenesulfonates, tend to stick and thus the Free flowing properties of the agents impair as well as when redissolving in aqueous liquor - especially if the agents also have ethoxylated nonionic surfactants - for Tend to gel.
- Inorganic builder substances like zeolite A, which has been the preferred one in recent years inorganic builders in detergents or cleaning agents are either considered (spray dried) powder, aqueous stabilized dispersion or as part of a solid, mostly granular additives incorporated into the washing or cleaning agents.
- Prefers are solid additives for the production of which aqueous dispersions have been used in particular were spray dried. Such spray-dried additives often contain additives Anionic surfactants, for example alkylbenzenesulfonates, and other non-temperature and Ingredients sensitive to spray drying, especially those which are also preferred in aqueous form can be used.
- Zeolite A has in the The past as an excellent carrier for those who tend to stick Alkylbenzenesulfonates, but also for the others mostly used in aqueous form Components or liquid at room temperature to slightly elevated temperatures
- Constituents of washing or cleaning agents for example nonionic surfactants, textile-softening cationic surfactants or foam inhibitors such as silicone oils and paraffin oils, proven.
- Newer inorganic builders such as zeolite P, layered crystalline disilicate or amorphous Silicates with delayed disintegration, however, are only limited by spray drying ready for use and are usually available as raw materials or separate, dry compounds posed.
- Spray drying processes are unfavorable manufacturing processes from an energetic point of view for detergents or cleaning agents. There has been no shortage of attempts Provide processes for the production of detergents or cleaning agents based on spray drying either entirely or at least to spray drying base granules can do without.
- zeolite A in amounts less than 10% by weight (based on the anhydrous active substance), and also have no alkylbenzenesulfonate as the anionic surfactant, and in particular no spray-dried granules containing zeolite A and optionally Alkylbenzenesulfonate and the usual others, mostly used in aqueous form Containing constituents, the problem arises, like the others mostly in aqueous Form used further ingredients of detergents or cleaning agents in the agent can be incorporated.
- the invention accordingly relates to an additive in a first embodiment for use in detergents or cleaning agents, which organic builder substances and at least 1 further ingredient selected from sequestrants and optical Brighteners and, if necessary, other ingredients of washing or cleaning agents contains, whereby alkylbenzenesulfonates are excluded and the content of the additives Zeolite A should not be more than 10% by weight, based on anhydrous active substance.
- the invention also relates to a washing or cleaning agent which comprises the inventive Additives and in particular the additives produced according to the invention contains, but is free of alkylbenzenesulfonates and zeolite A not in amounts above 10 % By weight, based on anhydrous active substance.
- the invention is based on the idea of as many as possible, and preferably all, of the components a washing or cleaning agent, which so-called small components such Represent cobuilders, optical brighteners, sequestering agents, graying inhibitors, soap, etc. and in particular those which are usually used in aqueous form, in one Unite additive.
- small components such Represent cobuilders, optical brighteners, sequestering agents, graying inhibitors, soap, etc. and in particular those which are usually used in aqueous form, in one Unite additive.
- This has the advantage that only a small part instead of the Most of the detergent or cleaning agent is spray dried or on another Way must be dried.
- this additive enables homogeneous distribution of these small components.
- the additives according to the invention have above all organic builder substances, which are usually used as cobuilders, preferably (co) polymers Polycarboxylates.
- copolymeric polycarboxylates also counted those polymers which are made up of more than 2 monomers are.
- the content of the organic builder substances in the additives according to the invention can vary widely. In principle, it could amount to Make up 2 to 98 wt .-%.
- preferred additives contain 20 to 80% by weight and in particular 30 to 70% by weight of organic builder substances, contents of 40 to 60 % By weight of (co) polymeric polycarboxylates are particularly advantageous.
- Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if provided such use is not objectionable for ecological reasons, as well as mixtures from these.
- Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures from these.
- the acids themselves can also be used.
- the acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH of detergents or cleaning agents.
- citric acid succinic acid, glutaric acid, adipic acid, To name gluconic acid and any mixtures of these.
- Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
- the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
- DE dextrose equivalent
- Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used.
- a preferred dextrin is described in British patent application 94 19 091.
- the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
- Oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO- A-92/18542, WO-A-93/08251, WO-A-93/16110, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A- 95/20608 known.
- Oxidized oligosaccharides according to DE-A-196 00 018 are also suitable.
- a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
- further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors.
- Polyaspartic acids are particularly preferred or their salts and derivatives, of which in the German patent application P 195 40 086.0 discloses that, in addition to cobuilder properties, it also has a have a bleach-stabilizing effect.
- polyacetals which are obtained by reacting dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have, for example as in European patent application EP-A-0 280 223 described, can be obtained.
- Preferred polyacetals are made from dialdehydes such as Glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
- Suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.
- ethylenediamine disuccinate preferably ethylenediamine disuccinate.
- glycerol disuccinates and glycerol trisuccinates such as those found in the United States Patents US 4,524,009, US 4,639,325, in the European patent application EP-A-0 150 930 and Japanese patent application JP 93/339896 will.
- organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups.
- Such cobuilders are used, for example, in the international Patent application WO-A-95/20029.
- Suitable polymeric polycarboxylates are, for example, sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid).
- Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain.
- Their relative molecular weight, based on free acids is in general 5000 to 200000, preferably 10000 to 120000 and in particular 50000 to 100000.
- Die (Co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution are used, in the context of this invention 20 to 55 wt .-% aqueous solutions are preferred.
- Such (co) polymeric polycarboxylates are particularly preferred in the context of this invention.
- This includes polymers from more than two different monomer units, for example, those according to DE-A-43 00 772 as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.
- copolymers are those described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
- the known sequestering agents are mainly the salts of polyphosphonic acids and in particular the neutral sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate (HEDP), diethylene triamine penta methylene phosphonate and / or ethylenediaminetetramethylenephosphonate is preferred.
- HEDP 1-hydroxyethane-1,1-diphosphonate
- NTA nitrilotriacetic acid and / or their salts
- NTA ethylenediaminetetraacetic acid
- EDTA ethylenediaminetetraacetic acid
- the content of the additives according to the invention in one or more of these sequestering agents is preferably 2 to 8% by weight and in particular 3 to 6% by weight. As special Values between 4 and 5% by weight have proven to be advantageous.
- the agents can be derivatives of diaminostilbenedisulfonic acid or their Contain alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar connections, which instead of the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Can continue Present brighteners of the substituted diphenylstyryl type, e.g.
- Phthalocyanines and their salts are among the optical brighteners. Mixtures of the aforementioned brighteners can be used
- the content of the additives according to the invention in one or more optical brighteners is preferably at least 1.5% by weight in total and in particular 2 to 5% by weight.
- dyes can also be incorporated into the additives.
- additives can - if they are used as an additive component in detergents or cleaning agents serve - for example, serve as colored speckles.
- the so-called small components in washing or cleaning agents generally include also soaps normally used in the finished products in quantities of less than 5 wt .-% are included.
- the additives according to the invention can therefore also be soaps, in particular saturated fatty acid soaps, but optionally also in combination with unsaturated Fatty acid soaps.
- the sodium and / or potassium salts are particularly suitable of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated Erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut-, Palm kernel or tallow fatty acids, derived soap mixtures.
- the known alkenyl succinic acid salts can also be used as a substitute for soaps will.
- the content of the additives in soaps and / or alkenyl succinic acid salts is 5 to 10% by weight in a preferred embodiment of the invention, but can well below and above.
- Non-ionic surfactants which are liquid at room temperature are not directly counted as small components, even if they are only present in amounts of about 2 to 3% by weight in some finished compositions. Even in these small quantities, the nonionic surfactants, in particular in combination with anionic surfactants, make a significant contribution to the washing performance and are usually included in one of the main components - generally the surfactants.
- nonionic liquid surfactants are rarely used in aqueous solution or dispersion - exceptions are, for example, pastes made from anionic surfactants and nonionic surfactants - their incorporation into detergents or cleaning agents can still cause problems regarding the free-flowing properties of the product or because of it Tendency to gel when the product is redissolved in an aqueous liquor.
- Nonionic surfactants which are liquid at room temperature or only slightly elevated temperature if appropriate also in combination with nonionic surfactants which are solid at these temperatures, are therefore further preferred ingredients of the additives according to the invention.
- ethoxylated and / or propoxylated alcohols such as fatty alcohols, oxo alcohols or petrochemical-based alcohols with a similar (but odd) carbon chain distribution as the fatty alcohols.
- fatty alcohols such as fatty alcohols, oxo alcohols or petrochemical-based alcohols with a similar (but odd) carbon chain distribution as the fatty alcohols.
- EO ethylene oxide
- the alcohol radical can be methyl-branched linearly or preferably in the 2-position, or linear and methyl-branched radicals in a mixture can contain, as they are usually present in oxo alcohol residues.
- alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
- the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7 EO.
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
- nonionic surfactants can also be used be contained in the additives, for example ethoxylated fatty acid methyl esters, alkyl glycosides, Polyhydroxy fatty acid amides (glucamides) or amine oxides (detailed description other non-ionic surfactants: see below). Your salary in the invention However, additives are less preferred.
- the content of nonionic surfactants in the additives according to the invention is preferably 2 to 15% by weight and in particular 5 to 10% by weight.
- the content of the additives at Room temperature or liquid nonionic surfactants at only a moderately elevated temperature depends on the type and amount of solid support material, since the invention Additives retain their free-flowing properties and should not stick together even during storage.
- anionic surfactants usually belong not to the so-called small components. But if they are not in solid powder or granular to compounded form, but as an aqueous paste, if necessary in a mixture with nonionic surfactants, in the manufacture of washing or Cleaning agents are to be used, it may be advantageous if these are aqueous Anionic surfactants are introduced into the additive according to the invention. According to the invention but alkylbenzenesulfonates are excluded as ingredients of the additives. A more precise one A description of the anionic surfactants that may be used is given below.
- the salary the additives according to the invention on anionic surfactants not containing alkylbenzenesulfonate is preferably 0.5 to 10% by weight, in particular 1 to 5% by weight.
- solid fillers and carrier salts Components of the additives.
- inorganic ones are suitable for this Builder substances such as crystalline layered silicates, in particular disilicates like SKS 6®, Zeolite P like Zeolite MAP® or silicates with delayed disintegration (see below for a more detailed description).
- the content of zeolite A preferably less than 10% by weight and in particular 0 to 5 % By weight.
- Suitable solid carriers are, however, inorganic salts such as, for example Sodium and / or potassium salts of carbonates, bicarbonates, sesquicarbonates, sulfates, Bisulfates and conventional water glasses, which are at least partially in aqueous form in the Processes for producing the additives can be introduced.
- the invention makes these inorganic carrier salts less than 50 wt .-%, preferably less than 40% by weight of the additives according to the invention.
- graying inhibitors which do the job have to keep the dirt detached from the fiber suspended in the liquor and so to prevent the dirt from re-opening.
- water-soluble colloids are used mostly of an organic nature, for example the water-soluble salts of polymeric carboxylic acids, Glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or the cellulose or salts of acidic sulfuric acid esters of cellulose or Strength.
- Water-soluble polyamides containing acidic groups are also suitable for this purpose suitable.
- Soluble starch preparations and others other than those mentioned above can also be used Use starch products, e.g. degraded starch, aldehyde starches, etc.
- Polyvinyl pyrrolidone is useful.
- cellulose ethers such as carboxymethyl cellulose are preferred (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the funds used.
- the additives according to the invention differ depending on the type of their production Bulk weights between about 250 to about 900 g / l, but bulk weights above of 400 g / l and in particular above 500 g / l are particularly preferred.
- the additives (after drying) have less than 10% by weight and preferably less than 5% by weight of free water. Especially it is even preferred that the total amount of water, ie the sum of chemical and / or physically bound and unbound, i.e. free water even makes up less than 10% by weight and in particular even less than 5% by weight.
- the Additives have typical granular structures, although they are optional - for example, if they are to be used as additives to almost spherical particles - rounded can be.
- Advantageous embodiments of the invention also provide that the additives - apart from of water and residual components / salts, which from the solutions used in the Additives were introduced - at least 90% by weight from no more than 7 different ones Ingredients, preferably at least 92% by weight of not more than 5 different components.
- 2 different optical Brighteners which are dosed separately in conventional processes, as 2 different ones Viewed components.
- a preferred additive contains organic, preferably (co) polymeric cobuilders, 1 to 3 optical brighteners, non-ionic surfactant and / or soap, 1 to 2 different phosphonates and 1 to 2 solids as filler salts and carriers, preferably carbonate, bicarbonate, Sulfate, bisulfate or mixtures thereof.
- a particularly preferred additive contains (co) polymeric polycarboxylates, non-ionic Surfactant and / or soap, 1 to 3 components selected from optical brighteners and phosphonates and sodium and / or potassium carbonate, the sum of the contents of (co) polymeric polycarboxylate and the carbonate make up between 70 and 85% by weight.
- the usual fine-particle surface modifiers known from the prior art can be used here such as zeolite A, X and / or P, silicas and silicic acid derivatives, calcium stearate etc. and mixtures of these are used.
- the amount of the optional The surface modifier used in zeolite A is the maximum that can be used in the additive The amount of zeolite A already included.
- the additives can be made by any of the known methods such as spray drying, granulation with water as granulation aid and drying as well as compacting and Make drying. If necessary, aftertreatment can then be carried out with other treatments Ingredients in solid and / or liquid form. What manufacturing process is chosen depends on the amount of water used by those in aqueous form Raw materials and possibly compounds is provided. So offers at Amounts of water above 30% by weight, based on the mixture to be dried, on each Do the spray drying. With water contents up to 10 wt .-% is also generally granulation possible without difficulty. With water contents between 10 and 30 wt .-%, it is left to the skilled person, the most effective method to select for the manufacture of the additives.
- (co) polymeric polycarboxylates are commercially available in aqueous form.
- organic builders can be citric acid and citrate as an aqueous solution be used.
- Acid and salt of citric acid can also be used as a solid be added.
