EP0270240B1 - Reinigungsmittel in Pulverform und deren Herstellungsverfahren - Google Patents
Reinigungsmittel in Pulverform und deren Herstellungsverfahren Download PDFInfo
- Publication number
- EP0270240B1 EP0270240B1 EP87309570A EP87309570A EP0270240B1 EP 0270240 B1 EP0270240 B1 EP 0270240B1 EP 87309570 A EP87309570 A EP 87309570A EP 87309570 A EP87309570 A EP 87309570A EP 0270240 B1 EP0270240 B1 EP 0270240B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- powder
- spray
- detergent
- postdosed
- 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.)
- Revoked
Links
- 239000000843 powder Substances 0.000 title claims description 128
- 239000003599 detergent Substances 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 42
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 28
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 25
- 239000003945 anionic surfactant Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 18
- 239000004615 ingredient Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 14
- 235000011152 sodium sulphate Nutrition 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 13
- 238000001694 spray drying Methods 0.000 claims description 12
- 125000000129 anionic group Chemical group 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 239000004115 Sodium Silicate Substances 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 229920005646 polycarboxylate Polymers 0.000 claims description 6
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 claims description 5
- 235000012217 sodium aluminium silicate Nutrition 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000429 sodium aluminium silicate Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002585 base Substances 0.000 description 43
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- 239000011343 solid material Substances 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- -1 for example Polymers 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001033 granulometry Methods 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 150000003138 primary alcohols Chemical class 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000002459 porosimetry Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- PTHBKNSHSCMKBV-UHFFFAOYSA-N 4,6,8-trihydroxy-3-(2-hydroxyethyl)-2,3-dihydronaphtho[2,3-f][1]benzofuran-5,10-dione Chemical compound O=C1C2=CC(O)=CC(O)=C2C(=O)C2=C1C=C1OCC(CCO)C1=C2O PTHBKNSHSCMKBV-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- UPBDXRPQPOWRKR-UHFFFAOYSA-N furan-2,5-dione;methoxyethene Chemical compound COC=C.O=C1OC(=O)C=C1 UPBDXRPQPOWRKR-UHFFFAOYSA-N 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001007 puffing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- PTHBKNSHSCMKBV-ZETCQYMHSA-N versicol Natural products OCC[C@H]1COc2cc3C(=O)c4cc(O)cc(O)c4C(=O)c3c(O)c12 PTHBKNSHSCMKBV-ZETCQYMHSA-N 0.000 description 1
- 238000004383 yellowing Methods 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/02—Preparation in the form of powder by spray drying
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
Definitions
- the present invention relates to spray-dried zero-phosphate powders suitable for use as detergent compositions or components thereof.
- the powders of the invention are built with crystalline or amorphous sodium aluminosilicate.
- sodium aluminosilicates both crystalline (zeolite) and amorphous (NAS) have become well known as detergency builders. These materials do not, however, possess an ability comparable to that of sodium tripolyphosphate to contribute to the structure of a spray-dried powder.
- Alkali metal silicates are frequently included in detergent powders as structurants, to reduce washing machine corrosion and to increase alkalinity.
- spray-dried zeolite-built powders of very high bulk density may be prepared by spray-drying slurries of defined moisture content, and low or zero levels of electrolyte.
- the presence of a polymeric polycarboxylate is also essential to provide building and structuring.
- the powders are characterised by exceptionally low particle porosity and excellent powder properties. If desired, the bulk density can be increased further, and powder properties enhanced, by postdosing high-bulk-density salts, notably sodium sulphate, to the spray-dried powder.
- Spray-dried powders containing anionic surfactants built with zeolite and polymeric polycarboxylate and containing inorganic salts such as sodium carbonate and sodium sulphate, are disclosed in EP-A-137,669 (Procter & Gamble), EP-A-209,840 (Henkel), EP-B-63,399 (Procter & Gamble) and GB-2,095,274 (Colgate-Palmolive), but these powders do not have the low electrolyte levels characteristic of the present invention.
- EP-A-193,360 (Procter & Gamble) discloses low-phosphate spray-dried detergent powders containing anionic surfactants, zeolite, polymeric polycarboxylate and sodium sulphate. However, these spray-dried powders do not contain any sodium carbonate and a low electrolyte level thereof is nowhere disclosed in EP-A-193,360.
- the present invention provides a process for the preparation of a zero-phosphate detergent powder which comprises spray-drying an aqueous slurry to form a powder, the slurry comprising
- the present invention is concerned with a spray-dried detergent powder containing anionic surfactant which is suitable for use as a base for a detergent composition, or indeed as a whole detergent composition in its own right.
