EP0552193B1 - Percarbonate-containing washing agent - Google Patents
Percarbonate-containing washing agent Download PDFInfo
- Publication number
- EP0552193B1 EP0552193B1 EP91917296A EP91917296A EP0552193B1 EP 0552193 B1 EP0552193 B1 EP 0552193B1 EP 91917296 A EP91917296 A EP 91917296A EP 91917296 A EP91917296 A EP 91917296A EP 0552193 B1 EP0552193 B1 EP 0552193B1
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- EP
- European Patent Office
- Prior art keywords
- weight
- component
- mixture
- water
- powder
- 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
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- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 title claims abstract description 14
- 238000005406 washing Methods 0.000 title claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000012190 activator Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 238000001694 spray drying Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 27
- 239000007844 bleaching agent Substances 0.000 claims description 20
- -1 alkali metal percarbonate Chemical class 0.000 claims description 13
- 239000003599 detergent Substances 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical group CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 claims 1
- UAOKXEHOENRFMP-ZJIFWQFVSA-N [(2r,3r,4s,5r)-2,3,4,5-tetraacetyloxy-6-oxohexyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O UAOKXEHOENRFMP-ZJIFWQFVSA-N 0.000 claims 1
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 238000004061 bleaching Methods 0.000 abstract description 11
- 125000000129 anionic group Chemical group 0.000 abstract description 2
- 239000011256 inorganic filler Substances 0.000 abstract description 2
- 229910003475 inorganic filler Inorganic materials 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229940045872 sodium percarbonate Drugs 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 239000004435 Oxo alcohol Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000004967 organic peroxy acids Chemical class 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- QECVIPBZOPUTRD-UHFFFAOYSA-N N=S(=O)=O Chemical class N=S(=O)=O QECVIPBZOPUTRD-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000003857 carboxamides Chemical group 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 229940079919 digestives enzyme preparation Drugs 0.000 description 1
- FSBVERYRVPGNGG-UHFFFAOYSA-N dimagnesium dioxido-bis[[oxido(oxo)silyl]oxy]silane hydrate Chemical compound O.[Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O FSBVERYRVPGNGG-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical group 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
- 239000000428 dust Substances 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
- 229940088598 enzyme Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000004492 methyl ester group Chemical group 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 150000004682 monohydrates Chemical class 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
- 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-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
- 239000004482 other powder Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 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
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/02—Preparation in the form of powder by spray drying
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
Definitions
- the invention relates to a powdery bleach and detergent for use in household laundry, which can be added to the wash liquor as the sole active detergent or which increases the cleaning action of a conventional detergent.
- Bleaching agents which contain a combination of an inorganic peroxide or perhydrate as a bleaching system with a bleach activator which forms an organic peracid under washing conditions have been known for a long time.
- the most frequently used bleaching components containing active oxygen are the alkali perborates, percarbonates, persulfates and persilicates, among which sodium perborate, which is used as tetra- or monohydrate, occupies a dominant position.
- activators such compounds are generally used which split off carboxylic acids or percarboxylic acids under hydrolysis or perhydrolysis conditions, predominantly those compounds being used which deliver peracetic acid in the presence of the oxidizing agents mentioned.
- European patent application EP-A-0 114 308 describes spray-dried multi-component detergents, the first spray-dried component comprising the main part of the zeolite builder and small amounts of nonionic surfactant and the second spray-dried component the remaining zeolite and higher amounts of anionic and / or nonionic surfactant contains.
- Other powder components which also include per compounds, can be added.
- the spray drying components disclosed therein contain 10-25% by weight or 5-15% by weight of water. It is also known from European patent application EP-A-0 061 295 and Japanese patent application JP-A-1 085 297 that detergent ingredients can be divided into various powder components, at least one of which is produced by spray drying and the bleaching agent and bleach activator are admixed can.
- detergents which contain 77-98.5 parts of a spray-dried powder containing aluminosilicate, 1-15 parts of percarbonate and 0.5-8 parts of TAED, with percarbonate and the bleach activator TAED in the ratio 1: 1 to 10: 1 must be present.
- the invention is a storage-stable, essentially phosphate-free powdered bleach and detergent mixture containing alkali percarbonate, bleach activator, surfactant and builder in 3 powdery components
- component A is a powder produced by spray drying, containing anionic surfactant, water-soluble and / or insoluble builder
- component B the alkali percarbonate and component C the activator for the percarbonate, which is characterized in that it is 10% by weight to 93% by weight, preferably 20% by weight to 85% by weight and in particular 40% by weight to 80% by weight of component A, 5% by weight to 70% by weight, preferably 13% by weight to 60% by weight .-% and in particular 18 wt .-% to 50 wt .-% of component B and 2 wt .-% to 20 wt .-%, preferably 2 wt .-% to 10 wt .-
- the amounts of water of the powder components specified in the context of the present invention relate to water which can be expelled when heated to a temperature of 200.degree.
- the phrase "essentially free” means that the substance or component mentioned consists for the most part of the substance or substances mentioned and no additives are added during the preparation of the agents according to the invention, of which they are essentially should be free.
- certain starting substances may contain small amounts of other substances due to the manufacturing process, but these do not have a negative effect in the context of the present invention.
- commercially available sodium percarbonate can contain small amounts, usually below 5% by weight, of phosphate.
- the agent according to the invention preferably has a bulk density of not more than 800 grams per liter, in particular from 300 to 800 grams per liter and particularly preferably from 400 to 700 grams per liter. It will preferably used as an additive to detergent-containing liquors, especially in the temperature range from 30 ° C to 60 ° C, to enhance the bleaching effect (bleach booster), but can also be used, especially if contaminated textiles are to be cleaned only with relatively small amounts of non-bleachable soiling can be used as the sole active cleaning component of the wash liquor.
- the builder contained in component A is a water-soluble or a water-insoluble compound or a mixture of two or more of such compounds.
- Suitable builder substances are, in particular, those from the classes of polycarboxylic acids, in particular polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, phyllosilicates, in particular bentonites, aluminum silicates, in particular zeolites, alkali metal silicates, in particular sodium silicate, and alkali metal carbonates, in particular sodium carbonate.
- the aforementioned polycarboxylic acids are usually used in the form of their alkali metal salts, in particular their sodium or potassium salts.
- the preferably incorporated zeolites are in particular those of the NaA or NaX type or mixtures thereof.
- alkali silicates those with molar ratios of SiO2 to alkali oxide in the range from 1.5 to 3.0 are preferred.
- Such builder substances are preferably present in component A in amounts from 20% by weight to 90% by weight, in particular from 40% by weight to 80% by weight.
- Suitable anionic surfactants are in particular those of the sulfate or sulfonate type, but other types such as soaps, long-chain N-acyl sarcosinates, salts of fatty acid cyanamides or salts of ether carboxylic acids, such as are obtainable from long-chain alkyl or alkylphenyl polyglycol ethers and chloroacetic acid, can also be used .
- the anionic surfactants are preferably used in the form of the sodium salts. Such surfactants are preferably contained in component A in amounts of from 2% by weight to 30% by weight, in particular from 5% by weight to 20% by weight.
- Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of long-chain primary alcohols of natural and synthetic origin with 10 to 20 carbon atoms, that is to say of fatty alcohols such as, for example, coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, or the C10- bis C20 oxo alcohols and those of secondary alcohols of these chain lengths.
- the sulfuric acid monoesters of the aliphatic primary alcohols, secondary alcohols or alkylphenols ethoxylated with 1 to 6 mol of ethylene oxide come into consideration.
- Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
- the surfactants of the sulfonate type are primarily the alkylbenzenesulfonates with C9 to C15 alkyl groups, sulfosuccinic acid monoesters and diesters with 6 to 22 C atoms in the alcohol parts and the esters of ⁇ -sulfofatty acids, for example the ⁇ -sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
- alkanesulfonates which can be obtained from C12- to C18-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins
- olefin sulfonates that is to say mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from long-chain monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
- alkylbenzenesulfonates with linear C9 to C15 alkyl groups the fatty alcohol sulfates with 12 to 18 C atoms and mixtures of these surfactants are particularly preferred.
- powder component A can contain inorganic filler salt, preferably in amounts not exceeding 50% by weight, in particular 1% by weight to 30% by weight.
- inorganic filler salts include in particular the alkali chlorides and alkali sulfates.
- Component A of the bleaching and washing agent according to the invention which contains builder and surfactant, is prepared in a manner known in principle by spray drying an aqueous suspension or slurry. Care should be taken to ensure that drying takes place in such a way that component A contains no more than 3% by weight of water.
- Component B contains alkali percarbonate, which is preferably the sole constituent of this component.
- Sodium percarbonate is particularly suitable, which, due to the production process, may contain small amounts, usually below 5% by weight, based on alkali percarbonate, of phosphate and, if appropriate, further salts.
- Component B can be present as a crystallized powder or, optionally with the aid of granulation aids, granulated powder.
- Suitable activator component C is any powder-formable compound that provides organic peracid under perhydrolysis conditions.
- These include in particular N- or 0-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, N-acylated triazines, in particular 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium isononanoylphenolsulfonate, and acylated sugar derivatives, especially pentaacetate.
- N- or 0-acyl compounds for
- the bleach activator may have been coated with coating substances in a known manner or, if appropriate using granulating aids, may have been granulated and, if desired, may contain further additives, for example colorants.
- the powder component C preferably contains more than 65% by weight, in particular more than 90% by weight, of bleach activator.
- a bleach activator is used which forms peracetic acid under the washing conditions.
- TAED tetraacetylethylene diamine
- TAED tetraacetylethylene diamine
- the washing and bleaching agent according to the invention can contain water-soluble salts as a further powdery component which do not give off water of crystallization in the range from 1 ° C. to 45 ° C. and whose melting point is above 45 ° C.
- water-soluble salts include in particular sodium chloride, anhydrous sodium carbonate, sodium nitrate, sodium acetate and mixtures thereof.
- Such powdery components are preferably not contained in the agents according to the invention in excess of 30% by weight, in particular from 5% by weight to 20% by weight.
- the agent according to the invention can contain, in addition to the previously mentioned constituents, complexing agents for heavy metals, which increase both the storage stability, in particular the percarbonate component, and the bleaching effect of the bleaching agent according to the invention under conditions of use.
- Suitable complexing agents include aminopolycarboxylic acids, in particular nitrilotriacetic acid, ethylenediaminetetraacetic acid, polyphosphonic acids, in particular aminotri- (methylenephosphonic acid), ethylenediaminetetra-methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid and their alkali metal salts, in particular their sodium salts.
- Such complexing agents are preferably present in amounts not exceeding 10% by weight, in particular from 0.1% by weight to 2% by weight, based on the finished composition. They can be part of component A, B or C and are preferably incorporated into the spray-dried powder (component A), in which they can be present in particular in amounts of 0.1% by weight to 10% by weight.
- the washing and bleaching agent according to the invention can additionally, preferably in amounts not exceeding 10% by weight, in particular from 2% by weight to 6% by weight, based on the finished composition, contain nonionic surfactant which may be present as part of the spray-dried component A or which may have been sprayed onto the optionally available powdered water-soluble salt. If it is present as part of component A, in which it can preferably be present in amounts not exceeding 10% by weight, in particular from 2% by weight to 6% by weight, the nonionic surfactant can be present as part of the aqueous slurry co-sprayed or sprayed onto the powder in a known manner after the other components have been spray-dried.
- Suitable nonionic surfactants include alkyl polyglycosides with 10 to 22 carbon atoms in the alkyl part and the alkoxylates, in particular the ethoxylates and / or propoxylates of linear or branched chain alcohols with 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
- the degree of alkoxylation of the alcohols is between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
- the derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used.
- the ethoxylates of primary alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful.
- Corresponding ethoxylation and / or propoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the alcohols mentioned with regard to the alkyl part, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical can also be used.
- the agent according to the invention can moreover contain further additives customary in bleaching and washing agents, such as enzymes, dyes and / or fragrances.
- These components are preferably present in amounts not exceeding 1% by weight, in particular from 0.05 to 0.5% by weight, based on the total composition. They can be part of one or more powder components or more or less homogeneously distributed over all powder components.
- the preparation of the agents according to the invention does not require any major technical effort. Usually are simple mixing devices, such as shovels or Drum mixer suitable in which the powdery components can be mixed. The use of automatic belt scales in combination with free-fall mixers is also possible and is preferred for continuous production of the agents according to the invention. If appropriate, the mixture can be carried out with simultaneous spraying of dyes and / or fragrances or liquid enzyme preparations.
- Table 1 Composition of powder component A [% by weight] A1 A2 Na-C12 alkyl benzene sulfonate 5 4.8 sodium 44 42.2 Turpinal (R) 4 NL a) 1 1.0 Sodium silicate 11 10.6 Sokalan (R) CP 5 b) 2nd 1.9 Sodium sulfate 35 33.6 Dehydol (R) LST c) - 4.0 water 2nd 1.9 a) Tetra-Na-hydroxyethane-1,1-diphosphonate (manufacturer Henkel) b) acrylic acid / maleic acid copolymer (30:70), sodium salt (manufacturer BASF) c) 3- to 5-fold ethoxylated C12 ⁇ 18 fatty alcohols (manufacturer Henkel)
- the bleaching agents M1 to M6 according to the invention characterized by their composition were produced by mixing the powder components listed in Table 2 below in a free-fall mixer while simultaneously spraying on an oxidation-stable perfume.