- organic builder substances as well as dye solutions, but optionally also solutions of the sequestering agents, the optical brighteners and Graying inhibitors and discoloration inhibitors, for example polyvinylpyrrolidone, optionally also water glass solutions, fatty acids and non-ionic surfactants, especially at room temperature or up to 30 ° C liquid nonionic surfactants Fat or oxo alcohol ethoxylates (for a more detailed description see below) represent the liquid ones Forms of preparation for the production of the additives according to the invention. Out For economic reasons, the highest possible with the aqueous preparation forms concentrated solutions or dispersions are used.
- citric acid serves as solid components or citrate, alkali metal soaps and the other possible inorganic fillers and Carrier salts, especially sodium carbonate and / or sodium sulfate.
- the solid and liquid components are mixed together, using it in principle It is irrelevant whether all liquid components are initially introduced and the solids mixed into them whether all solids are initially charged and the liquid components mixed or whether there is any order of addition. Out For reasons of process economy, however, the solids are preferred first submitted and then mixed in the liquids. Drying is done either by spray drying a slurry or in a conventional drying device after a performed granulation or compacting, the use of Fluid bed dryers is preferred. If desired - see above - can follow the drying still a surface modification according to the known methods of State of the art. The surface can be finely divided in a known manner Powders are coated.
- the Additives according to the invention in particular the spray-dried additives as carriers for other liquids, in particular for nonionic surfactants, cationic surfactants and / or liquid to wax-like foam inhibitors based on silicone or paraffin in one subsequent granulation or compacting step.
- the invention further relates to a powdery to granular washing or cleaning agent -
- a powdery to granular washing or cleaning agent - which contains the additive according to the invention but is free from alkylbenzenesulfonates and zeolite A not in amounts above 10% by weight, based on anhydrous active substance.
- the agents zeolite A only in amounts up to 8 wt .-%, advantageously contain up to 5% by weight and in particular 1 to 3% by weight even zeolite are A-free.
- Additive contains all components necessary for the production of the finished agent in aqueous form are used, a detergent or cleaning agent containing such an additive, which contains all raw materials or compounds used in aqueous form, another preferred embodiment.
- the detergents or cleaning agents can be any of the known methods are prepared, the spray drying from the given Problem should be essentially excluded.
- Preferred manufacturing process are conventional granulations, compactings and extrusions, whereby the additives according to the invention either subsequently as a separate component be mixed with the agent or a feed component in the selected manufacturing process represent.
- the additives according to the invention as an insert component in an extrusion process - advantageously in an extrusion process according to the teaching of European patent 0 486 592 B1 or the older one German patent application P 196 38 599.7 - are used.
- washing or cleaning agents have the following ingredients, the invention is not limited to the ingredients mentioned.
- anionic surfactants are those of the sulfonate type (to the exclusion of alkylbenzenesulfonates) and sulfates.
- Suitable surfactants of the sulfonate type include, for example, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the Receives sulfonation products.
- alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated Methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.
- Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and Triester and their mixtures represent how they are produced by esterification by a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides can be obtained with 0.3 to 2 mol of glycerol.
- the sulfonation products are a complex mixture represents the mono-, di- and triglyceride sulfonates with ⁇ -and / or internal Contains sulfonic acid grouping.
- sulfonated fatty acid salts are formed, Glyceride sulfates, glycerine sulfates, glycerin and soaps. If you go from the saturated of saturated Fatty acids or hardened fatty acid glycerol ester mixtures, so the Percentage of ⁇ -sulfonated fatty acid disalts, depending on the procedure, up to about 60 % By weight.
- Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
- alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length 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.
- C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates, as well as C 14 -C 15 alkyl sulfates and C 14 -C 16 alkyl sulfates are particularly preferred from the point of view of washing technology.
- 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as a commercial product from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
- the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
- the soaps already mentioned can be considered as further anionic surfactants. she if they are not completely incorporated into the agents via the additive according to the invention are preferably mixed in subsequently.
- the anionic surfactants can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
- the content of anionic surfactants in the washing or cleaning agents according to the invention is preferably 10 to 45% by weight in total, with it being preferred that Alk (en) yl sulfates or 2,3-alkyl sulfates are contained in amounts of 10 to 40% by weight.
- the preferred anionic surfactants are alk (en) yl sulfates and / or 2,3-alkyl sulfates, which From an application point of view, alkylbenzenesulfonates in the washing or Can replace cleaning agents without sacrificing performance.
- ingredients of the invention are primarily alkyl glycosides, polyhydroxy fatty acid amides and especially here the glucamides, ethoxylated fatty acid methyl esters and to name amine oxides.
- alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
- nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
- nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
- the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than that Half of it.
- Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in the R 2 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 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 stands.
- the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 5 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
- R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 4 represents a linear, branched or cyclic alkyl radical or an
- [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
- gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually identified by a so-called Spacer separated from each other. This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient distance so that they can act independently of one another. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants means not only dimeric but also trimeric surfactants.
- Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates according to international patent application WO-A-96/23768.
- End group capped dimeric and trimeric mixed ethers according to the German Patent application DE-A-195 13 391 are particularly characterized by their bi- and Multifunctionality.
- the end group-closed surfactants mentioned have good ones Network properties and are low-foaming, so that they are particularly suitable for use suitable in machine washing or cleaning processes.
- Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides can also be used. as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO95-A- / 19955 can be described.
- Zeolite P is crystalline as builder substances layered (di) silicates and amorphous silicates with delayed disintegration into consideration.
- Zeolite A is used - if at all - only in the amounts already mentioned above.
- Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
- Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
- the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties.
- the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
- the term “amorphous” also means “X-ray amorphous”.
- silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
- it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
- Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
- the agents can also contain components that make the oil and fat washable made of textiles. This effect is particularly evident when a textile is soiled that has already been washed several times with an inventive one Detergent containing this oil and fat-dissolving component has been washed.
- non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and from 1 to 15% by weight of hydroxypropoxyl groups, each based on the nonionic cellulose ether
- polymers of phthalic acid and / or terephthalic acid or their Derivatives in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these.
- sulfonated derivatives of phthalic acid and Terephthalic acid polymers are particularly preference is given to the sulfonated derivatives of phthalic acid and Terephthalic acid polymers.
- Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these;
- alkali carbonate and amorphous alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
- bleaching agents that serve as bleaching agents and supply H 2 O 2 in water
- sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
- the bleach content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.
- Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used.
- Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups.
- acylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated Glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the German patent applications DE-A-196 16
- the bleach activator can be coated with coating substances in a known manner or, if necessary using auxiliaries, in particular methyl celluloses and / or carboxymethyl celluloses, granulated or extruded / pelletized and, if desired, others Additives, such as dye, contain. Such granules preferably contain over 70% by weight, in particular from 90 to 99% by weight, of bleach activator. Preferably a bleach activator is used which forms peracetic acid under washing conditions.
- the transition metal compounds in question include in particular those known from the German patent application DE-A-195 29 905 manganese, iron, cobalt, Ruthenium or molybdenum salt complexes and those from the German patent application DE-A-196 20 267 known N-analog compounds, which from the German Patent application DE-A-195 36 082 known manganese, iron, cobalt, ruthenium or Molybdenum-carbonyl complexes, which are described in German patent application DE-A-196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and Copper complexes with nitrogenous tripod ligands resulting from the German patent application DE-A-196 20 411 known cobalt, iron, copper and ruthenium amine complexes, the manganese described in German patent application DE-A-44 16 438, Copper and cobalt complexes described in European patent application EP-A-0 272 030 described cobalt complexes, which from the
- Combinations of bleach activators and Transition metal bleaching catalysts are, for example, from the German patent application DE 196 13 103 and the international patent application WO-A-95/27775 known.
- Bleach-enhancing transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru are in customary amounts, preferably in an amount up to 1% by weight, in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total Means used.
- Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
- Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
- the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
- Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used.
- enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic acting enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic acting enzymes or protease, lipase or lipolytically acting enzymes and cellulase, in particular, however, mixtures or mixtures containing protease and / or lipase with lipolytic enzymes of particular interest.
- lipolytic acting enzymes are the well-known cutinases. Also peroxidases or oxidases have proven to be suitable in some cases.
- Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
- As cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which also Cellobiases are called, or mixtures of these are used. Because the different Distinguish cellulase types by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases will.
- the enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition.
- the proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
- a granulate 1 was produced by spray drying and subsequent post-treatment, which contained the following composition: 51.40% by weight of copolymeric sodium salt of acrylic acid and maleic acid (Sokalan CP 5®, commercial product from BASF, Federal Republic of Germany; used as 40% by weight % aqueous solution), 7.02% by weight of tallow fatty alcohol with 5 EO, 8.16% by weight of C 12 -C 18 sodium fatty acid soap, 27.14% by weight of sodium carbonate (used as a solid), 2.01 % By weight bis ((4-anilino-6-morpholino-s-triazin-2-yl) amino) -stilbene-2,2'-disulfonic acid disodium salt (used as an aqueous suspension), 2.77% by weight other salts and water and 1.50% by weight of C 12 -C 18 fatty alcohol with 7 EO, which was subsequently sprayed on.
- This granulate 1 had a bulk density of 250 g / l.
- the granulate 3 was obtained by granulation and subsequent drying of an aqueous Solution of Sokalan CP 5®, liquid at room temperature or slightly elevated temperature non-ionic surfactants, fatty acid soap (see above), sodium carbonate and 2 different optical brighteners bis ((4-anilino-6-morpholino-s-triazin-2-yl) amino) -stilbene-2,2'-disulfonic acid disodium salt and bis (2-sulfostyrene) biphenyl disodium salt.
- the salary polymer after drying was 49.1% by weight, sodium carbonate 27.4% by weight optical brighteners 2.88% by weight, 7.80% by weight of soap and nonionic surfactants 8.50% by weight.
- the rest consisted of water and other salts.
- the bulk density of Granulate 3 was 580 g / l.
- Granulate 3 was suitable as a separate subsequent admixture component in heavy Detergents or cleaning agents with bulk weights between 500 and 900 g / l.
- the granules 1 to 3 were also suitable as fixed components in granulation or compacting processes for the production of heavy detergents or cleaning agents.
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Abstract
Description
Die Erfindung betrifft ein Additiv für den Einsatz in Wasch- oder Reinigungsmitteln, ein Verfahren zu seiner Herstellung sowie Wasch- oder Reinigungsmittel, welche diese Additive enthalten.The invention relates to an additive for use in detergents or cleaning agents, a method for its manufacture as well as detergents or cleaning agents containing these additives contain.
Moderne pulverförmige bis granulare Wasch- oder Reinigungsmittel werden heute beispielsweise durch Mischen und/oder Granulieren von Additiven und/oder von Rohstoffen hergestellt, wobei gewisse Anteile der Additive und Rohstoffe auch flüssig, beispielsweise als wäßrige Lösung oder wäßrige Dispersion vorliegen können. Die festen Additive können durch Sprühtrocknung, Granulierung, Walzenkompaktierung, Extrusion oder andere Verdichtungsmaßnahmen hergestellt worden sein. Auch bei der Herstellung der Additive können flüssige organische Substanzen, beispielsweise nichtionische Tenside, oder wäßrige Lösungen oder wäßrige Dispersionen eingesetzt worden sein.Modern powdery to granular detergents or cleaning agents are used today, for example by mixing and / or granulating additives and / or raw materials produced, with certain proportions of additives and raw materials also liquid, for example can be present as an aqueous solution or aqueous dispersion. The solid additives can by spray drying, granulation, roller compaction, extrusion or other compaction measures have been produced. Also in the manufacture of the additives liquid organic substances, for example nonionic surfactants, or aqueous Solutions or aqueous dispersions have been used.
Zu den wesentlichen Bestandteilen von Wasch- oder Reinigungsmitteln zählen die Tenside. Von Tensiden, insbesondere Aniontensiden, ist bekannt, daß sie sowohl in wäßriger Form (als Paste) als auch in fester Form (als Pulver oder Additiv) eingesetzt werden können. Zu den bekanntesten und wichtigsten Aniontensiden in Wasch- oder Reinigungsmitteln zählen Alkylbenzolsulfonate und Alkylsulfate. Vor allem Alkylbenzolsulfonate sind zwar wichtige Aniontenside mit hervorragender Waschleistung, welche aber den Nachteil besitzen, daß sie stark klebrige Eigenschaften aufweisen, so daß Additive oder Wasch- oder Reinigungsmittel mit relativ hohen Konzentrationen an Alkylbenzolsulfonaten, beispielsweise Additive mit Gehalten oberhalb 30 Gew.-% Alkylbenzolsulfonaten, zum Verkleben neigen und somit die Rieselfähigkeit der Mittel beeinträchtigen als auch beim Wiederauflösen in wäßriger Flotte - insbesondere wenn die Mittel zusätzlich auch noch ethoxylierte Niotenside aufweisen - zum Gelieren neigen.The essential components of detergents or cleaning agents include surfactants. Surfactants, especially anionic surfactants, are known to be both in aqueous form (as a paste) as well as in solid form (as a powder or additive). To the best known and most important anionic surfactants in detergents or cleaning agents Alkyl benzene sulfonates and alkyl sulfates. Alkylbenzenesulfonates in particular are important Anionic surfactants with excellent washing performance, but which have the disadvantage that they have very sticky properties, so that additives or detergents or cleaning agents with relatively high concentrations of alkylbenzenesulfonates, for example additives with Held above 30 wt .-% alkylbenzenesulfonates, tend to stick and thus the Free flowing properties of the agents impair as well as when redissolving in aqueous liquor - especially if the agents also have ethoxylated nonionic surfactants - for Tend to gel.
