EP0728187B1 - Verfahren zur herstellung einer waschmittelzusammensetzung - Google Patents
Verfahren zur herstellung einer waschmittelzusammensetzung Download PDFInfo
- Publication number
- EP0728187B1 EP0728187B1 EP95900225A EP95900225A EP0728187B1 EP 0728187 B1 EP0728187 B1 EP 0728187B1 EP 95900225 A EP95900225 A EP 95900225A EP 95900225 A EP95900225 A EP 95900225A EP 0728187 B1 EP0728187 B1 EP 0728187B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fluorescer
- mixture
- composition
- component
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 103
- 238000000034 method Methods 0.000 title claims description 30
- 239000003599 detergent Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000007787 solid Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 22
- 239000002736 nonionic surfactant Substances 0.000 claims description 18
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 description 31
- 239000007844 bleaching agent Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 13
- PMPJQLCPEQFEJW-HPKCLRQXSA-L disodium;2-[(e)-2-[4-[4-[(e)-2-(2-sulfonatophenyl)ethenyl]phenyl]phenyl]ethenyl]benzenesulfonate Chemical group [Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC=C1\C=C\C1=CC=C(C=2C=CC(\C=C\C=3C(=CC=CC=3)S([O-])(=O)=O)=CC=2)C=C1 PMPJQLCPEQFEJW-HPKCLRQXSA-L 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- -1 biphenyl compound Chemical class 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
- 229920001983 poloxamer Polymers 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- 239000010457 zeolite Substances 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 239000000344 soap Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 238000000280 densification Methods 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
- 229940045872 sodium percarbonate Drugs 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 238000004851 dishwashing Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical class OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 2
- YGUMVDWOQQJBGA-VAWYXSNFSA-N 5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 YGUMVDWOQQJBGA-VAWYXSNFSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 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 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001860 citric acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical class OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- LVVZBNKWTVZSIU-UHFFFAOYSA-N 2-(carboxymethoxy)propanedioic acid Chemical class OC(=O)COC(C(O)=O)C(O)=O LVVZBNKWTVZSIU-UHFFFAOYSA-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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RKWGIWYCVPQPMF-UHFFFAOYSA-N Chloropropamide Chemical compound CCCNC(=O)NS(=O)(=O)C1=CC=C(Cl)C=C1 RKWGIWYCVPQPMF-UHFFFAOYSA-N 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 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
- 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 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical class OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- 229920002535 Polyethylene Glycol 1500 Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004904 UV filter Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye 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
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 230000002366 lipolytic effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WKGHJBXTMFXUNA-UHFFFAOYSA-N n,n,n',n'-tetrahexadecylethane-1,2-diamine Chemical compound CCCCCCCCCCCCCCCCN(CCCCCCCCCCCCCCCC)CCN(CCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCC WKGHJBXTMFXUNA-UHFFFAOYSA-N 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
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 125000005342 perphosphate group Chemical group 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000002797 proteolythic effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate 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
- 239000000126 substance Substances 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- VUYXVWGKCKTUMF-UHFFFAOYSA-N tetratriacontaethylene glycol monomethyl ether Chemical compound COCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO VUYXVWGKCKTUMF-UHFFFAOYSA-N 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
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000008096 xylene 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
-
- 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
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- 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
Definitions
- This invention relates to a process for the production of a detergent composition.
- this invention relates to a process for the production of a high bulk density detergent composition containing a fluorescer.
- Detergent powders typically include components in addition to the detergent-active materials necessary for detergency which provide the powder with characteristics which may be viewed as desirable by the market for example perfume and fluorescer. Fluorescers have been used for many years in conventional spray-dried powders to give improved whiteners.
- the fluorescer material is typically incorporated into the slurry of components which is to be spray-dried to produce the powder. Examples of this process are given in EP-A-352 892, Chemical Abstracts 109, 195, 198 and DE-A-2856687.
- Production of a detergent composition by a mixing process typically involves contacting and mixing the liquid components with the solid components of the composition so that the liquid binds the solid material thereby to form composition particles. With further mixing the particles increase in size to form granules.