- Table 2 Composition of agents according to the invention [% by weight] M1 M2 M3 M4 M5 M6 A1 65.9 - 55.9 - 55.9 - A2 - 65.9 - 55.9 - 55.9 - 55.9 Sodium percarbonate a) 27.0 27.0 27.0 27.0 27.0 27.0 TAED b) 7.0 7.0 7.0 7.0 7.0 sodium - - 10.0 10.0 - - Sodium carbonate / dehydol (R) LST c) - - - - 10.0 10.0 Perfume 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 a a) Active oxygen content 14% (manufacturer Interox) b) Granules according to EP 037
- the detergents and bleaches M1 to M6 were free-flowing, non-clumping powders with bulk densities of about 560 to 620 grams per liter. They were stored at temperatures from 20 ° C to 40 ° C for a period of 24 weeks without any noticeable loss of activity, while similar formulations, whose powder component A contained more than 3% by weight of water, showed clear decreases in their active oxygen content after only a few weeks of storage . In all cases, the bleaching performance of the detergents according to the invention was at least not worse than that of agents produced for comparison purposes which contained sodium perborate instead of sodium percarbonate.
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Abstract
Description
Die Erfindung betrifft ein pulverförmiges Bleich- und Waschmittel zur Anwendung in der Haushaltswäsche, das als alleiniges reinigungsaktives Mittel der Waschlauge zugesetzt werden kann oder die Reinigungswirkung eines üblichen Waschmittels verstärkt.The invention relates to a powdery bleach and detergent for use in household laundry, which can be added to the wash liquor as the sole active detergent or which increases the cleaning action of a conventional detergent.
Bleichmittel, die als Bleichsystem eine Kombination eines anorganischen Peroxids oder Perhydrats mit einem Bleichaktivator, der unter Waschbedingungen eine organische Persäure bildet, enthalten, sind seit langer Zeit bekannt. Die am häufigsten eingesetzten aktivsauerstoffhaltigen Bleichkomponenten sind die Alkaliperborate, -percarbonate, -persulfate und - persilikate, unter denen Natriumperborat, das als Tetra- oder Monohydrat verwendet wird, eine dominierende Position einnimmt. Als Aktivatoren werden in der Regel solche Verbindungen verwendet, die unter Hydrolyse- beziehungsweise Perhydrolysebedingungen Carbonsäuren beziehungsweise Percarbonsäuren abspalten, wobei in überwiegendem Maße solche Verbindungen eingesetzt werden, die in Gegenwart der erwähnten Oxidationsmittel Peressigsäure liefern. Da die Reaktion des Aktivators mit der Perverbindung, die erst unter den wäßrigen Waschbedingungen erfolgen soll, auch bei der Herstellung und insbesondere der Lagerung derartiger Mittel ablaufen kann, wodurch die Verfügbarkeit der Perverbindung für den eigentlichen Anwendungszweck zurückgeht, wird seit langer Zeit nach Stabilisatoren für die erwähnten Bleichsysteme gesucht. So ist zum Beispiel die Umhüllung der Aktivator- oder der Oxidationskomponente oder beider mit Fettsäuren vorgeschlagen worden. Auch die Zugabe bestimmter Stabilisatoren, beispielsweise Magnesiumsilikat, ist bekannt. Für Percarbonat-haltige Bleichsysteme ist das Problem der mangelhaften Lagerstabilität besonders schwer zu lösen, da dieses Perhydrat extrem hydrolyseanfällig ist und sowohl von der normalen Luftfeuchtigkeit rasch zersetzt wird als auch in Bleichmitteln, die in wasserundurchlässigen Verpackungen gelagert werden, unter Verlust von Aktivsauerstoff zerfällt.Bleaching agents which contain a combination of an inorganic peroxide or perhydrate as a bleaching system with a bleach activator which forms an organic peracid under washing conditions have been known for a long time. The most frequently used bleaching components containing active oxygen are the alkali perborates, percarbonates, persulfates and persilicates, among which sodium perborate, which is used as tetra- or monohydrate, occupies a dominant position. As activators such compounds are generally used which split off carboxylic acids or percarboxylic acids under hydrolysis or perhydrolysis conditions, predominantly those compounds being used which deliver peracetic acid in the presence of the oxidizing agents mentioned. Since the reaction of the activator with the per-compound, which is only to take place under the aqueous washing conditions, can also take place during the production and in particular the storage of such agents, as a result of which the availability of the per-compound for the actual intended use decreases, stabilizers for the have long been used Wanted bleaching systems mentioned. For example, the coating of the activator component or the oxidation component or both with fatty acids has been proposed. The addition of certain stabilizers, for example magnesium silicate, is also known. For percarbonate-containing bleaching systems, the problem of inadequate storage stability is particularly difficult to solve, since this perhydrate is extremely susceptible to hydrolysis and from both normal atmospheric moisture is rapidly decomposed and also in bleaches, which are stored in water-impermeable packaging, disintegrates with the loss of active oxygen.
In der europäischen Patentanmeldung EP-A-0 114 308 werden sprühgetrocknete Mehrkomponenten-Waschmittel beschrieben, wobei deren erste sprühgetrocknete Komponente den Hauptteil des zeolithischen Builders und geringe Mengen nichtionisches Tensid und deren zweite sprühgetrocknete Komponente den restlichen Zeolith und höhere Mengen anionischen und/oder nichtionischen Tensids enthält. Weitere Pulverkomponenten, zu denen auch Perverbindungen gehören, können zugemischt werden. Die dort offenbarten Sprühtrocknungskomponenten enthalten 10-25 Gew.-% beziehungsweise 5-15 Gew.-% Wasser. Auch aus der europäischen Patentanmeldung EP-A-0 061 295 und der japanischen Patentanmeldung JP-A-1 085 297 ist bekannt, daß Waschmittelinhaltsstoffe auf verschiedene Pulverkomponenten aufgeteilt werden können, von denen zumindest eine durch Sprühtrocknung hergestellt wird und der Bleichmittel sowie Bleichaktivator zugemischt werden kann. Aus der japanischen Patentanmeldung JP-A-1 006 098 sind Waschmittel bekannt, die 77-98,5 Teile eines sprühgetrockneten aluminosilikathaltigen Pulvers, 1-15 Teile Percarbonat und 0,5-8 Teile TAED enthalten, wobei Percarbonat und der Bleichaktivator TAED im Verhältnis 1:1 bis 10:1 vorliegen müssen.European patent application EP-A-0 114 308 describes spray-dried multi-component detergents, the first spray-dried component comprising the main part of the zeolite builder and small amounts of nonionic surfactant and the second spray-dried component the remaining zeolite and higher amounts of anionic and / or nonionic surfactant contains. Other powder components, which also include per compounds, can be added. The spray drying components disclosed therein contain 10-25% by weight or 5-15% by weight of water. It is also known from European patent application EP-A-0 061 295 and Japanese patent application JP-A-1 085 297 that detergent ingredients can be divided into various powder components, at least one of which is produced by spray drying and the bleaching agent and bleach activator are admixed can. From Japanese patent application JP-A-1 006 098, detergents are known which contain 77-98.5 parts of a spray-dried powder containing aluminosilicate, 1-15 parts of percarbonate and 0.5-8 parts of TAED, with percarbonate and the bleach activator TAED in the ratio 1: 1 to 10: 1 must be present.
