EP0839178B1 - Amorphous alkali silicate compound - Google Patents
Amorphous alkali silicate compound Download PDFInfo
- Publication number
- EP0839178B1 EP0839178B1 EP96924857A EP96924857A EP0839178B1 EP 0839178 B1 EP0839178 B1 EP 0839178B1 EP 96924857 A EP96924857 A EP 96924857A EP 96924857 A EP96924857 A EP 96924857A EP 0839178 B1 EP0839178 B1 EP 0839178B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkali metal
- weight
- metal silicate
- compound
- silicate
- 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.)
- Expired - Lifetime
Links
- 229910052910 alkali metal silicate Inorganic materials 0.000 title claims abstract description 92
- 150000001875 compounds Chemical class 0.000 title claims abstract description 47
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims abstract description 24
- 150000008041 alkali metal carbonates Chemical class 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 229910052681 coesite Inorganic materials 0.000 claims abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract 2
- 229910052682 stishovite Inorganic materials 0.000 claims abstract 2
- 229910052905 tridymite Inorganic materials 0.000 claims abstract 2
- -1 alkali metal carbonate compound Chemical class 0.000 claims description 38
- 239000010457 zeolite Substances 0.000 claims description 33
- 239000002736 nonionic surfactant Substances 0.000 claims description 32
- 229910021536 Zeolite Inorganic materials 0.000 claims description 30
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 30
- 239000003599 detergent Substances 0.000 claims description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 21
- 239000004615 ingredient Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 13
- 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 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000004115 Sodium Silicate Substances 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 239000013543 active substance Substances 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 7
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 150000004760 silicates Chemical class 0.000 description 41
- 239000012459 cleaning agent Substances 0.000 description 32
- 238000005406 washing Methods 0.000 description 32
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 29
- 150000003839 salts Chemical class 0.000 description 28
- 150000002191 fatty alcohols Chemical class 0.000 description 26
- 239000000047 product Substances 0.000 description 23
- 239000002253 acid Substances 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 16
- 235000014113 dietary fatty acids Nutrition 0.000 description 16
- 239000000194 fatty acid Substances 0.000 description 16
- 229930195729 fatty acid Natural products 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 13
- 150000004665 fatty acids Chemical class 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 12
- 150000008051 alkyl sulfates Chemical class 0.000 description 11
- 108091005804 Peptidases Proteins 0.000 description 10
- 239000004365 Protease Substances 0.000 description 10
- 239000003513 alkali Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 10
- 102000004190 Enzymes Human genes 0.000 description 9
- 108090000790 Enzymes Proteins 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 229940088598 enzyme Drugs 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 9
- 159000000000 sodium salts Chemical class 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 8
- 239000007844 bleaching agent Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000001694 spray drying Methods 0.000 description 8
- 239000003760 tallow Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000006260 foam Substances 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 102000004882 Lipase Human genes 0.000 description 6
- 239000004367 Lipase Substances 0.000 description 6
- 108090001060 Lipase Proteins 0.000 description 6
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 6
- 229920002472 Starch Chemical class 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
- 238000009826 distribution Methods 0.000 description 6
- 235000019421 lipase Nutrition 0.000 description 6
- 235000019353 potassium silicate Nutrition 0.000 description 6
- 239000000344 soap Substances 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 239000012190 activator Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920005646 polycarboxylate Polymers 0.000 description 5
- 235000019419 proteases Nutrition 0.000 description 5
- 239000008107 starch Chemical class 0.000 description 5
- 244000060011 Cocos nucifera Species 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 102000035195 Peptidases Human genes 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 102000013142 Amylases Human genes 0.000 description 3
- 108010065511 Amylases Proteins 0.000 description 3
- 108010059892 Cellulase Proteins 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 235000019418 amylase Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 229940106157 cellulase Drugs 0.000 description 3
- 229920003086 cellulose ether Polymers 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 150000003138 primary alcohols Chemical class 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004382 Amylase Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- 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 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
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 229920002678 cellulose Chemical class 0.000 description 2
- 239000001913 cellulose Chemical class 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
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- 238000010327 methods by industry Methods 0.000 description 2
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- 150000004682 monohydrates Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 235000019351 sodium silicates Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
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- SWMBOMMGMHMOHE-MHLULTLJSA-N (2r,3r,4r,5r)-hexane-1,2,3,4,5,6-hexol;(2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO SWMBOMMGMHMOHE-MHLULTLJSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- LYPVKWMHGFMDPD-UHFFFAOYSA-N 1,5-diacetyl-1,3,5-triazinane-2,4-dione Chemical compound CC(=O)N1CN(C(C)=O)C(=O)NC1=O LYPVKWMHGFMDPD-UHFFFAOYSA-N 0.000 description 1
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- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical class CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- NSMMFSKPGXCMOE-UHFFFAOYSA-N 2-[2-(2-sulfophenyl)ethenyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=CC1=CC=CC=C1S(O)(=O)=O NSMMFSKPGXCMOE-UHFFFAOYSA-N 0.000 description 1
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical class O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 1
- REJHVSOVQBJEBF-OWOJBTEDSA-N 5-azaniumyl-2-[(e)-2-(4-azaniumyl-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-OWOJBTEDSA-N 0.000 description 1
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- 241000193422 Bacillus lentus Species 0.000 description 1
- 241000194108 Bacillus licheniformis Species 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
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- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
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- 239000011575 calcium Substances 0.000 description 1
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- 159000000007 calcium salts Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
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- 150000004985 diamines Chemical class 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 230000000916 dilatatory effect Effects 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
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- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical class CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
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- 238000000227 grinding Methods 0.000 description 1
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 1
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- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- SXLLDUPXUVRMEE-UHFFFAOYSA-N nonanediperoxoic acid Chemical compound OOC(=O)CCCCCCCC(=O)OO SXLLDUPXUVRMEE-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
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- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical class OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical class [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 238000009420 retrofitting Methods 0.000 description 1
- 238000009490 roller compaction Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 229910000031 sodium sesquicarbonate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 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
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 238000006277 sulfonation reaction Methods 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
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical group OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
Definitions
- the invention relates to a method for producing a amorphous alkali silicate / alkali carbonate compounds containing surfactants Secondary washing ability, which as a water-soluble builder in Detergents or cleaning agents can be used, as well as the Use of such alkali silicate compounds in washing or cleaning agents, extruded detergents or cleaning agents and a Process for their production.
- Modern, compacted detergents or cleaning agents generally have the disadvantage that they are due to their compact structure show poorer dissolving behavior in aqueous liquor than, for example lighter spray-dried washing or cleaning agents the state of the art.
- Detergents or cleaning agents tend to do this generally at a slower dissolving rate in water, the higher their degree of compaction.
- Zeolites in Washing or cleaning agents are usually used as builder substances may be included due to their water insolubility contribute to the deterioration in dissolving behavior.
- a water-soluble alternative for the zeolite are amorphous Alkali silicates with secondary washing ability.
- Alkali silicates in granular form with higher bulk densities can according to the teaching of European patent application EP-A-0 526 978 can be obtained, using an alkali silicate solution with a Solids content between 30 and 53 wt .-% in a heated drum brings in the longitudinal axis of a shaft with a variety of arms rotating close to the inner surface of the drum, wherein the drum wall has a temperature between 150 and 200 ° C and the drying process by a gas fed into the drum is supported with a temperature between 175 and about 250 ° C. According to this process, a product is obtained, the middle one Particle size is in the range between 0.2 and 2 mm. A preferred one Drying gas is heated air.
- European patent application EP-A-0 542 131 describes a process in which a product which is completely soluble in water at room temperature and has a bulk density of between 500 and 1200 g / l is obtained. Drying is preferably carried out using heated air.
- a cylindrical dryer with a heated wall 160 to 200 ° C.
- a rotor with blade-shaped blades rotates at such a speed that the silicate solution has a solids content of between 40 and 60% by weight pseudoplastic mass with a free water content between 5 and 12 wt .-% arises. Drying is supported by a hot air stream (220 to 260 ° C).
- the older, unpublished application P 44 19 745.4 describes also a water-soluble, amorphous and granular Alkali silicate, which in a similar manner as in EP-A-0 526 978 described is produced, but is siliceous.
- amorphous means "X-ray amorphous”. This means that the alkali silicates have no sharp reflections in X-ray diffraction deliver, but at most one or more broad maxima, the width of which is several degree units of the diffraction angle. However, this does not rule out the fact that in electron diffraction experiments Areas are found that have sharp electron diffraction reflections deliver. This is to be interpreted as the substance microcrystalline areas on the order of up to approx. 20 nm (max. 50 nm).
- Granular amorphous sodium silicates which by spray drying aqueous Water glass solutions, subsequent grinding and subsequent Compacting and rounding with additional dehydration of the regrind are contained in the US patents 3,912,649, 3,956,467, 3,838,193 and 3,879,527.
- the water content the products obtained are about 18 to 20% by weight with bulk weights significantly above 500 g / l.
- EP-A-0 561 656 and EP-A-0 488 868 are compounds of alkali silicates with certain Q distributions and alkali carbonates.
- the products are made by powdered anhydrous Sodium carbonate using a sodium silicate solution (water glass solution) granulated and the products dry so that they have a certain residual water content bound to the silicate. After attempts by the applicant, such products prove relatively low absorption capacity for nonionic surfactants in the area of ⁇ 30 g nonionic surfactants per 100 g compound. In the state of the art it is not known to use such compounds to produce anionic surfactant-containing aqueous preparations.
- a method is known from international patent application WO-A-91/02047 known for producing high density extrudates, being a solid and free-flowing premix under pressure is pressed into a strand.
- the solid and free-flowing premix contains a plasticizer and / or lubricant, which causes that the premix under the pressure or the entry more specific Work softens plastically and thus becomes extrudable. After this Leaving the hole shape has no shear forces on the system more and the viscosity of the system increases so much that the extruded strand to predeterminable Extrudate dimensions can be cut.
- a common part of conventional laundry or detergent has dilatant properties; it are those used as builders and phosphate substitutes water-insoluble aluminosilicates such as zeolite.
- W0-A-94/09111 are extruded washing or cleaning agents known, which 19 wt .-% zeolite (based on anhydrous active substance) and 12.5% by weight sodium carbonate and contain 2.2% by weight of amorphous sodium silicate; however it was not known that zeolite partially from a process engineering point of view or even entirely through water-soluble inorganic Builder substances such as amorphous alkali silicates can be replaced, if they are used in a certain form.
- EP-A-651 050 describes a process for the production of granules, an amorphous silicate as essential components Anionic surfactant and another solid salt included, for example Can be sodium carbonate. This will add more salt submitted and with an aqueous "binder” Alkali metal silicate solution and anionic surfactant agglomerated.
- Sodium carbonate is one of many selectable salt components
- the alkali metal silicate and the anionic surfactant contains in weight ratios between 1: 3 and 3: 1 about the weight ratio between "binder" and salt component nothing said.
- the manufactured in the embodiments Agglomerates have sodium carbonate contents of less than 10% by weight.
- the preferred and in the exemplary embodiments in proportions of 35.5% by weight of the salt present is sodium sulfate.
- An object of the invention was to provide more water-soluble Builder substances for the partial or complete replacement of To provide zeolite in detergents or cleaning agents, whereby the dissolving behavior, in particular of heavy washing or cleaning agents should be improved.
- these should water-soluble builders also have a capacity for Liquid to waxy ingredients at processing temperature of detergents or cleaning agents.
- Another The object of the invention was extruded washing or cleaning agents and to provide a process for their production, which the water-soluble builder substances to the extent contain that on zeolite not only from an application but also partially or entirely from a procedural point of view can be dispensed with.
- Sodium and / or potassium silicate are particularly suitable here. Sodium silicates are preferred for economic reasons. However, if, for reasons of application technology, a particularly high dissolution rate in water is important, it is advisable to replace sodium at least partially with potassium.
- the composition of the alkali silicate can be chosen so that the silicate has a potassium content, calculated as K 2 O, of up to 5% by weight.
- Preferred alkali silicates are present as a compound with alkali carbonate, preferably sodium and / or potassium carbonate.
- the water content of these preferred amorphous alkali silicate compounds is advantageously between 10 and 22% by weight, in particular between 12 and 20% by weight. Water contents of 14 to 19% by weight can be particularly preferred.
- silicates can have been produced by spray drying, granulation and / or compacting, for example by roller compacting.
- Compounds containing carbonate and silicate can also be produced by spray drying, granulation and / or compaction, for example by roller compaction.
- Preferred carbonate-alkali silicate compounds are those which have a weight ratio of carbonate to silicate of 3: 1 to 1: 9 and in particular of 2.5: 1 to 1: 5.
- These commercially available alkali silicates or compounds can be granulated, for example, with aqueous solutions of anionic surfactants or with anionic surfactant acids.
- amorphous silicates which according to the above-mentioned US patents by spray drying or in granulators from the Type of turbo dryer, for example, manufactured by Vomm, Italy are suitable and quite preferred Starting materials with advantageous properties. It is at turbo granulation possible, the compounds directly on the to produce according to the invention.
- Alkali metal silicate / alkali metal carbonate compounds can be used in general proceed in such a way that in a suitable mixing unit or in a fluidized bed at least one of the components Specifies alkali metal silicate or alkali metal carbonate in powder form and by spraying an aqueous solution of an anionic surfactant, the if necessary, an additional component of the to be manufactured Contains compounds in dissolved and / or dispersed form, sprayed on.
- the anionic surfactant can be used as an alkali metal salt, for example as a sodium salt, as a surfactant acid or in partially neutralized Form are used.
- a powdery mixture from alkali metal silicate and alkali metal carbonate and this using an aqueous anionic surfactant preparation agglomerate.
- This aqueous preparation can be a real solution, an emulsion or a water-based one Trade surfactant paste.
- the method according to the invention also be carried out in the form that one is pre-educated Compound of alkali metal silicate and alkali metal carbonate with a such aqueous anionic surfactant preparation agglomerated.
- the preformed Compound of alkali metal silicate and alkali metal carbonate can for example by spray drying an aqueous solution or Suspension are obtained, which contains both components. It can however, a compound can also be used for this, which can be Agglomeration of one component in powder form with an aqueous Can get solution of the second components.
- the preferred alkali metal carbonate is sodium and / or Potassium carbonate, with sodium carbonate for economic reasons is preferred.
- the state of the art Use known mixing and agglomeration units.
- the turbo dryer described in more detail above may be mentioned or also slower rotating and preferably with mixing Built-in drums, pelletizing plates that are around rotate an axis, preferably inclined to the vertical, and a fluidized bed fluidized by a gas stream.
- Anionic surfactants that are used in the alkali silicate compounds are, above all, surfactants of the sulfonate and / or sulfate type.
- Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
- alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
- 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 16 -C 18 alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C 16 -C 18 alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize.
- the compounds therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 12 -C 14 fatty alkyl sulfates or C 12 -C 18 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates and in particular C 12 -C 16 -Fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates.
- not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
- 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 E0 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 Compounds 15 to 80% by weight alkali silicates, 1 to 20% by weight Anionic surfactants and 10 to 22 wt .-%, preferably 12 to 19 wt .-% and in particular 14 to 19 wt .-% water.
- the compounds according to the invention 15 to 50 wt .-%, preferably 20 to 40% by weight alkali silicates, 30 to 70% by weight, preferably 40 to 65% by weight of alkali carbonates, 1.5 to 15% by weight and in particular 2 to 12% by weight of anionic surfactants, advantageously Alkylbenzenesulfonates and / or alk (en) ylsulfates, and 12 to 19 % By weight of water.
- the alkali silicate compounds can also contain other ingredients of washing or cleaning agents, preferably in Amounts up to 10% by weight and especially in amounts not above 5 % By weight.
- these include, for example, neutral salts such as Sodium or potassium sulfates, but also graying inhibitors or nonionic surfactants such as alkyl polyglycosides.
- the alkali silicate compounds according to the invention have a significant one Capacity for at the usual processing temperatures liquid to waxy ingredients of washing or Detergents.