Weitere wesentliche Bestandteile von Wasch- oder Reinigungsmitteln sind Buildersubstanzen, die sowohl anorganischer als auch organischer Natur sein können. Anorganische Buildersubstanzen wie Zeolith A, der in den vergangenen Jahren der bevorzugt eingesetzte anorganische Builder in Wasch- oder Reinigungsmitteln war, werden entweder als (sprühgetrocknetes) Pulver, wäßrige stabilisierte Dispersion oder als Bestandteil eines festen, meist granularen Additivs in die Wasch- oder Reinigungsmitteln eingearbeitet. Bevorzugt sind feste Additive, zu deren Herstellung wäßrige Dispersionen eingesetzt wurden, die insbesondere sprühgetrocknet wurden. Häufig enthalten derartige sprühgetrocknete Additive Aniontenside, beispielsweise Alkylbenzolsulfonate, sowie andere nicht temperatur- und sprühtrocknungsempfindliche Bestandteile, vor allem derartige, die ebenfalls bevorzugt in wäßriger Form eingesetzt werden. Zu diesen zählen beispielsweise (co-)polymere Polycarboxylate (organische Builder), optische Aufheller oder Farbstoffe. Zeolith A hat sich in der Vergangenheit als hervorragender Träger für insbesondere die zum Verkleben neigenden Alkylbenzolsulfonate, aber auch für die sonstigen zumeist in wäßriger Form eingesetzten Bestandteile bzw. bei Raumtemperatur bis leicht erhöhten Temperaturen flüssigen Bestandteile von Wasch- oder Reinigungsmitteln, beispielsweise nichtionische Tenside, textilweichmachende Kationtenside oder Schauminhibitoren wie Silikonöle und Paraffinöle, erwiesen.Other essential components of detergents or cleaning agents are builder substances, which can be both inorganic and organic in nature. Inorganic builder substances like zeolite A, which has been the preferred one in recent years inorganic builders in detergents or cleaning agents are either considered (spray dried) powder, aqueous stabilized dispersion or as part of a solid, mostly granular additives incorporated into the washing or cleaning agents. Prefers are solid additives for the production of which aqueous dispersions have been used in particular were spray dried. Such spray-dried additives often contain additives Anionic surfactants, for example alkylbenzenesulfonates, and other non-temperature and Ingredients sensitive to spray drying, especially those which are also preferred in aqueous form can be used. These include, for example, (co) polymeric polycarboxylates (organic builders), optical brighteners or dyes. Zeolite A has in the The past as an excellent carrier for those who tend to stick Alkylbenzenesulfonates, but also for the others mostly used in aqueous form Components or liquid at room temperature to slightly elevated temperatures Constituents of washing or cleaning agents, for example nonionic surfactants, textile-softening cationic surfactants or foam inhibitors such as silicone oils and paraffin oils, proven.
Neuere anorganische Builder wie Zeolith P, schichtförmige kristalline Disilikate oder amorphe Silikate mit verzögerter Desintegration sind jedoch nur bedingt über die Sprühtrocknung einsatzfähig und werden meist als Rohstoffe oder separate, trockene Compounds zur Verfügung gestellt.Newer inorganic builders such as zeolite P, layered crystalline disilicate or amorphous Silicates with delayed disintegration, however, are only limited by spray drying ready for use and are usually available as raw materials or separate, dry compounds posed.
Sprühtrocknungsverfahren sind vom energetischen Standpunkt gesehen ungünstige Herstellungsverfahren für Wasch- oder Reinigungsmittel. Es hat daher nicht an Versuchen gefehlt, Verfahren zur Herstellung von Wasch- oder Reinigungsmitteln bereitzustellen, die auf eine Sprühtrocknung entweder ganz oder zumindest auf die Sprühtrocknung von Basisgranulaten verzichten können.Spray drying processes are unfavorable manufacturing processes from an energetic point of view for detergents or cleaning agents. There has been no shortage of attempts Provide processes for the production of detergents or cleaning agents based on spray drying either entirely or at least to spray drying base granules can do without.
In Wasch- oder Reinigungsmitteln, welche Zeolith A nicht als hauptsächliche Builderkomponente, also Zeolith A in Mengen weniger als 10 Gew.-% (bezogen auf die wasserfreie Aktivsubstanz), und außerdem kein Alkylbenzolsulfonat als Aniontensid aufweisen und die insbesondere kein sprühgetrocknetes Granulat enthalten, welches Zeolith A und gegebenenfalls Alkylbenzolsulfonat sowie die üblichen, zumeist in wäßriger Form eingesetzten weiteren Bestandteile beinhaltet, stellt sich somit das Problem, wie die sonstigen zumeist in wäßriger Form eingesetzten weiteren Bestandteile von Wasch- oder Reinigungsmitteln in das Mittel eingearbeitet werden können.In detergents or cleaning agents that do not use zeolite A as the main builder component, thus zeolite A in amounts less than 10% by weight (based on the anhydrous active substance), and also have no alkylbenzenesulfonate as the anionic surfactant, and in particular no spray-dried granules containing zeolite A and optionally Alkylbenzenesulfonate and the usual others, mostly used in aqueous form Containing constituents, the problem arises, like the others mostly in aqueous Form used further ingredients of detergents or cleaning agents in the agent can be incorporated.
Mit der vorliegenden Erfindung wird dieses Problem gelöst. This problem is solved with the present invention.
Gegenstand der Erfindung ist dementsprechend in einer ersten Ausführungsform ein Additiv für den Einsatz in Wasch- oder Reinigungsmitteln, welches organische Buildersubstanzen und mindestens 1 weiteren Inhaltsstoff ausgewählt aus Sequestriermitteln und optischen Aufhellern sowie gegebenenfalls weitere Inhaltsstoffe von Wasch- oder Reinigungsmitteln enthält, wobei Alkylbenzolsulfonate ausgeschlossen sind und der Gehalt der Additive an Zeolith A nicht mehr als 10 Gew.-%, bezogen auf wasserfreie Aktivsubstanz, betragen soll.The invention accordingly relates to an additive in a first embodiment for use in detergents or cleaning agents, which organic builder substances and at least 1 further ingredient selected from sequestrants and optical Brighteners and, if necessary, other ingredients of washing or cleaning agents contains, whereby alkylbenzenesulfonates are excluded and the content of the additives Zeolite A should not be more than 10% by weight, based on anhydrous active substance.
In einer weiteren Ausführungsform der Erfindung wird ein Verfahren zur Herstellung der erfindungsgemäßen Additive beansprucht, wobei mindestens ein Teil der organischen Buildersubstanzen und mindestens ein weiterer Inhaltsstoff, ausgewählt aus Sequestriermitteln und optischen Aufhellern, in wäßriger Form vorgelegt, gegebenenfalls mit Feststoffen vermischt und anschließend getrocknet werden. Vorzugsweise werden mindestens 60 Gew.-% und insbesondere 70 bis 100 Gew.-% der insgesamt vorhandenen organischen Buildersubstanzen in wäßriger Form vorgelegt. Optional kann eine Nachbehandlung mit Inhaltsstoffen von Wasch- oder Reinigungsmitteln in fester und/oder flüssiger Form durchgeführt werden.In a further embodiment of the invention, a method for producing the Additives according to the invention claimed, at least some of the organic Builder substances and at least one other ingredient selected from Sequestering agents and optical brighteners, presented in aqueous form, optionally with Solids mixed and then dried. Preferably be at least 60 wt .-% and in particular 70 to 100 wt .-% of the total available submitted organic builder substances in aqueous form. Optionally, one Aftertreatment with detergent or cleaning agent ingredients in solid and / or be carried out in liquid form.
Ebenfalls Gegenstand der Erfindung ist ein Wasch- oder Reinigungsmittel, welches die erfindungsgemäßen Additive und insbesondere die erfindungsgemäß hergestellten Additive enthält, aber frei von Alkylbenzolsulfonaten ist und Zeolith A nicht in Mengen oberhalb 10 Gew.-%, bezogen auf wasserfreie Aktivsubstanz, aufweist.The invention also relates to a washing or cleaning agent which comprises the inventive Additives and in particular the additives produced according to the invention contains, but is free of alkylbenzenesulfonates and zeolite A not in amounts above 10 % By weight, based on anhydrous active substance.
Der Erfindung liegt die Idee zugrunde, möglichst viele, wünschenswerterweise alle Komponenten eines Wasch- oder Reinigungsmittels, welche sogenannte Kleinkomponenten wie Cobuilder, optische Aufheller, Sequestriermittel, Vergrauungsinhibitoren, Seife etc. darstellen und insbesondere solche, die üblicherweise in wäßriger Form eingesetzt werden, in einem Additiv zu vereinigen. Dies weist den Vorteil auf, daß nur ein kleiner Teil anstelle des Hauptanteils des Wasch- oder Reinigungsmittels sprühgetrocknet oder auf eine andere Weise getrocknet werden muß. Außerdem gelingt durch den Einsatz dieses Additivs die homogene Verteilung dieser Kleinkomponenten. Dies ist ein Vorteil gegenüber der separaten Zumischung dieser Kleinkomponenten, da gerade die Zumischung und homogene Verteilung von Kleinkomponenten im Gemisch verständlicherweise mit einem hohen Fehler behaftet ist und außerdem durch Zumischung der wäßrigen Lösungen und/oder Dispersionen die Gefahr besteht, daß das Endprodukt verklebt, verklumpt, jedenfalls an Rieselfähigkeit verliert und gegebenenfalls sogar getrocknet werden muß. The invention is based on the idea of as many as possible, and preferably all, of the components a washing or cleaning agent, which so-called small components such Represent cobuilders, optical brighteners, sequestering agents, graying inhibitors, soap, etc. and in particular those which are usually used in aqueous form, in one Unite additive. This has the advantage that only a small part instead of the Most of the detergent or cleaning agent is spray dried or on another Way must be dried. In addition, the use of this additive enables homogeneous distribution of these small components. This is an advantage over the separate one Mixing in of these small components because of the mixing and homogeneous distribution of small components in the mixture understandably with a high error is afflicted and also by admixing the aqueous solutions and / or dispersions there is a risk that the end product will stick together, clump, at least in terms of flowability loses and may even have to be dried.
Dementsprechend weisen die erfindungsgemäßen Additive vor allem organische Buildersubstanzen, welche üblicherweise als Cobuilder eingesetzt werden, vorzugsweise (co-)polymere Polycarboxylate, auf. Im Rahmen dieser Erfindung werden zu copolymeren Polycarboxylaten auch solche Polymere gezählt, welche aus mehr als 2 Monomeren aufgebaut sind. Der Gehalt der organischen Buildersubstanzen in den erfindungsgemäßen Additiven kann in einem breiten Rahmen variieren. So könnte er im Prinzip durchaus einen Betrag von 2 bis 98 Gew.-% ausmachen. Bevorzugte Additive enthalten jedoch 20 bis 80 Gew.-% und insbesondere 30 bis 70 Gew.-% organische Buildersubstanzen, wobei Gehalte von 40 bis 60 Gew.-% an (co-)polymeren Polycarboxylaten besonders vorteilhaft sind.Accordingly, the additives according to the invention have above all organic builder substances, which are usually used as cobuilders, preferably (co) polymers Polycarboxylates. In the context of this invention, copolymeric polycarboxylates also counted those polymers which are made up of more than 2 monomers are. The content of the organic builder substances in the additives according to the invention can vary widely. In principle, it could amount to Make up 2 to 98 wt .-%. However, preferred additives contain 20 to 80% by weight and in particular 30 to 70% by weight of organic builder substances, contents of 40 to 60 % By weight of (co) polymeric polycarboxylates are particularly advantageous.
Brauchbare organische Gerüstsubstanzen sind beispielsweise die in Form ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren und Mischungen aus diesen.Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if provided such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures from these.
Auch die Säuren an sich können eingesetzt werden. Die Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Wertes von Wasch- oder Renigungsmitteln. Insbesondere sind hierbei Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen aus diesen zu nennen.The acids themselves can also be used. The acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH of detergents or cleaning agents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, To name gluconic acid and any mixtures of these.
Weitere geeignete organische Buildersubstanzen sind Dextrine, beispielsweise Oligomere bzw. Polymere von Kohlenhydraten, die durch partielle Hydrolyse von Stärken erhalten werden können. Die Hydrolyse kann nach üblichen, beispielsweise säure- oder enzymkatalysierten Verfahren durchgeführt werden. Vorzugsweise handelt es sich um Hydrolyseprodukte mit mittleren Molmassen im Bereich von 400 bis 500000. Dabei ist ein Polysaccharid mit einem Dextrose-Äquivalent (DE) im Bereich von 0,5 bis 40, insbesondere von 2 bis 30 bevorzugt, wobei DE ein gebräuchliches Maß für die reduzierende Wirkung eines Polysaccharids im Vergleich zu Dextrose, welche ein DE von 100 besitzt, ist. Brauchbar sind sowohl Maltodextrine mit einem DE zwischen 3 und 20 und Trockenglucosesirupe mit einem DE zwischen 20 und 37 als auch sogenannte Gelbdextrine und Weißdextrine mit höheren Molmassen im Bereich von 2000 bis 30000. Ein bevorzugtes Dextrin ist in der britischen Patentanmeldung 94 19 091 beschrieben. Bei den oxidierten Derivaten derartiger Dextrine handelt es sich um deren Umsetzungsprodukte mit Oxidationsmitteln, welche in der Lage sind, mindestens eine Alkoholfunktion des Saccharidrings zur Carbonsäurefunktion zu oxidieren. Derartige oxidierte Dextrine und Verfahren ihrer Herstellung sind beispielsweise aus den europäischen Patentanmeldungen EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 und EP-A-0 542 496 sowie den internationalen Patentanmeldungen WO-A-92/18542, WO-A-93/08251, WO-A-93/16110, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 und WO-A-95/20608 bekannt. Ebenfalls geeignet sind oxidierte Oligosaccharide gemäß der DE-A-196 00 018. Ein an C6 des Saccharidrings oxidiertes Produkt kann besonders vorteilhaft sein.Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure for is the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used. A preferred dextrin is described in British patent application 94 19 091. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO- A-92/18542, WO-A-93/08251, WO-A-93/16110, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A- 95/20608 known. Oxidized oligosaccharides according to DE-A-196 00 018 are also suitable. A product oxidized at C 6 of the saccharide ring can be particularly advantageous.
Ebenso sind als weitere bevorzugte Buildersubstanzen polymere Aminodicarbonsäuren, deren Salze oder deren Vorläufersubstanzen zu nennen. Besonders bevorzugt sind Polyasparaginsäuren bzw. deren Salze und Derivate, von denen in der deutschen Patentanmeldung P 195 40 086.0 offenbart wird, daß sie neben Cobuilder-Eigenschaften auch eine bleichstabilisierende Wirkung aufweisen.Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Polyaspartic acids are particularly preferred or their salts and derivatives, of which in the German patent application P 195 40 086.0 discloses that, in addition to cobuilder properties, it also has a have a bleach-stabilizing effect.