- the ratio of liquids to solids has to be sufficiently high to promote binding but not so high that discrete particles are not obtained.
- fluorescers have been incorporated into the powder as a solid material in the mixing/densification step.
- fluorescers may have an undesirable colour. Incorporating such fluorescers in solid form may impair the colour quality of the final powder.
- high bulk density powders having excellent colour properties may be produced by incorporating a fluorescer into a liquid component of the detergent composition to produce a pre-mix of the fluorescer which is then combined with solid components in a mixing step to produce the particulate composition.
- a process for the production of a high bulk density particulate detergent composition or component thereof containing a fluorescer which comprises mixing the fluorescer with a liquid component of the composition or component, said liquid component consisting essentially of a nonionic surfactant and water and optionally fatty acid, to form a fluorescer mixture, and mixing the said fluorescer mixture with a solid component of the composition or component whereby a particulate detergent composition or component is produced.
- High bulk density compositions having a bulk density of at least 750g/l may be produced by the present invention.
- the process of the present invention may be a continuous or a batch process as desired.
- the components of the detergent composition will be selected to provide the desired characteristics and will generally include a surfactant and a builder in addition to the fluorescer.
- the composition comprises at least one liquid component in order to bind the solid components together.
- the fluorescer is mixed with a liquid component, to form a fluorescer mixture which may be a slurry, dispersion or suspension. Agitation may be necessary in such cases to avoid undesirable sedimentation. It is especially preferred that the fluorescer mixture is a solution as particularly good powder colour may be secured.
- the fluorescer mixture comprises a liquid nonionic surfactant. Further, the fluorescer mixture consists of a mixture of a fluorescer, a nonionic surfactant and water and optionally a fatty acid.
- Suitable nonionic surfactants have an average degree of alkoxylation of 3 or more, preferably 5 or more, and desirably 20 or less.
- the fluorescer mixture is a solution to facilitate homogeneous dispersion of the fluorescer through the composition and the nonionic suitably has an average degree of alkoxylation of 6 or more.
- Ethoxylated alcohols are especially preferred. Suitable examples include SYNPERONIC A3, SYNPERONIC A7 ex ICI (SYNPERONIC is a Trademark) and coconut oil ethoxylates having an average degree of ethoxylation of 6.5.
- examples of other liquid components which may be employed with the nonionic surfactant include polyethylene glycols, for example PEG 1500, and glycerol.
- the fluorescer may comprise a fluorescer known in the art, such as a biphenyl compound for example a distyryl biphenyl compound.
- a fluorescer known in the art such as a biphenyl compound for example a distyryl biphenyl compound.
- An especially preferred fluorescer is TINOPAL CBS-X ex Ciba Geigy (TINOPAL is a trademark).
- the fluorescer is suitably present in the composition in an amount of 0.001 to 1%, preferably 0.005 to 0.5%, more preferably 0.01% to 0.4%, especially 0.01 to 0.25% by weight based on the total composition.
- the liquid component and fluorescer are suitably present in the fluorescer mixture in a ratio of 10:0.01 to 5 by weight preferably 10: 0.06 to 4 and more preferably 10:0.1 to 4.
- An especially preferred fluorescer mixture comprises a nonionic surfactant, for example SYNPERONIC A7 ex ICI, water and a fluorescer, for example TINOPAL CBS-X.
- the nonionic surfactant and water are present in a weight ratio of 50:1 to 1:10, preferably 20:1 to 3:8 and more preferably 10:1 to 3:8. Superior powder whiteness (lower 'b' value) is obtained at higher levels of nonionic in the fluoroescer mixture.
- the fluorescer suitably represents 1 to 25%, preferably 5 to 15% and more preferably 6 to 12% by weight of the fluorescer mixture.
- fluorescers are included in the composition to improve fabric whiteness, thus obviating the need for undesirably high levels of coloured fluorescer, for example TINOPAL CBS-X.
- a dimorpholino fluorescer is present in the composition together with the powder fluorescer.
- the fluorescer mixture is suitably prepared by mixing the fluorescer with the liquid component with agitation to obtain preferably a solution.