- the base powder of the invention is characterised by an exceptionally low particle porosity of less than 40%, preferably less than 35%.
- the particle porosity may be determined by the recognised technique of mercury porosimetry.
- the total level of electrolyte (salts) in the base powder of the invention does not exceed 25% by weight.
- the electrolyte level does not exceed 15% and more preferably 13%.
- the electrolyte present is constituted substantially wholly by sodium carbonate. The lowest particle porosities - around 25% - are obtained when no electrolyte whatsoever is present. Surprisingly, however, it has been found that when a fluorescer is present, the presence of a low level of sodium carbonate is beneficial in reducing or eliminating discolouration (yellowing), while giving particle porosities that are not substantially greater than those obtained at zero electrolyte.
- the preferred amount of sodium carbonate present for this benefit is from 5 to 15% by weight, of the spray-dried powder.
- the spray-dried particles obtained are strong enough to give excellent powder properties.
- Any silicate required in order to prevent washing machine corrosion can therefore be postdosed, for example as described in EP 240 356A (Unilever), to be published on 7 October 1987, and EP 242141A (Unilever), to be published on 21 October 1987, thus avoiding the problem of unfavourable interaction with aluminosilicate in the slurry.
- the slurry may contain sodium silicate, but preferably in an amount not exceeding 10% by weight, and more preferably not exceeding 5% by weight, based on the spray-dried powder.
- Salts other than sodium carbonate may if desired be present. It is preferred, however, that the slurry should be virtually free of sodium sulphate, other than the small quantities inevitably associated as impurities with other components such as anionic surfactants. Sodium sulphate levels as low as 25% (based on the powder) give particles of considerably greater porosity. Similar considerations apply to other inorganic salts: it is therefore preferred that no significant amounts of salts other than sodium carbonate and possibly sodium silicate be present.
- the powder of the invention contains crystalline or amorphous aluminosilicate, preferably zeolite, in an amount of from 15 to 86% by weight.
- the preferred level is from 20 to 70% by weight, more preferably from 30 to 70% by weight. This component is the principal builder in the powder of the invention.
- auxiliary builder there is also present a polymeric polycarboxylate in an amount from 2 to 40% by weight, preferably from 3 to 25% by weight, and more preferably from 4 to 15% by weight.
- the polymer appears to be essential not only for building but also for creating adequately structured spray-dried particles.
- Suitable polymer include the following, the list not being exhaustive: salts of polyacrylic acid, for example, Versicol (Trade Mark) E5, E7 and E9 ex Allied Colloids, average molecular weights 3500, 27 000 and 70 000 respectively; Narlex (Trade Mark) LD 30 and 34 ex National Adhesives and Resins Ltd, average molecular weights 5000 and 25 000 respectively; Acrysol (Trade Mark) LMW-10, LMW-20, LMW-45 and A-IN ex Rohm & Haas, average molecular weights 1000, 2000, 4500 and 60 000; and Sokalan (Trade Mark) PA 110S ex BASF, average molecular weight 250 000; ethylene/maleic acid copolymers, for example, the EMA (Trade Mark) series ex Monsanto; methyl vinyl ether/maleic acid copolymers, for example Gantrez (Trade Mark) AN119 ex GAF Corporation; acrylic acid/maleic acid copolymers, for example, Sokalan (Trade
- Mixtures of two or more of these polymers may of course be used if desired.
- the spray-dried base powders of the invention also contain as essential ingredients one or more anionic detergent-active compounds (surfactants), in an amount of from 5 to 60% by weight, preferably from 10 to 60% by weight, more preferably from 10 to 30% by weight, and especially from 12 to 30% by weight.
- anionic detergent-active compounds surfactants
- the weight ratio of sodium carbonate to anionic surfactant should not exceed 1.1:1 in order for particle porosities of 40% and below to be obtained.
- higher ratios can be tolerated: only the limitation on the total electrolyte level (maximum 25% by weight) need be considered.
- Anionic surfactants are well known to those skilled in the detergents art. Examples include alkylbenzene sulphonates, particularly sodium linear alkylbenzene sulphonates having an average chain length of about C12; primary and secondary alcohol sulphates, particularly sodium C12-C15 primary alcohol sulphates; olefin sulphonates; alkane sulphonates; and fatty acid ester sulphonates.
- nonionic detergent-active agents may also be present in the spray-dried base powders of the invention, in an amount not exceeding 30% by weight, and preferably not exceeding 15% by weight.
- a preferred range for nonionic surfactant content is from 1 to 10% by weight.
- the weight ratio of anionic surfactant to nonionic surfactant is preferably at least 0.67:1, more preferably at least 1:1.
- Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C12-C15 primary and secondary alcohols ethoxylated with an average of from 3 to 20 moles of ethylene oxide per mole of alcohol.
- the spray-dried powder of the invention may if desired contain one or more soaps of fatty acids, but the level of soap present is preferably not high enough to cause a significant reduction in particle porosity.
- the total amount of detergent-active material, including soap, in the spray-dried base powders of the invention is preferably within the range of from 10 to 75% by weight, more preferably from 12 to 65% by weight.
- the especially preferred range is from 12 to 50% by weight, with a weight ratio of anionic surfactant to nonionic surfactant within the range of from 1:1 to 10:1.
- the spray-dried base powder may of course contain any of the usual minor ingredients suitable for undergoing slurry-making and spray-drying processes, for example, antiredeposition agents and fluorescers.
- the spray-dried base powder will also contain a certain amount of moisture: both moisture bound to the zeolite (about 1 part of bound water to 4 parts of zeolite) and free moisture.
- the free moisture content influences powder porosity and can be determined by suitable choice of spray-drying conditions. The higher the free moisture content, the lower the porosity will be, but powder properties (flow, resistance to caking, compressibility, agglomerate strength) deteriorate as the moisture content rises.
- a convenient expression of powder moisture content is the relative humidity. This is the partial water vapour pressure of a powder sample in a relatively small closed container at 20°C, expressed as a percentage of the partial water vapour pressure of the atmosphere at that temperature.
- Spray-dried base powders of the present invention preferably have relative humidities not exceeding 70%, more preferably within the range of from 45 to 65%.
- the base powder of the invention is prepared, as indicated above, by spray-drying an aqueous slurry of the ingredients.
- spray-drying here is not restricted to high-temperature operation but also includes processes, more commonly referred to as spray-cooling, in which a tower inlet temperature lower than about 100-150°C is used.
- the drying process may be carried out in two stages.
- the slurry may be spray-dried to a relatively high powder moisture content, and the resulting wet powder dried further to its final desired moisture content using other apparatus, for example, a fluidised bed as described in GB 1 237 084 (Unilever).
- the base powders of the invention are characterised by excellent agglomerate strength. This is defined as the pressure that has to be exerted on a sample of powder to compress it to a bed porosity of 0.4.
- the latter value has been selected since it is known to be the bed porosity of densely packed granular solids, including detergent powders: to achieve bed porosities below 0.4 any agglomerates in a powder sample have to be broken down into the primary particles of which they are composed, these primary particles corresponding in size to the droplets formed when the detergent slurry was atomised in the spray-drying tower.
- the agglomerate strength is a measure of the resistance of the agglomerates in a powder, on compression, to breakdown into the smaller primary particles.
- the agglomerate strength is measured as follows. A 0.3 g sample of the 250-500 ⁇ m sieve fraction of the spray-dried base powder is subjected to compression in a compression cell of circular cross-section, having a diameter of 1.3 cm and (hence) a cross-sectional area of 1.33 cm2. The work of compression is measured and plotted against the height of the powder bed in the cell.
- Bed porosity as a function of bed height can be calculated from the bulk density of the powder bed (calculated from the weight of the powder sample, its height and the cross-sectional area of the compression cell), the true density of the material (solid density) and the powder porosity, by means of the following equation:
- the particle porosity may be determined by mercury porosimetry.
- Agglomerate strength values depend on bulk density as well as on the formulation of the slurry, and for powders having bulk densities of 400 g litre or above values above 7 N/cm2 are considered good.
- the spray-dried base powder of the invention is useful as a detergent composition in its own right. Generally, however, various additional ingredients may be sprayed on or postdosed to give a more efficient product, and the base powder may form a major or minor part of a more complex composition.
- granular detergent compositions in accordance with the present invention may contain, for example, from 10 to 100% of the spray-dried base powder of the invention.
- such detergent compositions may contain from 10 to 90% by weight, preferably from 30 to 90% by weight, of base powder and from 10 to 90% by weight, preferably from 10 to 70% by weight, of postdosed solid and/or liquid material.
- postdosing here encompasses any non-spray-drying method by which solid or liquid ingredients may be added to the base powder, for example, dry mixing, granulation, agglomeration, overspraying or any combination of these techniques.
- Some materials may be postdosed because they are sensitive to heat and thus unsuitable for undergoing spray-drying.
- examples of such materials include surfactants, enzymes, bleaches, bleach precursors, bleach stabilisers, lather suppressors, perfumes and dyes.
- Liquid or pasty ingredients may conveniently be adsorbed on to a solid, porous, particulate, generally inorganic, carrier which is then postdosed to the base powder of the invention.