Weitere geeignete Buildersubstanzen sind Polyacetale, welche durch Umsetzung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 C-Atome und mindestens 3 Hydroxylgruppen aufweisen, beispielsweise wie in der europäischen Patentanmeldung EP-A-0 280 223 beschrieben, erhalten werden können. Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaraldehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäuren wie Gluconsäure und/oder Glucoheptonsäure erhalten.Other suitable builder substances are polyacetals, which are obtained by reacting dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have, for example as in European patent application EP-A-0 280 223 described, can be obtained. Preferred polyacetals are made from dialdehydes such as Glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
Weitere geeignete Cobuilder sind Oxydisuccinate und andere Derivate von Disuccinaten, vorzugsweise Ethylendiamindisuccinat. Besonders bevorzugt sind in diesem Zusammenhang auch Glycerindisuccinate und Glycerintrisuccinate, wie sie beispielsweise in den US-amerikanischen Patentschriften US 4 524 009, US 4 639 325, in der europäischen Patentanmeldung EP-A-0 150 930 und der japanischen Patentanmeldung JP 93/339896 beschrieben werden.Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Are particularly preferred in this context also glycerol disuccinates and glycerol trisuccinates, such as those found in the United States Patents US 4,524,009, US 4,639,325, in the European patent application EP-A-0 150 930 and Japanese patent application JP 93/339896 will.
Weitere brauchbare organische Cobuilder sind beispielsweise acetylierte Hydroxycarbonsäuren bzw. deren Salze, welche gegebenenfalls auch in Lactonform vorliegen können und welche mindestens 4 Kohlenstoffatome und mindestens eine Hydroxygruppe sowie maximal zwei Säuregruppen enthalten. Derartige Cobuilder werden beispielsweise in der internationalen Patentanmeldung WO-A-95/20029 beschrieben.Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups. Such cobuilders are used, for example, in the international Patent application WO-A-95/20029.
Geeignete polymere Polycarboxylate sind beispielsweise Natriumsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 800 bis 150000 (auf Säure bezogen). Geeignete copolymere Polycarboxylate sind insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 5000 bis 200000, vorzugsweise 10000 bis 120000 und insbesondere 50000 bis 100000. Die (co-)polymeren Polycarboxylate können entweder als Pulver oder als wäßrige Lösung eingesetzt werden, wobei im Rahmen dieser Erfindung 20 bis 55 Gew.-%ige wäßrige Lösungen bevorzugt sind.Suitable polymeric polycarboxylates are, for example, sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain. Their relative molecular weight, based on free acids, is in general 5000 to 200000, preferably 10000 to 120000 and in particular 50000 to 100000. Die (Co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution are used, in the context of this invention 20 to 55 wt .-% aqueous solutions are preferred.
Derartige (co-)polymere Polycarboxylate sind im Rahmen dieser Erfindung besonders bevorzugt. Dazu gehören auch Polymere aus mehr als zwei verschiedenen Monomereinheiten, beispielsweise solche, die gemäß der DE-A-43 00 772 als Monomere Salze der Acrylsäure und der Maleinsäure sowie Vinylalkohol bzw. Vinylalkohol-Derivate oder gemäß der DE-C-42 21 381 als Monomere Salze der Acrylsäure und der 2-Alkylallylsulfonsäure sowie Zucker-Derivate enthalten.Such (co) polymeric polycarboxylates are particularly preferred in the context of this invention. This includes polymers from more than two different monomer units, for example, those according to DE-A-43 00 772 as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.
Weitere bevorzugte Copolymere sind solche, die in den deutschen Patentanmeldungen DE-A-43 03 320 und DE-A-44 17 734 beschrieben werden und als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäuresalze bzw. Acrolein und Vinylacetat aufweisen.Further preferred copolymers are those described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
Von den bekannten Sequestriermitteln werden vor allem die Salze von Polyphosphonsäuren und insbesondere die neutral reagierenden Natriumsalze von beispielsweise 1-Hydroxyethan-1,1-diphosphonat (HEDP), Diethylentriaminpenta-methylenphosphonat und/oder Ethylendiamintetramethylenphosphonat bevorzugt. Der Einsatz von Nitrilotriessigsäure und/oder deren Salzen (NTA) ist möglicherweise aus ökologischer Betrachtungsweise nur in geringerem Umfang denkbar. Ebenfalls wäre ein Einsatz von Ethylendiamintetraessigsäure und/oder deren Salzen (EDTA) vom Erfindungsprinzip her denkbar. Jedoch wird aus den bekannten Gründen auf den Einsatz von EDTA verzichtet.The known sequestering agents are mainly the salts of polyphosphonic acids and in particular the neutral sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate (HEDP), diethylene triamine penta methylene phosphonate and / or ethylenediaminetetramethylenephosphonate is preferred. The use of nitrilotriacetic acid and / or their salts (NTA) may be from an ecological perspective only conceivable to a lesser extent. The use of ethylenediaminetetraacetic acid would also be and / or their salts (EDTA) conceivable from the principle of the invention. However For the known reasons, EDTA is not used.
Der Gehalt der erfindungsgemäßen Additive an einem oder mehreren dieser Sequestriermittel beträgt vorzugsweise 2 bis 8 Gew.-% und insbesondere 3 bis 6 Gew.-%. Als besonders vorteilhaft haben sich Werte zwischen 4 und 5 Gew.-% erwiesen.The content of the additives according to the invention in one or more of these sequestering agents is preferably 2 to 8% by weight and in particular 3 to 6% by weight. As special Values between 4 and 5% by weight have proven to be advantageous.
Die Mittel können als optische Aufheller Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z.B. Salze der 4,4'-Bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholino-Gruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ der substituierten Diphenylstyryle anwesend sein, z.B. die Alkalisalze des 4,4'-Bis(2-sulfostyryl)-diphenyls, 4,4'-Bis(4-chlor-3-sulfostyryl)-diphenyls, oder 4-(4-Chlorstyryl)-4'-(2-sulfostyryl)-diphenyls. Im Rahmen dieser Erfindung werden auch Phthalocyanine und deren Salze zu den optischen Aufhellern gezählt. Auch Gemische der vorgenannten Aufheller können verwendet werdenAs optical brighteners, the agents can be derivatives of diaminostilbenedisulfonic acid or their Contain alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar connections, which instead of the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Can continue Present brighteners of the substituted diphenylstyryl type, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) - diphenyls. Also within the scope of this invention Phthalocyanines and their salts are among the optical brighteners. Mixtures of the aforementioned brighteners can be used
Der Gehalt der erfindungsgemäßen Additive an einem oder mehreren optischen Aufhellern beträgt insgesamt vorzugsweise mindestens 1,5 Gew.-% und insbesondere 2 bis 5 Gew.-%.The content of the additives according to the invention in one or more optical brighteners is preferably at least 1.5% by weight in total and in particular 2 to 5% by weight.
Ebenso wie optische Aufheller können auch Farbstoffe in die Additive eingearbeitet werden. Derartige Additive können dann - wenn sie als Zumischkomponente in Wasch- oder Reinigungsmitteln dienen - beispielsweise als farbige Sprenkel dienen.Just like optical brighteners, dyes can also be incorporated into the additives. Such additives can - if they are used as an additive component in detergents or cleaning agents serve - for example, serve as colored speckles.
Zu den sogenannten Kleinkomponenten in Wasch- oder Reinigungsmitteln gehören im allgemeinen auch Seifen, die in den fertigen Mitteln normalerweise in Mengen von weniger als 5 Gew.-% enthalten sind. Die erfindungsgemäßen Additive können daher auch Seifen, insbesondere gesättigte Fettsäureseifen, gegebenenfalls aber auch in Kombination mit ungesättigten Fettsäureseifen, enthalten. Geeignet sind insbesondere die Natrium- und/oder Kaliumsalze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierten Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengemische. Zusammen mit diesen Seifen oder als Ersatzmittel für Seifen können auch die bekannten Alkenylbernsteinsäuresalze eingesetzt werden. Der Gehalt der Additive an Seifen und/oder Alkenylbernsteinsäuresalzen beträgt in einer bevorzugten Ausführungsform der Erfindung 5 bis 10 Gew.-%, kann aber durchaus darunter wie auch darüber liegen.The so-called small components in washing or cleaning agents generally include also soaps normally used in the finished products in quantities of less than 5 wt .-% are included. The additives according to the invention can therefore also be soaps, in particular saturated fatty acid soaps, but optionally also in combination with unsaturated Fatty acid soaps. The sodium and / or potassium salts are particularly suitable of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated Erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut-, Palm kernel or tallow fatty acids, derived soap mixtures. Along with these soaps or the known alkenyl succinic acid salts can also be used as a substitute for soaps will. The content of the additives in soaps and / or alkenyl succinic acid salts is 5 to 10% by weight in a preferred embodiment of the invention, but can well below and above.
Nicht direkt zu den Kleinkomponenten werden bei Raumtemperatur flüssige nichtionische Tenside gezählt, selbst wenn sie in einigen fertigen Mitteln nur in Mengen von etwa 2 bis 3 Gew.-% vorliegen. Auch in diesen kleinen Mengen tragen die nichtionischen Tenside insbesondere in Kombination mit anionischen Tensiden signifkant zur Waschleistung bei und werden üblicherweise zu einer der Hauptkomponenten - allgemein den Tensiden - gezählt. Obwohl bei Raumtemperatur nichtionische flüssige Tenside in den wenigsten Fällen in wäßriger Lösung bzw. Dispersion eingesetzt werden - Ausnahmen stellen beispielsweise Pasten aus Aniontensiden und nichtionischen Tensiden dar - kann ihre Einarbeitung in die Wasch- oder Reinigungsmittel doch zu Problemen bezüglich der Rieselfähigkeit des Produkts oder aufgrund ihrer Neigung zu Gelierungen bei der Wiederauflösung des Produkts in wäßriger Flotte führen. Bei Raumtemperatur oder nur wenig erhöhter Temperatur flüssige nichtionische Tenside, gegebenenfalls auch in Kombination mit bei diesen Temperaturen festen nichtionischen Tensiden, stellen daher weitere bevorzugte Inhaltsstoffe der erfindungsgemäßen Additive dar. Zu diesen zählen in erster Linie ethoxylierte und/oder propoxylierte Alkohole, wie Fettalkohole, Oxoalkohole oder Alkohole auf petrochemischer Basis mit ähnlicher (aber ungerader) C-Kettenverteilung wie die Fettalkohole. Hierzu gehören insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-C14-Alkohole mit 3 EO oder 4 EO, C9-C11-Alkohole mit 7 EO, C13-C15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-C18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-C14-Alkohol mit 3 EO und C12-C18-Alkohol mit 7 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind (Talg-) Fettalkohole mit 14 EO, 16 EO, 20 EO, 25 EO, 30 EO oder 40 EO.Non-ionic surfactants which are liquid at room temperature are not directly counted as small components, even if they are only present in amounts of about 2 to 3% by weight in some finished compositions. Even in these small quantities, the nonionic surfactants, in particular in combination with anionic surfactants, make a significant contribution to the washing performance and are usually included in one of the main components - generally the surfactants. Although at room temperature nonionic liquid surfactants are rarely used in aqueous solution or dispersion - exceptions are, for example, pastes made from anionic surfactants and nonionic surfactants - their incorporation into detergents or cleaning agents can still cause problems regarding the free-flowing properties of the product or because of it Tendency to gel when the product is redissolved in an aqueous liquor. Nonionic surfactants which are liquid at room temperature or only slightly elevated temperature, if appropriate also in combination with nonionic surfactants which are solid at these temperatures, are therefore further preferred ingredients of the additives according to the invention. These include primarily ethoxylated and / or propoxylated alcohols, such as fatty alcohols, oxo alcohols or petrochemical-based alcohols with a similar (but odd) carbon chain distribution as the fatty alcohols. These include, in particular, primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be methyl-branched linearly or preferably in the 2-position, or linear and methyl-branched radicals in a mixture can contain, as they are usually present in oxo alcohol residues. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
Zusätzlich zu diesen nichtionischen Tensiden können auch noch weitere nichtionische Tenside in den Additiven enthalten sein, beispielsweise ethoxylierte Fettsäuremethylester, Alkylglykoside, Polyhydroxyfettsäureamide (Glucamide) oder Aminoxide (genauere Beschreibung der sonstigen nichtionischen Tenside: siehe unten). Ihr Gehalt in den erfindungsgemäßen Additiven ist jedoch weniger bevorzugt.In addition to these nonionic surfactants, other nonionic surfactants can also be used be contained in the additives, for example ethoxylated fatty acid methyl esters, alkyl glycosides, Polyhydroxy fatty acid amides (glucamides) or amine oxides (detailed description other non-ionic surfactants: see below). Your salary in the invention However, additives are less preferred.
Der Gehalt der erfindungsgemäßen Additive an nichtionischen Tensiden beträgt vorzugsweise 2 bis 15 Gew.-% und insbesondere 5 bis 10 Gew.-%. Der Gehalt der Additive an bei Raumtemperatur oder bei nur mäßig erhöhter Temperatur flüssigen nichtionischen Tenside hängt von der Art und Menge des festen Trägermaterials ab, da auch die erfindungsgemäßen Additive ihre Rieselfähigkeit behalten und auch bei Lagerung nicht verkleben sollen. The content of nonionic surfactants in the additives according to the invention is preferably 2 to 15% by weight and in particular 5 to 10% by weight. The content of the additives at Room temperature or liquid nonionic surfactants at only a moderately elevated temperature depends on the type and amount of solid support material, since the invention Additives retain their free-flowing properties and should not stick together even during storage.