- the fluorescer is mixed with the nonionic surfactant and the water is then added subsequently, or the fluorescer is added to a mixture of nonionic and water.
- the fluorescer mixture is prepared such that sedimentation of the fluorescer and 'gelling' of the liquid at ambient temperature is avoided.
- the solid component may comprise all of the components of the detergent composition excluding the fluorescer mixture or alternatively the solid component may comprise at least one of the said components and the other components may be incorporated into the composition during or subsequent to the mixing of the solid component and the fluorescer mixture.
- the solid component of the composition may comprise solid particles of individual components or solid particles comprising a plurality of components hereinafter referred to as "adjuncts", Components of the detergent composition which are liquid (excluding the fluorescer mixture) may be added to the solid component during or subsequent to the mixing step or incorporated by means of an adjunct as desired.
- the solid component may be spray-dried powder but preferably comprises materials which are not produced directly by spray-drying, especially if a high bulk density is required.
- the mixing of the fluorescer mixture and the non-spray-dried solid is effected in a high speed mixer with the fluorescer mixture being sprayed onto the solid.
- the particles obtained may be treated further as desired.
- the particles may be passed directly to a cooling and/or drying step to produce finished base powder particles, to which other ingredients may then be post-mixed.
- the particles may be passed to a second, preferably low speed, mixing step in order to increase the bulk density of the particles and optionally then cooled and/ or dried as desired.
- the mixing and densification steps may be carried out simultaneously using a high speed mixer, suitable examples include a Shugi (trademark) Granulator, a Drais (trade mark) K-TTP 80 Granulator and the Lodige (trade mark) CB30 recycler.
- the residence time in the mixing step is suitably about 5 to 30 seconds and the rate of mixing in the apparatus is suitably in the range 100 to 2500rpm depending upon the degree of densification and the particle size required.
- the granulation step if present may be carried out using a lower speed mixer for example, the Drais (trade mark) K-T 160 and the Lodige (trade mark) KM300 mixer.
- the residence time in the granulation step is suitably about 1 to 10 minutes and the rate of mixing in the apparatus is about 40 to 160 rpm.
- a batch process may be employed in which the solid components of the composition are dosed into a mixer and the fluorescer mixture is suitably sprayed onto the solid component.
- Suitable mixers include the FUKAE (a trademark) range of mixers. Other materials may be added subsequently as desired. Residence time is selected according to the required degree of granulation for example 1 to 20 minutes.
- the fluorescer mixture is preferably sprayed onto the solid component of the composition to provide an even distribution of the mixture over the solid component.
- the process of the invention provides a detergent composition having a bulk density of at least 750g/1 and which is not the product of a spray-drying process and which is obtainable by a process according to the invention comprising a surfactant, a detergency builder and a fluorescer and having a Delta R460 value of at least 3.5, preferably at least 5.5 and more preferably at least 6.5.
- the fluorescer is incorporated into the composition by a process according to the invention.
- Delta R460 values are determined by measuring the reflectance of light from the sample at 460 nm when irradiated with a tungsten lamp without a filter and measuring the reflectance, of the sample with a UV filter and calculating the difference between the two measurements.
- the sample analysed is a 355 to 500 ⁇ m fraction obtained by sieving. This method provides an indication of the contribution of the fluorescer to the reflectance of the sample.
- compositions produced according to the present invention will generally contain detergent-active compounds and detergency builders, and may optionally contain bleaching components and other active ingredients to enhance performance and properties.
- the detergent-active compounds may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof.
- Many suitable detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
- the preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds.
- Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 ; primary and secondary alkyl sulphates, particularly C 12 -C 15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
- Sodium salts are generally preferred.
- Nonionic surfactants may be included in any adjuncts employed in the composition in addition to that which may be present in the fluorescer mixture.
- Suitable nonionics include the primary and secondary alcohol ethoxylates, especially the C 8 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
- Non-ethoxylated nonionic surfactants include alkylpolyglycosides also glycerol monoethers, and polyhydroxyamides (glucamide).