- examples of such ingredients are anionic and nonionic surfactants, and liquid lather suppressors such as silicone oil.
- solid sodium silicate Another material that may be postdosed, as previously mentioned, is solid sodium silicate: thus unfavourable interaction with the sodium aluminosilicate in the slurry is avoided.
- an aqueous solution or dispersion of sodium silicate may be blown into the tower simultaneously with the introduction of the base powder slurry, as described and claimed in our European Patent Application No. 87 308239.0 filed on 17 September 1987.
- the base powder of the invention is characterised by an especially low particle porosity of less than 40%, preferably less than 35%. Its bulk density is therefore very high and it is exceptionally suitable for use as a base for granular detergent compositions of high bulk density, for example, of 650 g/litre and above, especially from 700 to 900 g/litre. In such compositions, it is important that any postdosed material does not lower the bulk density significantly.
- One especially preferred embodiment of the invention is a very high bulk density detergent composition obtained by filling the voids between the relatively large particles of base powder with postdosed solid material, preferably including a substantial proportion of sodium sulphate, in the form of a finely divided dense powder of low porosity. In this manner an increase in bulk density of 150 g/litre or more, preferably at least 200 g/litre, may be achieved.
- the final product comprises from 40 to 85% by weight of the base powder of the invention and from 15 to 60% by weight of postdosed ingredients of high bulk density and small particle size, for example from 15 to 35% by weight of sodium sulphate and from 0 to 45% of other postdosed ingredients.
- the granulometry of the postdosed material is matched to that of the base powder, the relationship being expressed in terms of the Rosin-Rammler particle size distribution described by Rosin and Rammler, J Inst Fuel 7 29-36 (1933).
- the postdosed solid material should have an overall Rosin-Rammler average particle size not exceeding 75%, and preferably not exceeding 70%, of that of the base powder.
- the Rosin-Rammler average particle size of the base powder may be from 350 to 800 ⁇ m, and that of the postdosed material from 200 to 400 ⁇ m.
- the postdosed solid material should also itself be of high bulk density: at least 850 g/litre, preferably at least 900 g/litre.
- the postdosed solid material contains a substantial proportion of sodium sulphate.
- This material may be obtained with a bulk density of 1200 g/litre or more, preferably at least 1300 g/litre, and a suitable particle size distribution.
- the use of very high bulk density sodium sulphate allows greater flexibility in the choice of any other solid postdosed ingredients.
- a detergent composition produced by the process of the invention will have a particle size distribution such that the larger particles are predominantly derived from the spray-dried base powder while the smaller particles are predominantly derived from the postdosed solid materials, including sodium sulphate.
- This embodiment of the invention offers another important benefit in addition to increased bulk density. Powders composed of a relatively coarse base powder and relatively fine postdosed material have surprisingly been found to exhibit significantly better dispensing properties in the washing machine, as compared with powders having a similar particle size distribution but composed of a relatively fine base powder and relatively coarse postdosed material.
- the postdosed material should not contain too high a level of very small particles or "fines": the content of particles smaller than 125 ⁇ m is preferably less than 15% by weight, and more preferably less than 10% by weight.
- the "fines" content of the base powder is also preferably less than 15% by weight.
- compositions in which the spray-dried powder of the invention is only a minor component, constituting for example from 10 to 30% by weight of the total product or possibly even less, and perhaps better regarded as an "adjunct" rather than as a base powder.
- Spray-dried base powders were prepared to the compositions set out in the following Tables IA, IIA, IIIA and IVA, and the properties of these powders are given in the corresponding Tables IB, IIB, IIIB and IVB. Examples identified by number are within the invention, while examples identified by letter are comparative.
- the polymer used in all the compositions was Sokalan (Trade Mark) CP5 ex BASF, an acrylic/maleic copolymer in sodium salt form.
- the minor ingredients referred to in the Tables included antiredeposition agent, fluorescer and EDTA.
- Compositions 1 to 6 in Tables IA and IB all contained relatively high levels, above 14.5% by weight, of anionic surfactant, and in every case the weight ratio of sodium carbonate to anionic surfactant was less than 1.1:1. It will be seen that at total electrolyte levels ranging from zero (insignificant) to 12.6% by weight, powders having particle porosites below 0.40 were obtained. The bulk density in every case exceeded 530 g/l. Although in some cases high moisture content led to rather high compressibility values, the other powder properties were excellent.
- compositions 7 to 11 in Tables IIA and IIB form a similar series but with lower levels, below 14.5% by weight, of anionic surfactant.
