AU7383294A - Process for the production of high bulk density detergent composition - Google Patents
Process for the production of high bulk density detergent compositionInfo
- Publication number
- AU7383294A AU7383294A AU73832/94A AU7383294A AU7383294A AU 7383294 A AU7383294 A AU 7383294A AU 73832/94 A AU73832/94 A AU 73832/94A AU 7383294 A AU7383294 A AU 7383294A AU 7383294 A AU7383294 A AU 7383294A
- Authority
- AU
- Australia
- Prior art keywords
- hydrophobic material
- detergent composition
- particulate
- surfactant
- mixing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims description 79
- 239000003599 detergent Substances 0.000 title claims description 48
- 238000000034 method Methods 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000463 material Substances 0.000 claims description 69
- 230000002209 hydrophobic effect Effects 0.000 claims description 60
- 238000002156 mixing Methods 0.000 claims description 24
- 239000011236 particulate material Substances 0.000 claims description 22
- 239000004094 surface-active agent Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000001694 spray drying Methods 0.000 claims description 11
- 230000009969 flowable effect Effects 0.000 claims description 10
- 239000002736 nonionic surfactant Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 description 34
- 238000012360 testing method Methods 0.000 description 22
- 239000007844 bleaching agent Substances 0.000 description 19
- 238000005406 washing Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 239000002243 precursor Substances 0.000 description 12
- 239000000344 soap Substances 0.000 description 9
- -1 alkyl sulphates Chemical class 0.000 description 8
- 239000004744 fabric Substances 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 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
- 125000000864 peroxy group Chemical group O(O*)* 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
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 4
- 239000002002 slurry Substances 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
- 239000000243 solution Substances 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 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
- 238000004090 dissolution Methods 0.000 description 3
- 238000009826 distribution 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
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 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
- 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
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229920000742 Cotton Polymers 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
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 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
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process 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
- 238000000280 densification Methods 0.000 description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 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
- 150000003839 salts Chemical class 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000002352 surface water 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
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 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
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-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
- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 0.000 description 1
- 108010081873 Persil Proteins 0.000 description 1
- GBFLZEXEOZUWRN-VKHMYHEASA-N S-carboxymethyl-L-cysteine Chemical compound OC(=O)[C@@H](N)CSCC(O)=O GBFLZEXEOZUWRN-VKHMYHEASA-N 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
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 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
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 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
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design 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
- 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
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 230000002366 lipolytic effect Effects 0.000 description 1
- 238000011068 loading method Methods 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
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-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
- 239000002304 perfume Substances 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
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002797 proteolythic effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 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
- 229920002545 silicone oil Polymers 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
- 235000019832 sodium triphosphate 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
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension 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
- 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
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Description
Process for the Production of a Detergent Composition
This invention relates to a process for the production of a detergent composition, in particular to a process for the production of a detergent composition having a high bulk density and which contains a hydrophobic material.
Spray-drying has been employed for many years in the production of detergent compositions. In the spray-drying process an aqueous slurry of heat-stable components of the detergent composition is formed and fed to a spray-drying tower at elevated temperature in order to provide a substantially homogeneous mixture of the components. The water in the slurry is then removed by evaporation in the spray-dry tower to produce a spray-dried detergent powder. This powder may then be processed further and/or further components added as desired.
EP-A-337523 (Unilever) discloses a process in which a hydrophobic material is incorporated into a detergent composition produced by a spray-drying process in order to provide improved dispensing and powder properties. The hydrophobic material may be incorporated either in the slurry which is to be spray-dried or it may be sprayed in liquefied form onto the spray-dried detergent composition powder. However, the spray drying process has several drawbacks, in particular, it is very energy intensive and requires significant capital investment.
In recent years there has been a trend towards high bulk density detergent powders in which bulk densities in excess of 700g/l have been achieved. Detergent compositions having a high bulk density, for example in excess of 700 g/1, may be produced without a spray-drying step, herein referred to as a non-tower process, by mixing together the components of the detergent composition in a
mixing apparatus, densifying and optionally granulating the components to produce a high density detergent composition. EP-A-367339 (Unilever) discloses a process for preparing a high bulk density granular detergent composition.
