CA1322704C - Detergent compositions and process for preparing them - Google Patents
Detergent compositions and process for preparing themInfo
- Publication number
- CA1322704C CA1322704C CA000597591A CA597591A CA1322704C CA 1322704 C CA1322704 C CA 1322704C CA 000597591 A CA000597591 A CA 000597591A CA 597591 A CA597591 A CA 597591A CA 1322704 C CA1322704 C CA 1322704C
- Authority
- CA
- Canada
- Prior art keywords
- sodium
- starting material
- detergent
- granulation
- rpm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 239000003599 detergent Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 28
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 235000019832 sodium triphosphate Nutrition 0.000 claims abstract description 23
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 14
- 239000000344 soap Substances 0.000 claims abstract description 12
- 239000007858 starting material Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000011149 active material Substances 0.000 claims abstract description 7
- 238000005520 cutting process Methods 0.000 claims abstract description 7
- 125000000129 anionic group Chemical group 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 44
- 238000005469 granulation Methods 0.000 claims description 41
- 230000003179 granulation Effects 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 24
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 16
- 239000008187 granular material Substances 0.000 claims description 16
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 claims description 11
- 235000012217 sodium aluminium silicate Nutrition 0.000 claims description 11
- 235000017550 sodium carbonate Nutrition 0.000 claims description 11
- 239000000429 sodium aluminium silicate Substances 0.000 claims description 10
- 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 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- 229910021538 borax Inorganic materials 0.000 claims description 7
- 239000004328 sodium tetraborate Substances 0.000 claims description 7
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 7
- 238000000280 densification Methods 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 2
- 229940001593 sodium carbonate Drugs 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 claims description 2
- 229960001922 sodium perborate Drugs 0.000 claims description 2
- 229940045872 sodium percarbonate Drugs 0.000 claims description 2
- 235000019794 sodium silicate Nutrition 0.000 claims description 2
- 229940074404 sodium succinate Drugs 0.000 claims description 2
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 claims description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 2
- 239000011236 particulate material Substances 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000010298 pulverizing process Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 238000001694 spray drying Methods 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 9
- 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 8
- 238000009472 formulation Methods 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000003945 anionic surfactant Substances 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- -1 for example Inorganic materials 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910017053 inorganic salt Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 229910021653 sulphate ion Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910000632 Alusil Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000019351 sodium silicates Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical group CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000592503 Speea Species 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
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- FTZNYGSHSMZEIA-UHFFFAOYSA-M sodium;hydrogen carbonate;sulfuric acid Chemical compound [Na+].OC([O-])=O.OS(O)(=O)=O FTZNYGSHSMZEIA-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000004711 α-olefin 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
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)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
C.3261 US
ABSTRACT
A granular detergent composition or component therefor having a bulk density of at least 650 g/litre is prepared by granulating a particulate material, preferably spray-dried, in a high-speed mixer/granulator having both a stirring action and a cutting action, in the absence of an agent for improving surface properties.
The particulate starting material comprises (a) from 12 to 70 wt% of non-soap detergent-active material (preferably consisting at least partially of anionic detergent-active material) and (b) at least 15 wt% of water-soluble crystalline inorganic salts, including sodium tripolyphosphate and/or sodium carbonate, the weight ratio of (b) to (a) being at least 0.4:1.
ABSTRACT
A granular detergent composition or component therefor having a bulk density of at least 650 g/litre is prepared by granulating a particulate material, preferably spray-dried, in a high-speed mixer/granulator having both a stirring action and a cutting action, in the absence of an agent for improving surface properties.
The particulate starting material comprises (a) from 12 to 70 wt% of non-soap detergent-active material (preferably consisting at least partially of anionic detergent-active material) and (b) at least 15 wt% of water-soluble crystalline inorganic salts, including sodium tripolyphosphate and/or sodium carbonate, the weight ratio of (b) to (a) being at least 0.4:1.
Description
~2~7~
- 1 - C. 3261 DETERGENT COMPOSITIONS
AND PROCESS FOR PREPARING T~IElq The present invention relates t:o granular detergent compositions of high bulk density having good washing performance and good powder propert.ies, and a process for preparing them.
BACKGROUND AND PRIOR ART
.
Recently thexe has b~en considerable interest within ~he detergents indus~ry in the production of de~ergent powders having relatively high bulk density, for exarnple, 60~ g/litre and above. Particular attention has been paid to the densification of spray-dried powders by 20 post-txeatment. EP 219 328A (~nilever) published April 22, 1987, discloses a granular low-phosphate detergent composition prepared by spray-drying a slurry to give a base powder contaîning a low to moderate level of sodium tripholyphosphate builder and low levels of inorganic salts, and th~n postdosing _ _ ~22~
solid material including sodium sulphate of high bulk density and of smaller particle size than the base powder~
thus filling the voids between base powder particles and producing a product of high bulk density.