- the powders all had particle porosities below 0.4 even though in some cases the ratio of sodium carbonate to anionic surfactant exceeded 1.1:1.
- compositions 1 to 4 and 6 to 11 contained no significant amounts of any electrolyte other than sodium carbonate, while Composition 5 contained sodium carbonate and sodium silicate.
- Composition 1 containing no sodium carbonate displayed a slight yellow discolouration, while the powders of Examples 2-11 were white.
- Comparative composition A contained just above 14.5% by weight of anionic surfactant, and the ratio of sodium carbonate to anionic surfactant was just above the limit of 1.1:1, and it will be seen that its particle porosity was 0.41: it should be compared with Example 10 which had the same ratio of sodium carbonate to anionic surfactant but a lower level (just below 14.5% by weight) of anionic surfactant, and a particle porosity of 0.36. Comparative Examples B, C and E show that higher levels of sodium carbonate, and higher ratios, gave even higher particle porosities. Comparative Example D shows the detrimental effect of including sodium sulphate.
- compositions 12 to 16 in Table IVA and IVB illustrate the invention in a series of compositions containing relatively higher proportions of anionic surfactant. The very high bulk densities of these powders will be noted. As with the earlier Examples, Composition 12 containing no sodium carbonate displayed a slight yellow discolouration, while the other powders were all white.
- Fully formulated detergent compositions were prepared by postdosing various ingredients, as specified below, to the base powders 4, B and 13 described above.
- Composition 17 was a powder in accordance with an especially preferred embodiment of the invention since the postdosed material had an overall Rosin-Rammler average particle size (315 ⁇ m) only 75% of that of the base powder, and was also of high bulk density (930 g/litre). An increase of bulk density of 180 g/litre to the very high figure of 740 g/litre was thereby achieved.
- Composition 18 is an example of a powder in which the base powder was of exceptionally high bulk density (595 g/litre).
- the postdosed material was also of very high bulk density (930 g/litre) but of larger particle size (320 ⁇ m, 84%) in relation to the base powder (380 ⁇ m) so the increase achieved by postdosing (145 g/litre) was smaller than in Composition 17.
- the bulk density of the final powder was just as high (740 g/litre) as that of Composition 17.
- Comparative Composition F was composed of a base powder of low bulk density (440 g/litre) and postdosed material of relatively low bulk density (720 g/litre) and a particle size not significantly smaller than that of the base powder. Postdosing achieved a bulk density increase of 140 g/litre, but the final figure (580 g/litre) was considerably lower than the preferred target figure of 650 g/litre.
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- Chemical Kinetics & Catalysis (AREA)
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- Detergent Compositions (AREA)
Claims (21)
- Ein Verfahren zur Herstellung eines phosphatfreien Reinigungsmittelpulvers, das das Sprühtrocknen eines wässrigen Breies zur Bildung eines Pulvers umfaßt, wobei der Brei umfaßt:a) von 5 bis 60 Gew.-%, bezogen auf das Pulver, einer oder mehrerer anorganischer reinigungsaktiver Verbindungen;b) von 0 bis 30 Gew.-%, bezogen auf das Pulver, einer oder mehrerer nichtionischer, waschaktiver Verbindungen;c) von 15 bis 86 Gew.-%, bezogen auf das Pulver, kristallinen oder amorphen Natriumaluminiumsilikatbuilders;d) von 2 bis 40 Gew.-%, bezogen auf das Pulver, eines polymeren Polycarboxylats;e) gegebenenfalls weitere Salze;f) gegebenenfalls herkömmliche kleinere Inhaltsstoffe;dadurch gekennzeichnet, daß der Brei 2 bis 20 Gew.-%, bezogen auf das Pulver, Natriumcarbonat umfaßt, das Pulver einen Gesamtelektrolytgehalt von nicht mehr als 20 Gew.-% und eine Teilchenporosität von nicht mehr als 0,40 besitzt, und daß, wenn die Menge an anionischer, waschaktiver Verbindung (a) 14,5 Gew.-% übersteigt, das Gewichtsverhältnis von Natriumcarbonat zu der anionischen waschaktiven Verbindung (a) 1.1:1 nicht übersteigt.
- Ein Verfahren wie in Anspruch 1 beansprucht, dadurch gekennzeichnet, daß der Gesamtelektrolytgehalt des gebildeten Pulvers 15 Gew.-% nicht übersteigt.
- Ein Verfahren wie in Anspruch 2 beansprucht, dadurch gekennzeichnet, daß der Gesamtelektrolytgehalt 13 Gew.-% nicht übersteigt.