Anionische Tenside gehören - mit Ausnahme der maschinellen Geschirrspülmittel - üblicherweise nicht zu den sogenannten Kleinkomponenten. Falls sie aber nicht in fester pulverförmiger oder granularer bis compoundierter Form, sondern als wäßrige Paste, gegebenenfalls in Mischung mit nichtionischen Tensiden, bei der Herstellung der Wasch- oder Reinigungsmittel eingesetzt werden sollen, so kann es von Vorteil sein, wenn diese wäßrigen Aniontenside in das erfindungsgemäße Additiv eingebracht werden. Erfindungsgemäß sind aber Alkylbenzolsulfonate als Inhaltsstoffe der Additive ausgeschlossen. Eine genauere Beschreibung der möglicherweise einsetzbaren Aniontenside erfolgt weiter unten. Der Gehalt der erfindungsgemäßen Additive an nicht Alkylbenzolsulfonat-haltigen Aniontensiden beträgt vorzugsweise 0,5 bis 10 Gew.-%, insbesondere 1 bis 5 Gew.-%.With the exception of machine dishwashing detergents, anionic surfactants usually belong not to the so-called small components. But if they are not in solid powder or granular to compounded form, but as an aqueous paste, if necessary in a mixture with nonionic surfactants, in the manufacture of washing or Cleaning agents are to be used, it may be advantageous if these are aqueous Anionic surfactants are introduced into the additive according to the invention. According to the invention but alkylbenzenesulfonates are excluded as ingredients of the additives. A more precise one A description of the anionic surfactants that may be used is given below. The salary the additives according to the invention on anionic surfactants not containing alkylbenzenesulfonate is preferably 0.5 to 10% by weight, in particular 1 to 5% by weight.
Neben den in flüssiger und insbesondere in wäßriger Form eingebrachten Inhaltsstoffe sind in einer bevorzugten Ausführungsform der Erfindung aber auch feste Füllstoffe und Trägersalze Bestandteile der Additive. Wie eingangs beschrieben eignen sich hierzu weniger anorganische Buildersubstanzen wie kristalline schichtförmige Silikate, insbesondere Disilikate wie SKS 6® , Zeolith P wie Zeolith MAP® oder Silikate mit verzögerter Desintegration (genauere Beschreibung siehe unten). Ebenso soll der Gehalt an Zeolith A (bezogen auf wasserfreie Aktivsubstanz) vorzugsweise weniger als 10 Gew.-% und insbesondere 0 bis 5 Gew.-% betragen. Geeignete feste Träger sind aber anorganische Salze wie beispielsweise Natrium- und/oder Kaliumsalze von Carbonaten, Bicarbonaten, Sesquicarbonaten, Sulfaten, Bisulfaten und üblichen Wassergläsern, die zumindest auch partiell in wäßriger Form in das Verfahren zur Herstellung der Additive eingebracht werden können. In bevorzugten Ausführungsformen der Erfindung machen diese anorganischen Trägersalze weniger als 50 Gew.-%, vorzugsweise weniger als 40 Gew.-% der erfindungsgemäßen Additive aus.In addition to the ingredients introduced in liquid and in particular in aqueous form in a preferred embodiment of the invention, however, also solid fillers and carrier salts Components of the additives. As described in the introduction, less inorganic ones are suitable for this Builder substances such as crystalline layered silicates, in particular disilicates like SKS 6®, Zeolite P like Zeolite MAP® or silicates with delayed disintegration (see below for a more detailed description). The content of zeolite A (based on anhydrous active substance) preferably less than 10% by weight and in particular 0 to 5 % By weight. Suitable solid carriers are, however, inorganic salts such as, for example Sodium and / or potassium salts of carbonates, bicarbonates, sesquicarbonates, sulfates, Bisulfates and conventional water glasses, which are at least partially in aqueous form in the Processes for producing the additives can be introduced. In preferred embodiments the invention makes these inorganic carrier salts less than 50 wt .-%, preferably less than 40% by weight of the additives according to the invention.
Mögliche weitere Inhaltsstoffe der Additive sind Vergrauungsinhibitoren, welche die Aufgabe haben, den von der Faser abgelösten Schmutz in der Flotte suspendiert zu halten und so das Wiederaufziehen des Schmutzes zu verhindern. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise die wasserlöslichen Salze polymerer Carbonsäuren, Leim, Gelatine, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich lösliche Stärkepräparate und andere als die obengenannten Stärkeprodukte verwenden, z.B. abgebaute Stärke, Aldehydstärken usw.. Auch Polyvinylpyrrolidon ist brauchbar. Bevorzugt werden jedoch Celluloseether, wie Carboxymethylcellulose (Na-Salz), Methylcellulose, Hydroxyalkylcellulose und Mischether, wie Methylhydroxyethylcellulose, Methylhydroxypropylcellulose, Methylcarboxymethylcellulose und deren Gemische, sowie Polyvinylpyrrolidon beispielsweise in Mengen von 0,1 bis 5 Gew.-%, bezogen auf die Mittel, eingesetzt.Possible further ingredients of the additives are graying inhibitors, which do the job have to keep the dirt detached from the fiber suspended in the liquor and so to prevent the dirt from re-opening. For this purpose, water-soluble colloids are used mostly of an organic nature, for example the water-soluble salts of polymeric carboxylic acids, Glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or the cellulose or salts of acidic sulfuric acid esters of cellulose or Strength. Water-soluble polyamides containing acidic groups are also suitable for this purpose suitable. Soluble starch preparations and others other than those mentioned above can also be used Use starch products, e.g. degraded starch, aldehyde starches, etc. Also Polyvinyl pyrrolidone is useful. However, cellulose ethers such as carboxymethyl cellulose are preferred (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the funds used.
Die erfindungsgemäßen Additive weisen je nach Art ihrer Herstellung unterschiedliche Schüttgewichte zwischen etwa 250 bis etwa 900 g/l, wobei aber Schüttgewichte oberhalb von 400 g/l und insbesondere oberhalb von 500 g/l insbesondere bevorzugt sind. In einer bevorzugten Ausführungsform der Erfindung weisen die Additive (nach dem Trocknen) weniger als 10 Gew.-% und vorzugsweise weniger als 5 Gew.-% freies Wasser auf. Besonders bevorzugt ist dabei sogar, daß die Gesamtmenge an Wasser, also die Summe aus chemisch und/oder physikalisch gebundenem und nicht-gebundenem, also freiem Wasser sogar weniger als 10 Gew.-% und insbesondere sogar weniger als 5 Gew.-% ausmacht. Die Additive weisen typische granulare Strukturen auf, wobei sie optional - beispielsweise wenn sie als Additive zu nahezu kugelförmigen Partikeln eingesetzt werden sollen - verrundet werden können.The additives according to the invention differ depending on the type of their production Bulk weights between about 250 to about 900 g / l, but bulk weights above of 400 g / l and in particular above 500 g / l are particularly preferred. In a preferred embodiment of the invention, the additives (after drying) have less than 10% by weight and preferably less than 5% by weight of free water. Especially it is even preferred that the total amount of water, ie the sum of chemical and / or physically bound and unbound, i.e. free water even makes up less than 10% by weight and in particular even less than 5% by weight. The Additives have typical granular structures, although they are optional - for example, if they are to be used as additives to almost spherical particles - rounded can be.
Vorteilhafte Ausführungsformen der Erfindung sehen auch vor, daß die Additive - abgesehen von Wasser und Restbestandteilen/Salzen, welche aus den eingesetzten Lösungen in die Additive eingeschleppt wurden - zu mindestens 90 Gew.-% aus nicht mehr als 7 verschiedenen Bestandteilen, vorzugsweise zu mindestens 92 Gew.-% aus nicht mehr als 5 verschiedenen Bestandteilen bestehen. Dabei werden beispielsweise 2 verschiedene optische Aufheller, die in herkömmlichen Verfahren separat dosiert werden, als 2 verschiedene Bestandteile angesehen.Advantageous embodiments of the invention also provide that the additives - apart from of water and residual components / salts, which from the solutions used in the Additives were introduced - at least 90% by weight from no more than 7 different ones Ingredients, preferably at least 92% by weight of not more than 5 different components. Here, for example, 2 different optical Brighteners, which are dosed separately in conventional processes, as 2 different ones Viewed components.
Ein bevorzugtes Additiv enthält organische, vorzugsweise (co-)polymere Cobuilder, 1 bis 3 optische Aufheller, nichtionisches Tensid und/oder Seife, 1 bis 2 unterschiedliche Phosphonate sowie 1 bis 2 Feststoffe als Füllsalze und Träger, vorzugsweise Carbonat, Bicarbonat, Sulfat, Bisulfat oder Mischungen daraus.A preferred additive contains organic, preferably (co) polymeric cobuilders, 1 to 3 optical brighteners, non-ionic surfactant and / or soap, 1 to 2 different phosphonates and 1 to 2 solids as filler salts and carriers, preferably carbonate, bicarbonate, Sulfate, bisulfate or mixtures thereof.
Ein besonders bevorzugtes Additiv enthält zwingend (co-)polymere Polycarboxylate, nichtionisches Tensid und/oder Seife, 1 bis 3 Bestandteile ausgewählt aus optischen Aufhellern und Phosphonaten sowie Natrium- und/oder Kaliumcarbonat, wobei die Summe der Gehalte an (co-)polymerem Polycarboxylat und dem Carbonat zwischen 70 und 85 Gew.-% ausmachen.A particularly preferred additive contains (co) polymeric polycarboxylates, non-ionic Surfactant and / or soap, 1 to 3 components selected from optical brighteners and phosphonates and sodium and / or potassium carbonate, the sum of the contents of (co) polymeric polycarboxylate and the carbonate make up between 70 and 85% by weight.
Eine Oberfiächenmodiflzierung zur Verbesserung des Rieselverhaltens ist im allgemeinen nicht erforderlich, kann aber zur Erhöhung des Schüttgewichts der Additive von Interesse sein. Hier können die üblichen feinteiligen, aus dem Stand der Technik bekannten Oberflächenmodifizierer wie Zeolith A, X und/oder P, Kieselsäuren und Kieselsäure-Derivate, Calciumstearat etc. und Mischungen aus diesen eingesetzt werden. Die Menge des optional eingesetzten Oberflächenmodifzierers Zeolith A ist dabei in die maximal im Additiv einsetzbare Menge an Zeolith A bereits eingerechnet.Surface modification to improve the flow behavior is in general Not required, but may be of interest to increase the bulk density of the additives be. The usual fine-particle surface modifiers known from the prior art can be used here such as zeolite A, X and / or P, silicas and silicic acid derivatives, calcium stearate etc. and mixtures of these are used. The amount of the optional The surface modifier used in zeolite A is the maximum that can be used in the additive The amount of zeolite A already included.
Die Additive lassen sich nach jedem der bekannten Verfahren wie Sprühtrocknung, Granulierung mit Wasser als Granulierhilfsmittel und Trocknung sowie Kompaktierung und Trocknung herstellen. Gegebenenfalls kann anschließend eine Nachbehandlung mit weiteren Inhaltsstoffen in fester und/oder flüssiger Form erfolgen. Welches Herstellungsverfahren gewählt wird, ist abhängig von der Menge an Wasser, die durch die in wäßriger Form eingesetzten Rohstoffe und gegebenenfalls Compounds bereitgestellt wird. So bietet sich bei Wassermengen oberhalb 30 Gew.-%, bezogen auf die zu trocknende Mischung, auf jeden Fall die Sprühtrocknung an. Bei Wassergehalten bis zu 10 Gew.-% ist im allgemeinen auch eine Granulierung ohne Schwierigkeiten möglich. Bei Wassergehalten, welche zwischen 10 und 30 Gew.-% liegen, bleibt es dem Fachmann überlassen, das wirkungsvollste Verfahren zur Herstellung der Additive auszuwählen.The additives can be made by any of the known methods such as spray drying, granulation with water as granulation aid and drying as well as compacting and Make drying. If necessary, aftertreatment can then be carried out with other treatments Ingredients in solid and / or liquid form. What manufacturing process is chosen depends on the amount of water used by those in aqueous form Raw materials and possibly compounds is provided. So offers at Amounts of water above 30% by weight, based on the mixture to be dried, on each Do the spray drying. With water contents up to 10 wt .-% is also generally granulation possible without difficulty. With water contents between 10 and 30 wt .-%, it is left to the skilled person, the most effective method to select for the manufacture of the additives.
Insbesondere (co-)polymere Polycarboxylate sind in wäßriger Form im Handel erhältlich. Als weitere organische Buildersubstanz können Citronensäure und Citrat als wäßrige Lösung eingesetzt werden. Säure und Salz der Citronensäure können allerdings auch als Feststoff zugegeben werden. Diese organischen Buildersubstanzen sowie Farbstofflösungen, gegebenenfalls aber auch Lösungen der Sequestriermittel, der optischen Aufheller und der Vergrauungsinhibitoren und Verfärbungsinhibitoren, beispielsweise Polyvinylpyrrolidon, optional aber auch Wasserglaslösungen, Fettsäuren und nichtionische Tenside, insbesondere bei Raumtemperatur oder bis 30 °C flüssige nichtionische Tenside, vor allem Fett- oder Oxoalkoholethoxylate (nähere Beschreibung siehe unten) stellen die flüssigen Zubereitungsformen für die Herstellung der erfindungsgemäßen Additive. Aus ökonomischen Gründen gilt, daß bei den wäßrigen Zubereitungformen möglichst hoch konzentrierte Lösungen bzw. Dispersionen eingesetzt werden.In particular, (co) polymeric polycarboxylates are commercially available in aqueous form. As Other organic builders can be citric acid and citrate as an aqueous solution be used. Acid and salt of citric acid can also be used as a solid be added. These organic builder substances as well as dye solutions, but optionally also solutions of the sequestering agents, the optical brighteners and Graying inhibitors and discoloration inhibitors, for example polyvinylpyrrolidone, optionally also water glass solutions, fatty acids and non-ionic surfactants, especially at room temperature or up to 30 ° C liquid nonionic surfactants Fat or oxo alcohol ethoxylates (for a more detailed description see below) represent the liquid ones Forms of preparation for the production of the additives according to the invention. Out For economic reasons, the highest possible with the aqueous preparation forms concentrated solutions or dispersions are used.
Als feste Bestandteile dienen beispielsweise - wie oben bereits angedeutet - Citronensäure bzw. Citrat, Alkalimetallseifen und die weiteren möglichen anorganischen Füll- und Trägersalze, insbesondere Natriumcarbonat und/oder Natriumsulfat.As already mentioned, citric acid serves as solid components or citrate, alkali metal soaps and the other possible inorganic fillers and Carrier salts, especially sodium carbonate and / or sodium sulfate.