- Alkali silicate compounds can also be used without Anionic surfactant add certain amounts of liquid components; However, it has been shown that the addition of anionic surfactants increases the absorption capacity of the alkali silicate compounds and that Trickle behavior is improved.
- the anionic surfactant according to the invention have a capacity for liquid components that is at least 20% higher than that of the same quantity Alkali silicate compounds without anionic surfactants.
- Alkali silicate compounds have a capacity for liquid components that is at least 20% higher than that of the same quantity Alkali silicate compounds without anionic surfactants.
- their absorption capacity for liquid components even by at least 30% and advantageously even by at least 50%, each based on the absorption capacity of the same quantity corresponding alkali silicate compounds without anionic surfactants has been.
- alkali silicate compounds produced according to the invention are therefore claimed, which have been aftertreated with liquid components, which in the context of this invention include liquid to waxy ingredients of washing or cleaning agents.
- suitable liquid components which can be absorbed by the alkali silicate compounds according to the invention are, for example, nonionic surfactants, cationic surfactants and / or foam inhibitors such as silicone oils and paraffin oils.
- nonionic surfactants are particularly preferred, for example alkoxylated, preferably ethoxylated and / or ethoxylated and propoxylated, aliphatic C 8 -C 22 alcohols.
- 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 contain linear and methyl-branched radicals in the mixture can, as is usually present in oxo alcohol residues.
- EO ethylene oxide
- alcohol ethoxylates with linear residues from 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 also preferred.
- the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohol 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 5 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 include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- those produced according to the invention can Alkali silicate compounds with ingredients of washing or cleaning agents be treated. This can be done in a conventional manner be carried out, for example by mixing or spraying in a mixer / granulator, optionally with a subsequent one Heat treatment.
- the amorphous alkali silicate compounds with secondary washing ability can be added as a component to powdery to granular Detergents or cleaning agents or as a component in the manufacture the granular washing or cleaning agents, preferably for granulation and / or compacting.
- Each the bulk weights of the Alkali silicate compounds between approximately 300 and, for example, 950 g / l vary. With continuous production, bulk weights can up to 1150 g / l can be achieved.
- the washing according to the invention or cleaning agents can have a bulk density between 300 and 1200 g / l, preferably from 500 to 1000 g / l, and preferably contain the alkali silicate compounds according to the invention in amounts of 5 to 50% by weight, in particular in amounts of 10 up to 40% by weight.
- They can be produced by any of the known processes like mixing, granulating, compacting like Roll compacting and extrusion take place. Are particularly suitable processes in which several sub-components, for example spray-dried components and granulated and / or extruded components are mixed together.
- Retrofitting components for example with nonionic surfactants, especially ethoxylated fatty alcohols, be applied according to the usual procedures.
- nonionic surfactants especially ethoxylated fatty alcohols
- further anionic surfactants in the form of a spray-dried, granulated or extruded compounds either as Additive component in the process or as an additive subsequently use other granules.
- finely divided zeolites, Silicas, amorphous silicates, fatty acids or fatty acid salts for example calcium stearate, but especially mixtures of Zeolite and silica, especially in the zeolite weight ratio to silica of at least 1: 1, or zeolite and calcium stearate particularly preferred.
- Particularly preferred embodiments of the invention are extruded washing or cleaning agents with a bulk weight above 600 g / l, which are anionic and optionally nonionic Surfactants and an amorphous alkali silicate compound Type according to the invention contained in the extrudate.
- this extruded detergent or cleaning agent is on the known methods of extrusion, especially on the international Patent application WO-A-91/02047.
- the finished detergents or cleaning agents can also be used now contain the following ingredients.
- surfactants especially anionic surfactants as well optionally non-ionic surfactants, but also cationic, amphoteric or zwitterionic surfactants.
- the anionic surfactants of the sulfonate type include those already mentioned above Alkyl benzene sulfonates, olefin sulfonates and alkane sulfonates into consideration.
- the esters of ⁇ -sulfofatty acids are also suitable (Ester sulfonates), e.g. the ⁇ -sulfonated methyl esters hydrogenated coconut, palm kernel or tallow fatty acids.
- Further suitable anionic surfactants are those by ester cleavage of the ⁇ -sulfofatty acid alkyl esters available ⁇ -sulfo fatty acids or their Di salts.
- the mono-salts of the ⁇ -sulfofatty acid alkyl esters fall even in their industrial production as an aqueous mixture with limited amounts of di-salts.
- the disalt content of such Surfactants is usually less than 50% by weight of the anionic surfactant mixture, for example up to about 30% by weight.
- Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which represent mono-, di- and triesters and their mixtures, as in the manufacture by esterification through a Monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of Triglycerides with 0.3 to 2 moles of glycerin can be obtained.
- Suitable surfactants of the sulfate type are the aforementioned sulfuric acid monoesters from primary alcohols of natural and synthetic origin and, if appropriate, their alkoxylated, preferably ethoxylated, derivatives.
- 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 are nonionic surfactants in themselves. 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.
- the agents can also contain soaps, preferably contained in amounts of 0.2 to 5 wt .-%.
- soaps preferably contained in amounts of 0.2 to 5 wt .-%.
- Suitable are saturated fatty acid soaps, like the salts 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 anionic surfactants and soaps can be in the form of their sodium, Potassium or ammonium salts as well as organic organic salts Bases, such as mono-, di- or triethanolamine, are present.
- the anionic surfactants in the form of their sodium or potassium salts, especially in the form of the sodium salts.
- detergents or cleaning agents in particular extruded washing or cleaning agents preferred, which contain 10 to 30 wt .-% anionic surfactants.
- sulfate surfactants are in the means - based on the total anionic surfactants - at least 15% by weight, in particular Contain 20 to 100 wt .-% sulfate surfactants.
- Preferred nonionic surfactants are those already described above alkoxylated, advantageously ethoxylated alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) used per mole of alcohol.
- EO ethylene oxide
- 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.
- 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 be suitable.
- the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of them.
- 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 known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- Nonionic surfactants are preferred in the agents according to the invention in quantities of 0.5 to 15% by weight, in particular in quantities contain from 2 to 10 wt .-%.
- the compositions can also contain further, additional builder substances and cobuilders.
- customary builder substances such as phosphates, zeolites and crystalline layered silicates can be contained in the agents.
- the synthetic zeolite used is preferably finely crystalline and contains bound water. Zeolite A, for example, but also zeolite X and zeolite P and mixtures of A, X and / or P are suitable.
- the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
- the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. It is also possible to use zeolite suspensions and zeolite powder. Suitable zeolite powders have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. Zeolite can be contained in the washing or cleaning agents in amounts of up to about 40% by weight (based on anhydrous active substances).
- Washing or cleaning agents 10 to 16 wt .-% zeolite (based on anhydrous active substance) and 10 to 30 wt .-% of one Alkali silicate compounds produced according to the invention.
- the detergents or cleaning agents contain 0 to 5 % By weight of zeolite (based on anhydrous active substance) and 15 to 40% by weight of an alkali silicate compound produced according to the invention. It is possible that the zeolite not only is coextruded, but that the zeolite is partially or wholly subsequently, ie after the extrusion step into the washing or Detergent is introduced. Are particularly preferred here Detergents or cleaning agents that contain an extrudate that in the Inside of the extrudate grain is free of zeolite.
- Crystalline can also be used as substitutes for the zeolite Layered silicates and / or conventional phosphates are used. However, it is preferred that phosphates only in small amounts, in particular up to a maximum of 10% by weight in the washing or cleaning agents are included.
- Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
- Preferred crystalline phyllosilicates of the formula given are those in which M is sodium and x is 2 or 3.
- both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred.
- these crystalline layered silicates are preferably only contained in the extrudates according to the invention in amounts of not more than 10% by weight, in particular less than 8% by weight, advantageously not more than 5% by weight.
- Polymeric polycarboxylates for example, can be used as cobuilders become.
- Suitable polymeric polycarboxylates are, for example the sodium salts of polyacrylic acid or Polymethacrylic acid, for example those with a molecular weight from 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, which 50 to 90 wt .-% Contain acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molecular mass, based on free acids, is generally 5000 to 200000, preferably 10000 to 120000 and in particular 50,000 to 100,000.
- Terpolymers are also particularly preferred, for example those according to DE-A-43 00 772 as monomers Salts acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomers Salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar Derivatives included.
- organic cobuilders are preferably in the form their sodium salts used polycarboxylic acids, such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use cannot be objected to for ecological reasons is, and mixtures of 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 of this.
- Suitable builder systems are oxidation products from carboxyl-containing polyglucosans and / or their water-soluble salts, such as those found in international Patent application WO-A-93/08251 can be described or their Manufacturing, for example, in the international patent application WO-A-93/16110.
- polyacetals which by Reaction of dialdehydes with polyol carboxylic acids, which 5 to 7 C atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223 can be obtained.
- Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde as well their mixtures and from polyol carboxylic acids such as gluconic acid and / or Obtain glucoheptonic acid.
- cobuilders can be used in amounts of, for example, 0.5 to 20 % By weight, preferably from 2 to 15% by weight in the finished washing or cleaning agents.
- the agents can also contain components which Oil and fat washability from textiles have a positive impact. This effect is particularly evident when a textile is dirty is that previously several times with an inventive Detergent containing this oil and fat-dissolving component is washed becomes.
- nonionic cellulose ethers such as Methyl cellulose and methyl hydroxypropyl cellulose with a proportion on methoxyl groups from 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ether, as well as the polymers known from the prior art phthalic acid and / or terephthalic acid or their Derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these.
- the agents can also contain components which have solubility especially the heavy granules.
- Such components and the introduction of such components are, for example, in the international patent application WO-A-93/02176 and in German patent application DE-A-42 03 031.
- the preferred ingredients include in particular fatty alcohols with 20 to 80 moles Ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol 30 E0 and tallow fatty alcohol with 40 E0, but also fatty alcohols with 14 E0 and polyethylene glycols with a molecular weight between 200 and 2000.
- Sodium perborate monohydrate is of particular importance among the compounds which serve as bleaching agents and produce H 2 O 2 in water.
- Further bleaching agents which can be used are, for example, sodium perborate tetrahydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
- the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used.
- Percarbonate is also preferred as an ingredient. However, percarbonate is preferably not co-extruded, but optionally mixed in subsequently.
- bleach activators can be incorporated into the preparations.
- these are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
- Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239.
- the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
- Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
- TAED N, N, N ', N'-tetraacetylethylene diamine
- DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine
- SORMAN acetylated sorbitol-mannitol mixtures
- 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.
- Enzymes come from the class of proteases, lipases, Amylases, cellulases or their mixtures in question. Particularly good are suitable from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola Insolens obtained enzymatic agents. Preferably be Subtilisin-type proteases, and in particular proteases derived from Bacillus lentus are used.
- enzyme mixtures for example from protease and amylase or protease and Lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and Cellulase, but especially protease and / or lipase-containing Mixtures of special interest.
- peroxidases or oxidases have proven to be suitable in some cases.
- the enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition.
- enzyme mixtures or enzyme granules can, for example about 0.1 to 5% by weight, preferably 0.1 to about 2 % By weight.
- HEDP 1-hydroxyethane-1,1-diphosphonic acid
- DETPMP Diethylenetriaminepentamethylenephosphonic acid
- Ethylenediaminetetramethylenephosphonic acid especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP), Diethylenetriaminepentamethylenephosphonic acid (DETPMP) or Ethylenediaminetetramethylenephosphonic acid into consideration.
- the agents can also contain further enzyme stabilizers.
- enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
- boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
- Graying inhibitors have the task of removing the fiber To keep dirt suspended in the fleet and so that To prevent graying.
- Water-soluble colloids are usually used for this suitable for organic nature, for example the water-soluble salts of polymer Carboxylic acids, glue, gelatin, salts of ether carboxylic acids or Starch or cellulose or salts of ether sulfonic acids acidic sulfuric acid esters of cellulose or starch. Also water-soluble polyamides containing acid groups are for this Suitable purpose. Soluble starch preparations and use starch products other than the above, e.g. degraded Starch, aldehyde starches etc. Polyvinylpyrrolidone is also useful.
- cellulose ethers such as Carboxymethyl cellulose (sodium salt), methyl cellulose, Hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, Methylcarboxymethylcellulose and their mixtures, as well Polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the funds used.
- the agents can be used as optical brighteners Contain diaminostilbenedisulfonic acid or its 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, an anilino group or a 2-methoxyethylamino group carry. Brighteners of the type of the substituted diphenyl styrenes, e.g.
- the alkali salts 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl.
- Mixtures of the aforementioned Brighteners can be used.
- the agent can add other inorganic salts, too further amorphous alkali silicates of the type described above and Alkali carbonates and / or alkali hydrogen carbonates of those described above Kind included.
- Other inorganic salts, which as Ingredients to be considered are neutral salts such as sulfates and optionally also chlorides in the form of their sodium and / or potassium salts.
- Example 1 Preparation of alkali silicate / alkali carbonate compounds containing anionic surfactants
- the alkali silicate compounds B1 to B4 according to the invention were obtained in different ways.
- the composition of the compounds was as follows: B1 B2 B3 B4 amorphous sodium disilicate 28.1 28.1 28.1 28.1 sodium 53.4 53.4 53.4 53.4 C 12 -C 18 alkyl sulfate (sodium salt) 3.0 ---- ---- ----- C 12 alkyl benzene sulfonate (sodium salt) ---- 3.0 3.0 3.0 water 15.5 15.5 15.5 15.5 15.5 15.5 15.5
- the sample to be examined is evenly distributed on an aluminum weighing pan and dried from above by infrared heating.
- the drying temperature is controlled by a thermal sensor near the heating coil and is around 130 ° C.
- the exact drying temperature and the required drying time must be determined by calibration. With this determination method, only the water that can be evaporated up to a temperature of about 130 ° C. is recorded, but not the water chemically bound to the amorphous silicate, for the elimination of which higher temperatures are required.
- product B1 53.4 parts by weight were in the mixing unit calcined soda and 27.5 parts by weight of sodium silicate and mixed for a period of 2 minutes. Subsequently 5.5 parts by weight of an aqueous paste of Alkylbenzenesulfonate (solids content 55% by weight) and 13.6 Parts by weight of the water glass solution used for product B1 are metered in. The mixture was then mixed for 2 minutes.
- the products had the following bulk densities (g / l): B1 809, B2 465, B3 704 and B4 719.
- the absorption capacity of the alkali silicate compounds B1 to B4 according to the invention was compared to the reference compound Nabion R 15, surfactant-free soda / silicate compound from Rhône-Poulenc, which is believed to have been produced in accordance with EP-A-488 868, tested with the nonionic surfactant C 12 -C 18 fatty alcohol with 7 E0.
- the nonionic surfactant absorption capacity was determined in accordance with DIN ISO 787, the above-mentioned nonionic surfactant being used instead of the linseed oil specified there. For this determination, a weighed amount of sample is placed on a plate. Slowly add 4 or 5 drops of nonionic surfactant from a burette.
- the nonionic surfactant is rubbed into the powder with a spatula.
- the addition of the nonionic surfactant continues accordingly until aggregations of nonionic surfactant and powder have formed. From this point on, a drop of nonionic surfactant is added and rubbed with the spatula.
- the non-ionic surfactant addition is stopped when a soft paste has formed. This paste should just be able to spread without tearing or crumbling and just stick to the plate.
- the amount of nonionic surfactant added is read off the burette and converted to ml nonionic surfactant per 100 g sample. The following results were obtained: ml nonionic surfactant per 100 g carrier B1 75 B2 80 B3 97 B4 70 Nabion R 15 ⁇ 30
- extrudates E5 to E8 were produced in accordance with the teaching of international patent application WO-A-91/02047.
- the extrusion mixtures of agents E5 to E8 could be extruded without any process problems.
- the compositions of the extrudates were as listed in Table 1.
- the bulk density of the extrudates was between 800 and 830 g / l.
- the extrudates according to the invention showed good dissolving behavior: only small residues were obtained in the flushing-in behavior and in the solubility test.