Gegenstand der Erfindung, mit der die oben geschilderten Nachteile der mangelhaften Lagerstabilität Percarbonat-haltiger Bleichsysteme vermieden werden können, ist ein lagerstabiles, im wesentlichen phosphatfreies pulverförmiges Bleich- und Waschmittelgemisch, enthaltend Alkalipercarbonat, Bleichaktivator, Tensid und Builder in 3 pulverförmigen Komponenten, wobei Komponente A ein durch Sprühtrocknen hergestelltes Pulver ist, enthaltend Aniontensid, wasserlöslichen und/oder unlöslichen Builder, Komponente B das Alkalipercarbonat und Komponente C den Aktivator für das Percarbonat enthält, das dadurch gekennzeichnet ist, daß es 10 Gew.-% bis 93 Gew.-%, vorzugsweise 20 Gew.-% bis 85 Gew.-% und insbesondere 40 Gew.-% bis 80 Gew.-% der Komponente A, 5 Gew.-% bis 70 Gew.-%, vorzugsweise 13 Gew.-% bis 60 Gew.-% und insbesondere 18 Gew.-% bis 50 Gew.-% der Komponente B und 2 Gew.-% bis 20 Gew.-%, vorzugsweise 2 Gew.-% bis 10 Gew.-% der Komponente C enthält und die Komponente A weniger als 3 Gew.-% Wasser enthält.The invention, with which the above-mentioned disadvantages of poor storage stability of percarbonate-containing bleaching systems can be avoided, is a storage-stable, essentially phosphate-free powdered bleach and detergent mixture containing alkali percarbonate, bleach activator, surfactant and builder in 3 powdery components, component A is a powder produced by spray drying, containing anionic surfactant, water-soluble and / or insoluble builder, component B the alkali percarbonate and component C the activator for the percarbonate, which is characterized in that it is 10% by weight to 93% by weight, preferably 20% by weight to 85% by weight and in particular 40% by weight to 80% by weight of component A, 5% by weight to 70% by weight, preferably 13% by weight to 60% by weight .-% and in particular 18 wt .-% to 50 wt .-% of component B and 2 wt .-% to 20 wt .-%, preferably 2 wt .-% to 10 wt .-% of the component C contains and component A contains less than 3 wt .-% water.
Die im Rahmen der vorliegenden Erfindung angegebenen Wassermengen der Pulverkomponenten beziehen sich auf Wasser, das bei Erhitzen auf eine Temperatur von 200 °C ausgetrieben werden kann.The amounts of water of the powder components specified in the context of the present invention relate to water which can be expelled when heated to a temperature of 200.degree.
Die Formulierung "im wesenlichen frei" bedeutet im Rahmen des vorliegenden Textes, daß die angesprochene Substanz oder Komponente zum weitaus überwiegenden Teil aus dem genannten Stoff oder den genannten Stoffen besteht und während der Herstellung der erfindungsgemäßen Mittel keine Zusätze hinzugegeben werden, von der sie im wesentlichen frei sein soll. Allerdings können bestimmte Ausgangssubstanzen herstellungsbedingt geringe Mengen anderer Stoffe enthalten, die sich im Rahmen der vorliegenden Erfindung jedoch nicht negativ auswirken. So kann zum Beispiel handelsübliches Natriumpercarbonat geringe Mengen, in der Regel unter 5 Gew.-%, Phosphat enthalten.In the context of the present text, the phrase "essentially free" means that the substance or component mentioned consists for the most part of the substance or substances mentioned and no additives are added during the preparation of the agents according to the invention, of which they are essentially should be free. However, certain starting substances may contain small amounts of other substances due to the manufacturing process, but these do not have a negative effect in the context of the present invention. For example, commercially available sodium percarbonate can contain small amounts, usually below 5% by weight, of phosphate.
Das erfindungsgemäße Mittel weist vorzugsweise ein Schüttgewicht von nicht über 800 Gramm pro Liter, insbesondere von 300 bis 800 Gramm pro Liter und besonders bevorzugt von 400 bis 700 Gramm pro Liter auf. Es wird vorzugsweise als Zusatz zu waschmittelhaltigen Flotten, insbesondere im Temperaturbereich von 30 °C bis 60 °C, zur Verstärkung der Bleichwirkung (Bleichbooster) eingesetzt, kann allerdings auch, insbesondere wenn nur mit relativ geringen Mengen an nicht-bleichbaren Anschmutzungen verunreinigte Textilien gereinigt werden sollen, als alleinige reinigungsaktive Komponente der Waschflotte verwendet werden.The agent according to the invention preferably has a bulk density of not more than 800 grams per liter, in particular from 300 to 800 grams per liter and particularly preferably from 400 to 700 grams per liter. It will preferably used as an additive to detergent-containing liquors, especially in the temperature range from 30 ° C to 60 ° C, to enhance the bleaching effect (bleach booster), but can also be used, especially if contaminated textiles are to be cleaned only with relatively small amounts of non-bleachable soiling can be used as the sole active cleaning component of the wash liquor.
Bei dem in der Komponente A enthaltenen Builder handelt es sich um eine wasserlösliche oder eine wasserunlösliche Verbindung oder um ein Gemisch aus zwei oder mehreren derartiger Verbindungen. Geeignete Buildersubstanzen sind insbesondere solche aus den Klassen der Polycarbonsäuren, insbesondere polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und Copolymere aus diesen, Schichtsilikate, insbesondere Bentonite, Alumosilikate, insbesondere Zeolithe, Alkalisilikate, insbesondere Natriumsilikat, und Alkalicarbonate, insbesondere Natriumcarbonat. Die vorgenannten Polycarbonsäuren werden üblicherweise in Form ihrer Alkalisalze, insbesondere ihrer Natrium- oder Kaliumsalze eingesetzt. Die vorzugsweise eingearbeiteten Zeolithe sind insbesondere solche des NaA- oder NaX-Typs oder deren Gemische. Unter den Alkalisilikaten sind solche mit Molverhältnissen von SiO₂ zu Alkalioxid im Bereich von 1,5 bis 3,0 bevorzugt. Derartige Buildersubstanzen sind in Komponente A vorzugsweise in Mengen von 20 Gew.-% bis 90 Gew.-%, insbesondere von 40 Gew.-% bis 80 Gew.-% enthalten.The builder contained in component A is a water-soluble or a water-insoluble compound or a mixture of two or more of such compounds. Suitable builder substances are, in particular, those from the classes of polycarboxylic acids, in particular polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, phyllosilicates, in particular bentonites, aluminum silicates, in particular zeolites, alkali metal silicates, in particular sodium silicate, and alkali metal carbonates, in particular sodium carbonate. The aforementioned polycarboxylic acids are usually used in the form of their alkali metal salts, in particular their sodium or potassium salts. The preferably incorporated zeolites are in particular those of the NaA or NaX type or mixtures thereof. Among the alkali silicates, those with molar ratios of SiO₂ to alkali oxide in the range from 1.5 to 3.0 are preferred. Such builder substances are preferably present in component A in amounts from 20% by weight to 90% by weight, in particular from 40% by weight to 80% by weight.