Die festen und flüssigen Bestandteile werden miteinander vermischt, wobei es im Prinzip unerheblich ist, ob zunächst alle flüssigen Bestandteile vorgelegt und die Feststoffe hineingemischt werden, ob erst alle Feststoffe vorgelegt und die flüssigen Bestandteile zugemischt werden oder ob eine ganz beliebige Reihenfolge der Zugabe erfolgt. Aus verfahrensökonomischen Gründen werden jedoch vorzugsweise zunächst die Feststoffe vorgelegt und anschließend die Flüssigkeiten zugemischt. Die Trocknung erfolgt entweder durch Sprühtrocknung eines Slurries oder in herkömmlichen Trockenvorrichtung nach einer durchgeführten Granulierung oder Kompaktierung, wobei der Einsatz von Wirbelschichtrocknern bevorzugt ist. Falls gewünscht - siehe oben - kann im Anschluß an die Trocknung noch eine Oberflächenmodifzierung nach den bekannten Verfahren des Standes der Technik erfolgen. Dabei kann die Oberfläche in bekannter Weise mit feinteiligen Pulvern überzogen werden. In einer bevorzugten Ausführungsform der Erfindung dienen die erfindungsgemäßen Additive, insbesondere die sprühgetrockneten Additive als Träger für weitere Flüssigkeiten, insbesondere für nichtionische Tenside, kationische Tenside und/oder flüssige bis wachsartige Schauminhibitoren auf Silikon- oder Paraffinbasis in einem anschließenden Granulations- bzw. Kompaktierungsschritt.The solid and liquid components are mixed together, using it in principle It is irrelevant whether all liquid components are initially introduced and the solids mixed into them whether all solids are initially charged and the liquid components mixed or whether there is any order of addition. Out For reasons of process economy, however, the solids are preferred first submitted and then mixed in the liquids. Drying is done either by spray drying a slurry or in a conventional drying device after a performed granulation or compacting, the use of Fluid bed dryers is preferred. If desired - see above - can follow the drying still a surface modification according to the known methods of State of the art. The surface can be finely divided in a known manner Powders are coated. In a preferred embodiment of the invention, the Additives according to the invention, in particular the spray-dried additives as carriers for other liquids, in particular for nonionic surfactants, cationic surfactants and / or liquid to wax-like foam inhibitors based on silicone or paraffin in one subsequent granulation or compacting step.
Gegenstand der Erfindung ist weiterhin ein pulverförmiges bis granulares Wasch- oder Reinigungsmittel - wobei im Rahmen dieser Erfindung auch extrudierte Wasch- oder Reinigungsmittel zu den granularen Wasch- oder Reinigungsmitteln gezählt werden- , welches das erfindungsgemäße Additiv enthält, aber frei von Alkylbenzolsulfonaten ist und Zeolith A nicht in Mengen oberhalb 10 Gew.-%, bezogen auf wasserfreie Aktivsubstanz, aufweist. Dabei ist es insbesondere bevorzugt, daß die Mittel Zeolith A nur in Mengen bis zu 8 Gew.-%, vorteilhafterweise bis zu 5 Gew.-% und insbesondere 1 bis 3 Gew.-% enthalten oder sogar Zeolith A-frei sind. Da in einer bevorzugten Ausführungsform das erfindungsgemäße Additiv alle Bestandteile enthält, die zur Herstellung des fertigen Mittels in wäßriger Form eingesetzt werden, stellt ein Wasch- oder Reinigungsmittel, welche ein derartiges Additiv, das alle in wäßriger Form eingesetzten Rohstoffe bzw. Compounds enthält, eine weitere bevorzugte Ausführungsform dar. Die Wasch- oder Reinigungsmittel können nach jedem der bekannten Verfahren hergestellt werden, wobei die Sprühtrocknung aus der gegebenen Problemstellung heraus im wesentlichen ausgeschlossen sein soll. Bevorzugte Herstellungsverfahren sind herkömmliche Granulierungen, Kompaktierungen und Extrusionen, wobei die erfindungsgemäßen Additive entweder als separate Komponente nachträglich zu dem Mittel zugemischt werden oder eine Einsatzkomponente in dem gewählten Herstellungverfahren darstellen. Insbesondere ist es bevorzugt, daß die erfindungsgemäßen Additive als Einsatzkomponente in einem Extrusionsverfahren - vorteilhafterweise in einem Extrusionsverfahren gemäß der Lehre des europäischen Patents 0 486 592 B1 oder der älteren deutschen Patentanmeldung P 196 38 599.7 - eingesetzt werden. The invention further relates to a powdery to granular washing or cleaning agent - In the context of this invention also extruded washing or cleaning agents granular detergents or cleaning agents - which contains the additive according to the invention but is free from alkylbenzenesulfonates and zeolite A not in amounts above 10% by weight, based on anhydrous active substance. It is particularly preferred that the agents zeolite A only in amounts up to 8 wt .-%, advantageously contain up to 5% by weight and in particular 1 to 3% by weight even zeolite are A-free. Since in a preferred embodiment the invention Additive contains all components necessary for the production of the finished agent in aqueous form are used, a detergent or cleaning agent containing such an additive, which contains all raw materials or compounds used in aqueous form, another preferred embodiment. The detergents or cleaning agents can be any of the known methods are prepared, the spray drying from the given Problem should be essentially excluded. Preferred manufacturing process are conventional granulations, compactings and extrusions, whereby the additives according to the invention either subsequently as a separate component be mixed with the agent or a feed component in the selected manufacturing process represent. In particular, it is preferred that the additives according to the invention as an insert component in an extrusion process - advantageously in an extrusion process according to the teaching of European patent 0 486 592 B1 or the older one German patent application P 196 38 599.7 - are used.
Zusätzlich zu den bereits genannten Inhaltsstoffen der erfindungsgemäßen Additive können die Wasch- oder Reinigungsmittel folgende Inhaltsstoffe aufweisen, wobei die Erfindung nicht auf die genannten Inhaltsstoffe beschränkt ist.In addition to the ingredients of the additives according to the invention which have already been mentioned the washing or cleaning agents have the following ingredients, the invention is not limited to the ingredients mentioned.
Als anionische Tenside werden beispielsweise solche vom Typ der Sulfonate (unter Ausschluß der Alkylbenzolsulfonate) und Sulfate eingesetzt.Examples of anionic surfactants are those of the sulfonate type (to the exclusion of alkylbenzenesulfonates) and sulfates.
Als Tenside vom Sulfonat-Typ kommen beispielsweise Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C12-C18-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht.Suitable surfactants of the sulfonate type include, for example, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the Receives sulfonation products.
Geeignet sind auch Alkansulfonate, die aus C12-C18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden.Also suitable are alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
Geeignet sind auch die Ester von α-Sulfofettsäuren (Estersulfonate), z.B. die α-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren.Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), e.g. the α-sulfonated Methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.
Weitere geeignete Aniontenside sind sulfierte Fettsäureglycerinester, welche Mono-, Di- und Triester sowie deren Gemische darstellen, wie sie bei der Herstellung durch Veresterung durch ein Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden. Die Sulfierprodukte stellen ein komplexes Gemisch dar, das Mono-, Di- und Triglyceridsulfonate mit α-ständiger und/oder innenständiger Sulfonsäuregruppierung enthält. Als Nebenprodukte bilden sich sulfonierte Fettsäuresalze, Glyceridsulfate, Glycerinsulfate, Glycerin und Seifen. Geht man bei der Sulflerung von gesättigten Fettsäuren oder gehärteten Fettsäureglycerinestergemischen aus, so kann der Anteil der α-sulfonierten Fettsäure-Disalze je nach Verfahrensführung durchaus bis etwa 60 Gew.-% betragen.Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and Triester and their mixtures represent how they are produced by esterification by a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides can be obtained with 0.3 to 2 mol of glycerol. The sulfonation products are a complex mixture represents the mono-, di- and triglyceride sulfonates with α-and / or internal Contains sulfonic acid grouping. As by-products, sulfonated fatty acid salts are formed, Glyceride sulfates, glycerine sulfates, glycerin and soaps. If you go from the saturated of saturated Fatty acids or hardened fatty acid glycerol ester mixtures, so the Percentage of α-sulfonated fatty acid disalts, depending on the procedure, up to about 60 % By weight.
Bevorzugte Aniontenside sind auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C8- bis C18-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen (Beschreibung siehe unten). Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen.Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettalkohole beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der C10-C20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlänge bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. Aus waschtechnischem Interesse sind C12-C16-Alkylsulfate und C12-C15-Alkylsulfate sowie C14-C15-Alkylsulfate und C14-C16-Alkylsulfate insbesondere bevorzugt. Auch 2,3-Alkylsulfate, welche beispielsweise gemäß den US-Patentschriften 3,234,258 oder 5,075,041 hergestellt werden und als Handelsprodukt der Shell Oil Company unter dem Namen DAN® erhalten werden können, sind geeignete Aniontenside.As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length 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. C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates, as well as C 14 -C 15 alkyl sulfates and C 14 -C 16 alkyl sulfates are particularly preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as a commercial product from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-C21-Alkohole, wie 2-Methyl-verzweigte C9-C11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12-C18-Fettalkohole mit 1 bis 4 EO, sind geeignet. Sie werden in Waschmitteln aufgrund ihres hohen Schaumverhaltens nur in relativ geringen Mengen, beispielsweise in Mengen von 1 bis 5 Gew.-%, eingesetzt.The sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
Als weitere anionische Tenside kommen die bereits oben genannten Seifen in Betracht. Sie werden, falls sie nicht vollständig über das erfindungsgemäße Additiv in die Mittel eingearbeitet werden, vorzugsweise nachträglich zugemischt.The soaps already mentioned can be considered as further anionic surfactants. she if they are not completely incorporated into the agents via the additive according to the invention are preferably mixed in subsequently.
Die anionischen Tenside können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor.The anionic surfactants can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
Der Gehalt der erfindungsgemäßen Wasch- oder Reinigungsmittel an anionischen Tensiden beträgt vorzugsweise insgesamt 10 bis 45 Gew.-%, wobei es bevorzugt ist, daß Alk(en)ylsulfate bzw. 2,3-Alkylsulfate in Mengen von 10 bis 40 Gew.-% enthalten sind. Die bevorzugten Aniontenside sind Alk(en)ylsulfate und/oder 2,3-Alkylsulfate, welche Alkylbenzolsulfonate aus anwendungstechnischer Sicht in den erfindungsgemäßen Wasch- oder Reinigungsmitteln ohne Leistungseinbußen zu ersetzen vermögen.The content of anionic surfactants in the washing or cleaning agents according to the invention is preferably 10 to 45% by weight in total, with it being preferred that Alk (en) yl sulfates or 2,3-alkyl sulfates are contained in amounts of 10 to 40% by weight. The preferred anionic surfactants are alk (en) yl sulfates and / or 2,3-alkyl sulfates, which From an application point of view, alkylbenzenesulfonates in the washing or Can replace cleaning agents without sacrificing performance.
Zusätzlich zu den bereits genannten nichtionischen Tensiden, die Inhaltsstoffe der erfindungsgemäßen Additive, aber auch außerhalb der Additive in den Wasch- oder Reinigungsmittel enthalten sein können, sind an dieser Stelle vor allem Alkylglykoside, Polyhydroxyfettsäureamide und insbesondere hier die Glucamide, ethoxylierte Fettsäuremethylester und Aminoxide zu nennen.In addition to the non-ionic surfactants already mentioned, the ingredients of the invention Additives, but also outside of the additives in the detergent or cleaning agent may be contained at this point are primarily alkyl glycosides, polyhydroxy fatty acid amides and especially here the glucamides, ethoxylated fatty acid methyl esters and to name amine oxides.
Außerdem können als weitere nichtionische Tenside auch Alkylglykoside der allgemeinen Formel RO(G)x eingesetzt werden, in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4.In addition, alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen und/oder Alkylglykosiden, eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester, wie sie beispielsweise in der japanischen Patentanmeldung JP 58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung WO-A-90/13533 beschriebenen Verfahren hergestellt werden. Besonders bevorzugt sind C12-C18-Fettsäuremethylester mit durchschnittlich 3 bis 15 EO, insbesondere mit durchschnittlich 5 bis 12 EO.Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533. C 12 -C 18 fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO, are particularly preferred.
Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than that Half of it.
Weitere geeignete Tenside sind Polyhydroxyfettsäureamide der Formel (I), in der R2CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R3 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. Vorzugsweise leiten sich die Polyhydroxyfettsäureamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in the R 2 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 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 stands. The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel (II), in der R3 für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R4 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R5 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C1-C4-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise nach der Lehre der internationalen Patentanmeldung WO-A-95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.The group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 5 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
Als weitere Tenside kommen sogenannte Gemini-Tenside in Betracht. Hierunter werden im allgemeinen solche Verbindungen verstanden, die zwei hydrophile Gruppen und zwei hydrophobe Gruppen pro Molekül besitzen. Diese Gruppen sind in der Regel durch einen sogenannten Spacer voneinander getrennt. Dieser Spacer ist in der Regel eine Kohlenstoffkette, die lang genug sein sollte, daß die hydrophilen Gruppen einen ausreichenden Abstand haben, damit sie unabhängig voneinander agieren können. Derartige Tenside zeichnen sich im allgemeinen durch eine ungewöhnlich geringe kritische Micellkonzentration und die Fähigkeit, die Oberflächenspannung des Wassers stark zu reduzieren, aus. In Ausnahmefällen werden jedoch unter dem Ausdruck Gemini-Tenside nicht nur dimere, sondern auch trimere Tenside verstanden.So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually identified by a so-called Spacer separated from each other. This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient distance so that they can act independently of one another. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants means not only dimeric but also trimeric surfactants.