- detergent-active compound surfactant
- amount present will depend on the intended use of the detergent composition. For example, for machine dishwashing a relatively low level of a low-foaming nonionic surfactant is generally preferred. In fabric washing compositions, different surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine.
- the total amount of surfactant present will also depend on the intended end use and may be as low as 0.5 wt%, for example, in a machine dishwashing composition, or as high as 60 wt%, for example, in a composition for washing fabrics by hand. In compositions for machine washing of fabrics, an amount of from 5 to 40 wt% is generally appropriate.
- Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or nonionic surfactant, or combinations of the two in any ratio, optionally together with soap.
- the detergent compositions produced according to the invention will generally also contain one or more detergency builders.
- the total amount of detergency builder in the compositions will suitably range from 10 to 80 wt%, preferably from 15 to 60 wt%.
- Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever); crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 201 (Henkel), amorphous aluminosilicates as disclosed in GB 1 473 202 (Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 (Procter & Gamble); and layered silicates as disclosed in EP 164 514B (Hoechst).
- Inorganic phosphate builders for example, sodium orthophosphate, pyrophosphate and tripolyphosphate, may also be present.
- zeolite builders may suitably be present in amounts of from 10 to 45 wt%, amounts of from 15 to 35 wt% being especially suitable for (machine) fabric washing compositions.
- the zeolite used in most commercial particulate detergent compositions is zeolite A.
- maximum aluminium zeolite P zeolite MAP
- Zeolite MAP is an alkali metal aluminosilicate of the P type having a silicon to aluminium ratio not exceeding 1.33, preferably not exceeding 1.15, and more preferably not exceeding 1.07.
- Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
- polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates
- monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates,
- Especially preferred organic builders are citrates, nitrilotriacetic acid and oxydisuccinate and are suitably used in amounts of from 5 to 30 wt%, preferably from 10 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.
- Builders both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
- Detergent compositions produced according to the invention may also suitably contain a bleach system.
- Machine dishwashing compositions may suitably contain a chlorine bleach system, while fabric washing compositions may more desirably contain peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
- peroxy bleach compounds for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
- Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates.
- organic peroxides such as urea peroxide
- inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates.
- Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.
- sodium percarbonate having a protective coating against destabilisation by moisture Especially preferred is sodium percarbonate having a protective coating against destabilisation by moisture.
- Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao).
- the peroxy bleach compound is suitably present in an amount of from 5 to 35 wt%, preferably from 10 to 25 wt%.
- the peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures.
- the bleach precursor is suitably present in an amount of from 1 to 8 wt%, preferably from 2 to 5 wt%.
- Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors.
- An especially preferred bleach precursor suitable for use in the present invention is N,N,N',N'-tetracetyl ethylenediamine (TAED).
- novel quaternary ammonium and phosphonium bleach precursors disclosed in US 4 751 015 and US 4 818 426 (Lever Brothers Company) and EP 402 971A (Unilever) are also of great interest.
- peroxycarbonic acid precursors in particular cholyl-4-sulphophenyl carbonate.
- peroxybenzoic acid precursors in particular, N,N,N-trimethylammonium toluoyloxy benzene sulphonate; and the cationic bleach precursors disclosed in EP 284 292A and EP 303 520A (Kao).
- a bleach stabiliser may also be present.
- Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark), EDTMP.
- An especially preferred bleach system comprises a peroxy bleach compound (preferably sodium percarbonate optionally together with a bleach activator), and a transition metal bleach catalyst as described and claimed in EP 458 397A, EP 458 398A and EP 509 787A (Unilever).
- a peroxy bleach compound preferably sodium percarbonate optionally together with a bleach activator
- a transition metal bleach catalyst as described and claimed in EP 458 397A, EP 458 398A and EP 509 787A (Unilever).
- compositions produced according to the invention may contain alkali metal, preferably sodium, carbonate, in order to increase detergency and ease processing.
- Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%.
- compositions containing little or no sodium carbonate are also within the scope of the invention.
- Powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate polymer, or sodium silicate.
- a powder structurant for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate polymer, or sodium silicate.
- One preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt%.