Geeignete anionische Tenside sind insbesondere solche vom Sulfat- oder Sulfonattyp, doch können auch andere Typen wie Seifen, langkettige N-Acylsarkosinate, Salze von Fettsäurecyanamiden oder Salze von Ethercarbonsäuren, wie sie aus langkettigen Alkyl- oder Alkylphenyl-Polyglykolethern und Chloressigsäure zuganglich sind, verwendet werden. Die anionischen Tenside werden vorzugsweise in Form der Natriumsalze verwendet. Derartige Tenside sind in Komponente A vorzugsweise in Mengen von 2 Gew.-% bis 30 Gew.-%, insbesondere von 5 Gew.-% bis 20 Gew.-% enthalten.Suitable anionic surfactants are in particular those of the sulfate or sulfonate type, but other types such as soaps, long-chain N-acyl sarcosinates, salts of fatty acid cyanamides or salts of ether carboxylic acids, such as are obtainable from long-chain alkyl or alkylphenyl polyglycol ethers and chloroacetic acid, can also be used . The anionic surfactants are preferably used in the form of the sodium salts. Such surfactants are preferably contained in component A in amounts of from 2% by weight to 30% by weight, in particular from 5% by weight to 20% by weight.
Besonders geeignete Tenside vom Sulfattyp sind die Schwefelsäuremonoester von langkettigen primären Alkoholen natürlichen und synthetischen Ursprungs mit 10 bis 20 C-Atomen, das heißt von Fettalkoholen wie zum Beispiel Kokosfettalkoholen, Talgfettalkoholen, Oleylalkohol, oder den C₁₀- bis C₂₀-Oxoalkoholen und solche von sekundären Alkoholen dieser Kettenlängen. Daneben kommen die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten aliphatischen primären Alkohole, sekundären Alkohole oder Alkylphenole in Betracht. Ferner eignen sich sulfatierte Fettsäurealkanolamide und sulfatierte Fettsäuremonoglyceride.Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of long-chain primary alcohols of natural and synthetic origin with 10 to 20 carbon atoms, that is to say of fatty alcohols such as, for example, coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, or the C₁₀- bis C₂₀ oxo alcohols and those of secondary alcohols of these chain lengths. In addition, the sulfuric acid monoesters of the aliphatic primary alcohols, secondary alcohols or alkylphenols ethoxylated with 1 to 6 mol of ethylene oxide come into consideration. Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
Bei den Tensiden vom Sulfonattyp handelt es sich in erster Linie um die Alkylbenzolsulfonate mit C₉- bis C₁₅-Alkygruppen, um Sulfobernsteinsäuremono- und -diester mit 6 bis 22 C-Atomen in den Alkoholteilen und um die Ester von α-Sulfofettsäuren, beispeilsweise die α-sulfonierten Methyl- oder Ethylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren. Weitere brauchbare Tenside vom Sulfonattyp sind die Alkansulfonate, die aus C₁₂- bis C₁₈-Alkanen durch Sulfochlorierung oder Sulfoxidation und anschließende Hydrolyse bzw. Neutralisation oder durch Bisulfitaddition an Olefine erhältlich sind, sowie die Olefinsulfonate, das heißt Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie zum Beispiel aus langkettigen Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließender alkalischer oder saurer Hydrolyse der Sulfonierungsprodukte erhält.The surfactants of the sulfonate type are primarily the alkylbenzenesulfonates with C₉ to C₁₅ alkyl groups, sulfosuccinic acid monoesters and diesters with 6 to 22 C atoms in the alcohol parts and the esters of α-sulfofatty acids, for example the α -sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Other useful surfactants of the sulfonate type are the alkanesulfonates which can be obtained from C₁₂- to C₁₈-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and also the olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from long-chain monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
Besonders bevorzugt werden die Alkylbenzolsulfonate mit linearen C₉- bis C₁₅-Alkylgruppen, die Fettalkoholsulfate mit 12 bis 18 C-Atomen und Gemische dieser Tenside verwendet.The alkylbenzenesulfonates with linear C₉ to C₁₅ alkyl groups, the fatty alcohol sulfates with 12 to 18 C atoms and mixtures of these surfactants are particularly preferred.
Zusätzlich kann die Pulverkomponente A anorganisches Füllsalz, vorzugsweise in Mengen nicht über 50 Gew.-%, insbesondere 1 Gew.-% bis 30 Gew.-% enthalten. Zu derartigen Füllsalzen gehören insbesondere die Alkalichloride und Alkalisulfate.In addition, powder component A can contain inorganic filler salt, preferably in amounts not exceeding 50% by weight, in particular 1% by weight to 30% by weight. Such filling salts include in particular the alkali chlorides and alkali sulfates.
Die Builder- und Tensid-haltige Komponente A des erfindungsgemäßen Bleich- und Waschmittels wird in im Prinzip bekannter Weise durch Sprühtrocknen einer wäßrigen Suspension oder Aufschlämmung hergestellt. Dabei ist darauf zu achten, daß die Trocknung derart erfolgt, daß Komponente A nicht mehr als 3 Gew.-% Wasser enthält. Vorzugsweise geht man daher so vor, daß eine etwa 30 Gew.-% bis 65 Gew.-% Wasser enthaltende Suspension der Inhaltsstoffe der Pulverkomponente A auf Temperaturen von etwa 40 °C bis 100 °C erwärmt und mittels Düsen unter einem Zerstäubungsdruck von etwa 20 bis 120 bar, insbesondere von 30 bis 60 bar, in einen Fallraum gesprüht wird, in den im Gleichstrom oder vorzugsweise im Gegenstrom Trocknungsgase eingeleitet werden, die Eingangstemperaturen von etwa 150 °C bis etwa 350 °C, insbesondere von 200 °C bis 250 °C aufweisen. Die auf diese Weise erzeugten Pulver enthalten normalerweise weniger als 5 % Bestandteile mit Korngrößen unter 0,1 mm, eventuell auftretende höhere Staubanteile können durch einfaches Aussieben entfernt und in den Herstellungsprozeß zurückgeführt werden. Vorzugsweise weist die derart hergestellte Pulverkomponente A ein Schüttgewicht von 250 Gramm pro Liter bis 750 Gramm pro Liter auf.Component A of the bleaching and washing agent according to the invention, which contains builder and surfactant, is prepared in a manner known in principle by spray drying an aqueous suspension or slurry. Care should be taken to ensure that drying takes place in such a way that component A contains no more than 3% by weight of water. It is therefore preferred to proceed in such a way that an approximately 30% by weight to 65% by weight water-containing suspension of the Ingredients of powder component A heated to temperatures of about 40 ° C to 100 ° C and sprayed into a falling space by means of nozzles under an atomizing pressure of about 20 to 120 bar, in particular from 30 to 60 bar, in which in cocurrent or preferably in countercurrent Drying gases are introduced, which have inlet temperatures of about 150 ° C to about 350 ° C, in particular from 200 ° C to 250 ° C. The powders produced in this way normally contain less than 5% of constituents with particle sizes below 0.1 mm; any higher dust content that may occur can be removed by simple sieving and returned to the production process. The powder component A produced in this way preferably has a bulk density of 250 grams per liter to 750 grams per liter.