However powders having a high bulk density may be prone to poor dispersion in the wash. A need exists for the dispersion properties of high bulk density detergent powders produced by mixing the components of the. composition rather than by spray-drying (thus avoiding the drawbacks of spray-drying) be improved further.
We have now surprisingly found that by introducing a hydrophobic material into the mixing process, that is, prior to formation of the detergent composition, a detergent composition or component therefor having a high bulk density and improved dispersion properties may be secured.
Accordingly, a first aspect of the invention provides a process for the production of a high bulk density detergent composition or a component therefor, comprising a particulate material which is not the direct product of a spray-drying process, and a hydrophobic material which process comprises mixing the hydrophobic material with the particulate material, densifying the resulting mixture during or subsequent to the said mixing and optionally granulating the said mixture thereby to form a particulate high bulk density detergent composition or component.
The term "composition" as employed herein with regard to this invention also includes components may be processed further for inclusion in such compositions or included as is in such compositions.
Preferably a composition produced by the present invention has a bulk density of at least 700g/l. The process of the present invention may be a continuous or a batch process as desired.
The particulate material may comprise all of the components of the detergent composition excluding the hydrophobic material or alternatively it 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 particulate material and the hydrophobic material. 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 hydrophobic material.
Suitably, the particulate material comprises an adjunct, that is, a particle comprising at least 2 components of the composition. Components of the detergent composition which are liquid may be added to the particulate material during or subsequent to the mixing step or incorporated by means of an adjunct as desired.
Preferably, the hydrophobic material is incorporated into the particulate material in a flowable form, for example as a melt, solution, suspension, or a slurry.
According to a second aspect of the invention there is provided a non-tower process for the production of a detergent composition which comprises mixing a hydrophobic material in a flowable form with a particulate material, densifying the resulting mixture during or subsequent to the said mixing step and optionally granulating the said mixture thereby to form a high density particulate detergent composition.
Suitably the hydrophobic material is in the liquid phase when it is mixed with the base material. The hydrophobic material may be heated to a temperature above its melting point and then mixed with the particulate material. The hydrophobic material is suitably mixed with the particulate material at a rate sufficient to permit efficient mixing between the two components. Preferably the hydrophobic material is substantially uniformly dispersed within the particles of the composition.
Suitably, the hydrophobic material has a viscosity of no more than lOOOmPa and preferably no more than 500mPa at a shear rate of 200 s"1 at the temperature at which it is mixed with the base material.
It is especially preferred that the hydrophobic material be mixed in the liquid phase with a liquid component, preferably a surfactant and more preferably a non-ionic surfactant to form a flowable premix prior to mixing with the particulate material. The premix may then be mixed with the particulate material. Preferably, the hydrophobic material in flowable form is dribbled or sprayed onto the particulate material to provide a substantially even distribution of the flowable material over the particulate material during the mixing step.
By incorporating a hydrophobic material into the detergent composition excellent dispersion properties may be secured without any significant drawbacks being introduced as regards dissolution. This is particularly surprising in that a hydrophobic material would be expected to hinder dissolution in water. A practical benefit is that there is less powder residue in the washing machine and on the washed articles following the washing process.
The hydrophobic material may be a substantially pure material or may be a mixture of different materials. Suitably the hydrophobic material is substantially insoluble in water and has a contact angle to water of at least 75° and preferably at least 85°. The hydrophobic material is suitably solid at ambient temperature and preferably has a melting point in the range 25 to 110°C, more preferably in the range 30 to 80°C, especially 35 to 60°C and optimally 35 to 50°C. It is particularly preferred that the hydrophobic material is solid at ambient temperature for ease of handling but has a melting point below the wash temperature as this reduces undesirable deposition of the material.
Suitable hydrophobic materials include silicone oils; long chain esters preferably having at least 9 carbon atoms in both the acid and the alcohol parts thereof for example stearyl stearate; and preferably hydrocarbon waxes.