- detergent compositions produced according to the invention include sodium silicate and sodium metasilicate; antiredeposition agents such as cellulosic polymers; inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; proteolytic and lipolytic enzymes; dyes; coloured speckles; perfumes; foam controllers; and fabric softening compounds. This list is not intended to be exhaustive.
- compositions were produced by mixing a fluorescer mixture with the other composition components in a FUKAE FS-30 mixer (trademark) to produce a granular detergent composition.
- the fluorescer mixture was varied for each example as listed in Table 1 and the other composition components were as listed below: Na LAS 20 Sodium tripolyphosphate 25 Zeolite 4A 23 Sodium carbonate 19
- Examples 1 and 2 were comparative examples in which fluorescer mixture contained non ionic surfactant but no water.
- the final composition had the following components: EXAMPLE FLUORESCENT MIXTURE 1 0.02 TINOPAL CBS-X in 2 NI (suspension) (0.18 TINOPAL CBS-X added to mixer as solid) 2 0.2 TINOPAL CBS-X in 2 NI (suspension) 3 0.5 NI:0.05 TINOPAL CBS-X:0.05 water (solution) (1.5 NI added to mixer as liquid) 4 1.0 NI:0.1 TINOPAL CBS-X:0.1 water (solution) (1.0 NI added to mixer as liquid) 5 1.5 NI:0.15 TINOPAL CBS-X:0.15 water (solution) (0.5 NI added to mixer as liquid) 6 2.0 NI:0.2 TINOPAL CBS-X:0.2 water solution
- the nonionic used was SYNPERONIC A7 ex ICI. (SYNPERONIC AND TINOPAL ARE TRADEMARKS)
- the fluorescer mixtures were produced by mixing the TINOPAL CBS-X fluorescer and nonionic to form a suspension. Where present, water was then added to this suspension. The mixture was then stirred slowly (to avoid sedimentation) for 30 minutes and then allowed to stand for 1 hour.
- the final product was sieved to provide a fraction having a particle size of 355 to 500 ⁇ m.
- the reflectance of this fraction was measured at 460nm under UV light and UV excluded light from which the F value was calculated as described herein. The results are shown in Table 2.
- composition not according to the invention having the same components as listed for Examples 1 to 6 and solid fluorescer (0.2 parts) and non-active solid surfactant (2 parts) was produced by mixing under the same conditions as Examples 1 to 6.
- a series of powders were produced having a fixed level of CBS-X fluorescer which was introduced as a fluorescer mixture consisting of the fluorescer and varying ratios of SYNPERONIC A7 (SYNPERONIC is a TRADEMARK), nonionic surfactant and water.
- the compositions contained the following components (parts by weight): SODIUM CARBONATE 16 SODIUM TRIPOLYPHOSPHATE 40 ZEOLITE 4A 11 Na LAS 27 TINOPAL CBS-X (TRADE MARK) 0.2 SYNPERONIC A7 2 WATER 1.8 MINORS to 100
- FUKAE FS-30 FUKAE is a TRADEMARK
- a fluorescer mixture containing 0.2 parts fluorescer having a nonionic/fluorescer/water ratio) as listed in Table 3 was then sprayed onto the solid with mixing and the Na LAS and any remaining nonionic and water was then dosed into the mixer.
- Powders produced in these Examples exhibit excellent colour characteristics both as a fresh powder and after 2 weeks.
- a higher proportion of nonionic in the fluorescer mixture was found to be advantageous in providing improved whiteness (lower 'b' value).
- Powders were produced by the same process and having the same composition as those of Examples 7 to 14 with fluorescer mixture compositions as follows: EXAMPLE NONIONIC FLUORESCER WATER 15 10 1 1 16 10 1 2 17 10 1 3 18 10 1 4
- the F values of these powders were determined and observed to be in excess of 8 both for the fresh powder and after 9 days.
- the 'b' values were also determined and found to be between 2.5 and 4 for fresh powder and between 4 and 5 after 9 days.
- the 'b' and F values illustrate that powders having excellent colour properties may be obtained by the process of the invention.