- compositions from E5 to E8 (in% by weight): E5 E6 E7 E8 C 9 -C 13 alkylbenzenesulfonate 11.5 11.5 11.5 11.5 C 12 -C 18 alkyl sulfate 10.5 10.5 10.5 10.5 C 12 -C 18 alcohol with 7 EO 4.0 4.0 4.0 C 12 -C 18 fatty acid soap 1.0 1.0 1.0 1.0 1.0 Polyethylene glycol with a molecular weight of 400 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Zeolite (anhydrous active substance) 19.0 19.0 19.0 19.0 Acrylic acid-maleic acid copolymer (sodium salt) 6.0 6.0 6.0 6.0 Alkali silicate compound B1 14.0 ---- ---- ---- Alkali silicate compound B2 --- 14.0 ---- ---- Alkali silicate compound B3 --- ---- 14.0 ---- Alkali silicate
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung eines tensidhaltigen amorphen Alkalisilicat/Alkalicarbonat-Compounds mit Sekundärwaschvermögen, das als wasserlösliche Buildersubstanz in Wasch- oder Reinigungsmitteln eingesetzt werden kann, sowie die Verwendung derartiger Alkalisilicat-Compounds in Wasch- oder Reinigungsmitteln, extrudierte Wasch- oder Reinigungsmittel sowie ein Verfahren zu ihrer Herstellung.The invention relates to a method for producing a amorphous alkali silicate / alkali carbonate compounds containing surfactants Secondary washing ability, which as a water-soluble builder in Detergents or cleaning agents can be used, as well as the Use of such alkali silicate compounds in washing or cleaning agents, extruded detergents or cleaning agents and a Process for their production.
Moderne, verdichtete Wasch- oder Reinigungsmittel weisen allgemein den Nachteil auf, daß sie aufgrund ihrer kompakten Struktur ein schlechteres Löseverhalten in wäßriger Flotte zeigen als beispielsweise leichtere sprühgetrocknete Wasch- oder Reinigungsmittel des Standes der Technik. Dabei tendieren Wasch- oder Reinigungs-mittel im allgemeinen zu einer um so schlechteren Lösegeschwindigkeit in Wasser, je höher ihr Verdichtungsgrad ist. Zeolithe, die in Wasch- oder Reinigungsmitteln als Buildersubstanzen üblicherweise enthalten sind, können aufgrund ihrer Wasserunlöslichkeit zusätzlich zu dem verschlechterten Löseverhalten beitragen.Modern, compacted detergents or cleaning agents generally have the disadvantage that they are due to their compact structure show poorer dissolving behavior in aqueous liquor than, for example lighter spray-dried washing or cleaning agents the state of the art. Detergents or cleaning agents tend to do this generally at a slower dissolving rate in water, the higher their degree of compaction. Zeolites in Washing or cleaning agents are usually used as builder substances may be included due to their water insolubility contribute to the deterioration in dissolving behavior.
Eine wasserlösliche Alternative für den Zeolith stellen amorphe Alkalisilicate mit Sekundärwaschvermögen dar. A water-soluble alternative for the zeolite are amorphous Alkali silicates with secondary washing ability.
Durch Sprüh- oder Walzentrocknung von Wasserglas lösungen lassen sich bekanntermaßen hydratisierte wasserlösliche Silicate in Pulverform erhalten, die noch etwa 20 Gew.-% Wasser enthalten (vgl. Ullmanns Enzyclopädie der technischen Chemie, 4. Auflage 1982, Band 21, Seite 412). Solche Produkte sind für verschiedene Zwecke im Handel. Derartige Pulver weisen aufgrund der Sprühtrocknung eine sehr lockere Struktur auf; ihre Schüttgewichte liegen im allgemeinen deutlich unter 700 g/l.Allow solutions by spray or roller drying water glass known to be hydrated water-soluble silicates in powder form obtained, which still contain about 20 wt .-% water (cf. Ullmann's Encyclopedia of Technical Chemistry, 4th edition 1982, volume 21, page 412). Such products are used for different purposes Trade. Such powders have a due to the spray drying very loose structure; their bulk weights are generally well below 700 g / l.
Alkalisilicate in granularer Form mit höheren Schüttgewichten können gemäß der Lehre der europäischen Patentanmeldung EP-A-0 526 978 erhalten werden, wobei man eine Alkalisilicat-Lösung mit einem Feststoffgehalt zwischen 30 und 53 Gew.-% in eine beheizte Trommel einbringt, in deren Längsachse eine Welle mit einer Vielzahl von nahe an die Innenfläche der Trommel reichenden Armen rotiert, wobei die Trommelwand eine Temperatur zwischen 150 und 200 °C aufweist und der Trockenvorgang durch ein in die Trommel eingespeistes Gas mit einer Temperatur zwischen 175 und etwa 250 °C unterstützt wird. Nach diesem Verfahren wird ein Produkt erhalten, dessen mittlere Teilchengröße im Bereich zwischen 0,2 und 2 mm liegt. Ein bevorzugtes Trocknungsgas ist beheizte Luft.Alkali silicates in granular form with higher bulk densities can according to the teaching of European patent application EP-A-0 526 978 can be obtained, using an alkali silicate solution with a Solids content between 30 and 53 wt .-% in a heated drum brings in the longitudinal axis of a shaft with a variety of arms rotating close to the inner surface of the drum, wherein the drum wall has a temperature between 150 and 200 ° C and the drying process by a gas fed into the drum is supported with a temperature between 175 and about 250 ° C. According to this process, a product is obtained, the middle one Particle size is in the range between 0.2 and 2 mm. A preferred one Drying gas is heated air.
Die europäische Patentanmeldung EP-A-0 542 131 beschreibt ein Verfahren, bei dem man ein in Wasser bei Raumtemperatur vollständig lösliches Produkt mit einem Schüttgewicht zwischen 500 und 1200 g/l erhält. Die Trocknung erfolgt vorzugsweise unter Verwendung von erhitzter Luft. Auch hierbei wird mit einem zylindrischen Trockner mit beheizter Wand (160 bis 200 °C) gearbeitet, in dessen Längsachse ein Rotor mit schaufelförmigen Blättern sich mit einer derartigen Geschwindigkeit dreht, daß aus der Silicatlösung mit einem Feststoffgehalt zwischen 40 und 60 Gew.-% eine pseudoplastische Masse mit einem freien Wassergehalt zwischen 5 und 12 Gew.-% entsteht. Die Trocknung wird durch einen heißen Luftstrom (220 bis 260°C) unterstützt.European patent application EP-A-0 542 131 describes a process in which a product which is completely soluble in water at room temperature and has a bulk density of between 500 and 1200 g / l is obtained. Drying is preferably carried out using heated air. Here, too, a cylindrical dryer with a heated wall (160 to 200 ° C.) is used, in the longitudinal axis of which a rotor with blade-shaped blades rotates at such a speed that the silicate solution has a solids content of between 40 and 60% by weight pseudoplastic mass with a free water content between 5 and 12 wt .-% arises. Drying is supported by a hot air stream (220 to 260 ° C).
Die ältere, nicht vorveröffentlichte Anmeldung P 44 19 745.4 beschreibt ebenfalls ein wasserlösliches, amorphes und granulares Alkalisilicat, welches auf ähnliche Weise wie in der EP-A-0 526 978 beschrieben hergestellt wird, jedoch kieselsäurehaltig ist. Mit dem Begriff "amorph" ist "röntgenamorph" gemeint. Dies bedeutet, daß die Alkalisilicate bei Röntgenbeugungsaufnahmen keine scharfen Reflexe liefern, sondern allenfalls eine oder mehrere breite Maxima, deren Breite mehrere Gradeinheiten des Beugungswinkels beträgt. Damit ist jedoch nicht ausgeschlossen, daß bei Elektronenbeugungsexperimenten Bereiche gefunden werden, die scharfe Elektronenbeugungsreflexe liefern. Dies ist so zu interpretieren, daß die Substanz mikrokristalline Bereiche in einer Größenordnung bis zu ca. 20 nm (max. 50 nm) aufweist.The older, unpublished application P 44 19 745.4 describes also a water-soluble, amorphous and granular Alkali silicate, which in a similar manner as in EP-A-0 526 978 described is produced, but is siliceous. With the The term "amorphous" means "X-ray amorphous". This means that the alkali silicates have no sharp reflections in X-ray diffraction deliver, but at most one or more broad maxima, the width of which is several degree units of the diffraction angle. However, this does not rule out the fact that in electron diffraction experiments Areas are found that have sharp electron diffraction reflections deliver. This is to be interpreted as the substance microcrystalline areas on the order of up to approx. 20 nm (max. 50 nm).
Granulare amorphe Natriumsilicate, welche durch Sprühtrockung wäßriger Wasserglas lösungen, anschließendes Mahlen und nachfolgendes Verdichten und Abrunden unter zusätzlichem Wasserentzug des Mahlgutes erhalten werden, sind Inhalt der US-amerikanischen Patentschriften 3,912,649, 3,956,467, 3,838,193 und 3,879,527. Der Wassergehalt der erhaltenen Produkte liegt bei etwa 18 bis 20 Gew.-% bei Schüttgewichten deutlich oberhalb 500 g/l.Granular amorphous sodium silicates, which by spray drying aqueous Water glass solutions, subsequent grinding and subsequent Compacting and rounding with additional dehydration of the regrind are contained in the US patents 3,912,649, 3,956,467, 3,838,193 and 3,879,527. The water content the products obtained are about 18 to 20% by weight with bulk weights significantly above 500 g / l.
Weitere granulare Alkalisilicate mit Sekundärwaschvermögen sind aus den europäische Patentanmeldungen EP-A-0 561 656 und EP-A-0 488 868 bekannt. Es handelt sich hierbei um Compounds von Alkalisilicaten mit bestimmten Q-Verteilungen und Alkalicarbonaten. Die Produkte werden dadurch hergestellt, daß man pulverförmiges wasserfreies Natriumcarbonat unter Verwendung einer Natriumsilicatlösung (Wasserglaslösung) granuliert und die Produkte derart trocknet, daß sie einen bestimmten an das Silicat gebundenen Restwassergehalt aufweisen. Nach Versuchen der Anmelderin weisen derartige Produkte ein verhältnismäßig geringes Aufnahmevermögen für Niotenside im Bereich von < 30 g Niotenside pro 100 g Compound auf. Im Stand der Technik ist es nicht bekannt, derartige Compounds unter Verwendung aniontensidhaltiger wäßriger Zubereitungen herzustellen.Other granular alkali silicates with secondary washing ability are out European patent applications EP-A-0 561 656 and EP-A-0 488 868 known. These are compounds of alkali silicates with certain Q distributions and alkali carbonates. The products are made by powdered anhydrous Sodium carbonate using a sodium silicate solution (water glass solution) granulated and the products dry so that they have a certain residual water content bound to the silicate. After attempts by the applicant, such products prove relatively low absorption capacity for nonionic surfactants in the area of <30 g nonionic surfactants per 100 g compound. In the state of the art it is not known to use such compounds to produce anionic surfactant-containing aqueous preparations.
Aus der internationalen Patentanmeldung WO-A-91/02047 ist ein Verfahren zur Herstellung von Extrudaten mit hoher Dichte bekannt, wobei ein festes und rieselfähiges Vorgemisch unter Druck strangförmig verpreßt wird. Das feste und rieselfähige Vorgemisch enthält ein Plastifizier- und/oder Gleitmittel, welches bewirkt, daß das Vorgemisch unter dem Druck bzw. dem Eintrag spezifischer Arbeit plastisch erweicht und damit extrudierbar wird. Nach dem Austritt aus der Lochform wirken auf das System keine Scherkräfte mehr ein und die Viskosität des Systems steigt dadurch derart an, daß der extrudierte Strang auf vorherbestimmbare Extrudatdimensionen geschnitten werden kann. Aus der internationalen Patentanmeldung WO-A-94/09111 ist nun bekannt, daß in dem zu extrudierenden Vorgemisch sowohl Bestandteile, welche ein strukturviskoses Verhalten aufweisen, als auch Bestandteile, welche dilatante Eigenschaften besitzen, enthalten sein müssen. Lägen nur strukturviskos wirkende Bestandteile in dem Vorgemisch vor, so würde es aufgrund des starken Schergefälles derart erweichen, ja nahezu flüssig werden, daß der Strang nach dem Austritt aus der Lochform nicht mehr schneidfähig wäre. Es werden daher auch dilatant wirkende Bestandteile eingesetzt, welche bei steigendem Schergefälle eine steigende Plastizität aufweisen und dadurch die Schneidfähigkeit des extrudierten Stranges sicherstellen. Die meisten Inhaltsstoffe von Wasch- oder Reinigungsmitteln zeigen ein strukturviskoses Verhalten. Ein dilatantes Verhalten stellt eher die Ausnahme dar. Ein üblicher Bestandteil von herkömmlichen Wasch- oder Reinigungsmittel besitzt jedoch dilatante Eigenschaften; es sind die als Buildersubstanz und Phosphatersatz eingesetzten wasserunlöslichen Alumosilicate wie Zeolith. Aus der internationalen Patentanmeldung W0-A-94/09111 sind zwar extrudierte Wasch- oder Reinigungs-mittel bekannt, welche 19 Gew.-% Zeolith (bezogen auf wasserfreie Aktivsubstanz) sowie 12,5 Gew.-% Natriumcarbonat und 2,2 Gew.-% amorphes Natriumsilicat enthalten; es war jedoch nicht bekannt, daß Zeolith aus verfahrenstechnischer Sicht teilweise oder sogar ganz durch wasserlösliche anorganische Buildersubstanzen wie amorphe Alkalisilicate ersetzt werden kann, wenn diese in bestimmter Form eingesetzt werden.A method is known from international patent application WO-A-91/02047 known for producing high density extrudates, being a solid and free-flowing premix under pressure is pressed into a strand. The solid and free-flowing premix contains a plasticizer and / or lubricant, which causes that the premix under the pressure or the entry more specific Work softens plastically and thus becomes extrudable. After this Leaving the hole shape has no shear forces on the system more and the viscosity of the system increases so much that the extruded strand to predeterminable Extrudate dimensions can be cut. From the international Patent application WO-A-94/09111 is now known to in the extruding premix both ingredients which a have pseudoplastic behavior, as well as components that have dilatant properties, must be included. Just lay Components with a pseudoplastic action in the premix, see above it would soften like that because of the strong shear gradient, yes become almost liquid that the strand after exiting the Hole shape would no longer be able to be cut. Therefore, it will also dilating ingredients used, which with increasing Shear gradients have an increasing plasticity and thus the Ensure the cutting ability of the extruded strand. Most Ingredients of washing or cleaning agents show a pseudoplastic behavior. A dilatante behavior is more likely the exception. A common part of conventional laundry or detergent has dilatant properties; it are those used as builders and phosphate substitutes water-insoluble aluminosilicates such as zeolite. From the international Patent application W0-A-94/09111 are extruded washing or cleaning agents known, which 19 wt .-% zeolite (based on anhydrous active substance) and 12.5% by weight sodium carbonate and contain 2.2% by weight of amorphous sodium silicate; however it was not known that zeolite partially from a process engineering point of view or even entirely through water-soluble inorganic Builder substances such as amorphous alkali silicates can be replaced, if they are used in a certain form.
Aus der deutschen Patentanmeldung Aktenzeichen 195 01 269.0 sind amorphe Alkalisilicat-Compounds mit Sekundärwaschvermögen und einem Molverhältnis M2O : SiO2 (M = Alkalimetall) zwischen 1 : 1,5 und 1 : 3,3 bekannt, die anionische Tenside, bevorzugt Alkylbenzolsulfonate und/oder Alk(en)ylsulfate, enthalten. In einer bevorzugten Ausführungsform enthalten diese Compounds zusätzlich 30 bis 70 Gew.-% Alkalicarbonat. Sie werden durch Sprühtrocknung einer wäßrigen Aufschlämmung, welche sämtliche Bestandteile des Alkalisilicat-Compounds enthält, hergestellt.Amorphous alkali silicate compounds with secondary washing power and a molar ratio M 2 O: SiO 2 (M = alkali metal) between 1: 1.5 and 1: 3.3 are known from German patent application Aktenzeichen 195 01 269.0, which are anionic surfactants, preferably alkylbenzenesulfonates and / or alk (en) yl sulfates. In a preferred embodiment, these compounds additionally contain 30 to 70% by weight of alkali carbonate. They are produced by spray drying an aqueous slurry which contains all the constituents of the alkali silicate compound.