Komponente B enthält Alkalipercarbonat, das vorzugsweise der alleinige Bestandteil dieser Komponente ist. In Frage kommt insbesondere Natriumpercarbonat, das bedingt durch das Herstellungsverfahren geringe Mengen, normalerweise unter 5 Gew.-% bezogen auf Alkalipercarbonat, an Phosphat sowie gegebenenfalls weitere Salze enthalten kann. Komponente B kann als kristallisiertes oder, gegebenenfalls mit Hilfe von Granulationshilfsmitteln, granuliertes Pulver vorliegen.Component B contains alkali percarbonate, which is preferably the sole constituent of this component. Sodium percarbonate is particularly suitable, which, due to the production process, may contain small amounts, usually below 5% by weight, based on alkali percarbonate, of phosphate and, if appropriate, further salts. Component B can be present as a crystallized powder or, optionally with the aid of granulation aids, granulated powder.
Als Aktivatorkomponente C ist jede pulverförmig konfektionierbare, unter Perhydrolysebedingungen organische Persäure liefernde Verbindung geeignet. Zu diesen gehören insbesondere N- oder 0-Acylverbindungen, beispielsweise mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin, N-acylierte Triazine, insbesondere 1,5-Diacetyl-2,4-dioxo-hexahydro-1,3,5-triazin, acylierte Glykolurile, insbesondere Tetraacetylglykoluril, N-acylierte Hydantoine, Hydrazide, Triazole, Urazole, Diketopiperazine, Sulfurylamide und Cyanurate, außerdem Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, Carbonsäureester, insbesondere Natrium-isononanoylphenolsulfonat, und acylierte Zuckerderivate, insbesondere Pentaacetylglukose. Der Bleichaktivator kann in bekannter Weise mit Hüllsubstanzen überzogen oder, gegebenenfalls unter Einsatz von Granulierhilfsmittlen, granuliert worden sein und gewünschtenfalls weitere Zusatzstoffe, beispielsweise Farbstoft, enthalten. Vorzugsweise enthält die Pulverkomponente C über 65 Gew.-%, insbesondere über 90 Gew.-% Bleichaktivator. Vorzugsweise wird ein Bleichaktivator eingesetzt, der unter den Waschbedingungen Peressigsäure bildet. Unter diesen ist mit Hilfe von Carboxymethylcellulose granuliertes Tetraacetylethylendiamin (TAED) mit mittleren Korngrößen von 0,01 mm bis 0,8 mm, wie es nach dem in der europäischen Patentschrift EP 037 026 beschriebenen Verfahren hergestellt werden kann, besonders bevorzugt. TAED ist vorzugsweise in Mengen von 94 Gew.-% bis 99 Gew.-% in der Pulverkomponente C enthalten.Suitable activator component C is any powder-formable compound that provides organic peracid under perhydrolysis conditions. These include in particular N- or 0-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, N-acylated triazines, in particular 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium isononanoylphenolsulfonate, and acylated sugar derivatives, especially pentaacetate. The bleach activator may have been coated with coating substances in a known manner or, if appropriate using granulating aids, may have been granulated and, if desired, may contain further additives, for example colorants. The powder component C preferably contains more than 65% by weight, in particular more than 90% by weight, of bleach activator. Preferably a bleach activator is used which forms peracetic acid under the washing conditions. Among these, tetraacetylethylene diamine (TAED) granulated with the aid of carboxymethyl cellulose and having average grain sizes of 0.01 mm to 0.8 mm, as can be produced by the process described in European Patent EP 037 026, is particularly preferred. TAED is preferably contained in the powder component C in amounts of 94% by weight to 99% by weight.
Zusätzlich zu den Komponenten A, B und C kann das erfindungsgemäße Wasch- und Bleichmittel als weitere pulverförmige Komponente wasserlösliche Salze enthalten, die im Bereich von 1 °C bis 45 °C kein Kristallwasser abgeben und deren Schmelzpunkt über 45 °C liegt. Zu diesen gehören insbesondere Natriumchlorid, wasserfreies Natriumcarbonat, Natriumnitrat, Natriumacetat und deren Gemische. Derartige pulverförmige Komponenten sind in den erfindungsgemäßen Mitteln vorzugsweise nicht über 30 Gew.-%, insbesondere von 5 Gew.-% bis 20 Gew.-% enthalten.In addition to components A, B and C, the washing and bleaching agent according to the invention can contain water-soluble salts as a further powdery component which do not give off water of crystallization in the range from 1 ° C. to 45 ° C. and whose melting point is above 45 ° C. These include in particular sodium chloride, anhydrous sodium carbonate, sodium nitrate, sodium acetate and mixtures thereof. Such powdery components are preferably not contained in the agents according to the invention in excess of 30% by weight, in particular from 5% by weight to 20% by weight.
Das erfindungsgemäße Mittel kann zusätzlich zu den bisher genannten Bestandteilen Komplexbildner für Schwermetalle enthalten, die sowohl die Lagerstabilität, insbesondere der Percarbonat-Komponente, wie auch die Bleichwirkung des erfindungsgemäßen Bleichmittels unter Anwendungsbedingungen erhöhen. Zu den geeigneten Komplexierungsmitteln gehören Aminopolycarbonsäuren, insbesondere Nitrilotriessigsäure, Ethylendiamintetraessigsäure, Polyphosphonsäuren, insbesondere Aminotri-(methylenphosphonsäure), Ethylendiamintetra-methylenphosphonsäure) und 1-Hydroxyethan-1,1-diphosphonsäure sowie deren Alkalisalze, insbesondere deren Natriumsalze. Derartige Komplexbildner sind vorzugsweise in Mengen nicht über 10 Gew.-%, insbesondere von 0,1 Gew.-% bis 2 Gew.-%, bezogen auf das fertige Mittel, vorhanden. Sie können Teil der Komponente A, B oder C sein und werden vorzugsweise in das sprühgetrocknete Pulver (Komponente A) eingearbeitet, in dem sie insbesondere in Mengen von 0,1 Gew.-% bis 10 Gew.-% vorhanden sein können.The agent according to the invention can contain, in addition to the previously mentioned constituents, complexing agents for heavy metals, which increase both the storage stability, in particular the percarbonate component, and the bleaching effect of the bleaching agent according to the invention under conditions of use. Suitable complexing agents include aminopolycarboxylic acids, in particular nitrilotriacetic acid, ethylenediaminetetraacetic acid, polyphosphonic acids, in particular aminotri- (methylenephosphonic acid), ethylenediaminetetra-methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid and their alkali metal salts, in particular their sodium salts. Such complexing agents are preferably present in amounts not exceeding 10% by weight, in particular from 0.1% by weight to 2% by weight, based on the finished composition. They can be part of component A, B or C and are preferably incorporated into the spray-dried powder (component A), in which they can be present in particular in amounts of 0.1% by weight to 10% by weight.