- Ein Verfahren wie in einem der vorhergehenden Ansprüche beansprucht, dadurch gekennzeichnet, daß der Brei 5 bis 15 Gew.-%, bezogen auf das Pulver, Natriumcarbonat umfaßt.
- Ein Verfahren wie in einem vorhergehenden Anspruch beansprucht, dadurch gekennzeichnet, daß der Brei Natriumcarbonat in einem Gewichtsverhältnis zu dem anionischen oberflächenaktiven Mittel (a) im Bereich von 0.1:1 bis 0.8:1 umfaßt.
- Ein Verfahren wie in einem vorhergehenden Anspruch beansprucht, dadurch gekennzeichnet, daß das gebildete Pulver eine Teilchenporosität von weniger als 0,35 besitzt.
- Ein Verfahren wie in einem der Ansprüche 1 bis 6 beansprucht, dadurch gekennzeichnet, daß das Pulver im wesentlichen frei von anderen Elektrolyten als Natriumcarbonat ist.
- Ein Verfahren wie in einem der Ansprüche 1 bis 6 beansprucht, dadurch gekennzeichnet, daß das Pulver als ein Salz Natriumsilikat einer Menge von nicht mehr als 10 Gew.-% umfaßt.
- Ein Verfahren wie in Anspruch 8 beansprucht, dadurch gekennzeichnet, daß die Menge an Natriumsilikat 5 Gew.-% nicht übersteigt.
- Ein Verfahren wie in Anspruch 8 oder 9 beansprucht, dadurch gekennzeichnet, daß das Pulver im wesentlichen frei von anderen Elektrolyten als Natriumcarbonat und Natriumsilikat (e) ist.
- Ein Verfahren wie in einem vorhergehenden Anspruch beansprucht, dadurch gekennzeichnet, daß das Pulver 10 bis 60 Gew.-% insgesamt an anionischen reinigungsaktiven Verbindungen (a) enthält.
- Ein Verfahren wie in einem vorhergehenden Anspruch beansprucht, dadurch gekennzeichnet, daß eine nichtionische waschaktive Verbindung (b) vorhanden ist, wobei das Gewichtsverhältnis einer anionischen reinigungsaktiven Verbindung (a) zu der nichtionische reinigungsaktiven Verbindung (b) wenigstens 0.67:1 beträgt.
- Ein Verfahren wie in Anspruch 12 beansprucht, dadurch gekennzeichnet, daß das Gewichtsverhältnis an anionischer reinigungsaktiver Verbindung zu nichtionischer reinigungsaktiver Verbindung im Bereich von 1:1 bis 10:1 liegt.
- Ein Verfahren wie in einem vorhergehenden Anspruch beansprucht, dadurch gekennzeichnet, daß die relative Feuchtigkeit des gebildeten Pulvers 70 % nicht übersteigt.
- Ein Verfahren wie in Anspruch 14 beansprucht, gekennzeichnet durch eine relative Feuchtigkeit im Bereich von 45 bis 65 Gew.-%.
- Eine granuläre, phosphatfreie Reinigungsmittelzusammensetzung, dadurch gekennzeichnet, daß sie umfaßt:i) von 10 bis 100 Gew.-% eines sprühgetrockneten Pulvers, hergestellt durch ein Verfahren wie in einem der Ansprüche 1 bis 15 beansprucht.ii) von 0 bis 90 Gew.-% eines oder mehrerer nachdosierter fester und/oder flüssiger Inhaltsstoffe.
- Ein Verfahren wie in Anspruch 16 beansprucht, dadurch gekennzeichnet, daß es umfaßt:i) von 30 bis 90 Gew.-% eines sprühgetrockneten Pulvers, undii) von 10 bis 70 Gew.-% an nachdosierten Inhaltsstoffen.
- Eine Zusammensetzung wie in Anspruch 17 beansprucht, dadurch gekennzeichnet, daß sie umfaßt:i) von 40 bis 85 Gew.-% eines sprühgetrockneten Pulvers, undii) von 15 bis 60 Gew.-% an nachdosierten Inhaltsstoffen.
- Eine Zusammensetzung wie in Anspruch 18 beansprucht, dadurch gekennzeichnet, daß sie umfaßt:i) von 40 bis 85 Gew.-% des sprühgetrockneten Pulvers,ii) von 15 bis 35 Gew.-% an nachdosiertem Natriumsulfat, undiii) gegebenenfalls von 0 bis 45 Gew.-% an anderem nachdosiertem Material
- Eine Zusammensetzung wie in Anspruch 18 oder Anspruch 19 beansprucht, dadurch gekennzeichnet, daß jedes feste nachdosierte Material eine Gesamt-Rosin-Rammler-Durchschnittsteilchengröße von nicht mehr als 75 % der Rosin-Rammler-Durchschnittsteilchengröße des sprühgetrockeneten Pulvers (i) besitzt.