JP 61 069897A (Kao) publishad April lO, 1986, discloses a process in which a spray-dried detergent powder containing a high level of anionic sur~actant and a low level o~ builder (zeolite) is subjected successively to pulverising and granulating treatments in a high-speed mixer/granula~or, the granulation being carried out in the presence of an "agent for improving surface properties~' and optionally a binder. It would appear that in the high-speed mixer/granulator, the spray-dried powder is initially broken down to a fine state of division; the surface-improving agent and optional binder are then added and the pulverised material granulated to form a final product of high bulk density. -The surface-improving agent, which is a finely divided particulate solid such as fine sodium aluminosilicate, is apparently requixed in order to prevent the composition from forming into large balls or cakes.
EP 229 671A (Kao) published July 22, 1987, discloses postdosing a crystalline alkaline inorganic salt, for example, sodium carbonate, to a spray-dried base powder prepared as in the above-mentioned JP 61 069897A (Kao) and containing a restricted level of water-soluble crystalline inorganic salts, to produce a high bulk density product.
GB 1 517 713 (Unilever) published July 12, 1978, discloses a process in which spray-dried or granulated detergent powders containing sodium tripolyphosphate and sodium sulphate are densified and sphexonised in a "marumerizer~' (Trade Mark).
~3227~
- 3 - C.3261 GB 1 453 697 (Unilever) discloses the use of the same apparatus to granulate together detergent powder components in the presence of a liquid binder to form a granular detergent composition. The "marumerizer~
comprises a substantially horizontal roughened rotatable table positioned within and at the base of a substantially vertical smooth-walled cylinder. The disadvantage associated with this apparatus is tha~ it produces powders or granules having a rather wide particle size distribution, and in particular containing a relatively high proportion of oversize particles.
Such products exhibit poor dissolution and dispersion characteristics, particularly in low-temperature short duration machine washes as used in Japanese and other far-eastern washing machines. This can be apparent to the consumer as deposits on washed fabrics, and in machine washing leads to a high level of wastage.
EP 220 024A ~Procter & Gamble) published April 29, 1987, disclosed a process in which a spray-dried detergent powder containing a high level (30-135 wt~) of anionic surfactant is mixed with an inorganic builder ~sodium tripolyphosphatel or sodium aluminosilicate and sodium carbonate) and compacted under high pressure using a roll compactor (~chilsonatox~; the compacted material, after removal of oversize material and fines, is then granulated using convantional apparatus, for example, a fluidised bed, tumble mixer, or rotating drum or pan.
EP 158 419A (Hashimura) published October 16, 1985, disclosPs the preparation of a detergent powder by mixing a majox proportion of soda ash (preferably 70 to 85 wt~ of the mixture) and a minor proportion of surfactan~ (wholly or predominantly nonionic) in a high-speed mixer/granulator.
~L 3 2 2 r~
~ 4 - C.3261 It has now been found that spray-dried powders containing moderate or high levels of water-soluble crystalline inorganic salts, including sodium tripolyphosphate and/or sodium carbonate, can be granulated and densified in a high-speed mixer/granulator, if necessary after pulverisation, without the need for an "agent for improving surface properties" or similar pulverulent material, even when high levels of anionic surfactant are present.
DEFINITION OF THE INVENTION
The present invention provides a process for the preparation of a granular detergen~ composition or component having a bulk density of at least 650 g/litre, which comprises the step of treating a particulate starting material comprising:
(a) from 12 to 70 wt% of non-soap detergent-active material, and (b) at least lS wt~ of water-soluble crystalline inorganic salts, including sodium tripolyphosphate and/or sodium carbonate, the weight ratio of (b) to (a) being at least 0.4:1, and optionally other detergent components to 100 wt%, in a high-speed mixer/granulator having both a stirring action and a cutting action, in the absence of a finely divided particu~ate agent for improving surface properties, whereby granulation and densification to a bulk density of at least 650 g/litre are effected.
~ 3 ~
- 5 - C.3261 DETAILED DESCRIPTION OF T~E INVENTION
The invention is concerned with a process for the preparation of a detergent powder combining high bulk density, good powder properties and excellent washing and c]eaning performance.
The present inventors have found that a detergent base powder prepared by any suitable method and containing substantial levels of water-soluble crystalline inorganic salts may be processed in a high-speed mixer/granulator, without the need for the use of an ~ayent for improving surface properties" during the granulation step as prescribed by JP 61 069897A (Kao), to give a dense granulate having good flow properties, even if relatively high levels of anionic surfactant are present. The product is characterised by an especially narrow particle size distribution, and in particular by a very small proportion of oversize material, giving good and rapid cold water dispersability and low insoluhle~.