Suitably, the hydrophobic material is present in an amount of up to 5 %, preferably from 0.1 to 3%, more preferably from 0.2 to 2%, especially 0.4 to 1.8% by weight based on the detergent composition. Where the hydrophobic material is introduced in a flowable form with a liquid component, the amount of hydrophobic material which may be present in the premix may be limited in order to ensure that the premix is sufficiently mobile to allow for an even distribution of the hydrophobic material during mixing with the particulate material.
Where a continuous process is employed, 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) K 300 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.
The invention further provides a particulate detergent composition comprising a hydrophobic material, a surfactant and a detergency builder obtainable by a non-tower process wherein the hydrophobic material is mixed with the surfactant or builder prior to or whilst the surfactant and builder are mixed.
Preferably the detergent composition is produced by a non-tower process in which the hydrophobic material is mixed with a liquid surfactant, preferably a nonionic surfactant, to produce a solution. The hydrophobic material is preferably melted to aid formation of a solution with the surfactant.
Although, it is preferred that the hydrophobic material be distributed substantially uniformly through the detergent particle, a composition having an inner core which optionally contains a hydrophobic material and which has an outer coating comprising the hydrophobic material is also within the scope of the invention.
Another aspect of the invention provides a particulate detergent composition comprising a hydrophobic material, a surfactant and a detergency builder wherein the detergent particle comprises an inner core not being the direct product of a spray-drying process which comprises the
surfactant, builder and optionally a part of the hydrophobic material and, on the inner core, a coating which comprises the hydrophobic material.
Preferably the distribution of components in the inner core is substantially homogeneous.
Preferably the hydrophobic material in the coating is the major component of the coating and more preferably the coating consists essentially of the hydrophobic material. It is further preferred that the proportion of hydrophobic material in the coating is not in excess of 10% and more preferably not in excess of 5% by weight of the total amount of the hydrophobic material in the particle.
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 (surfactants) 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 C8-C15; primary and secondary alkyl
sulphates, particularly C12-C15 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 that may be used include the primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 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) .
The choice of detergent-active compound (surfactant), and the 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 of 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, but on environmental grounds those are no longer preferred.
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. Advantageously, however, maximum aluminium zeolite P (zeolite MAP) described and claimed in EP 384 070A (Unilever) may be use$ . 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.
Especially preferred organic builders are citrates, nitrolotriacetic 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 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.
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. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.
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 peroxycarboxylie 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) .
The 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. Especially preferred are peroxycarbonic acid precursors, in particular cholyl-4-sulphophenyl carbonate. Also of interest are 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 (heavy metal sequestrant) 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) .
Fluorescer is preferably present in an amount within the range of from 0.02 to 0.8 wt%, more preferably from 0.03 to 0.5 wt%.
The compositions of 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%. However, 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.
One preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt%.
Other materials that may be present in detergent compositions of the invention include sodium silicate and sodium metasilicate; antiredeposition agents such as cellulosic polymers; fluorescers; 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.
The invention is illustrated by the following non- limiting Examples.
Example 1 to 4
A particulate detergent composition was prepared by feeding a particulate material and a flowable premix to a Lodige CB30 recycler high speed mixer/densifier. The flowable premix comprised the wax and nonionic surfactant components listed in Table 1. The particulate material comprised particles of the other solid components listed in Table 1. The hydrocarbon wax was melted prior to mixing with the nonionic surfactant to provide a sprayable solution. The premix was introduced to the mixer and the components mixed and densified for 15 seconds at about 1400rpm. The mixture was then fed to a Lodige Ploughshare granulator operated at about 120 rpm for granulation to form granules of the detergent composition. The residence time was about 2 minutes.
Comparative Examples A to D
Compositions not according to the invention as listed in Table 1 were produced by the same method as in Examples 1 to 4 except that hydrophobic material was not included in the formulation.