Die EP-A-651 050 beschreibt ein Verfahren zur Herstellung von Granulaten, die als essentielle Komponenten ein amorphes Silicat, ein Aniontensid sowie ein weiteres festes Salz enthalten, das beispielsweise Natriumcarbonat sein kann. Dabei wird das weitere Salz vorgelegt und mit einem wäßrigen "Binder" aus Alkalimetallsilicatlösung und Aniontensid agglomeriert. Natriumcarbonat stellt eine von vielen wählbaren Salzkomponenten dar. Während der Binder das Alkalimetallsilicat und das Aniontensid in Gewichtsverhältnissen zwischen 1 : 3 und 3 : 1 enthält, wird über das Gewichtsverhältnis zwischen "Binder" und Salzkomponente nichts ausgesagt. Die in den Ausführungsbeispielen hergestellten Agglomerate weisen Natriumcarbonatgehalte von unter 10 Gew.-% auf. Das bevorzugte und in den Ausführungsbeispielen in Anteilen von 35,5 Gew.-% anwesende Salz ist Natriumsulfat.EP-A-651 050 describes a process for the production of granules, an amorphous silicate as essential components Anionic surfactant and another solid salt included, for example Can be sodium carbonate. This will add more salt submitted and with an aqueous "binder" Alkali metal silicate solution and anionic surfactant agglomerated. Sodium carbonate is one of many selectable salt components During the binder, the alkali metal silicate and the anionic surfactant contains in weight ratios between 1: 3 and 3: 1 about the weight ratio between "binder" and salt component nothing said. The manufactured in the embodiments Agglomerates have sodium carbonate contents of less than 10% by weight. The preferred and in the exemplary embodiments in proportions of 35.5% by weight of the salt present is sodium sulfate.
Eine Aufgabe der Erfindung bestand darin, weitere wasserlösliche Buildersubstanzen für den teilweisen oder vollständigen Ersatz von Zeolith in Wasch- oder Reinigungsmitteln bereitzustellen, wodurch das Löseverhalten insbesondere von schweren Wasch- oder Reinigungsmitteln verbessert werden sollte. Zusätzlich sollten diese wasserlöslichen Buildersubstanzen auch eine Aufnahmekapazität für bei der Verarbeitungstemperatur flüssige bis wachsartige Inhaltsstoffe von Wasch- oder Reinigungsmitteln besitzen. Eine weitere Aufgabe der Erfindung bestand darin, extrudierte Wasch- oder Reinigungsmittel sowie ein Verfahren zu ihrer Herstellung bereitzustellen, welche die wasserlöslichen Buildersubstanzen in dem Maße enthalten, daß auf Zeolith nicht nur aus anwendungstechnischer sondern auch aus verfahrenstechnischer Sicht teilweise oder ganz verzichtet werden kann.An object of the invention was to provide more water-soluble Builder substances for the partial or complete replacement of To provide zeolite in detergents or cleaning agents, whereby the dissolving behavior, in particular of heavy washing or cleaning agents should be improved. In addition, these should water-soluble builders also have a capacity for Liquid to waxy ingredients at processing temperature of detergents or cleaning agents. Another The object of the invention was extruded washing or cleaning agents and to provide a process for their production, which the water-soluble builder substances to the extent contain that on zeolite not only from an application but also partially or entirely from a procedural point of view can be dispensed with.
Gegenstand der Erfindung ist dementsprechend ein Verfahren zur Herstellung eines aniontensidhaltigen Alkalimetallsilicat/Alkalimetallcarbonat-Compounds mit Sekundärwaschvermögen, wobei das Alkalimetallsilicat röntgenamorph ist und ein Molverhältnis M2O : SiO2 (M = Alkalimetall) zwischen 1 : 1,5 und 1 : 3,3 aufweist und wobei das Compound 15 bis 50 Gew.-% Alkalimetallsilicat, 30 bis 70 Gew.-% Alkalimetallcarbonat, 1,5 bis 15 Gew.-% Aniontenside und 12 bis 19 Gew.-% Wasser enthält, dadurch gekennzeichnet, daß man eine pulverförmige Komponente ausgewählt aus Alkalimetallcarbonat, Alkalimetallsilicat oder einer Mischung hiervon unter Verwendung einer wäßrigen Zubereitung agglomeriert, die eines oder mehrere Aniontenside und erforderlichenfalls diejenige Komponente des herzustellenden Compounds enthält, die nicht in Pulverform vorgelegt wird. Unter "Alkalimetallcarbonat" werden dabei Salze der Kohlensäure verstanden, bei denen ein bis zwei Wasserstoffionen durch Alkalimetallionen ersetzt sind. Beispiele sind eigentliche Carbonate M2CO3 (M = Alkalimetall), Hydrogencarbonate MHCO3 und gemischte Carbonate wie beispielsweise Trona, Na3H(CO3)2 · 2 H2O.The invention accordingly relates to a process for the preparation of an alkali metal silicate / alkali metal carbonate compound containing anionic surfactants with secondary washing power, the alkali metal silicate being X-ray amorphous and a molar ratio M 2 O: SiO 2 (M = alkali metal) between 1: 1.5 and 1: 3.3 and wherein the compound contains 15 to 50 wt .-% alkali metal silicate, 30 to 70 wt .-% alkali metal carbonate, 1.5 to 15 wt .-% anionic surfactants and 12 to 19 wt .-% water, characterized in that one powdery component selected from alkali metal carbonate, alkali metal silicate or a mixture thereof agglomerated using an aqueous preparation which contains one or more anionic surfactants and, if necessary, the component of the compound to be prepared which is not presented in powder form. "Alkali metal carbonate" is understood to mean carbonic acid salts in which one or two hydrogen ions have been replaced by alkali metal ions. Examples are actual carbonates M 2 CO 3 (M = alkali metal), bicarbonates MHCO 3 and mixed carbonates such as Trona, Na 3 H (CO 3 ) 2 .2 H 2 O.
Dabei bedeuten hier und im folgenden die Begriffe "Pulverform" bzw. "pulverförmig", daß die Substanzen in fester, rieselförmiger Form vorliegen und mindestens 90 Gew.-% der Teilchen einen Teilchendurchmesser von 1 mm oder darunter aufweisen.Here and below, the terms "powder form" or "Powdery" that the substances in solid, free-flowing form are present and at least 90% by weight of the particles have a particle diameter of 1 mm or less.
Bevorzugte amorphe Alkalisilicate weisen ein Molverhältnis M2O : SiO2 (M = Alkalimetall) zwischen 1:1,9 und 1:3, insbesondere bis 1:2,5 auf. Hierbei kommen insbesondere Natrium- und/oder Kaliumsilicat in Betracht. Aus ökonomischen Gründen sind die Natriumsilicate bevorzugt. Legt man aus anwendungstechnischen Gründen jedoch auf eine besonders hohe Lösegeschwindigkeit in Wasser Wert, so empfiehlt es sich, Natrium mindestens anteilsweise durch Kalium zu ersetzen. Beispielsweise kann die Zusammensetzung des Alkalisilicats so gewählt werden, daß das Silicat einen Kalium-Gehalt, berechnet als K2O, von bis zu 5 Gew.-% aufweist. Bevorzugte Alkalisilicate liegen als Compound mit Alkalicarbonat, vorzugsweise Natrium- und/oder Kaliumcarbonat, vor. Der Wassergehalt dieser bevorzugten amorphen Alkali-silicat-Compounds, liegt vorteilhafterweise zwischen 10 und 22 Gew.-%, insbesondere zwischen 12 und 20 Gew.-%. Dabei können Wassergehalte von 14 bis 19 Gew.-% besonders bevorzugt sein.Preferred amorphous alkali silicates have a molar ratio M 2 O: SiO 2 (M = alkali metal) between 1: 1.9 and 1: 3, in particular up to 1: 2.5. Sodium and / or potassium silicate are particularly suitable here. Sodium silicates are preferred for economic reasons. However, if, for reasons of application technology, a particularly high dissolution rate in water is important, it is advisable to replace sodium at least partially with potassium. For example, the composition of the alkali silicate can be chosen so that the silicate has a potassium content, calculated as K 2 O, of up to 5% by weight. Preferred alkali silicates are present as a compound with alkali carbonate, preferably sodium and / or potassium carbonate. The water content of these preferred amorphous alkali silicate compounds is advantageously between 10 and 22% by weight, in particular between 12 and 20% by weight. Water contents of 14 to 19% by weight can be particularly preferred.
Es wird ausdrücklich darauf hingewiesen, daß alle bekannten röntgenamorphen Alkalisilicate, Mischungen aus Alkalisilicaten und Alkalicarbonaten und Alkalisilicat-Compounds zur Herstellung der erfindungsgemäßen Compounds eingesetzt werden können. Diese Silicate können durch Sprühtrocknung, Granulierung und/oder Kompaktierung, beispielsweise durch Walzenkompaktierung hergestellt worden sein. Carbonat- und silicathaltige Compounds können ebenfalls durch Sprühtrocknung, Granulierung und/oder Kompaktierung, beispielsweise durch Walzenkompaktierung hergestellt werden. Einige dieser Silicate und carbonat- und silicathaltigen Compounds liegen als Handelsprodukte vor. Es wird hierbei beispielshaft auf die Handelsprodukte Britesil(R) der Firma Akzo & Nobel, Nabion 15(R) der Firma Rhône-Poulenc, Gransil(R) der Firma Colin Stewart oder Dizzil(R) G der Firma Akzo & Nobel verwiesen. Dabei sind als Carbonat-Alkalisilicat-Compounds solche bevorzugt, welche ein Gewichtsverhältnis von Carbonat zu Silicat von 3:1 bis 1:9 und insbesondere von 2,5:1 bis 1:5 aufweisen. Diese handelsüblichen Alkalisilicate bzw. Compounds können beispielsweise mit wäßrigen Lösungen von Aniontensiden oder auch mit Aniontensidsäuren granuliert werden.It is expressly pointed out that all known X-ray amorphous alkali silicates, mixtures of alkali silicates and alkali carbonates and alkali silicate compounds can be used to produce the compounds according to the invention. These silicates can have been produced by spray drying, granulation and / or compacting, for example by roller compacting. Compounds containing carbonate and silicate can also be produced by spray drying, granulation and / or compaction, for example by roller compaction. Some of these silicates and carbonate and silicate-containing compounds are available as commercial products. Reference is made here, for example, to the commercial products Britesil (R) from Akzo & Nobel, Nabion 15 (R) from Rhône-Poulenc, Gransil (R) from Colin Stewart or Dizzil (R) G from Akzo & Nobel. Preferred carbonate-alkali silicate compounds are those which have a weight ratio of carbonate to silicate of 3: 1 to 1: 9 and in particular of 2.5: 1 to 1: 5. These commercially available alkali silicates or compounds can be granulated, for example, with aqueous solutions of anionic surfactants or with anionic surfactant acids.
Auch amorphe Silicate, welche gemäß den obengenannten US-Patentschriften durch Sprühtrocknung oder in Granulatoren von der Art der Turbotrockner beispielsweise der Firma Vomm, Italien, hergestellt werden können, sind geeignete und durchaus bevorzugte Ausgangsstoffe mit vorteilhaften Eigenschaften. Dabei ist es bei der Turbogranulierung möglich, die Compounds direkt auf die erfindungsgemäße Weise herzustellen. Bei dem erfindungsgemäßen Verfahren zur Herstellung von aniontensidhaltigen Alkalimetallsilicat/Alkalimetallcarbonat-Compounds kann man generell so vorgehen, daß man in einem geeigneten Mischaggregat oder in einer Wirbelschicht mindestens eine der Komponenten Alkalimetallsilicat oder Alkalimetallcarbonat in Pulverform vorgibt und durch Aufdüsen einer wäßrigen Lösung eines Aniontensids, die erforderlichenfalls zusätzlich eine weitere Komponente des herzustellenden Compounds in gelöster und/oder dispergierter Form enthält, aufsprüht. Dabei kann das Aniontensid als Alkalimetallsalz, beispielsweise als Natriumsalz, als Tensidsäure oder in teilneutralisierter Form eingesetzt werden. Beispielsweise kann man pulverförmiges Alkalimetallcarbonat vorlegen und unter Verwendung einer wäßrigen aniontensidhaltigen Alkalimetallsilicatlösung, die gegebenenfalls ungelöste Anteile an Alkalimetallsilicat enthalten kann, agglomerieren. Alternativ hierzu kann man pulverförmiges Alkalimetallsilicat vorlegen und unter Verwendung einer aniontensidhaltigen Alkalimetallcarbonatlösung agglomerieren. In einer weiteren Ausführungsform kann man ein pulverförmiges Gemenge aus Alkalimetallsilicat und Alkalimetallcarbonat vorlegen und dieses unter Verwendung einer wäßrigen Aniontensidzubereitung agglomerieren. Bei dieser wäßrigen Zubereitung kann es sich um eine echte Lösung, eine Emulsion oder auch eine wasserhaltige Tensidpaste handeln. Schließlich kann das erfindungsgemäße Verfahren auch in der Form ausgeführt werden, daß man ein vorgebildetes Compound aus Alkalimetallsilicat und Alkalimetallcarbonat mit einer derartigen wäßrigen Aniontensidzubereitung agglomeriert. Das vorgebildete Compound aus Alkalimetallsilicat und Alkalimetallcarbonat kann beispielsweise durch Sprühtrocknung einer wäßrigen Lösung oder Suspension erhalten werden, die beide Komponenten enthält. Es kann hierfür jedoch auch ein Compound eingesetzt werden, das man durch Agglomeration der einen Komponenten in Pulverform mit einer wäßrigen Lösung der zweiten Komponenten erhalten kann.Also amorphous silicates, which according to the above-mentioned US patents by spray drying or in granulators from the Type of turbo dryer, for example, manufactured by Vomm, Italy are suitable and quite preferred Starting materials with advantageous properties. It is at turbo granulation possible, the compounds directly on the to produce according to the invention. In the inventive Process for the preparation of anionic surfactant Alkali metal silicate / alkali metal carbonate compounds can be used in general proceed in such a way that in a suitable mixing unit or in a fluidized bed at least one of the components Specifies alkali metal silicate or alkali metal carbonate in powder form and by spraying an aqueous solution of an anionic surfactant, the if necessary, an additional component of the to be manufactured Contains compounds in dissolved and / or dispersed form, sprayed on. The anionic surfactant can be used as an alkali metal salt, for example as a sodium salt, as a surfactant acid or in partially neutralized Form are used. For example, one can Submit powdered alkali metal carbonate and use an aqueous alkali metal silicate solution containing anionic surfactants, the optionally contain undissolved portions of alkali metal silicate can agglomerate. Alternatively, you can powder Submit alkali metal silicate and use a Agglomerate alkali metal carbonate solution containing anionic surfactants. In a further embodiment, a powdery mixture from alkali metal silicate and alkali metal carbonate and this using an aqueous anionic surfactant preparation agglomerate. This aqueous preparation can be a real solution, an emulsion or a water-based one Trade surfactant paste. Finally, the method according to the invention also be carried out in the form that one is pre-educated Compound of alkali metal silicate and alkali metal carbonate with a such aqueous anionic surfactant preparation agglomerated. The preformed Compound of alkali metal silicate and alkali metal carbonate can for example by spray drying an aqueous solution or Suspension are obtained, which contains both components. It can however, a compound can also be used for this, which can be Agglomeration of one component in powder form with an aqueous Can get solution of the second components.