- Eine Zusammensetzung wie in einem der Ansprüche 18 bis 20 beansprucht, gekennzeichnet durch eine Schüttdichte von wenigstens 650 g/l.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8626082 | 1986-10-31 | ||
GB868626082A GB8626082D0 (en) | 1986-10-31 | 1986-10-31 | Detergent powders |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0270240A2 EP0270240A2 (de) | 1988-06-08 |
EP0270240A3 EP0270240A3 (en) | 1990-01-03 |
EP0270240B1 true EP0270240B1 (de) | 1993-09-22 |
Family
ID=10606625
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87309570A Revoked EP0270240B1 (de) | 1986-10-31 | 1987-10-29 | Reinigungsmittel in Pulverform und deren Herstellungsverfahren |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP0270240B1 (de) |
JP (1) | JP2544636B2 (de) |
KR (1) | KR920001993B1 (de) |
AU (1) | AU602932B2 (de) |
BR (1) | BR8705812A (de) |
CA (1) | CA1303938C (de) |
DE (1) | DE3787511T2 (de) |
ES (1) | ES2059393T3 (de) |
GB (1) | GB8626082D0 (de) |
TR (1) | TR24414A (de) |
ZA (1) | ZA878120B (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0942958B1 (de) * | 1996-12-02 | 2001-12-19 | Unilever Plc | Verfahren zur herstellung einer waschmittelzusammensetzung |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1286563C (en) * | 1986-04-04 | 1991-07-23 | Jan Hendrik Eertink | Detergent powders and processes for preparing them |
GB8810193D0 (en) * | 1988-04-29 | 1988-06-02 | Unilever Plc | Detergent compositions & process for preparing them |
US5024782A (en) * | 1989-06-16 | 1991-06-18 | The Clorox Company | Zeolite agglomeration process and product |
GB8918984D0 (en) * | 1989-08-21 | 1989-10-04 | Unilever Plc | Detergent compositions |
GB8924294D0 (en) * | 1989-10-27 | 1989-12-13 | Unilever Plc | Detergent compositions |
GB9012612D0 (en) * | 1990-06-06 | 1990-07-25 | Unilever Plc | Detergents compositions |
DE4100306A1 (de) * | 1991-01-08 | 1992-07-09 | Henkel Kgaa | Kornfoermige, leicht loesliche trockenkonzentrate von inhaltsstoffen aus wasch- und/oder reinigungsmitteln und verfahren zu ihrer herstellung |
DE4104085A1 (de) * | 1991-02-11 | 1992-08-13 | Henkel Kgaa | Granulares additiv fuer wasch- und reinigungsmittel |
GB9104547D0 (en) * | 1991-03-05 | 1991-04-17 | Unilever Plc | Detergent compositions |
DE4211699A1 (de) * | 1992-04-08 | 1993-10-14 | Henkel Kgaa | Verfahren zur Erhöhung des Schüttgewichts sprühgetrockneter Waschmittel |
EP0578871B1 (de) * | 1992-07-15 | 1998-05-27 | The Procter & Gamble Company | Verfahren zur Herstellung von kompakten Reinigungsmitteln |
EP0659208A1 (de) * | 1992-09-08 | 1995-06-28 | Unilever Plc | Waschmittelzusammensetzung und verfahren zur herstellung |
GB9313878D0 (en) * | 1993-07-05 | 1993-08-18 | Unilever Plc | Detergent composition or component containing anionic surfactant and process for its preparation |
GB9317180D0 (en) * | 1993-08-18 | 1993-10-06 | Unilever Plc | Granular detergent compositions containing zeolite and process for their preparation |
EP0653481A1 (de) * | 1993-11-11 | 1995-05-17 | The Procter & Gamble Company | Granulare Waschmittelzusammensetzung |
DK0745119T3 (da) * | 1994-02-18 | 2000-05-08 | Henkel Ecolab Gmbh & Co Ohg | Fremgangsmåde til fremstilling af sprøjtetørrede granulater |
US5962401A (en) * | 1994-12-15 | 1999-10-05 | Nippon Shokubai Co., Ltd. | Detergent builder process of manufacturing same and detergent composition containing same |
DE19500644B4 (de) * | 1995-01-12 | 2010-09-09 | Henkel Ag & Co. Kgaa | Sprühgetrocknetes Waschmittel oder Komponente hierfür |