Geeignete Gemini-Tenside sind beispielsweise sulfatierte Hydroxymischether gemäß der deutschen Patentanmeldung DE-A-43 21 022 oder Dimeralkohol-bis- und Trimeralkohol-tris-sulfate und -ethersulfate gemäß der internationalen Patentanmeldung WO-A-96/23768. Endgruppenverschlossene dimere und trimere Mischether gemäß der deutschen Patentanmeldung DE-A-195 13 391 zeichnen sich insbesondere durch ihre Bi- und Multifunktionalität aus. So besitzen die genannten endgruppenverschlossenen Tenside gute Netzeigenschaften und sind dabei schaumarm, so daß sie sich insbesondere für den Einsatz in maschinellen Wasch- oder Reinigungsverfahren eignen.Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates according to international patent application WO-A-96/23768. End group capped dimeric and trimeric mixed ethers according to the German Patent application DE-A-195 13 391 are particularly characterized by their bi- and Multifunctionality. For example, the end group-closed surfactants mentioned have good ones Network properties and are low-foaming, so that they are particularly suitable for use suitable in machine washing or cleaning processes.
Eingesetzt werden können aber auch Gemini-Polyhydroxyfettsäureamide oder Poly-Polyhydroxyfettsäureamide, wie sie in den internationalen Patentanmeldungen WO-A-95/19953, WO-A-95/19954 und WO95-A-/19955 beschrieben werden.Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides can also be used. as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO95-A- / 19955 can be described.
Als Buildersubstanzen kommen vor allem Zeolith P, gegebenenfalls auch X, kristalline schichtförmige (Di-)Silikate und amorphe Silikate mit verzögerter Desintegration in Betracht. Zeolith A wird - falls überhaupt - nur in den bereits obengenannten Mengen eingesetzt.Zeolite P, optionally also X, is crystalline as builder substances layered (di) silicates and amorphous silicates with delayed disintegration into consideration. Zeolite A is used - if at all - only in the amounts already mentioned above.
Kristalline, schichtförmige Natriumsilikate der allgemeinen Formel NaMSixO2x+1·yH2O, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind, sind als geeignete Substitute für Phosphate und Zeolithe bekannt. Derartige kristalline Schichtsilikate werden beispielsweise in der europäischen Patentanmeldung EP-A-0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate der angegebenen Formel sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl β- als auch δ-Natriumdisilikate Na2Si2O5·yH2O bevorzugt.Crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are known as suitable substitutes for phosphates and zeolites. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
Zu den bevorzugten Buildersubstanzen gehören auch amorphe Natriumsilikate mit einem Modul Na2O : SiO2 von 1:2 bis 1:3,3, vorzugsweise von 1:2 bis 1:2,8 und insbesondere von 1:2 bis 1:2,6, welche löseverzögert sind und Sekundärwascheigenschaften aufweisen. Die Löseverzögerung gegenüber herkömmlichen amorphen Natriumsilikaten kann dabei auf verschiedene Weise, beispielsweise durch Oberflächenbehandlung, Compoundierung, Kompaktierung/Verdichtung oder durch Übertrocknung hervorgerufen worden sein. Im Rahmen dieser Erfindung wird unter dem Begriff "amorph" auch "röntgenamorph" verstanden. Dies heißt, daß die Silikate bei Röntgenbeugungsexperimenten keine scharfen Röntgenreflexe liefern, wie sie für kristalline Substanzen typisch sind, sondern allenfalls ein oder mehrere Maxima der gestreuten Röntgenstrahlung, die eine Breite von mehreren Gradeinheiten des Beugungswinkels aufweisen. Es kann jedoch sehr wohl sogar zu besonders guten Buildereigenschaften führen, wenn die Silikatpartikel bei Elektronenbeugungsexperimenten verwaschene oder sogar scharfe Beugungsmaxima liefern. Dies ist so zu interpretieren, daß die Produkte mikrokristalline Bereiche der Größe 10 bis einige Hundert nm aufweisen, wobei Werte bis max. 50 nm und insbesondere bis max. 20 nm bevorzugt sind. Derartige sogenannte röntgenamorphe Silikate, welche ebenfalls eine Löseverzögerung gegenüber den herkömmlichen Wassergläsern aufweisen, werden beispielsweise in der deutschen Patentanmeldung DE-A- 44 00 024 beschrieben. Insbesondere bevorzugt sind verdichtete/kompaktierte amorphe Silikate, compoundierte amorphe Silikate und übertrocknete röntgenamorphe Silikate.The preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” also means “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
Zusätzlich können die Mittel auch Komponenten enthalten, welche die Öl- und Fett-auswaschbarkeit aus Textilien positiv beeinflussen. Dieser Effekt wird besonders deutlich, wenn ein Textil verschmutzt wird, das bereits vorher mehrfach mit einem erfin-dungsgemäßen Waschmittel, das diese öl- und fettlösende Komponente enthält, gewaschen wurde. Zu den bevorzugten öl- und fettlösenden Komponenten zählen beispielsweise nicht-ionische Celluloseether wie Methylcellulose und Methylhydroxy-propylcellulose mit einem Anteil an Methoxyl-Gruppen von 15 bis 30 Gew.-% und an Hydroxypropoxyl-Gruppen von 1 bis 15 Gew.-%, jeweils bezogen auf den nichtionischen Celluloseether, sowie die aus dem Stand der Technik bekannten Polymere der Phthalsäure und/oder der Terephthalsäure bzw. von deren Derivaten, insbesondere Polymere aus Ethylenterephthalaten und/oder Polyethylenglykolterephthalaten oder anionisch und/oder nichtionisch modifzierten Derivaten von diesen. Besonders bevorzugt von diesen sind die sulfonierten Derivate der Phthalsäure- und der Terephthalsäure-Polymere.In addition, the agents can also contain components that make the oil and fat washable made of textiles. This effect is particularly evident when a textile is soiled that has already been washed several times with an inventive one Detergent containing this oil and fat-dissolving component has been washed. To the preferred oil- and fat-dissolving components include, for example, non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and from 1 to 15% by weight of hydroxypropoxyl groups, each based on the nonionic cellulose ether, and those from the prior art Technically known polymers of phthalic acid and / or terephthalic acid or their Derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Of these, particular preference is given to the sulfonated derivatives of phthalic acid and Terephthalic acid polymers.
Weitere geeignete Inhaltsstoffe der Mittel sind wasserlösliche anorganische Salze wie Bicarbonate, Carbonate, amorphe Silikate oder Mischungen aus diesen; insbesondere werden Alkalicarbonat und amorphes Alkalisilikat, vor allem Natriumsilikat mit einem molaren Verhältnis Na2O: SiO2 von 1:1 bis 1:4,5, vorzugsweise von 1:2 bis 1:3,5, eingesetzt.Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; In particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumperborattetrahydrat und das Natriumperboratmonohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Natriumpercarbonat, Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure, Phthaloiminopersäure oder Diperdodecandisäure. Der Gehalt der Mittel an Bleichmitteln beträgt vorzugsweise 5 bis 25 Gew.-% und insbesondere 10 bis 20 Gew.-%, wobei vorteilhafterweise Perboratmonohydrat oder Percarbonat eingesetzt wird.Among the compounds which serve as bleaching agents and supply H 2 O 2 in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. The bleach content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.
Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat, 2,5-Diacetoxy-2,5-dihydrofuran und die aus den deutschen Patentanmeldungen DE-A-196 16 693 und DE-A-196 16 767 bekannten Enolester sowie acetyliertes Sorbitol und Mannitol beziehungsweise deren in der europäischen Patentanmeldung EP-A-0 525 239 beschriebene Mischungen (SORMAN), acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactose sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton, und/oder N-acylierte Lactame, beispielsweise N-Benzoylcaprolactam, die aus den internationalen Patentanmeldungen WO-A-94/27970, WO-A-94/28102, WO-A-94/28103, WO-A-95/00626, WO-A-95/14759 und WO-A-95/17498 bekannt sind. Die aus der deutschen Patentanmeldung DE-A-196 16 769 bekannten hydrophil substituierten Acylacetale und die in der deutschen Patentanmeldung DE-A-196 16 770 sowie der internationalen Patentanmeldung WO-A-95/14075 beschriebenen Acyllactame werden ebenfalls bevorzugt eingesetzt. Auch die aus der deutschen Patentanmeldung DE-A-44 43 177 bekannten Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. Derartige Bleichaktivatoren sind im üblichen Mengenbereich, vorzugsweise in Mengen von 1 Gew.-% bis 10 Gew.-%, insbesondere 2 Gew.-% bis 8 Gew.-%, bezogen auf gesamtes Mittel, enthalten. Compounds which are aliphatic under perhydrolysis conditions can be used as bleach activators Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Multiple are preferred acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated Glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the German patent applications DE-A-196 16 693 and DE-A-196 16 767 known enol esters and acetylated sorbitol and Mannitol or their in European patent application EP-A-0 525 239 described mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), Pentaacetylfruktose, Tetraacetylxylose and Octaacetyllactose as well acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated Lactams, for example N-benzoylcaprolactam, from the international patent applications WO-A-94/27970, WO-A-94/28102, WO-A-94/28103, WO-A-95/00626, WO-A-95/14759 and WO-A-95/17498 are known. The from the German patent application DE-A-196 16 769 known hydrophilically substituted acylacetals and those in the German Patent application DE-A-196 16 770 and international patent application WO-A-95/14075 Acyllactams described are also preferably used. Also the Combinations of conventional known from German patent application DE-A-44 43 177 Bleach activators can be used. Such bleach activators are in usual amount range, preferably in amounts of 1 wt .-% to 10 wt .-%, in particular 2% by weight to 8% by weight, based on the total average.
Der Bleichaktivator kann in bekannter Weise mit Hüllsubstanzen überzogen oder, gegebenenfalls unter Einsatz von Hilfsmitteln, insbesondere Methylcellulosen und/oder Carboxymethylcellulosen, granuliert oder extrudiert/pelletiert worden sein und gewünschtenfalls weitere Zusatzstoffe, beispielsweise Farbstoff, enthalten. Vorzugsweise enthält ein derartiges Granulat über 70 Gew.-%, insbesondere von 90 bis 99 Gew.-% Bleichaktivator. Vorzugsweise wird ein Bleichaktivator eingesetzt, der unter Waschbedingungen Peressigsäure bildet.The bleach activator can be coated with coating substances in a known manner or, if necessary using auxiliaries, in particular methyl celluloses and / or carboxymethyl celluloses, granulated or extruded / pelletized and, if desired, others Additives, such as dye, contain. Such granules preferably contain over 70% by weight, in particular from 90 to 99% by weight, of bleach activator. Preferably a bleach activator is used which forms peracetic acid under washing conditions.
Zusätzlich zu den oben aufgeführten konventionellen Bleichaktivatoren oder an deren Stelle können auch die aus den europäischen Patentschriften EP-A-0 446 982 und EP-A-0 453 003 bekannten Sulfonimine und/oder bleichverstärkende Übergangsmetallsalze beziehungsweise Übergangsmetallkomplexe als sogenannte Bleichkatalysatoren enthalten sein. Zu den in Frage kommenden Übergangsmetallverbindungen gehören insbesondere die aus der deutschen Patentanmeldung DE-A-195 29 905 bekannten Mangan-, Eisen-, Kobalt-, Ruthenium- oder Molybdän-Salenkomplexe und deren aus der deutschen Patentanmeldung DE-A-196 20 267 bekannte N-Analogverbindungen, die aus der deutschen Patentanmeldung DE-A-195 36 082 bekannten Mangan-, Eisen-, Kobalt-, Ruthenium- oder Molybdän-Carbonylkomplexe, die in der deutschen Patentanmeldung DE-A-196 05 688 beschriebenen Mangan-, Eisen-, Kobalt-, Ruthenium-, Molybdän-, Titan-, Vanadium- und Kupfer-Komplexe mit stickstoffhaltigen Tripod-Liganden, die aus der deutschen Patentanmeldung DE-A-196 20 411 bekannten Kobalt-, Eisen-, Kupfer- und Ruthenium-Amminkomplexe, die in der deutschen Patentanmeldung DE-A-44 16 438 beschriebenen Mangan-, Kupfer- und Kobalt-Komplexe, die in der europäischen Patentanmeldung EP-A-0 272 030 beschriebenen Kobalt-Komplexe, die aus der europäischen Patentanmeldung EP-A-0 693 550 bekannten Mangan-Komplexe, die aus der europäischen Patentschrift EP-A-0 392 592 bekannten Mangan-, Eisen-, Kobalt- und Kupfer-Komplexe und/oder die in der europäischen Patentschrift EP-A-0 443 651 oder den europäischen Patentanmeldungen EP-A-0 458 397, EP-A-0 458 398, EP-A-0 549 271, EP-A-0 549 272, EP-A-0 544 490 und EP-A-0 544 519 beschriebenen Mangan-Komplexe. Kombinationen aus Bleichaktivatoren und Übergangsmetall-Bleichkatalysatoren sind beispielsweise aus der deutschen Patentanmeldung DE 196 13 103 und der internationalen Patentanmeldung WO-A-95/27775 bekannt. Bleichverstärkende Übergangsmetallkomplexe, insbesondere mit den Zentralatomen Mn, Fe, Co, Cu, Mo, V, Ti und/oder Ru, werden in üblichen Mengen, vorzugsweise in einer Menge bis zu 1 Gew.-%, insbesondere von 0,0025 Gew.-% bis 0,25 Gew.-% und besonders bevorzugt von 0,01 Gew.-% bis 0,1 Gew.-%, jeweils bezogen auf gesamtes Mittel, eingesetzt.In addition to the conventional bleach activators listed above or in their place can also those from European patent specifications EP-A-0 446 982 and EP-A-0 453 003 known sulfonimines and / or bleach-enhancing transition metal salts or contain transition metal complexes as so-called bleaching catalysts be. The transition metal compounds in question include in particular those known from the German patent application DE-A-195 29 905 manganese, iron, cobalt, Ruthenium or molybdenum salt complexes and those from the German patent application DE-A-196 20 267 known N-analog compounds, which from the German Patent application DE-A-195 36 082 known manganese, iron, cobalt, ruthenium or Molybdenum-carbonyl complexes, which are described in German patent application DE-A-196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and Copper complexes with nitrogenous tripod ligands resulting from the German patent application DE-A-196 20 411 known cobalt, iron, copper and ruthenium amine complexes, the manganese described in German patent application DE-A-44 16 438, Copper and cobalt complexes described in European patent application EP-A-0 272 030 described cobalt complexes, which from the European patent application EP-A-0 693 550 known manganese complexes, which are known from the European patent EP-A-0 392 592 known manganese, iron, cobalt and copper complexes and / or those in the European patent specification EP-A-0 443 651 or European patent applications EP-A-0 458 397, EP-A-0 458 398, EP-A-0 549 271, EP-A-0 549 272, EP-A-0 544 490 and EP-A-0 544,519 manganese complexes described. Combinations of bleach activators and Transition metal bleaching catalysts are, for example, from the German patent application DE 196 13 103 and the international patent application WO-A-95/27775 known. Bleach-enhancing transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru are in customary amounts, preferably in an amount up to 1% by weight, in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total Means used.