Als Alkalimetallcarbonat wählt man bevorzugt Natrium- und/oder Kaliumcarbonat, wobei aus wirtschaftlichen Gründen Natriumcarbonat bevorzugt ist. The preferred alkali metal carbonate is sodium and / or Potassium carbonate, with sodium carbonate for economic reasons is preferred.
Für die Herstellung der Compounds lassen sich die im Stand der Technik bekannten Misch- und Agglomerieraggregate einsetzen. Beispielsweise genannt seien der vorstehend näher beschriebene Turbotrockner oder auch langsamer rotierende und vorzugsweise mit mischenden Einbauten versehene Trommeln, Granulierteller, die sich um eine vorzugsweise zur Senkrechten geneigte Achse drehen, sowie ein durch einen Gasstrom fluidisiertes Fließbett.For the manufacture of the compounds, the state of the art Use known mixing and agglomeration units. For example the turbo dryer described in more detail above may be mentioned or also slower rotating and preferably with mixing Built-in drums, pelletizing plates that are around rotate an axis, preferably inclined to the vertical, and a fluidized bed fluidized by a gas stream.
Als Aniontenside, die in den Alkalisilicat-Compounds eingesetzt werden, kommen vor allem Tenside des Sulfonat- und/oder Sulfat-Typs in Betracht. Als Tenside vom Sulfonat-Typ kommen vorzugsweise C9-C13-Alkylbenzolsulfonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C12-C18-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Alkansulfonate, die aus C12-C18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden. Geeignete Tenside vom Sulfat-Typ sind die Schwefelsäuremonoester aus primären Alkoholen natürlichen und synthetischen Ursprungs. 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 C16-C18-Alk(en)ylsulfate insbesondere bevorzugt. Dabei kann es auch von besonderem Vorteil und insbesondere für maschinelle Waschmittel von Vorteil sein, C16-C18-Alk(en)ylsulfate in Kombination mit niedriger schmelzenden Aniontensiden und insbesondere mit solchen Aniontensiden, die einen niedrigeren Krafft-Punkt aufweisen und bei relativ niedrigen Waschtemperaturen von beispielsweise Raumtemperatur bis 40 °C eine geringe Kristallisationsneigung zeigen, einzusetzen. In einer bevorzugten Ausführungsform der Erfindung enthalten die Compounds daher Mischungen aus kurzkettigen und langkettigen Fettalkylsulfaten, vorzugsweise Mischungen aus C12-C14-Fettalkylsulfaten oder C12-C18-Fettalkylsulfaten mit C16-C18-Fettalkylsulfaten und insbesondere C12-C16-Fettalkylsulfaten mit C16-C18-Fettalkylsulfaten. In einer weiteren bevorzugten Ausführungsform der Erfindung werden jedoch nicht nur gesättigte Alkylsulfate, sondern auch ungesättigte Alkenylsulfate mit einer Alkenylkettenlänge von vorzugsweise C16 bis C22 eingesetzt. Dabei sind insbesondere Mischungen aus gesättigten, überwiegend aus C16 bestehenden sulfierten Fettalkoholen und ungesättigten, überwiegend aus C18 bestehenden sulfierten Fettalkoholen bevorzugt, beispielsweise solche, die sich von festen oder flüssigen Fettalkoholmischungen des Typs HD-Ocenol (R) (Handelsprodukt des Anmelders) ableiten. Dabei sind Gewichtsverhältnisse von Alkylsulfaten zu Alkenylsulfaten von 10:1 bis 1:2 und insbesondere von etwa 5:1 bis 1:1 bevorzugt.Anionic surfactants that are used in the alkali silicate compounds are, above all, surfactants of the sulfonate and / or sulfate type. Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin. 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 16 -C 18 alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C 16 -C 18 alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize. In a preferred embodiment of the invention, the compounds therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 12 -C 14 fatty alkyl sulfates or C 12 -C 18 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates and in particular C 12 -C 16 -Fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates. In a further preferred embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used. Mixtures of saturated sulfonated fatty alcohols predominantly consisting of C 16 and unsaturated sulfated fatty alcohols predominantly consisting of C 18 are particularly preferred, for example those derived from solid or liquid HD-Ocenol (R) fatty alcohol mixtures (commercial product of the applicant) . Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.
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 E0, 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 E0 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.
In einer bevorzugten Ausführungsform der Erfindung enthalten die Compounds 15 bis 80 Gew.-% Alkalisilicate, 1 bis 20 Gew.-% Aniontenside und 10 bis 22 Gew.-%, vorzugsweise 12 bis 19 Gew-% und inbesondere 14 bis 19 Gew.-% Wasser.In a preferred embodiment of the invention, the Compounds 15 to 80% by weight alkali silicates, 1 to 20% by weight Anionic surfactants and 10 to 22 wt .-%, preferably 12 to 19 wt .-% and in particular 14 to 19 wt .-% water.
In einer weiteren bevorzugten Ausführungsform der Erfindung enthalten die erfindungsgemäßen Compounds 15 bis 50 Gew.-%, vorzugsweise 20 bis 40 Gew.-% Alkalisilicate, 30 bis 70 Gew.-%, vorzugsweise 40 bis 65 Gew.-% Alkalicarbonate, 1,5 bis 15 Gew.-% und insbesondere 2 bis 12 Gew.-% Aniontenside, vorteilhafterweise Alkylbenzolsulfonate und/oder Alk(en)ylsulfate, und 12 bis 19 Gew.-% Wasser.Included in a further preferred embodiment of the invention the compounds according to the invention 15 to 50 wt .-%, preferably 20 to 40% by weight alkali silicates, 30 to 70% by weight, preferably 40 to 65% by weight of alkali carbonates, 1.5 to 15% by weight and in particular 2 to 12% by weight of anionic surfactants, advantageously Alkylbenzenesulfonates and / or alk (en) ylsulfates, and 12 to 19 % By weight of water.
Die Alkalisilicat-Compounds können zusätzlich noch weitere Inhaltsstoffe von Wasch- oder Reinigungsmitteln, vorzugsweise in Mengen bis 10 Gew.-% und insbesondere in Mengen nicht oberhalb 5 Gew.-% enthalten. Hierzu zählen beispielsweise Neutralsalze wie Natrium - oder Kaliumsulfate, aber auch Vergrauungsinhibitoren oder nichtionische Tenside wie Alkylpolyglykoside.The alkali silicate compounds can also contain other ingredients of washing or cleaning agents, preferably in Amounts up to 10% by weight and especially in amounts not above 5 % By weight. These include, for example, neutral salts such as Sodium or potassium sulfates, but also graying inhibitors or nonionic surfactants such as alkyl polyglycosides.
Die erfindungsgemäßen Alkalisilicat-Compounds besitzen ein signifikantes Aufnahmevermögen für bei den üblichen Verarbeitungstemperaturen flüssige bis wachsartige Inhaltsstoffe von Wasch- oder Reinigungsmitteln. Zwar können auch Alkalisilicat-Compounds ohne Aniontensid-Zusatz gewisse Mengen an Flüssigkomponenten aufnehmen; es hat sich jedoch gezeigt, daß durch den Zusatz von Aniontensiden die Aufnahmekapazität der Alkalisilicat-Compounds erhöht und das Rieselverhalten verbessert wird. In einer bevorzugten Ausführungsform der Erfindung weisen die erfindungsgemäßen aniontensidhaltigen Alkalisilicat-Compounds ein Aufnahmevermögen für Flüssigkomponenten auf, das um mindestens 20 % höher ist als das der mengengleichen Alkalisilicat-Compounds ohne Aniontenside. Insbesondere sind dabei Compounds bevorzugt, deren Aufnahmevermögen für Flüssigkomponenten sogar um mindestens 30 % und vorteilhafterweise sogar um mindestens 50 %, jeweils bezogen auf das Aufnahmevermögen der mengengleichen entsprechenden Alkalisilicat-Compounds ohne Aniontenside, gesteigert wurde.The alkali silicate compounds according to the invention have a significant one Capacity for at the usual processing temperatures liquid to waxy ingredients of washing or Detergents. Alkali silicate compounds can also be used without Anionic surfactant add certain amounts of liquid components; However, it has been shown that the addition of anionic surfactants increases the absorption capacity of the alkali silicate compounds and that Trickle behavior is improved. In a preferred embodiment of the invention have the anionic surfactant according to the invention Alkali silicate compounds have a capacity for liquid components that is at least 20% higher than that of the same quantity Alkali silicate compounds without anionic surfactants. In particular are there Compounds preferred, their absorption capacity for liquid components even by at least 30% and advantageously even by at least 50%, each based on the absorption capacity of the same quantity corresponding alkali silicate compounds without anionic surfactants has been.
In einer weiteren Ausführungsform der Erfindung werden daher erfindungsgemäß hergestellte Alkalisilicat-Compounds beansprucht, welche mit Flüssigkomponenten, zu denen im Rahmen dieser Erfindung bei der Verarbeitungstemperatur flüssige bis wachsartige Inhaltsstoffe von Wasch- oder Reinigungsmitteln gezählt werden, nachbehandelt wurden. Geeignete Flüssigkomponenten, die von den erfindungsgemäßen Alkalisilicat-Compounds aufgenommen werden können, sind beispielsweise nichtionische Tenside, Kationtenside und/oder Schauminhibitoren wie Silikonöle und Paraffinöle. Insbesondere bevorzugt sind jedoch nichtionische Tenside, beispielsweise alkoxylierte, vorzugsweise ethoxylierte und/oder ethoxylierte und propoxylierte aliphatische C8-C22-Alkohole. Hierzu zählen insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol, 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. Ebenso 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-Alkohol mit 7 EO, C13-C15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-C18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-C14-Alkohol mit 3 EO und C12-C18-Alkohol mit 5 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 Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO.In a further embodiment of the invention, alkali silicate compounds produced according to the invention are therefore claimed, which have been aftertreated with liquid components, which in the context of this invention include liquid to waxy ingredients of washing or cleaning agents. Suitable liquid components which can be absorbed by the alkali silicate compounds according to the invention are, for example, nonionic surfactants, cationic surfactants and / or foam inhibitors such as silicone oils and paraffin oils. However, nonionic surfactants are particularly preferred, for example alkoxylated, preferably ethoxylated and / or ethoxylated and propoxylated, aliphatic C 8 -C 22 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 contain linear and methyl-branched radicals in the mixture can, as is usually present in oxo alcohol residues. However, alcohol ethoxylates with linear residues from 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 also preferred. The preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohol 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 5 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 include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
Nachträglich können die erfindungsgemäß hergestellten Alkalisilicat-Compounds mit Inhaltsstoffen von Wasch- oder Reinigungsmitteln behandelt werden. Dies kann auf herkömmliche Weise durchgeführt werden, beispielsweise durch Mischen oder durch Aufsprühen in einem Mischer/Granulator gegebenenfalls mit anschließender Wärmebehandlung.Subsequently, those produced according to the invention can Alkali silicate compounds with ingredients of washing or cleaning agents be treated. This can be done in a conventional manner be carried out, for example by mixing or spraying in a mixer / granulator, optionally with a subsequent one Heat treatment.
Die amorphen Alkalisilicat-Compounds mit Sekundärwaschvermögen können als Zumischkomponente zu pulverförmigen bis granularen Wasch- oder Reinigungsmitteln oder als Bestandteil bei der Herstellung der granularen Wasch- oder Reinigungsmittel, vorzugsweise bei der Granulierung und/oder Kompaktierung, verwendet werden. Je nach der Art ihrer Herstellung können die Schüttgewichte der Alkalisilicat-Compounds zwischen etwa 300 und beispielsweise 950 g/l variieren. Bei kontinuierlicher Herstellung können Schüttgewichte bis 1150 g/l erreicht werden. Die erfindungsgemäßen Wasch- oder Reinigungsmittel können hingegen ein Schüttgewicht zwischen 300 und 1200 g/l, vorzugsweise von 500 bis 1000 g/l, aufweisen und enthalten die erfindungsgemäßen Alkalisilicat-Compounds vorzugsweise in Mengen von 5 bis 50 Gew.-%, insbesondere in Mengen von 10 bis 40 Gew.-%. Ihre Herstellung kann nach jedem der bekannten Verfahren wie Mischen, Granulieren, Kompaktieren wie Walzenkompaktierung und Extrusion erfolgen. Geeignet sind insbesondere solche Verfahren, in denen mehrere Teilkomponenten, beispielsweise sprühgetrocknete Komponenten und granulierte und/oder extrudierte Komponenten miteinander vermischt werden. Dabei ist es auch möglich, daß sprühgetrocknete oder granulierte Komponenten nachträglich in der Aufbereitung beispielsweise mit nichtionischen Tensiden, insbesondere ethoxylierten Fettalkoholen, nach den üblichen Verfahren beaufschlagt werden. Insbesondere in Granulations- und Extrusionsverfahren ist es bevorzugt, die gegebenenfalls vorhandenen weiteren Aniontenside in Form eines sprühgetrockneten, granulierten oder extrudierten Compounds entweder als Zumischkomponente in dem Verfahren oder als Additiv nachträglich zu anderen Granulaten einzusetzen. Ebenso ist es möglich und kann in Abhängigkeit von der Rezeptur von Vorteil sein, wenn weitere einzelne Bestandteile des Mittels, beispielsweise Carbonate, Citrat bzw. Citronensäure oder andere Polycarboxylate bzw. Polycarbonsäuren, polymere Polycarboxylate, Zeolith und/oder Schichtsilicate, beispielsweise schichtförmige kristalline Disilicate, nachträglich zu sprühgetrockneten, granulierten und/oder extrudierten Komponenten, die gegebenenfalls mit nichtionischen Tensiden und/oder anderen bei der Verarbeitungstemperatur flüssigen bis wachsartigen Inhaltsstoffen beaufschlagt sind, hinzugemischt werden. Bevorzugt ist dabei ein Verfahren, bei dem die Oberfläche von Teilkomponenten des Mittels oder des gesamten Mittels zur Reduzierung der Klebrigkeit der Granulate und/oder zu ihrer verbesserten Löslichkeit nachträglich behandelt wird. Geeignete Oberflächenmodifizierer sind dabei aus dem Stand der Technik bekannt. Neben weiteren geeigneten sind dabei feinteilige Zeolithe, Kieselsäuren, amorphe Silicate, Fettsäuren oder Fettsäuresalze, beispielsweise Calciumstearat, vor allem jedoch Mischungen aus Zeolith und Kieselsäure, insbesondere im Gewichtsverhältnis Zeolith zu Kieselsäure von mindestens 1:1, oder Zeolith und Calciumstearat besonders bevorzugt. The amorphous alkali silicate compounds with secondary washing ability can be added as a component to powdery to granular Detergents or cleaning agents or as a component in the manufacture the granular washing or cleaning agents, preferably for granulation and / or compacting. Each the bulk weights of the Alkali silicate compounds between approximately 300 and, for example, 950 g / l vary. With continuous production, bulk weights can up to 1150 g / l can be achieved. The washing according to the invention or cleaning agents, however, can have a bulk density between 300 and 1200 g / l, preferably from 500 to 1000 g / l, and preferably contain the alkali silicate compounds according to the invention in amounts of 5 to 50% by weight, in particular in amounts of 10 up to 40% by weight. They can be produced by any of the known processes like mixing, granulating, compacting like Roll compacting and extrusion take place. Are particularly suitable processes in which several sub-components, for example spray-dried components and granulated and / or extruded components are mixed together. Here it is also possible that spray-dried or granulated Retrofitting components, for example with nonionic surfactants, especially ethoxylated fatty alcohols, be applied according to the usual procedures. Especially in Granulation and extrusion processes, it is preferred, if necessary existing further anionic surfactants in the form of a spray-dried, granulated or extruded compounds either as Additive component in the process or as an additive subsequently use other granules. It is also possible and can in Dependence on the recipe can be beneficial if more individual Components of the agent, for example carbonates, citrate or citric acid or other polycarboxylates or Polycarboxylic acids, polymeric polycarboxylates, zeolite and / or Layered silicates, for example layered crystalline ones Disilicate, subsequently spray-dried, granulated and / or extruded components, optionally with nonionic Surfactants and / or others at processing temperature liquid to waxy ingredients are added become. A method is preferred in which the Surface of partial components of the agent or all of the agent to reduce the stickiness of the granules and / or their improved solubility is treated subsequently. Suitable Surface modifiers are known from the prior art. In addition to other suitable ones, finely divided zeolites, Silicas, amorphous silicates, fatty acids or fatty acid salts, for example calcium stearate, but especially mixtures of Zeolite and silica, especially in the zeolite weight ratio to silica of at least 1: 1, or zeolite and calcium stearate particularly preferred.