GB9510695D0 (en) * | 1995-05-26 | 1995-07-19 | Unilever Plc | Detergent composition and process for its production |
GB0125212D0 (en) | 2001-10-19 | 2001-12-12 | Unilever Plc | Detergent compositions |
EP1529833A1 (de) * | 2003-11-10 | 2005-05-11 | The Procter & Gamble Company | Waschmittelteilchen |
EP1529834A1 (de) * | 2003-11-10 | 2005-05-11 | The Procter & Gamble Company | Waschmittelteilchen |
JP5705525B2 (ja) * | 2010-12-16 | 2015-04-22 | 花王株式会社 | ゼオライト複合粒子群 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IN161821B (de) * | 1981-02-26 | 1988-02-06 | Colgate Palmolive Co | |
US4379080A (en) * | 1981-04-22 | 1983-04-05 | The Procter & Gamble Company | Granular detergent compositions containing film-forming polymers |
JPS6042279B2 (ja) * | 1982-05-25 | 1985-09-20 | 花王株式会社 | 洗浄剤組成物 |
GR81618B (de) * | 1983-06-15 | 1984-12-11 | Procter & Gamble | |
US4609473A (en) * | 1984-11-26 | 1986-09-02 | Colgate Palmolive Company | Bentonite-sulfate fabric softening particulate agglomerate, processes for manufacture and use thereof, and detergent compositions containing it |
ZA858950B (en) * | 1984-12-03 | 1987-07-29 | Colgate Palmolive Co | Antistatic built synthetic organic detergent composition |
DE3444960A1 (de) * | 1984-12-10 | 1986-06-12 | Henkel KGaA, 4000 Düsseldorf | Koerniges adsorptionsmittel |
GB8504733D0 (en) * | 1985-02-23 | 1985-03-27 | Procter & Gamble Ltd | Detergent compositions |
JPH0665720B2 (ja) * | 1985-04-03 | 1994-08-24 | 花王株式会社 | 濃縮粉末洗剤組成物 |
DE3514364A1 (de) * | 1985-04-20 | 1986-10-23 | Henkel KGaA, 4000 Düsseldorf | Koerniges waschmittel mit verbessertem reinigungsvermoegen |
GB8526999D0 (en) * | 1985-11-01 | 1985-12-04 | Unilever Plc | Detergent compositions |
JPS62167399A (ja) * | 1986-01-17 | 1987-07-23 | 花王株式会社 | 高密度粒状洗剤の製法 |
GB8609044D0 (en) * | 1986-04-14 | 1986-05-21 | Unilever Plc | Detergent powders |
-
1986
- 1986-10-31 GB GB868626082A patent/GB8626082D0/en active Pending
-
1987
- 1987-10-26 CA CA000550260A patent/CA1303938C/en not_active Expired - Lifetime
- 1987-10-28 AU AU80416/87A patent/AU602932B2/en not_active Ceased
- 1987-10-29 EP EP87309570A patent/EP0270240B1/de not_active Revoked
- 1987-10-29 ES ES87309570T patent/ES2059393T3/es not_active Expired - Lifetime
- 1987-10-29 ZA ZA878120A patent/ZA878120B/xx unknown
- 1987-10-29 JP JP62274583A patent/JP2544636B2/ja not_active Expired - Lifetime
- 1987-10-29 DE DE87309570T patent/DE3787511T2/de not_active Expired - Lifetime
- 1987-10-30 BR BR8705812A patent/BR8705812A/pt not_active IP Right Cessation
- 1987-10-31 KR KR1019870012175A patent/KR920001993B1/ko not_active IP Right Cessation
- 1987-11-02 TR TR87/0749A patent/TR24414A/xx unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0942958B1 (de) * | 1996-12-02 | 2001-12-19 | Unilever Plc | Verfahren zur herstellung einer waschmittelzusammensetzung |
Also Published As
Publication number | Publication date |
---|---|
BR8705812A (pt) | 1988-05-31 |
EP0270240A3 (en) | 1990-01-03 |
ZA878120B (en) | 1989-07-26 |
KR880005245A (ko) | 1988-06-28 |
JPS63122797A (ja) | 1988-05-26 |
JP2544636B2 (ja) | 1996-10-16 |
DE3787511T2 (de) | 1994-01-20 |
AU8041687A (en) | 1988-05-05 |
DE3787511D1 (de) | 1993-10-28 |
CA1303938C (en) | 1992-06-23 |
AU602932B2 (en) | 1990-11-01 |
ES2059393T3 (es) | 1994-11-16 |
EP0270240A2 (de) | 1988-06-08 |
TR24414A (tr) | 1991-10-08 |
GB8626082D0 (en) | 1986-12-03 |
KR920001993B1 (ko) | 1992-03-09 |
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