Table 1
Example A 1 B 2 C 3 D 4
PAS Na 18.8 18.6 19 18.9 0 0 9.48 9.48
LAS Na 0 0 0 0 27.5 27.5 0 0 A24 Zeolite 49.6 49.2 49.0 48.8 45.2 45.0 55.2 55.2
Carbonate 3.3 3.3 3.3 3.3 4.8 4.8 1.62 1.62 Nonionic
3 EO 8.27 8.3 0 0 4.78 4.75 11.9611.85
7 EO 10.5 10.5 19.8 19.8 8.87 8.83 9.48 9.4 Soap 0 0 0 0 0 0 3.3 3.3
SCMC 0.99 0.99 0.99 0.99 0.99 0.99 1.49 1.49
Wax 0 0.62 0 0.51 0 0.49 0 1 (PRIWAX41)
Water/Salts to to to to to to to to 100 100 100 100 100 100 100 100
The compositions had bulk densities in excess of 700g/l and were formulated with conventional post-dosing materials and then analysed.
Example 5
Compositions A to D and 1 to 4 were subjected to the following tests to assess the delivery into the wash, dispersion and dissolution characteristics. The results are shown below in Table 2.
Test 1: caσe test
Delivery characteristics of the powders were compared using a model system which simulates the delivery of a powder in an automatic washing machine, under more adverse conditions (low temperature, minimal agitation) than those normally encountered in a real wash situation) .
For this test a cylindrical vessel having a diameter of 4 cm and a height of 7 cm, made of 600 micrometre pore size stainless steel mesh, and having a top closure made of Teflon and a bottom closure of the mesh just described, was used. The top closure had inserted therein a 30 cm metal rod to act as a handle, and this handle was attached to an agitator arm positioned above 1 litre of water at 20°C in an open container. By means of this agitator apparatus the cylindrical vessel, held at 45 degrees, could be rotated through a circle with a 10 cm radius over a period of 2 seconds and allowed to rest for 2 seconds, before the start of the next rotation/rest cycle.
A 50 g powder sample was introduced into the cylindrical vessel which was then closed. The vessel was attached to the agitator arm which was then moved down to a position such that the top of the cylindrical vessel was just below the surface of the water. After a 10 second delay, the apparatus was operated for 15 rotation/rest cycles.
The cylindrical vessel and handle were removed from the water and the vessel detached from the handle. Surface water was carefully poured off, and any powder residues transferred to a preweighed container and dried for 24 hours at 100°C. The weight of dried residue as a percentage of the initial powder weight (50 g) was then calculated.
Test 2: delivery device test
Delivery characteristics of the powders were also compared using a model system which emulates the delivery of a powder in an automatic washing machine from a flexible delivery device of the type supplied with Lever's Persil (TradeMark) Micro System powder in the UK: a spherical
container of flexible plastics material having a diameter of approximately 4 cm and a top opening of diameter approximately 3 cm.
In this test the, delivery device was attached in an upright position (opening uppermost) to an agitator arm positioned above water. By means of this apparatus the device could be moved vertically up and down through a distance of 30 cm, the lowest 5 cm of this travel being under water. Each up or down journey had a duration of 2 seconds, the device being allowed to rest 5 cm under water for 4 seconds at the lowest position, and at the highest position being rotated through 100° and allowed to rest in the resulting tilted orientation for 2 seconds before redescending. 5 litres of water at a temperature of 20°C were used.
A preweighed powder sample was introduced into the device in its highest position, and the apparatus then allowed to operate for six cycles and stopped when the device was again in its highest position. Surface water was carefully poured off, and any powder residues transferred to a preweighed container. The container was then dried at 100°C for 24 hours, and the weight of dried residue as a percentage of the initial powder weight calculated.
Test 3: black pillowcase test
A washing machine test was also used to determine the extent that insoluble residues were deposited on washed articles. The machine used was a Siemens Siwamat (TradeMark) Plus 3700 front-loading automatic washer.
A 100 g dose of powder was placed in a flexible delivery device as described previously. The delivery
device was placed inside a black cotton pillowcase having dimensions of 30 cm by 60 cm, taking care to keep it upright, and then pillowcase was then closed by means of a zip fastener. The pillowcase containing the (upright) delivery device was then placed on top of a 3.5 kg dry cotton washload in the drum of the washing machine.