Beim Einsatz in maschinellen Waschverfahren kann es von Vorteil sein, den Mitteln übliche Schauminhibitoren zuzusetzen. Als Schauminhibitoren eignen sich beispielsweise Seifen natürlicher oder synthetischer Herkunft, die einen hohen Anteil an C18-C24-Fettsäuren aufweisen. Geeignete nichttensidartige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, ggf. silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure oder Bistearylethylendiamid. Mit Vorteilen werden auch Gemische aus verschiedenen Schauminhibitoren verwendet, z.B. solche aus Silikonen, Paraffinen oder Wachsen. Vorzugsweise sind die Schauminhibitoren, insbesondere Silikon- und/oder Paraffin-haltige Schauminhibitoren, an eine granulare, in Wasser lösliche bzw. dispergierbare Trägersubstanz gebunden. Insbesondere sind dabei Mischungen aus Paraffinen und Bistearylethylendiamiden bevorzugt.When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
Als Enzyme kommen insbesondere solche aus der Klasse der Hydrolasen, wie der Proteasen, Lipasen bzw. lipolytisch wirkenden Enzyme, Amylasen, Cellulasen bzw. deren Gemische in Frage. Auch Oxireduktasen sind geeignet.Enzymes in particular come from the class of hydrolases, such as proteases, Lipases or lipolytic enzymes, amylases, cellulases or mixtures thereof in question. Oxireductases are also suitable.
Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus und Humicola insolens gewonnene enzymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Dabei sind Enzymmischungen, beispielsweise aus Protease und Amylase oder Protease und Lipase bzw. lipolytisch wirkenden Enzymen oder Protease und Cellulase oder aus Cellulase und Lipase bzw. lipolytisch wirkenden Enzymen oder aus Protease, Amylase und Lipase bzw. lipolytisch wirkenden Enzymen oder Protease, Lipase bzw. lipolytisch wirkenden Enzymen und Cellulase, insbesondere jedoch Protease- und/oder Lipase-haltige Mischungen bzw. Mischungen mit lipolytisch wirkenden Enzymen von besonderem Interesse. Beispiele für derartige lipolytisch wirkende Enzyme sind die bekannten Cutinasen. Auch Peroxidasen oder Oxidasen haben sich in einigen Fällen als geeignet erwiesen. Zu den geeigneten Amylasen zählen insbesondere α-Amylasen, Iso-Amylasen, Pullulanasen und Pektinasen. Als Cellulasen werden vorzugsweise Cellobiohydrolasen, Endoglucanasen und β-Glucosidasen, die auch Cellobiasen genannt werden, bzw. Mischungen aus diesen eingesetzt. Da sich die verschiedenen Cellulase-Typen durch ihre CMCase- und Avicelase-Aktivitäten unterscheiden, können durch gezielte Mischungen der Cellulasen die gewünschten Aktivitäten eingestellt werden. From bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens Active ingredients. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic acting enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic acting enzymes or protease, lipase or lipolytically acting enzymes and cellulase, in particular, however, mixtures or mixtures containing protease and / or lipase with lipolytic enzymes of particular interest. Examples of such lipolytic acting enzymes are the well-known cutinases. Also peroxidases or oxidases have proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which also Cellobiases are called, or mixtures of these are used. Because the different Distinguish cellulase types by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases will.
Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen. Der Anteil der Enzyme, Enzymmischungen oder Enzymgranulate kann beispielsweise etwa 0,1 bis 5 Gew.-%, vorzugsweise 0,1 bis etwa 2 Gew.-% betragen. The enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
Es wurde ein Granulat 1 durch Sprühtrocknung und anschließende Nachbehandlung hergestellt, welches folgende Zusammensetzung enthielt: 51,40 Gew.-% copolymeres Natriumsalz der Acrylsäure und der Maleinsäure (Sokalan CP 5®, Handelsprodukt der BASF, Bundesrepublik Deutschland; eingesetzt als 40 Gew.-%ige wäßrige Lösung), 7,02 Gew.-% Talgfettalkohol mit 5 EO, 8,16 Gew.-% C12-C18-Natriumfettsäureseife, 27,14 Gew.-% Natriumcarbonat (eingesetzt als Feststoff), 2,01 Gew.-% Bis((4-anilino-6-morpholino-s-triazin-2-yl)amino)-stilben-2,2'-disulfonsäure-dinatriumsalz (eingesetzt als wäßrige Suspension), 2,77 Gew.-% sonstige Salze und Wasser sowie 1,50 Gew.-% C12-C18-Fettalkohol mit 7 EO, welcher nachträglich aufgesprüht wurde. Dieses Granulat 1 wies ein Schüttgewicht von 250 g/l auf.A granulate 1 was produced by spray drying and subsequent post-treatment, which contained the following composition: 51.40% by weight of copolymeric sodium salt of acrylic acid and maleic acid (Sokalan CP 5®, commercial product from BASF, Federal Republic of Germany; used as 40% by weight % aqueous solution), 7.02% by weight of tallow fatty alcohol with 5 EO, 8.16% by weight of C 12 -C 18 sodium fatty acid soap, 27.14% by weight of sodium carbonate (used as a solid), 2.01 % By weight bis ((4-anilino-6-morpholino-s-triazin-2-yl) amino) -stilbene-2,2'-disulfonic acid disodium salt (used as an aqueous suspension), 2.77% by weight other salts and water and 1.50% by weight of C 12 -C 18 fatty alcohol with 7 EO, which was subsequently sprayed on. This granulate 1 had a bulk density of 250 g / l.
100 Gew.-Teile des Granulats 1 wurden in einem weiteren nachfolgenden Schritt mit 4,60 Gew.-Teilen einer 40 Gew.-%igen wäßrigen Lösung von 1-Hydroxyethan-1,1-diphosphonat besprüht. Das erhaltene Granulat 2 wies ein Schüttgewicht von 410 g/l auf. Eine weitere Trocknung oder eine Oberflachenmodifizierung mit feinteiligen Feststoffen waren zur Verbesserung der Rieselfähigkeit nicht erforderlich, erhöhten aber das Schüttgewicht. Wurde das Phosphonat als wäßrige Lösung in den sprühzutrocknenden Slurry eingearbeitet, so wurde ein Granulat 1* erhalten, welches ebenfalls ein erhöhtes Schüttgewicht von etwa 410 g/l aufwies.100 parts by weight of the granules 1 were in a further subsequent step with 4.60 Parts by weight of a 40% by weight aqueous solution of 1-hydroxyethane-1,1-diphosphonate sprayed. The granules 2 obtained had a bulk density of 410 g / l. Another Drying or surface modification with finely divided solids were an improvement the flowability is not required, but increased the bulk weight. Has been the phosphonate is incorporated as an aqueous solution in the slurry to be spray-dried, so a 1 * granulate was obtained, which also has an increased bulk density of about 410 had g / l.
Das Granulat 3 wurde durch Granulierung und anschließende Trocknung einer wäßrigen Lösung von Sokalan CP 5®, bei Raumtemperatur oder leicht erhöhter Temperatur flüssigen nichtionischen Tensiden, Fettsäureseife (siehe oben), Natriumcarbonat und 2 verschiedenen optischen Aufhellern Bis((4-anilino-6-morpholino-s-triazin-2-yl)amino)-stilben-2,2'-disulfonsäure-dinatriumsalz und Bis(2-sulfostyrol)biphenyl-dinatriumsalz hergestellt. Der Gehalt an Polymer betrug nach der Trocknung 49,1 Gew.-%, an Natriumcarbonat 27,4 Gew.-%, an optischen Aufhellern 2,88 Gew.-%, an Seife 7,80 Gew.-% und an nichtionischen Tensiden 8,50 Gew.-%. Der Rest bestand aus Wasser und sonstigen Salzen. Das Schüttgewicht von Granulat 3 betrug 580 g/l.The granulate 3 was obtained by granulation and subsequent drying of an aqueous Solution of Sokalan CP 5®, liquid at room temperature or slightly elevated temperature non-ionic surfactants, fatty acid soap (see above), sodium carbonate and 2 different optical brighteners bis ((4-anilino-6-morpholino-s-triazin-2-yl) amino) -stilbene-2,2'-disulfonic acid disodium salt and bis (2-sulfostyrene) biphenyl disodium salt. The salary polymer after drying was 49.1% by weight, sodium carbonate 27.4% by weight optical brighteners 2.88% by weight, 7.80% by weight of soap and nonionic surfactants 8.50% by weight. The rest consisted of water and other salts. The bulk density of Granulate 3 was 580 g / l.
Granulat 3 eignete sich als separate nachträgliche Zumischkomponente in schweren Wasch- oder Reinigungsmitteln mit Schüttgewichten zwischen 500 und 900 g/l. Die Granulate 1 bis 3 eigneten sich auch als feste Einsatzkomponente in Granulier- oder Kompaktierverfahren zur Herstellung schwerer Wasch- oder Reinigungsmittel. Insbesondere waren die Granulate 1 bis 3 geeignet, in Extrusionsverfahren gemäß der Lehren des europäischen Patents 0 486 592 oder der deutschen Patentanmeldung DE-A-196 38 599 eingesetzt zu werden.Granulate 3 was suitable as a separate subsequent admixture component in heavy Detergents or cleaning agents with bulk weights between 500 and 900 g / l. The granules 1 to 3 were also suitable as fixed components in granulation or compacting processes for the production of heavy detergents or cleaning agents. In particular, they were Granules 1 to 3 suitable in extrusion processes according to the teachings of the European Patents 0 486 592 or the German patent application DE-A-196 38 599 used will.
Claims (17)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19651072 | 1996-12-09 | ||
DE19651072A DE19651072A1 (en) | 1996-12-09 | 1996-12-09 | Additive for detergents or cleaning agents |
Publications (3)
Publication Number | Publication Date |
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EP0846758A2 true EP0846758A2 (en) | 1998-06-10 |
EP0846758A3 EP0846758A3 (en) | 1998-12-16 |
EP0846758B1 EP0846758B1 (en) | 2006-03-01 |
Family
ID=7814096
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP97121101A Expired - Lifetime EP0846758B1 (en) | 1996-12-09 | 1997-12-01 | Detergent additive |
Country Status (4)
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EP (1) | EP0846758B1 (en) |
AT (1) | ATE318887T1 (en) |
DE (2) | DE19651072A1 (en) |
ES (1) | ES2258785T3 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000020550A1 (en) * | 1998-10-05 | 2000-04-13 | The Procter & Gamble Company | Process for delivering chelant agglomerate into detergent composition for improving its storage stability, flowability and scoopability |
US6635612B1 (en) | 1999-10-01 | 2003-10-21 | The Procter & Gamble Company | Process for delivering chelant agglomerate into detergent composition for improving its storage stability, flowability and scoopability |
EP1500696A1 (en) * | 2003-07-25 | 2005-01-26 | Clariant GmbH | Detergent additive |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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DE19858859A1 (en) | 1998-12-19 | 2000-06-21 | Henkel Kgaa | Production of storage-stable, homogeneous detergent optionally containing heavy components by agglomeration in a rotatable mixer with anionic surfactant introduced in acid form |
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DE3604223A1 (en) * | 1985-02-14 | 1986-08-14 | Basf Ag, 67063 Ludwigshafen | Additive for detergents and cleaners |
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WO1992013937A1 (en) * | 1991-02-11 | 1992-08-20 | Henkel Kommanditgesellschaft Auf Aktien | Granular additive for washing and cleaning agents |
DE4213036A1 (en) * | 1992-04-21 | 1993-10-28 | Henkel Kgaa | Stable, free-flowing granulate of alkaline cleaning additive - contg. (meth)acrylic] acid (co)polymer, sodium silicate, sodium carbonate or sodium sulphate, sequestering agent and water |
WO1997029175A1 (en) * | 1996-02-12 | 1997-08-14 | Unilever N.V. | Nta/edta-containing detergent composition |
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1996
- 1996-12-09 DE DE19651072A patent/DE19651072A1/en not_active Ceased
-
1997
- 1997-12-01 AT AT97121101T patent/ATE318887T1/en not_active IP Right Cessation
- 1997-12-01 DE DE59712584T patent/DE59712584D1/en not_active Expired - Lifetime
- 1997-12-01 ES ES97121101T patent/ES2258785T3/en not_active Expired - Lifetime
- 1997-12-01 EP EP97121101A patent/EP0846758B1/en not_active Expired - Lifetime
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DE2442423A1 (en) * | 1973-09-14 | 1975-04-03 | Ciba Geigy Ag | DUST-FREE, GOOD GRAINABLE GRANULES OF OPTICAL BRIGHTENERS |
DE3604223A1 (en) * | 1985-02-14 | 1986-08-14 | Basf Ag, 67063 Ludwigshafen | Additive for detergents and cleaners |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000020550A1 (en) * | 1998-10-05 | 2000-04-13 | The Procter & Gamble Company | Process for delivering chelant agglomerate into detergent composition for improving its storage stability, flowability and scoopability |
US6635612B1 (en) | 1999-10-01 | 2003-10-21 | The Procter & Gamble Company | Process for delivering chelant agglomerate into detergent composition for improving its storage stability, flowability and scoopability |
EP1500696A1 (en) * | 2003-07-25 | 2005-01-26 | Clariant GmbH | Detergent additive |
Also Published As
Publication number | Publication date |
---|---|
DE19651072A1 (en) | 1998-06-10 |
EP0846758B1 (en) | 2006-03-01 |
ATE318887T1 (en) | 2006-03-15 |
DE59712584D1 (en) | 2006-04-27 |
EP0846758A3 (en) | 1998-12-16 |
ES2258785T3 (en) | 2006-09-01 |
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