Weiterhin kann das erfindungsgemäße Wasch- und Bleichmittel zusätzlich, vorzugsweise in Mengen nicht über 10 Gew.-%, insbesondere von 2 Gew.-% bis 6 Gew.-%, bezogen auf das fertige Mittel nichtionisches Tensid enthalten, das als Teil der sprühgetrockneten Komponente A vorliegen oder auf das fakultativ vorhandene pulverförmige wasserlösliche Salz aufgedüst worden sein kann. Falls es als Teil der Komponente A, in der es vorzugsweise in Mengen nicht über 10 Gew.-%, insbesondere von 2 Gew.-% bis 6 Gew.-% enthalten sein kann, vorliegt, kann das nichtionische Tensid als Teil der wäßrigen Aufschlämmung mitversprüht oder nach dem Sprühtrocknen der übrigen Bestandteile in im Prinzip bekannter Weise auf das Pulver aufgedüst werden. Zu den in Frage kommenden nichtionischen Tensiden gehören Alkylpolyglykoside mit 10 bis 22 C-Atomen im Alkylteil und die Alkoxylate, insbesondere die Ethoxylate und/oder Propoxylate von linearen oder verzweigtkettigen Alkoholen mit 10 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen. Der Alkoxylierungsgrad der Alkohole liegt dabei zwischen 1 und 20, vorzugsweise zwischen 3 und 10. Sie können in bekannter Weise durch Umsetzung der entsprechenden Alkohole mit den entsprechenden Alkylenoxiden hergestellt werden. Geeignet sind insbesondere die Derivate der Fettalkohole, obwohl auch deren verzweigtkertige Isomere, insbesondere sogenannte Oxoalkohole, zur Herstellung verwendbarer Alkoxylate eingesetzt werden können. Brauchbar sind demgemäß insbesondere die Ethoxylate primärer Alkohole mit linearen Dodecyl-, Tetradecyl-, Hexadecyl- oder Octadecylresten sowie deren Gemische. Außerdem sind entsprechende Ethoxylierungs- und/oder Propoxylierungsprodukte von Alkylaminen, vicinalen Diolen und Carbonsäureamiden, die hinsichtlich des Alkylteils den genannten Alkoholen entsprechen, sowie von Alkylphenolen mit 5 bis 12 C-Atomen im Alkylrest verwendbar.Furthermore, the washing and bleaching agent according to the invention can additionally, preferably in amounts not exceeding 10% by weight, in particular from 2% by weight to 6% by weight, based on the finished composition, contain nonionic surfactant which may be present as part of the spray-dried component A or which may have been sprayed onto the optionally available powdered water-soluble salt. If it is present as part of component A, in which it can preferably be present in amounts not exceeding 10% by weight, in particular from 2% by weight to 6% by weight, the nonionic surfactant can be present as part of the aqueous slurry co-sprayed or sprayed onto the powder in a known manner after the other components have been spray-dried. Suitable nonionic surfactants include alkyl polyglycosides with 10 to 22 carbon atoms in the alkyl part and the alkoxylates, in particular the ethoxylates and / or propoxylates of linear or branched chain alcohols with 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The degree of alkoxylation of the alcohols is between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. The derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used. Accordingly, the ethoxylates of primary alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. Corresponding ethoxylation and / or propoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the alcohols mentioned with regard to the alkyl part, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical can also be used.
Das erfindungsgemäße Mittel kann darüberhinaus weitere in Bleich- und Waschmitteln übliche Zusatzstoffe, wie Enzyme, Farbstoffe und/oder Duftstoffe, enthalten. Diese Bestandteile sind vorzugsweise in Mengen nicht über 1 Gew.-%, insbesondere von 0,05 bis 0,5 Gew.-%, bezogen auf das gesamte Mittel, vorhanden. Sie können Teil einer oder mehrerer Pulverkomponenten sein oder mehr oder weniger homogen auf alle pulverförmigen Bestandteile verteilt sein.The agent according to the invention can moreover contain further additives customary in bleaching and washing agents, such as enzymes, dyes and / or fragrances. These components are preferably present in amounts not exceeding 1% by weight, in particular from 0.05 to 0.5% by weight, based on the total composition. They can be part of one or more powder components or more or less homogeneously distributed over all powder components.
Die Herstellung der erfindungsgemäßen Mittel erfordert keinen größeren technischen Aufwand. Meist sind einfache Mischapparaturen, wie Schaufel- oder Trommelmischer geeignet, in denen die pulverförmigen Komponenten gemischt werden können. Auch die Verwendung automatisch arbeitender Bandwaagen in Kombination mit Freifallmischern ist möglich und wird für eine kontiniuerliche Produktion der erfindungsgemäßen Mittel bevorzugt. Gegebenenfalls kann die Mischung unter gleichzeitigem Aufdüsen von Farb- und/oder Duftstoffen beziehungsweise flüssigen Enzymzubereitungen erfolgen.The preparation of the agents according to the invention does not require any major technical effort. Mostly are simple mixing devices, such as shovels or Drum mixer suitable in which the powdery components can be mixed. The use of automatic belt scales in combination with free-fall mixers is also possible and is preferred for continuous production of the agents according to the invention. If appropriate, the mixture can be carried out with simultaneous spraying of dyes and / or fragrances or liquid enzyme preparations.
Durch Versprühen von etwa 35 Gew.-% Wasser enthaltenden Aufschlämmungen, die auf 60 °C bis 70 °C erwärmt worden waren, unter einem Druck von etwa 60 bar und Temperaturen des Trocknungsgases von 220 °C bis 230 °C wurden die in der nachfolgenden Tabelle 1 durch ihre Zusammensetzung charakterisierten Pulver (Komponente A) hergestellt. Diese wiesen Schüttdichten von etwa 450 Gramm pro Liter auf.
Durch Vermischen der in der nachfolgenden Tabelle 2 angegebenen Pulverkomponenten in einem Freifallmischer unter gleichzeitigem Aufdüsen eines oxidationsstabilen Parfüms wurden die durch ihre Zusammensetzung charakterisierten erfindungsgemäßen Bleichmittel M1 bis M6 hergestellt.
Die Wasch- und Bleichmittel M1 bis M6 waren freifließende, nicht klumpende Pulver mit Schüttdichten von etwa 560 bis 620 Gramm pro Liter. Sie wurden bei Temperaturen von 20 °C bis 40 °C über einen Zeitraum von 24 Wochen ohne nennenswerten Aktivitätsverlust gelagert, während gleichartige Formulierungen, deren Pulverkomponente A über 3 Gew.-% Wasser enthielt, schon nach Lagerungszeiten von wenigen Wochen deutliche Abnahmen ihres Aktivsauerstoffgehaltes zeigten. Die Bleichleistung der erfindungsgemäßen Waschmittel war in allen Fällen zumindest nicht schlechter als die von zu Vergleichszwecken hergestellten Mitteln, die statt Natriumpercarbonat Natriumperborat enthielten.The detergents and bleaches M1 to M6 were free-flowing, non-clumping powders with bulk densities of about 560 to 620 grams per liter. They were stored at temperatures from 20 ° C to 40 ° C for a period of 24 weeks without any noticeable loss of activity, while similar formulations, whose powder component A contained more than 3% by weight of water, showed clear decreases in their active oxygen content after only a few weeks of storage . In all cases, the bleaching performance of the detergents according to the invention was at least not worse than that of agents produced for comparison purposes which contained sodium perborate instead of sodium percarbonate.