Besonders bevorzugte Ausführungsformen der Erfindung sind extrudierte Wasch- oder Reinigungsmittel mit einem Schüttgewicht oberhalb 600 g/l, welche anionische sowie gegebenenfalls nichtionische Tenside sowie ein amorphes Alkalisilicat-Compound der erfindungsgemäß hergestellten Art im Extrudat enthalten. Zur Herstellung dieser extrudierten Wasch- oder Reinigungsmittel wird auf die bekannten Verfahren zur Extrusion, insbesondere auf die internationale Patentanmeldung WO-A-91/02047 verwiesen. Dabei werden ein festes und rieselfähiges Vorgemisch bei Drucken bis 200 bar strangförmig verpreßt, der Strang nach dem Austritt aus der Lochform mittels einer Schneidevorrichtung auf die vorbestimmte Granulatdimension zugeschnitten sowie das plastische und gegebenenfalls noch feuchte Rohextrudat einem weiteren formgebenden Verarbeitungsschritt zugeführt und anschließend getrocknet, wobei die erfindungsgemäßen Alkalisilicat-Compounds in dem Vorgemisch eingesetzt werden.Particularly preferred embodiments of the invention are extruded washing or cleaning agents with a bulk weight above 600 g / l, which are anionic and optionally nonionic Surfactants and an amorphous alkali silicate compound Type according to the invention contained in the extrudate. For the production this extruded detergent or cleaning agent is on the known methods of extrusion, especially on the international Patent application WO-A-91/02047. Doing so solid and free-flowing premix at pressures up to 200 bar strand-pressed, the strand after exiting the hole shape by means of a cutting device to the predetermined granule dimension tailored as well as the plastic and if necessary raw extrudate still moist in a further shaping processing step fed and then dried, the Alkali silicate compounds according to the invention used in the premix become.
Insbesondere bei der Herstellung von extrudierten Wasch- oder Reinigungsmitteln weisen die aniontensidhaltigen Alkalisilicat-Compounds überraschenderweise auch aus verfahrenstechnischer Sicht Vorteile gegenüber den aniontensidfreien Alkalisilicat-Compound-Alternativen auf. Es hat sich gezeigt, daß Extrusionsprozesse, in denen insbesondere aniontensidfreie Alkalisilicat-Carbonat-Compounds eingesetzt wurden, nicht unterbrochen werden durften, da das Extrusionsgemisch in der Ruhephase seine Plastizität und Gleitfähigkeit derartig schnell verlor, daß ein erneutes Anfahren der Anlage sicherheitstechnische Probleme mit sich brachte. Dieses Problem wurde durch den Ersatz der aniontensidfreien durch aniontensidhaltige Alkalisilicat-Compounds, insbesondere durch aniontensid- und carbonathaltige Alkalisilicat-Compounds gelöst. Especially in the production of extruded washing or cleaning agents exhibit the alkali silicate compounds containing anionic surfactants Surprisingly also from a process engineering point of view Advantages over the anionic surfactant-free alkali silicate compound alternatives on. It has been shown that extrusion processes, in which in particular anionic surfactant-free alkali silicate carbonate compounds were not allowed to be interrupted because the extrusion mixture in the resting phase its plasticity and Slidability lost so quickly that a new start the system caused safety-related problems. This Problem was replaced by the replacement of anionic surfactants Alkali silicate compounds containing anionic surfactant, in particular by Alkali silicate compounds containing anionic surfactants and carbonate dissolved.
Die fertigen Wasch- oder Reinigungsmittel können zusätzlich die nun folgenden Inhaltsstoffe enthalten.The finished detergents or cleaning agents can also be used now contain the following ingredients.
Zu diesen zählen insbesondere Tenside, vor allem Aniontenside sowie gegebenenfalls nichtionische Tenside, aber auch kationische, amphotere oder zwitterionische Tenside.These include in particular surfactants, especially anionic surfactants as well optionally non-ionic surfactants, but also cationic, amphoteric or zwitterionic surfactants.
Als Aniontenside vom Sulfonat-Typ kommen einmal die bereits obengenannten Alkylbenzolsulfonate, Olefinsulfonate und Alkansulfonate in Betracht. Geeignet sind aber auch die Ester von α-Sulfofettsäuren (Estersulfonate), z.B. die α-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren. Weitere geeignete Aniontenside sind die durch Esterspaltung der α-Sulfofettsäurealkylester erhältlichen α-Sulfofettsäuren bzw. ihre Di-Salze. Die Mono-Salze der α-Sulfofettsäurealkylester fallen schon bei ihrer großtechnischen Herstellung als wäßrige Mischung mit begrenzten Mengen an Di-Salzen an. Der Disalz-Gehalt solcher Tenside liegt üblicherweise unter 50 Gew.-% des Aniontensidgemisches, beispielsweise bis etwa 30 Gew.-%.The anionic surfactants of the sulfonate type include those already mentioned above Alkyl benzene sulfonates, olefin sulfonates and alkane sulfonates into consideration. However, the esters of α-sulfofatty acids are also suitable (Ester sulfonates), e.g. the α-sulfonated methyl esters hydrogenated coconut, palm kernel or tallow fatty acids. Further suitable anionic surfactants are those by ester cleavage of the α-sulfofatty acid alkyl esters available α-sulfo fatty acids or their Di salts. The mono-salts of the α-sulfofatty acid alkyl esters fall even in their industrial production as an aqueous mixture with limited amounts of di-salts. The disalt content of such Surfactants is usually less than 50% by weight of the anionic surfactant mixture, for example up to about 30% by weight.
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.Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which represent mono-, di- and triesters and their mixtures, as in the manufacture by esterification through a Monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of Triglycerides with 0.3 to 2 moles of glycerin can be obtained.
Geeignete Tenside vom Sulfat-Typ sind die genannten Schwefelsäuremonoester aus primären Alkoholen natürlichen und synthetischen Ursprungs sowie gegebenenfalls deren alkoxylierte, vorzugsweise ethoxylierte Derivate. 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. 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.Suitable surfactants of the sulfate type are the aforementioned sulfuric acid monoesters from primary alcohols of natural and synthetic origin and, if appropriate, their alkoxylated, preferably ethoxylated, derivatives. 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 are nonionic surfactants in themselves. 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.
Zusätzlich zu den anionischen Tensiden können die Mittel auch Seifen, vorzugsweise in Mengen von 0,2 bis 5 Gew.-%, enthalten. Geeignet sind gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierte Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengemische.In addition to the anionic surfactants, the agents can also contain soaps, preferably contained in amounts of 0.2 to 5 wt .-%. Suitable are saturated fatty acid soaps, like the salts 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.
Die anionischen Tenside und Seifen können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor.The anionic surfactants and soaps can be in the form of their sodium, Potassium or ammonium salts as well as organic organic salts Bases, such as mono-, di- or triethanolamine, are present. Preferably are the anionic surfactants in the form of their sodium or potassium salts, especially in the form of the sodium salts.
In einer Ausführungsform der Erfindung werden Wasch- oder Reinigungsmittel, insbesondere extrudierte Wasch- oder Reinigungsmittel bevorzugt, welche 10 bis 30 Gew.-% anionische Tenside enthalten. Vorteilhafterweise sind davon vorzugsweise mindestens 3 Gew.-% und insbesondere mindestens 5 Gew.-% sulfatische Tenside. In einer vorteilhaften Ausführungsform sind in den Mitteln - bezogen auf die anionischen Tenside insgesamt - mindestens 15 Gew.-%, insbesondere 20 bis 100 Gew.-% sulfatische Tenside enthalten.In one embodiment of the invention, detergents or cleaning agents, in particular extruded washing or cleaning agents preferred, which contain 10 to 30 wt .-% anionic surfactants. Advantageously, at least 3% by weight and in particular at least 5% by weight of sulfate surfactants. In a advantageous embodiment are in the means - based on the total anionic surfactants - at least 15% by weight, in particular Contain 20 to 100 wt .-% sulfate surfactants.
Als nichtionische Tenside werden vorzugsweise die bereits oben beschriebenen alkoxylierten, vorteilhafterweise ethoxylierten Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt.Preferred nonionic surfactants are those already described above alkoxylated, advantageously ethoxylated alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) used per mole of alcohol.
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.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.
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 be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of them.
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. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.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 known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
Nichtionische Tenside sind in den erfindungsgemäßen Mitteln vorzugsweise in Mengen von 0,5 bis 15 Gew.-%, insbesondere in Mengen von 2 bis 10 Gew.-% enthalten.Nonionic surfactants are preferred in the agents according to the invention in quantities of 0.5 to 15% by weight, in particular in quantities contain from 2 to 10 wt .-%.
Neben den erfindungsgemäß hergestellten amorphen Alkalisilicat-Compounds mit Sekundärwaschvermögen können die Mittel auch noch weitere, zusätzliche Buildersubstanzen und Cobuilder enthalten. Beispielsweise können übliche Buildersubstanzen wie Phosphate, Zeolithe und kristalline Schichtsilicate in den Mitteln enthalten sein. Der eingesetzte, synthetische Zeolith ist vorzugsweise feinkristallin und enthält gebundenes Wasser. Geeignet sind beispielsweise Zeolith A, jedoch auch Zeolith X und Zeolith P sowie Mischungen aus A, X und/oder P. Der Zeolith kann als sprühgetrocknetes Pulver oder auch als ungetrocknete, von ihrer Herstellung noch feuchte, stabilisierte Suspension zum Einsatz kommen. Für den Fall, daß der Zeolith als Suspension eingesetzt wird, kann diese geringe Zusätze an nichtionischen Tensiden als Stabilisatoren enthalten, beispielsweise 1 bis 3 Gew.-%, bezogen auf Zeolith, an ethoxylierten C12-C18-Fettalkoholen mit 2 bis 5 Ethylenoxidgruppen, C12-C14-Fettalkoholen mit 4 bis 5 Ethylenoxidgruppen oder ethoxylierten Isotridecanolen. Ebenso ist es auch möglich, Zeolith-Suspensionen und Zeolith-Pulver einzusetzen. Geeignete Zeolith-Pulver weisen eine mittlere Teilchengröße von weniger als 10 µm (Volumenverteilung; Meßmethode: Coulter Counter) auf und enthalten vorzugsweise 18 bis 22 Gew.-%, insbesondere 20 bis 22 Gew.-% an gebundenem Wasser. Zeolith kann in den Wasch- oder Reinigungsmitteln in Mengen bis etwa 40 Gew.-% (bezogen auf wasserfreie Aktivsubstanzen) enthalten sein.In addition to the amorphous alkali silicate compounds with secondary washability produced according to the invention, the compositions can also contain further, additional builder substances and cobuilders. For example, customary builder substances such as phosphates, zeolites and crystalline layered silicates can be contained in the agents. The synthetic zeolite used is preferably finely crystalline and contains bound water. Zeolite A, for example, but also zeolite X and zeolite P and mixtures of A, X and / or P are suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. It is also possible to use zeolite suspensions and zeolite powder. Suitable zeolite powders have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. Zeolite can be contained in the washing or cleaning agents in amounts of up to about 40% by weight (based on anhydrous active substances).
In einer besonders bevorzugten Ausführungsform der Erfindung enthalten Wasch- oder Reinigungsmittel jedoch 10 bis 16 Gew.-% Zeolith (bezogen auf wasserfreie Aktivsubstanz) und 10 bis 30 Gew.-% eines erfindungsgemäß hergestellten Alkalisilicat-Compounds.Included in a particularly preferred embodiment of the invention Washing or cleaning agents, however, 10 to 16 wt .-% zeolite (based on anhydrous active substance) and 10 to 30 wt .-% of one Alkali silicate compounds produced according to the invention.
In einer weiteren besonders bevorzugten Ausführungsform der Erfindung enthalten die Wasch- oder Reinigungsmittel jedoch 0 bis 5 Gew.-% Zeolith (bezogen auf wasserfreie Aktivsubstanz) und 15 bis 40 Gew.-% eines erfindungsgemäß hergestellten Alkalisilicat-Compounds. Dabei ist es möglich, daß der Zeolith nicht nur coextrudiert wird, sondern daß der Zeolith teilweise oder ganz nachträglich, also nach dem Extrusionsschritt in das Wasch- oder Reinigungsmittel eingebracht wird. Besonders bevorzugt sind hierbei Wasch- oder Reinigungsmittel, welche ein Extrudat enthalten, das im Inneren des Extrudatkorns frei von Zeolith ist.In a further particularly preferred embodiment of the invention however, the detergents or cleaning agents contain 0 to 5 % By weight of zeolite (based on anhydrous active substance) and 15 to 40% by weight of an alkali silicate compound produced according to the invention. It is possible that the zeolite not only is coextruded, but that the zeolite is partially or wholly subsequently, ie after the extrusion step into the washing or Detergent is introduced. Are particularly preferred here Detergents or cleaning agents that contain an extrudate that in the Inside of the extrudate grain is free of zeolite.
Als Ersatzstoffe für den Zeolith können auch kristalline Schichtsilicate und/oder herkömmliche Phosphate eingesetzt werden. Dabei ist es jedoch bevorzugt, daß Phosphate nur in geringen Mengen, insbesondere bis maximal 10 Gew.-%, in den Wasch- oder Reinigungsmitteln enthalten sind.Crystalline can also be used as substitutes for the zeolite Layered silicates and / or conventional phosphates are used. However, it is preferred that phosphates only in small amounts, in particular up to a maximum of 10% by weight in the washing or cleaning agents are included.
Als kristalline Schichtsilicate sind insbesondere kristalline, schichtförmige Natriumsilicate 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, geeignet. Derartige kristalline Schichtsilicate werden beispielsweise in der europäischen Patentanmeldung EP-A-0 164 514 beschrieben. Bevorzugte kristalline Schichtsilicate 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-Natriumdisilicate Na2Si2O5·yH2O bevorzugt. Diese kristallinen Schichtsilicate sind jedoch in den erfindungsgemäßen Extrudaten vorzugsweise lediglich in Mengen von nicht mehr als 10 Gew.-%, insbesondere von weniger als 8 Gew.-%, vorteilhafterweise von maximal 5 Gew.-% enthalten.Crystalline layered 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 are preferred as crystalline layered silicates Values for x 2, 3 or 4 are suitable. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline phyllosilicates of the formula given are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred. However, these crystalline layered silicates are preferably only contained in the extrudates according to the invention in amounts of not more than 10% by weight, in particular less than 8% by weight, advantageously not more than 5% by weight.
Als Cobuilder können beispielsweise polymere Polycarboxylate eingesetzt werden. Geeignete polymere Polycarboxylate sind beispielsweise die 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. Insbesondere bevorzugt sind auch Terpolymere, beispielsweise solche, die gemäß der DE-A-43 00 772 als Monomere Salze 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. Polymeric polycarboxylates, for example, can be used as cobuilders become. Suitable polymeric polycarboxylates are, for example the sodium salts of polyacrylic acid or Polymethacrylic acid, for example those with a molecular weight from 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, which 50 to 90 wt .-% Contain acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molecular mass, based on free acids, is generally 5000 to 200000, preferably 10000 to 120000 and in particular 50,000 to 100,000. Terpolymers are also particularly preferred, for example those according to DE-A-43 00 772 as monomers Salts acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomers Salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar Derivatives included.