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- Detergent Compositions (AREA)
Claims (9)
- Verfahren zur Herstellung eines Fluoreszenzmittelenthaltenden, gekörnten Waschmittels oder einer Komponente davon mit hoher Schüttdichte, umfassend Vermischen des Fluoreszenzmittels mit einem flüssigen Bestandteil des Mittels oder der Komponente, wobei der flüssige Bestandteil aus einem nichtionischen Tensid und Wasser und gegebenenfalls einer Fettsäure besteht, unter Herstellung eines Fluoreszenzmittelgemisches und Vermischen des Fluoreszenzmittelgemisches mit einem festen Bestandteil des Mittels oder der Komponente, wodurch ein gekörntes Waschmittel oder eine gekörnte Komponente hergestellt wird.
- Verfahren nach Anspruch 1, wobei das Fluoreszenzmittelgemisch eine Lösung ist.
- Verfahren nach Anspruch 1 oder Anspruch 2, wobei der flüssige Bestandteil aus einem nichtionischen Tensid und Wasser besteht.
- Verfahren nach Anspruch 1 oder Anspruch 2, wobei der flüssige Bestandteil aus einem nichtionischen Tensid, Wasser und einer Fettsäure besteht.
- Verfahren nach einem der Ansprüche 2 bis 4, wobei das Gewichtsverhältnis von nichtionischem Tensid zu Wasser im Bereich von 50:1 bis 1:10, vorzugsweise 20:1 bis 3:8 und bevorzugter 10:1 bis 3:8, liegt.
- Verfahren nach einem vorangehenden Anspruch, wobei die Gewichtsmenge an Fluoreszenzmittel in dem Fluoreszenzmittelgemisch im Bereich 1 bis 25%, vorzugsweise 5 bis 15% und bevorzugter 6 bis 12%, liegt.
- Verfahren nach einem vorangehenden Anspruch, wobei der flüssige Bestandteil und das Fluoreszenzmittel in einem Gewichtsverhältnis von 10:0,01 bis 5 vorliegen.
- Verfahren nach einem vorangehenden Anspruch, wobei der feste Bestandteil ein anionisches Tensid und/oder einen Waschmittelbuilder als getrennte Komponenten und/oder als Hilfsstoff umfaßt.
- Verfahren nach einem vorangehenden Anspruch, wobei der feste Bestandteil kein Produkt aus einem Sprühtrockenverfahren ist.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9323250 | 1993-11-11 | ||
GB939323250A GB9323250D0 (en) | 1993-11-11 | 1993-11-11 | Process for the production of a detergent composition |
PCT/GB1994/002458 WO1995013358A1 (en) | 1993-11-11 | 1994-11-09 | Process for the production of a detergent composition |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0728187A1 EP0728187A1 (de) | 1996-08-28 |
EP0728187B1 true EP0728187B1 (de) | 1999-01-20 |
Family
ID=10744991
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP95900225A Expired - Lifetime EP0728187B1 (de) | 1993-11-11 | 1994-11-09 | Verfahren zur herstellung einer waschmittelzusammensetzung |
Country Status (15)
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EP (1) | EP0728187B1 (de) |
JP (1) | JP2813469B2 (de) |
CN (1) | CN1063481C (de) |
AU (1) | AU8112494A (de) |
BR (1) | BR9408035A (de) |
CA (1) | CA2173445C (de) |
CZ (1) | CZ290773B6 (de) |
DE (1) | DE69416157T2 (de) |
ES (1) | ES2127503T3 (de) |
GB (1) | GB9323250D0 (de) |
HU (1) | HU217767B (de) |
PL (1) | PL177611B1 (de) |
SK (1) | SK281898B6 (de) |
WO (1) | WO1995013358A1 (de) |
ZA (1) | ZA948557B (de) |
Families Citing this family (3)