The machine was operated on the "heavy duty cycle" at a wash temperature of 40°C, using water of 15° French hardness and an inlet temperature of 20°C/ At the end of the wash cycle the pillowcase was removed, opened and turned inside out, and the level of powder residues on its inside surfaces determined by visual assessment using a scoring system of 1 to 5 : a score of 5 corresponds to a residue of approximately 75 wt% of the powder, while 1 indicates no residue. A panel of five assessors was used to judge each pillowcases and allot a score. With each powder the wash process was carried out ten times and the scores were averaged over the ten repeats.
Test 4: Insolubles
4g of powder was stirred in 1 litre of water at 20°C for 1 minute. The mixture was then filtered through a 50 u sieve and dried to constant weight. The residue was weighed to determine the level of ' insolubles ' .
Test 5: Dispensing
For the purposes of the present invention, dispensing is assessed by means of a standard procedure using a test rig based on the main wash compartment of the dispenser drawer of the Philips (Trade Mark) AWB 126/7 washing machine. This drawer design provides an especially stringent test of dispensing characteristics especially
when used under conditions of low temperature, low water pressure and low rate of water flow.
In the test, a 100 g dose of powder is placed in a heap at the front end of the main compartment of the drawer, and subjected to a water fill of 5 litres at 10°C and an inlet pressure of 50 kPa, flowing in over a period of 1 minute.
After 1 minute the flow of water is ceased, and the powder remaining is then collected and dried to constant weight. The dry weight of powder recovered from the dispenser drawer, in grams, represents the weight percentage of powder not dispensed into the machine (the residue) . Every result is the average of two duplicate measurements.
TABLE 2
Example l E Z Q i
Test 1 19.1 20.8 31.4 17.0 16.3 16.1 28.8 25.8
Test 2 57.1 0 38.1 0 23.6 0 50.5 0 Test 3 0.8 0.5 2.1 1.7 2.6 1.8 0.8 0.2
Test 4 2.3 2.0 1.8 2.1 6.8 6.3 3.4 2.1
Test 5 0 0 15 6 11 8 11 0
For tests 1, 2, 4 and 5 the figures denote wt% residue. For test 3 the figure is a score on a scale of 0 to 5.
The results in Table 2 show that the dispensing dispersion and delivery characteristics of powders containing a hydrophobic material incorporated into a Non- Tower powder in accordance with the present invention are
significantly superior to those of equivalent powders without the hydrophobic material.
Claims (10)
1. Process for the production of a high bulk density detergent composition or component therefor which comprises a particulate material which is not the direct product of a spray-drying process, and a hydrophobic material the process comprising mixing the hydrophobic material with the particulate material, densifying the mixture of the particulate material and hydrophobic material during or subsequent to the said mixing and optionally granulating the said mixture thereby to form a particulate high bulk density detergent composition or component therefor.
2. A non-tower process for the production of a detergent composition or component therefor which comprises mixing a hydrophobic material in a flowable form with a particulate material, densifying the mixture and the hydrophobic material during or subsequent to the said mixing step and optionally granulating the said mixture thereby to form a high density particulate detergent composition or component therefor.
3. A process according to claim 1 or claim 2 in which the hydrophobic material is mixed in the liquid phase with a liquid component to form a flowable premix prior to mixing with the particulate material.
4. A process according to claim 3 in which the liquid component is a nonionic surfactant.
5. A process according to any preceding claim in which the hydrophobic material has a contact angle to water of at least 75°.
6. A process according to any preceding claim in which the hydrophobic material has a melting point in the range 25 to 110°C.
7. A particulate detergent composition or component therefor having a high bulk density comprising a hydrophobic material, a surfactant and a detergency builder obtainable by a non-tower process wherein the hydrophobic material is mixed with the surfactant or builder, prior to or whilst the surfactant and builder are mixed.
8. A particulate detergent composition or component according to claim 7 in which the components of the composition are substantially homogeneously distributed within the particles.