Weitere brauchbare organische Cobuilder sind die bevorzugt in Form ihrer Natriumsalze eingesetzten Polycarbonsäuren, wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zukkersäuren, 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.Other useful organic cobuilders are preferably in the form their sodium salts used polycarboxylic acids, such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use cannot be objected to for ecological reasons is, and mixtures of 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 of this.
Weitere geeignete Buildersysteme sind Oxidationsprodukte von carboxylgruppenhaltigen Polyglucosanen und/oder deren wasserlöslichen Salzen, wie sie beispielsweise in der internationalen Patentanmeldung WO-A-93/08251 beschrieben werden oder deren Herstellung beispielsweise in der internationalen Patentanmeldung WO-A-93/16110 beschrieben wird.Other suitable builder systems are oxidation products from carboxyl-containing polyglucosans and / or their water-soluble salts, such as those found in international Patent application WO-A-93/08251 can be described or their Manufacturing, for example, in the international patent application WO-A-93/16110.
Ebenso sind als weitere bevorzugte Buildersubstanzen auch die bekannten Polyasparaginsäuren bzw. deren Salze und Derivate zu nennen.Also known are the other preferred builder substances To name polyaspartic acids or their salts and derivatives.
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 by Reaction of dialdehydes with polyol carboxylic acids, which 5 to 7 C atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223 can be obtained. Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde as well their mixtures and from polyol carboxylic acids such as gluconic acid and / or Obtain glucoheptonic acid.
Diese Cobuilder können in Mengen von beispielsweise 0,5 bis 20 Gew.-%, vorzugsweise von 2 bis 15 Gew.-% in den fertigen Wasch- oder Reinigungsmitteln enthalten sein.These cobuilders can be used in amounts of, for example, 0.5 to 20 % By weight, preferably from 2 to 15% by weight in the finished washing or cleaning agents.
Zusätzlich können die Mittel auch Komponenten enthalten, welche die Öl- und Fettauswaschbarkeit aus Textilien positiv beeinflussen. Dieser Effekt wird besonders deutlich, wenn ein Textil verschmutzt wird, das bereits vorher mehrfach mit einem erfindungsgemäßen Waschmittel, das diese öl- und fettlösende Komponente enthält, gewaschen wird. Zu den bevorzugten öl- und fettlösenden Komponenten zählen beispielsweise nichtionische Celluloseether wie Methylcellulose und Methylhydroxypropylcellulose 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 nichtionische modifizierten Derivaten von diesen.In addition, the agents can also contain components which Oil and fat washability from textiles have a positive impact. This effect is particularly evident when a textile is dirty is that previously several times with an inventive Detergent containing this oil and fat-dissolving component is washed becomes. Among the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as Methyl cellulose and methyl hydroxypropyl cellulose with a proportion on methoxyl groups from 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ether, as well as the polymers known from the prior art phthalic acid and / or terephthalic acid or their Derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these.
Die Mittel können außerdem Bestandteile enthalten, welche die Löslichkeit insbesondere der schweren Granulate noch weiter verbessern. Derartige Bestandteile und das Einbringen derartiger Bestandteile werden beispielsweise in der internationalen Patentanmeldung WO-A-93/02176 und in der deutschen Patentanmeldung DE-A-42 03 031 beschrieben. Zu den bevorzugt eingesetzten Bestandteilen gehören insbesondere Fettalkohole mit 20 bis 80 Mol Ethylenoxid pro Mol Fettalkohol, beispielsweise Talgfettalkohol mit 30 E0 und Talgfettalkohol mit 40 E0, aber auch Fettalkohole mit 14 E0 sowie Polyethylenglykole mit einer relativen Molekülmasse zwischen 200 und 2000. The agents can also contain components which have solubility especially the heavy granules. Such components and the introduction of such components are, for example, in the international patent application WO-A-93/02176 and in German patent application DE-A-42 03 031. The preferred ingredients include in particular fatty alcohols with 20 to 80 moles Ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol 30 E0 and tallow fatty alcohol with 40 E0, but also fatty alcohols with 14 E0 and polyethylene glycols with a molecular weight between 200 and 2000.
Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen hat das Natriumperboratmonohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Natriumperborattetrahydrat, Natriumpercarbonat, Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure oder Diperdodecandisäure. Der Gehalt der Mittel an Bleichmitteln beträgt vorzugsweise 5 bis 25 Gew.-% und insbesondere 10 bis 20 Gew.-%, wobei vorteilhafterweise Perboratmonohydrat eingesetzt wird. Percarbonat ist als Bestandteil ebenfalls bevorzugt. Jedoch wird Percarbonat vorzugsweise nicht coextrudiert, sondern gegebenenfalls nachträglich zugemischt.Sodium perborate monohydrate is of particular importance among the compounds which serve as bleaching agents and produce H 2 O 2 in water. Further bleaching agents which can be used are, for example, sodium perborate tetrahydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used. Percarbonate is also preferred as an ingredient. However, percarbonate is preferably not co-extruded, but optionally mixed in subsequently.
Um beim Waschen bei Temperaturen von 60 °C und darunter eine verbesserte Bleichwirkung zu erreichen, können Bleichaktivatoren in die Präparate eingearbeitet werden. Beispiele hierfür sind mit H2O2 organische Persäuren bildende N-Acyl- bzw. O-Acyl-Verbindungen, vorzugsweise N,N'-tetraacylierte Diamine, p-(Alkanoyloxy)benzolsulfonate, ferner Carbonsäureanhydride und Ester von Polyolen wie Glucosepentaacetat. Weitere bekannte Bleichaktivatoren sind acetylierte Mischungen aus Sorbitol und Mannitol, wie sie beispielsweise in der europäischen Patentanmeldung EP-A-0 525 239 beschrieben werden. Der Gehalt der bleichmittelhaltigen Mittel an Bleichaktivatoren liegt in dem üblichen Bereich, vorzugsweise zwischen 1 und 10 Gew.-% und insbesondere zwischen 3 und 8 Gew.-%. Besonders bevorzugte Bleichaktivatoren sind N,N,N',N'-Tetraacetylethylendiamin (TAED), 1,5-Diacetyl-2,4-dioxo-hexahydro-1,3,5-triazin (DADHT) und acetylierte Sorbitol-Mannitol-Mischungen (SORMAN).In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239. The bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
Es kann 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.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 solche aus der Klasse der Proteasen, Lipasen, Amylasen, Cellulasen bzw. deren Gemische in Frage. 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 oder Protease und Cellulase oder aus Cellulase und Lipase oder aus Protease, Amylase und Lipase oder Protease, Lipase und Cellulase, insbesondere jedoch Protease- und/oder Lipase-haltige Mischungen von besonderem Interesse. Auch Peroxidasen oder Oxidasen haben sich in einigen Fällen als geeignet erwiesen. 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. Enzymes come from the class of proteases, lipases, Amylases, cellulases or their mixtures in question. Particularly good are suitable from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola Insolens obtained enzymatic agents. Preferably be Subtilisin-type proteases, and in particular proteases derived from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and Lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and Cellulase, but especially protease and / or lipase-containing Mixtures of special interest. Also peroxidases or oxidases have proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition. Of the Proportion of the enzymes, enzyme mixtures or enzyme granules can, for example about 0.1 to 5% by weight, preferably 0.1 to about 2 % By weight.
Als Stabilisatoren insbesondere für Perverbindungen und Enzyme kommen die Salze von Polyphosphonsäuren, insbesondere 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), Diethylentriaminpentamethylenphosphonsäure (DETPMP) oder Ethylendiamintetramethylenphosphonsäure in Betracht.As stabilizers, especially for per-compounds and enzymes come the salts of polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP), Diethylenetriaminepentamethylenephosphonic acid (DETPMP) or Ethylenediaminetetramethylenephosphonic acid into consideration.
Die Mittel können auch weitere Enzymstabilisatoren enthalten. Beispielsweise können 0,5 bis 1 Gew.-% Natriumformiat eingesetzt werden. Möglich ist auch der Einsatz von Proteasen, die mit löslichen Calciumsalzen und einem Calciumgehalt von vorzugsweise etwa 1,2-Gew.-%, bezogen auf das Enzym, stabilisiert sind. Besonders vorteilhaft ist jedoch der Einsatz von Borverbindungen, beispielsweise von Borsäure, Boroxid, Borax und anderen Alkalimetallboraten wie den Salzen der Orthoborsäure (H3BO3), der Metaborsäure (HBO2) und der Pyroborsäure (Tetraborsäure H2B4O7).The agents can also contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
Vergrauungsinhibitoren haben die Aufgabe, den von der Faser abgelösten Schmutz in der Flotte suspendiert zu halten und so das Vergrauen 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.Graying inhibitors have the task of removing the fiber To keep dirt suspended in the fleet and so that To prevent graying. Water-soluble colloids are usually used for this suitable for organic nature, for example the water-soluble salts of polymer Carboxylic acids, glue, gelatin, salts of ether carboxylic acids or Starch or cellulose or salts of ether sulfonic acids acidic sulfuric acid esters of cellulose or starch. Also water-soluble polyamides containing acid groups are for this Suitable purpose. Soluble starch preparations and use starch products other than the above, e.g. degraded Starch, aldehyde starches etc. Polyvinylpyrrolidone is also useful. However, cellulose ethers such as Carboxymethyl cellulose (sodium salt), methyl cellulose, Hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, Methylcarboxymethylcellulose and their mixtures, as well Polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the funds used.
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. Auch Gemische der vorgenannten Aufheller können verwendet werden.The agents can be used as optical brighteners Contain diaminostilbenedisulfonic acid or its 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, an anilino group or a 2-methoxyethylamino group carry. Brighteners of the type of the substituted diphenyl styrenes, e.g. the alkali salts 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned Brighteners can be used.
Zusätzlich zu den erfindungsgemäß hergestellten Alkalisilicat-Compounds können die Mittel weitere anorganische Salze, auch weitere amorphe Alkalisilicate der oben beschriebenen Art und Alkalicarbonate und/oder Alkalihydrogencarbonate der oben beschriebenen Art enthalten. Weitere anorganische Salze, welche als Inhaltsstoffe in Betracht kommen, sind Neutralsalze wie Sulfate und ggf. auch Chloride in Form ihrer Natrium-und/oder Kaliumsalze.In addition to the alkali silicate compounds produced according to the invention the agent can add other inorganic salts, too further amorphous alkali silicates of the type described above and Alkali carbonates and / or alkali hydrogen carbonates of those described above Kind included. Other inorganic salts, which as Ingredients to be considered are neutral salts such as sulfates and optionally also chlorides in the form of their sodium and / or potassium salts.
Selbstverständlich können auch die üblicherweise in Wasch- oder Reinigungsmitteln enthaltenen Farb- und Duftstoffe enthalten sein. Of course, the usually in washing or Colorants and fragrances contained in cleaning agents.
Die erfindungsgemäßen Alkalisilicat-Compounds B1 bis B4 wurden auf
unterschiedliche Weise erhalten. Die Zusammensetzung der Compounds
(in Gew.-% ) war wie folgt:
In einem Lödige-Pflugscharmischer FKM 130 D wurden 53,4 Gewichtsteile calcinierte Soda mit 31,4 Gewichtsteilen sprühgetrocknetem Natriumsilicat mit einem Molverhältnis Na2O : SiO2 = 1 : 2,0 (PortilRA, Henkel KGaA) für etwa 2 Minuten vermischt. Auf dieses Gemisch wurde eine wäßrige Zubereitung aus 6,6 Gewichtsteilen Wasserglaslösung (Molverhältnis 1 : 2, Feststoffgehalt 50 Gew.-%) und 8,6 Gewichtsteile einer wäßrigen Alkylsulfatpaste (Feststoffgehalt 35 Gew.-%) zudosiert und 2 Minuten nachgemischt.53.4 parts by weight of calcined soda with 31.4 parts by weight of spray-dried sodium silicate with a molar ratio of Na 2 O: SiO 2 = 1: 2.0 (Portil R A, Henkel KGaA) were mixed in a Lödige ploughshare mixer FKM 130 D for about 2 minutes . An aqueous preparation of 6.6 parts by weight of water glass solution (molar ratio 1: 2, solids content 50% by weight) and 8.6 parts by weight of an aqueous alkyl sulfate paste (solids content 35% by weight) was metered into this mixture and mixed in for 2 minutes.
In das vorstehend beschriebene Mischaggregat wurden 94,7 Gewichtsteile eines durch Sprühtrocknung einer Lösung von Soda und Natriumsilicat mit einem Molverhältnis Na2O : SiO2 von 1 : 2 gemäß der deutschen Patentanmeldung 195 01 269.0 erhaltenes Soda/Silicat-Compound vorgelegt. Hierzu wurden 5,3 Gewichtsteile einer wäßrigen Paste von Alkylbenzolsulfonat (Feststoffgehalt 56,6 Gew.-%) unter Vermischen während einer Minute zudosiert und anschließend für 3 Minuten nachgemischt. Die Mischung wurde durch Erhitzen auf 70 °C für eine Zeitdauer von 15 Minuten auf einen freien Wassergehalt von 2,4 Gew.-% getrocknet. Die Bestimmung des freien Wassergehaltes erfolgte mit Hilfe eines Moisture Analyzer MA 30 der Firma Satorius. Dabei wird die zu untersuchende Probe auf einer Aluminium-Wägeschale gleichmäßig verteilt und durch Infrarotheizung von oben getrocknet. Die Trocknungstemperatur wird durch einen Thermofühler in der Nähe der Heizspirale kontrolliert und beträgt etwa 130 °C. Die genaue Trocknungstemperatur und die erforderliche Trocknungszeit muß durch eine Kalibrierung bestimmt werden. Bei dieser Bestimmungsmethode wird nur das bis zu einer Temperatur von etwa 130 °C verdampfbare Wasser erfaßt, nicht jedoch das an das amorphe Silicat chemisch gebundene Wasser, zu dessen Abspaltung höhere Temperaturen erforderlich sind.94.7 parts by weight of a soda / silicate compound obtained by spray drying a solution of soda and sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 2 according to German patent application 195 01 269.0 were placed in the mixing unit described above. For this purpose, 5.3 parts by weight of an aqueous paste of alkylbenzenesulfonate (solids content 56.6% by weight) were metered in with mixing for one minute and then mixed in for 3 minutes. The mixture was dried to a free water content of 2.4% by weight by heating at 70 ° C. for a period of 15 minutes. The free water content was determined using a MA 30 moisture analyzer from Satorius. The sample to be examined is evenly distributed on an aluminum weighing pan and dried from above by infrared heating. The drying temperature is controlled by a thermal sensor near the heating coil and is around 130 ° C. The exact drying temperature and the required drying time must be determined by calibration. With this determination method, only the water that can be evaporated up to a temperature of about 130 ° C. is recorded, but not the water chemically bound to the amorphous silicate, for the elimination of which higher temperatures are required.
Entsprechend der Herstellung des Produkts B1 wurden in das Mischaggregat 53,4 Gewichtsteile calcinierte Soda und 35,13 Gewichtsteile Natriumsilicat gegeben und für 2 Minuten vermischt. Zu dieser Mischung wurden 5,45 Gewichtsteile einer wäßrigen Paste von Alkylbenzolsulfonat (Feststoffgehalt 55 Gew.-%) sowie 6,02 Gewichtsteile Wasser zugegeben und für weitere 2 Minuten vermischt.According to the production of the product B1 were in the mixing unit 53.4 parts by weight of calcined soda and 35.13 parts by weight Added sodium silicate and mixed for 2 minutes. To this 5.45 parts by weight of an aqueous paste of Alkylbenzenesulfonate (solids content 55% by weight) and 6.02 parts by weight Water was added and mixed for a further 2 minutes.