Claims (9)
- A substantially phosphate-free powder-form bleach and detergent mixture containing alkali metal percarbonate, bleach activator, surfactant and builder in 3 powder-form components, component A being a powder prepared by spray drying containing anionic surfactant and water-soluble and/or insoluble builder, component B containing the alkali metal percarbonate and component C containing an activator for the percarbonate, characterized in that it contains 10% by weight to 93% by weight of component A, 5% by weight to 70% by weight of component B and 2% by weight to 20% by weight of component C and component A contains less than 3% by weight of water.
- A mixture as claimed in claim 1, characterized in that it contains 20% by weight to 85% by weight and more particularly 40% by weight to 80% by weight of component A, 13% by weight to 60% by weight and more particularly 18% by weight to 50% by weight of component B and 2% by weight to 20% by weight and more particularly 2% by weight to 10% by weight of component C.
- A mixture as claimed in claim 1 or 2, characterized in that component A contains 2% by weight to 40% by weight and more particularly 5% by weight to 20% by weight of anionic surfactant, 20% by weight to 90% by weight and more particularly 40% by weight to 80% by weight of builder, not more than 50% by weight and more particularly 1% by weight to 30% by weight of inorganic filling salt, not more than 10% by weight and more particularly 0.1% by weight to 2% by weight of complexing agent and not more than 10% by weight and more particularly 2% by weight to 6% by weight of nonionic surfactant.
- A mixture as claimed in any of claims 1 to 3, characterized in that the bleach activator present in component C is a compound which forms peracetic acid under washing conditions.
- A mixture as claimed in claim 4, characterized in that the bleach activator is N,N,N',N'-tetraacetyl ethylene diamine, 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, tetraacetyl glycol uril and/or pentaacetyl glucose.
- A mixture as claimed in any of claims 1 to 5, characterized in that it contains as an additional component not more than 30% by weight and more particularly 5% by weight to 20% by weight of a powder-form water-soluble salt which does not release any water of crystallization at temperatures in the range from 1°C to 45°C and of which the melting point is above 45°C.
- A mixture as claimed in claim 6, characterized in that the water-soluble salt is selected from the group consisting of sodium chloride, anhydrous sodium carbonate, sodium nitrate, sodium acetate and mixtures thereof.
- A mixture as claimed in claim 6 or 7, characterized in that the water-soluble salt contains no more than 10% by weight and, in particular, 2% by weight to 10% by weight, based on the mixture as a whole, of nonionic surfactant.
- A mixture as claimed in any of claims 1 to 8, characterized in that it has an apparent density below 800 grams per litre, preferably between 300 and 800 grams per litre and more particularly between 400 and 700 grams per litre.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4031910 | 1990-10-08 | ||
| DE4031910A DE4031910A1 (en) | 1990-10-08 | 1990-10-08 | PERCARBONATE DETERGENT |
| PCT/EP1991/001872 WO1992006167A1 (en) | 1990-10-08 | 1991-09-30 | Percarbonate-containing washing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0552193A1 EP0552193A1 (en) | 1993-07-28 |
| EP0552193B1 true EP0552193B1 (en) | 1995-10-25 |
Family
ID=6415871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91917296A Expired - Lifetime EP0552193B1 (en) | 1990-10-08 | 1991-09-30 | Percarbonate-containing washing agent |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0552193B1 (en) |
| JP (1) | JPH06501723A (en) |
| AT (1) | ATE129521T1 (en) |
| DE (2) | DE4031910A1 (en) |
| ES (1) | ES2079678T3 (en) |
| WO (1) | WO1992006167A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11659838B2 (en) | 2021-04-01 | 2023-05-30 | Sterilex, Llc | Quat-free powdered disinfectant/sanitizer |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9021761D0 (en) * | 1990-10-06 | 1990-11-21 | Procter & Gamble | Detergent compositions |
| DE4424005A1 (en) * | 1994-07-07 | 1996-01-11 | Henkel Kgaa | Powdery bleach and detergent |
| DE4433027A1 (en) * | 1994-09-16 | 1996-03-21 | Henkel Kgaa | Powdery, enzyme-containing bleach and detergent |
| DE19501117A1 (en) * | 1995-01-17 | 1996-07-18 | Henkel Kgaa | Bleaching detergent in granular form |
| US5565422A (en) * | 1995-06-23 | 1996-10-15 | The Procter & Gamble Company | Process for preparing a free-flowing particulate detergent composition having improved solubility |
| DE60040462D1 (en) * | 1999-06-16 | 2008-11-20 | Kao Corp | PARTICULATE DETERGENT ADDITIVE |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA774818B (en) * | 1976-08-17 | 1979-03-28 | Colgate Palmolive Co | Disintegrable detergent builder agglomerates |
| PH20653A (en) * | 1981-03-23 | 1987-03-16 | Unilever Nv | Process for preparing low silicate detergent compositions |
| DE3248022A1 (en) * | 1982-12-24 | 1984-06-28 | Henkel KGaA, 4000 Düsseldorf | SPRAY-DRIED MULTI-COMPONENT DETERGENT |
| GB8334017D0 (en) * | 1983-12-21 | 1984-02-01 | Unilever Plc | Detergent composition |
| GB8401770D0 (en) * | 1984-01-24 | 1984-02-29 | Unilever Plc | Detergent and bleaching compositions |
| DE3545947A1 (en) * | 1985-12-23 | 1987-07-02 | Henkel Kgaa | PHOSPHATE-FREE, GRANULAR DETERGENT |
-
1990
- 1990-10-08 DE DE4031910A patent/DE4031910A1/en not_active Ceased
-
1991
- 1991-09-30 JP JP3515475A patent/JPH06501723A/en active Pending
- 1991-09-30 WO PCT/EP1991/001872 patent/WO1992006167A1/en active IP Right Grant
- 1991-09-30 AT AT91917296T patent/ATE129521T1/en not_active IP Right Cessation
- 1991-09-30 EP EP91917296A patent/EP0552193B1/en not_active Expired - Lifetime
- 1991-09-30 DE DE59106781T patent/DE59106781D1/en not_active Expired - Lifetime
- 1991-09-30 ES ES91917296T patent/ES2079678T3/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| WORLD PATENTS INDEX LATEST Derwent Publications Ltd., London, GB; AN 89-140880 & JP,A, 1085297 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11659838B2 (en) | 2021-04-01 | 2023-05-30 | Sterilex, Llc | Quat-free powdered disinfectant/sanitizer |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59106781D1 (en) | 1995-11-30 |
| ES2079678T3 (en) | 1996-01-16 |
| WO1992006167A1 (en) | 1992-04-16 |
| DE4031910A1 (en) | 1992-04-09 |
| ATE129521T1 (en) | 1995-11-15 |
| EP0552193A1 (en) | 1993-07-28 |
| JPH06501723A (en) | 1994-02-24 |
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