9. A particulate detergent composition or component therefor having a high bulk density comprising a hydrophobic material, a surfactant and a detergency builder wherein the detergent particle comprises an inner core comprising the surfactant, builder and optionally part of the hydrophobic material and on the inner core a coating which comprises the remainder of the hydrophobic material.
10. A process according to any one of claims 1 to 6 or a composition according any one of claims 7 to 9 wherein the hydrophobic material comprises a paraffin wax.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP93305236 | 1993-07-02 | ||
| EP93305236 | 1993-07-02 | ||
| PCT/EP1994/002064 WO1995001418A1 (en) | 1993-07-02 | 1994-06-23 | Process for the production of a detergent composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU7383294A true AU7383294A (en) | 1995-01-24 |
| AU699818B2 AU699818B2 (en) | 1998-12-17 |
Family
ID=8214463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU73832/94A Ceased AU699818B2 (en) | 1993-07-02 | 1994-06-23 | Process for the production of high bulk density detergent composition |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0706560B1 (en) |
| JP (1) | JPH08512072A (en) |
| AU (1) | AU699818B2 (en) |
| CZ (1) | CZ286742B6 (en) |
| DE (1) | DE69405238T2 (en) |
| ES (1) | ES2106557T3 (en) |
| HU (1) | HU219207B (en) |
| PL (1) | PL176757B1 (en) |
| WO (1) | WO1995001418A1 (en) |
| ZA (1) | ZA944679B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9601920D0 (en) * | 1996-01-31 | 1996-04-03 | Unilever Plc | Process for the production of a detergent composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3617756C2 (en) * | 1985-05-29 | 1995-01-19 | Lion Corp | A process for producing a high bulk density granular detergent composition |
| JPS62228000A (en) * | 1986-03-28 | 1987-10-06 | 花王株式会社 | High density granular detergent composition |
| GB8806702D0 (en) * | 1988-03-21 | 1988-04-20 | Unilever Plc | Detergent powders & processes for preparing them |
| GB9025673D0 (en) * | 1990-11-26 | 1991-01-09 | Unilever Plc | Detergent powders and process for preparing them |
-
1994
- 1994-06-23 AU AU73832/94A patent/AU699818B2/en not_active Ceased
- 1994-06-23 CZ CZ19964A patent/CZ286742B6/en not_active IP Right Cessation
- 1994-06-23 PL PL94312420A patent/PL176757B1/en unknown
- 1994-06-23 WO PCT/EP1994/002064 patent/WO1995001418A1/en not_active Application Discontinuation
- 1994-06-23 EP EP94923685A patent/EP0706560B1/en not_active Revoked
- 1994-06-23 ES ES94923685T patent/ES2106557T3/en not_active Expired - Lifetime
- 1994-06-23 DE DE69405238T patent/DE69405238T2/en not_active Revoked
- 1994-06-23 JP JP7503251A patent/JPH08512072A/en not_active Withdrawn
- 1994-06-23 HU HU9503926A patent/HU219207B/en not_active IP Right Cessation
- 1994-06-29 ZA ZA944679A patent/ZA944679B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| HUT74077A (en) | 1996-10-28 |
| WO1995001418A1 (en) | 1995-01-12 |
| CZ286742B6 (en) | 2000-06-14 |
| ZA944679B (en) | 1995-12-29 |
| AU699818B2 (en) | 1998-12-17 |
| JPH08512072A (en) | 1996-12-17 |
| HU219207B (en) | 2001-03-28 |
| PL176757B1 (en) | 1999-07-30 |
| EP0706560B1 (en) | 1997-08-27 |
| PL312420A1 (en) | 1996-04-15 |
| EP0706560A1 (en) | 1996-04-17 |
| DE69405238D1 (en) | 1997-10-02 |
| DE69405238T2 (en) | 1998-01-02 |
| HU9503926D0 (en) | 1996-03-28 |
| CZ496A3 (en) | 1996-06-12 |
| ES2106557T3 (en) | 1997-11-01 |
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