Entsprechend Produkt B1 wurden in dem Mischaggregat 53,4 Gewichtsteile calcinierte Soda und 27,5 Gewichtsteile Natriumsilicat vorgelegt und für eine Zeitdauer von 2 Minuten vermischt. Anschließend wurden 5,5 Gewichtsteile einer wäßrigen Paste von Alkylbenzolsulfonat (Feststoffgehalt 55 Gew.-%) sowie 13,6 Gewichtsteile der für Produkt B1 verwendeten Wasserglaslösung zudosiert. Danach wurde 2 Minuten nachgemischt.According to product B1, 53.4 parts by weight were in the mixing unit calcined soda and 27.5 parts by weight of sodium silicate and mixed for a period of 2 minutes. Subsequently 5.5 parts by weight of an aqueous paste of Alkylbenzenesulfonate (solids content 55% by weight) and 13.6 Parts by weight of the water glass solution used for product B1 are metered in. The mixture was then mixed for 2 minutes.
Das Kornspektrum der erhaltenen Produkte wurde durch Siebanalyse
bestimmt. Dabei wurden folgende Verteilungen erhalten:
Die Produkte hatten folgende Schüttgewichte (g/l): B1 809, B2 465, B3 704 und B4 719.The products had the following bulk densities (g / l): B1 809, B2 465, B3 704 and B4 719.
Es wurde das Aufnahmevermögen der erfindungsgemäßen Alkalisilicat-Compounds
B1 bis B4 gegenüber dem mengengleich eingesetzten
Vergleichscompound NabionR15, tensidfreies Soda/Silicat-Compound
der Firma Rhône-Poulenc, von dem angenommen wird, daß es gemäß
EP-A-488 868 hergestellt wurde, anhand des nichtionischen Tensids
C12-C18-Fettalkohol mit 7 E0 getestet. Das Niotensid-Aufnahmevermögen
wurde entsprechend der DIN ISO 787 bestimmt, wobei
anstelle des dort angegebenen Leinöls das vorstehend genannte
Niotensid verwendet wurde. Für diese Bestimmung wird eine abgewogene
Probenmenge auf eine Platte gegeben. Aus einer Bürette wird
langsam, 4 oder 5 Tropfen auf einmal, Niotensid zugegeben. Nach
jeder Zugabe wird das Niotensid mit einem Spatel in das Pulver
eingerieben. Die Zugabe des Niotensids wird entsprechend fortgesetzt,
bis sich Zusammenballungen von Niotensid und Pulver gebildet
haben. Von diesem Punkt an wird jeweils ein Tropfen Niotensid zugegeben
und mit dem Spatel verrieben. Die Niotensidzugabe wird beendet,
wenn eine weiche Paste entstanden ist. Diese Paste sollte
sich gerade noch ohne zu reißen oder krümeln verteilen lassen und
gerade noch auf der Platte haften. An der Bürette wird die zugegebene
Menge Niotensid abgelesen und auf ml Niotensid pro 100 g Probe
umgerechnet. Dabei wurden folgende Ergebnisse erhalten:
Gemäß der Lehre der internationalen Patentanmeldung WO-A-91/02047
wurden die folgenden erfindungsgemäßen Extrudate E5 bis E8 hergestellt.
Die Extrusionsmischungen der Mittel E5 bis E8 ließen sich
ohne verfahrenstechnische Probleme extrudieren. Die Zusammensetzungen
der Extrudate waren wie in Tabelle 1 aufgeführt. Das
Schüttgewicht der Extrudate lag zwischen 800 und 830 g/l. Die
erfindungsgemäßen Extrudate zeigten ein gutes Löseverhalten: es
wurden nur geringe Rückstände beim Einspülverhalten und beim Löslichkeitstest
erhalten.
Claims (15)
- A process for the production of an anionic-surfactant-containing alkali metal silicate/alkali metal carbonate compound with multiple wash cycle performance, the alkali metal silicate being X-ray amorphous and having a molar M2O to SiO2 ratio (M = alkali metal) of 1:1.5 to 1:3.3 and the compound containing 15 to 50% by weight of alkali metal silicate, 30 to 70% by weight of alkali metal carbonate, 1.5 to 15% by weight of anionic surfactants and 12 to 19% by weight of water, characterized in that a powder-form component selected from alkali metal carbonate, alkali metal silicate or a mixture thereof is agglomerated using an aqueous preparation containing one or more anionic surfactants and, if necessary, that component of the compound to be produced which is not initially introduced in powder form.
- A process as claimed in claim 1, characterized in that powder-form alkali metal carbonate is agglomerated using an aqueous alkali metal silicate solution containing anionic surfactant.
- A process as claimed in claim 1, characterized in that powder-form alkali metal silicate is agglomerated using an alkali metal carbonate solution containing anionic surfactant.
- A process as claimed in claim 1, characterized in that a powder-form mixture of alkali metal silicate and alkali metal carbonate is agglomerated using an aqueous anionic surfactant preparation.
- A process as claimed in claim 1, characterized in that a preformed compound of alkali metal silicate and alkali metal carbonate is agglomerated with an aqueous anionic surfactant preparation.
- A process as claimed in one or more of claims 1 to 5, characterized in that sodium carbonate is used as the alkali metal carbonate.
- A process as claimed in one or more of claims 1 to 6, characterized in that sodium silicate is used as the alkali metal silicate.
- A process as claimed in one or more of claims 1 to 6, characterized in that sodium silicate in which the sodium has been replaced by potassium in such a quantity that the calculated K2O content is between 0.1 and 5% by weight is used as the alkali metal silicate.
- A process as claimed in one or more of claims 1 to 8, characterized in that alkyl benzenesulfonates and/or alk(en)yl sulfates are used as the anionic surfactants.
- A process as claimed in one or more of claims 1 to 9, characterized in that the alkali metal silicate compound produced in accordance with the invention is subsequently treated with liquid ingredients of detergents or cleaners, more particularly with nonionic surfactants.
- The use of an alkali metal silicate compound with multiple wash cycle performance produced by the process claimed in any of claims 1 to 9 in detergents or cleaners produced by granulation, compacting, such as roll compacting, or extrusion or by blending.
- Detergents or deaners containing 10 to 16% by weight zeolite (based on water-free active substance) and 10 to 30% by weight of an alkali metal silicate compound produced by the process claimed in any of claims 1 to 9.
- Detergents or cleaners containing 0 to 5% by weight of zeolite (based on water-free active substance) and 15 to 40% by weight of an alkali metal silicate compound produced by the process claimed in any of claims 1 to 9.
- An extruded detergent or cleaner with a bulk density above 600 g/l containing anionic and optionally nonionic surfactants and an amorphous alkali metal silicate, characterized in that it contains the amorphous alkali metal silicate compound with multiple wash cycle performance produced by the process claimed in any of claims 1 to 9.
- A process for the production of a detergent or cleaner in which a solid free-flowing compound is extruded under pressures of up to 200 bar to form a strand, the strand is cut by a cutting unit to granules of predetermined size as its leaves the multiple-bore extrusion die and the plastic and optionally still moist crude extrudate is subjected to another shaping step and subsequently dried, characterized in that an amorphous alkali metal silicate compound produced by the process claimed in any of claims 1 to 9 is used in the compound.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19525378A DE19525378A1 (en) | 1995-07-12 | 1995-07-12 | Amorphous alkali silicate compound |
DE19525378 | 1995-07-12 | ||
PCT/EP1996/002902 WO1997003168A1 (en) | 1995-07-12 | 1996-07-03 | Amorphous alkali silicate compound |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0839178A1 EP0839178A1 (en) | 1998-05-06 |
EP0839178B1 true EP0839178B1 (en) | 1999-12-08 |
Family
ID=7766637
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96924857A Expired - Lifetime EP0839178B1 (en) | 1995-07-12 | 1996-07-03 | Amorphous alkali silicate compound |
Country Status (10)
Country | Link |
---|---|
US (1) | US6034050A (en) |
EP (1) | EP0839178B1 (en) |
JP (1) | JPH11509248A (en) |
KR (1) | KR19990028914A (en) |
CN (1) | CN1190430A (en) |
AT (1) | ATE187486T1 (en) |
DE (2) | DE19525378A1 (en) |
ES (1) | ES2142078T3 (en) |
HU (1) | HUP9802735A3 (en) |
WO (1) | WO1997003168A1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19501269A1 (en) * | 1995-01-18 | 1996-07-25 | Henkel Kgaa | Amorphous alkali silicate compound |
DE19611013A1 (en) * | 1996-03-21 | 1997-09-25 | Henkel Kgaa | Solid detergent or builder-containing detergent or cleaning agent with a high bulk density or compound therefor |
GB9825558D0 (en) * | 1998-11-20 | 1999-01-13 | Unilever Plc | Granular detergent components and particulate detergent compositions containing them |
GB0006443D0 (en) * | 2000-03-18 | 2000-05-10 | Pilkington Plc | Fire resistant glazings |
DE10027624A1 (en) * | 2000-06-02 | 2001-12-06 | Zschimmer & Schwarz Mohsdorf G | Final cleaning of dyed or printed polyester-containing textiles, comprises oxidative washing in bath containing perborate, ethoxylated fatty acid or alkaryl sulfonate dispersant and alkali |
CA2684585A1 (en) * | 2007-05-17 | 2008-11-27 | The Procter & Gamble Company | Detergent additive extrudates containing alkyl benzene sulphonate |
EP3231770A1 (en) * | 2016-04-13 | 2017-10-18 | Solvay SA | Extrusion process for the preparation of alkali metal carbonate, bicarbonate and sesquicarbonate formulation using a dissolved functionalizing agent |
WO2018049029A1 (en) * | 2016-09-07 | 2018-03-15 | Ecolab Usa Inc. | Solid detergent compositions and methods of adjusting the dispense rate of solid detergents using solid anionic surfactants |
Family Cites Families (26)
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---|---|---|---|---|
CA966980A (en) * | 1971-03-13 | 1975-05-06 | Kawasaki Jukogyo Kabushiki Kaisha | Method of treating nitrogen oxide generating substances by combustion |
US3838192A (en) * | 1971-10-28 | 1974-09-24 | Huber Corp J M | Production of alkali metal polysilicates |
US3879527A (en) * | 1971-10-28 | 1975-04-22 | Huber Corp J M | Alkali metal polysilicates and their production |
US3956467A (en) * | 1974-06-07 | 1976-05-11 | Bertorelli Orlando L | Process for producing alkali metal polysilicates |
US4265790A (en) * | 1979-08-09 | 1981-05-05 | Church & Dwight Co., Inc. | Method of preparing a dry blended laundry detergent containing coarse granular silicate particles |
DE3413571A1 (en) * | 1984-04-11 | 1985-10-24 | Hoechst Ag, 6230 Frankfurt | USE OF CRYSTALLINE LAYERED SODIUM SILICATES FOR WATER SOFTENING AND METHOD FOR WATER SOFTENING |
DE3706036A1 (en) * | 1987-02-25 | 1988-09-08 | Basf Ag | POLYACETALS, METHOD FOR THE PRODUCTION THEREOF FROM DIALDEHYDES AND POLYOLCARBONIC ACIDS AND USE OF THE POLYACETALS |
DE3825858A1 (en) * | 1988-07-29 | 1990-02-01 | Henkel Kgaa | LOW-PHOSPHATE BUILDER SALT COMBINATION |
ATE107352T1 (en) * | 1989-08-09 | 1994-07-15 | Henkel Kgaa | PRODUCTION OF COMPACT GRANULES FOR DETERGENT. |
EP0488868B1 (en) * | 1990-11-30 | 1996-02-21 | Rhone-Poulenc Chimie | Alcaline metal silicate based builder for detergent compositions |
ATE133637T1 (en) * | 1991-07-02 | 1996-02-15 | Crosfield Joseph & Sons | SILICATES |
DE4124701A1 (en) * | 1991-07-25 | 1993-01-28 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF SOLID DETERGENT AND CLEANING AGENT WITH HIGH SHOCK WEIGHT AND IMPROVED SOLUTION SPEED |
DE69126778T2 (en) * | 1991-07-31 | 1998-01-02 | Ausimont Spa | Process for increasing the bleaching efficiency of an inorganic persalt |
DE4134914A1 (en) * | 1991-10-23 | 1993-04-29 | Henkel Kgaa | DETERGENT AND CLEANING AGENT WITH SELECTED BUILDER SYSTEMS |
IT1252682B (en) * | 1991-11-13 | 1995-06-23 | Vomm Impianti & Processi Srl | PRODUCT IN HIGH SPECIFIC WEIGHT GRANULES, PARTICULARLY AS A POWDER DETERGENT ADDITIVE AND METHOD FOR ITS OBTAINING |
DE4221381C1 (en) * | 1992-07-02 | 1994-02-10 | Stockhausen Chem Fab Gmbh | Graft copolymers of unsaturated monomers and sugars, process for their preparation and their use |
DE4203031A1 (en) * | 1992-02-04 | 1993-08-05 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF SOLID DETERGENT AND CLEANING AGENT WITH HIGH SHOCK WEIGHT AND IMPROVED SOLUTION SPEED |
DE4203923A1 (en) * | 1992-02-11 | 1993-08-12 | Henkel Kgaa | METHOD FOR PRODUCING POLYCARBOXYLATES ON A POLYSACCHARIDE BASE |
FR2688798B1 (en) * | 1992-03-20 | 1994-10-14 | Rhobb Poulenc Chimie | BUILDER AGENT BASED ON SILICATE AND A MINERAL PRODUCT. |
DE4235646A1 (en) * | 1992-10-22 | 1994-04-28 | Henkel Kgaa | Process for the production of extrudates that are active in washing and cleaning |
DE4300772C2 (en) * | 1993-01-14 | 1997-03-27 | Stockhausen Chem Fab Gmbh | Water-soluble, biodegradable copolymers based on unsaturated mono- and dicarboxylic acids, process for their preparation and their use |
EP0651050A1 (en) * | 1993-11-03 | 1995-05-03 | The Procter & Gamble Company | Surfactant agglomerate particle |
DE4435743C2 (en) * | 1994-02-17 | 1998-11-26 | Chemolux Sarl | Process for the production of a multi-component granulate |
DE4419745A1 (en) * | 1994-06-06 | 1995-12-07 | Henkel Kgaa | Granulated water-soluble silicic acid-containing alkali silicate |
DE4442977A1 (en) * | 1994-12-02 | 1996-06-05 | Henkel Kgaa | Detergent or cleaning agent with water-soluble builder substances |
DE19501269A1 (en) * | 1995-01-18 | 1996-07-25 | Henkel Kgaa | Amorphous alkali silicate compound |
-
1995
- 1995-07-12 DE DE19525378A patent/DE19525378A1/en not_active Withdrawn
-
1996
- 1996-07-03 DE DE59603874T patent/DE59603874D1/en not_active Expired - Lifetime
- 1996-07-03 KR KR1019980700216A patent/KR19990028914A/en not_active Application Discontinuation
- 1996-07-03 US US08/981,923 patent/US6034050A/en not_active Expired - Lifetime
- 1996-07-03 EP EP96924857A patent/EP0839178B1/en not_active Expired - Lifetime
- 1996-07-03 HU HU9802735A patent/HUP9802735A3/en unknown
- 1996-07-03 CN CN96195409A patent/CN1190430A/en active Pending
- 1996-07-03 WO PCT/EP1996/002902 patent/WO1997003168A1/en not_active Application Discontinuation
- 1996-07-03 JP JP9505475A patent/JPH11509248A/en active Pending
- 1996-07-03 ES ES96924857T patent/ES2142078T3/en not_active Expired - Lifetime
- 1996-07-03 AT AT96924857T patent/ATE187486T1/en active
Also Published As
Publication number | Publication date |
---|---|
HUP9802735A2 (en) | 1999-03-29 |
ES2142078T3 (en) | 2000-04-01 |
CN1190430A (en) | 1998-08-12 |
US6034050A (en) | 2000-03-07 |
WO1997003168A1 (en) | 1997-01-30 |
ATE187486T1 (en) | 1999-12-15 |
DE19525378A1 (en) | 1997-01-16 |
KR19990028914A (en) | 1999-04-15 |
EP0839178A1 (en) | 1998-05-06 |
HUP9802735A3 (en) | 1999-08-30 |
JPH11509248A (en) | 1999-08-17 |
DE59603874D1 (en) | 2000-01-13 |
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