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DE19538029A1 (de) | 1995-10-12 | 1997-04-17 | Sued Chemie Ag | Waschmittelzusatz |
GB2318360A (en) * | 1996-10-15 | 1998-04-22 | Ciba Geigy Ag | Fluorescent whitening agent formulation |
JP2017509774A (ja) | 2014-01-20 | 2017-04-06 | ザ プロクター アンド ギャンブル カンパニー | 蛍光増白剤プレミックス |
Family Cites Families (6)
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DE2856087A1 (de) * | 1978-12-23 | 1980-07-10 | Henkel Kgaa | Verfahren zur herstellung weisser, optische aufheller und kationenaustauschfaehige alumosilikate enthaltender, pulverfoermiger waschmittel |
JPS63265999A (ja) * | 1987-04-22 | 1988-11-02 | Kao Corp | 高密度粒状濃縮洗剤組成物 |
JPH0633439B2 (ja) * | 1988-07-28 | 1994-05-02 | 花王株式会社 | 高密度粒状濃縮洗剤組成物 |
FR2655658B1 (fr) * | 1989-12-08 | 1994-11-18 | Rhone Poulenc Chimie | Compose lessiviel a base d'un polyphosphate et notamment d'un agent optiquement actif, son procede de preparation et son utilisation en detergence. |
DE69227311T2 (de) * | 1992-07-15 | 1999-06-02 | The Procter & Gamble Co., Cincinnati, Ohio | Waschmittelzusammensetzungen |
JPH07302401A (ja) * | 1994-04-28 | 1995-11-14 | Narita Giken Kk | 磁気記録再生装置の回転磁気ヘッド装置 |
-
1993
- 1993-11-11 GB GB939323250A patent/GB9323250D0/en active Pending
-
1994
- 1994-10-31 ZA ZA948557A patent/ZA948557B/xx unknown
- 1994-11-09 SK SK577-96A patent/SK281898B6/sk unknown
- 1994-11-09 ES ES95900225T patent/ES2127503T3/es not_active Expired - Lifetime
- 1994-11-09 CZ CZ19961360A patent/CZ290773B6/cs not_active IP Right Cessation
- 1994-11-09 HU HU9601255A patent/HU217767B/hu not_active IP Right Cessation
- 1994-11-09 JP JP7513678A patent/JP2813469B2/ja not_active Expired - Lifetime
- 1994-11-09 CN CN94194112A patent/CN1063481C/zh not_active Expired - Fee Related
- 1994-11-09 BR BR9408035A patent/BR9408035A/pt not_active IP Right Cessation
- 1994-11-09 AU AU81124/94A patent/AU8112494A/en not_active Abandoned
- 1994-11-09 WO PCT/GB1994/002458 patent/WO1995013358A1/en active IP Right Grant
- 1994-11-09 PL PL94315358A patent/PL177611B1/pl not_active IP Right Cessation
- 1994-11-09 CA CA002173445A patent/CA2173445C/en not_active Expired - Fee Related
- 1994-11-09 DE DE69416157T patent/DE69416157T2/de not_active Expired - Lifetime
- 1994-11-09 EP EP95900225A patent/EP0728187B1/de not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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HUT75017A (en) | 1997-03-28 |
BR9408035A (pt) | 1996-12-17 |
JP2813469B2 (ja) | 1998-10-22 |
ZA948557B (en) | 1996-04-30 |
CA2173445C (en) | 2000-07-18 |
PL177611B1 (pl) | 1999-12-31 |
JPH09506122A (ja) | 1997-06-17 |
CZ136096A3 (en) | 1996-10-16 |
WO1995013358A1 (en) | 1995-05-18 |
DE69416157T2 (de) | 1999-06-02 |
CN1134723A (zh) | 1996-10-30 |
HU9601255D0 (en) | 1996-07-29 |
HU217767B (hu) | 2000-04-28 |
DE69416157D1 (de) | 1999-03-04 |
EP0728187A1 (de) | 1996-08-28 |
CA2173445A1 (en) | 1995-05-18 |
GB9323250D0 (en) | 1994-01-05 |
SK281898B6 (sk) | 2001-09-11 |
AU8112494A (en) | 1995-05-29 |
SK57796A3 (en) | 1997-06-04 |
CZ290773B6 (cs) | 2002-10-16 |
CN1063481C (zh) | 2001-03-21 |
ES2127503T3 (es) | 1999-04-16 |
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