The starting ~owder A preferred starting powder has a ratio of total water~soluble crystalline inorganic salts (b) to total non-soap surfactant la~ within the range of from 0.4:1 to 9:1, more preferably from 0.4:1 to 5:1. An especially preferred range for the xatio of ~b) to (a) is from 1~1 3 0 t:o 5 1 r Preferably the starting powder contains a total of from 15 to 70 wt~ of water-soluble crystalline inorganic salts. A5 well as sodium tripolyphosphate and sodium carbonate, examples of such salts include sodium 1 322 ~
- 6 - C.3261 sulphate, sodium ortho- and pyrophosphates, and crystalline sodium silicates, that is to say, sodium silicates having a ratio (SiO2 to Na20) < 1, such as sodium orthosilicate and sodium metasilicate. The alkaline and neutral silicates of higher ratio commonly used in detergent compositions are not to be regarded as crystalline.
According to a preferred embodiment of the invention, the starting powder contains from 15 to 50 wt%, more preferably from 20 to 40 wt4, of sodium tripolyphosphate.
The non-soap surfactant present in the starting powder preferably consists at least partially of anionic surfactant. Suitable anionic surfactants will be well known to those skilled in the art, and include linear alkylbenzene sulphonates, particularly sodium linear alkylbenzenesulphonates having an alkyl chain length of C8-C15; primary and secondary alkyl sulphates, particularly sodium C12-C15 primary alcohol sulphates;
alkyl ether sulphates; alpha-olefin and internal olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; fatty acid ester sulphonates; and combinations thereof.
If desired, the starting powder may contain nonionic surfactant. Nonionic surfactants too will be well known to those skilled in the art, and include 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~
- 1 - C. 3261 DETERGENT COMPOSITIONS
AND PROCESS FOR PREPARING T~IElq The present invention relates t:o granular detergent compositions of high bulk density having good washing performance and good powder propert.ies, and a process for preparing them.
BACKGROUND AND PRIOR ART
.
Recently thexe has b~en considerable interest within ~he detergents indus~ry in the production of de~ergent powders having relatively high bulk density, for exarnple, 60~ g/litre and above. Particular attention has been paid to the densification of spray-dried powders by 20 post-txeatment. EP 219 328A (~nilever) published April 22, 1987, discloses a granular low-phosphate detergent composition prepared by spray-drying a slurry to give a base powder contaîning a low to moderate level of sodium tripholyphosphate builder and low levels of inorganic salts, and th~n postdosing _ _ ~22~
solid material including sodium sulphate of high bulk density and of smaller particle size than the base powder~
thus filling the voids between base powder particles and producing a product of high bulk density.
JP 61 069897A (Kao) publishad April lO, 1986, discloses a process in which a spray-dried detergent powder containing a high level of anionic sur~actant and a low level o~ builder (zeolite) is subjected successively to pulverising and granulating treatments in a high-speed mixer/granula~or, the granulation being carried out in the presence of an "agent for improving surface properties~' and optionally a binder. It would appear that in the high-speed mixer/granulator, the spray-dried powder is initially broken down to a fine state of division; the surface-improving agent and optional binder are then added and the pulverised material granulated to form a final product of high bulk density. -The surface-improving agent, which is a finely divided particulate solid such as fine sodium aluminosilicate, is apparently requixed in order to prevent the composition from forming into large balls or cakes.
EP 229 671A (Kao) published July 22, 1987, discloses postdosing a crystalline alkaline inorganic salt, for example, sodium carbonate, to a spray-dried base powder prepared as in the above-mentioned JP 61 069897A (Kao) and containing a restricted level of water-soluble crystalline inorganic salts, to produce a high bulk density product.
GB 1 517 713 (Unilever) published July 12, 1978, discloses a process in which spray-dried or granulated detergent powders containing sodium tripolyphosphate and sodium sulphate are densified and sphexonised in a "marumerizer~' (Trade Mark).
~3227~
- 3 - C.3261 GB 1 453 697 (Unilever) discloses the use of the same apparatus to granulate together detergent powder components in the presence of a liquid binder to form a granular detergent composition. The "marumerizer~
comprises a substantially horizontal roughened rotatable table positioned within and at the base of a substantially vertical smooth-walled cylinder. The disadvantage associated with this apparatus is tha~ it produces powders or granules having a rather wide particle size distribution, and in particular containing a relatively high proportion of oversize particles.
Such products exhibit poor dissolution and dispersion characteristics, particularly in low-temperature short duration machine washes as used in Japanese and other far-eastern washing machines. This can be apparent to the consumer as deposits on washed fabrics, and in machine washing leads to a high level of wastage.
EP 220 024A ~Procter & Gamble) published April 29, 1987, disclosed a process in which a spray-dried detergent powder containing a high level (30-135 wt~) of anionic surfactant is mixed with an inorganic builder ~sodium tripolyphosphatel or sodium aluminosilicate and sodium carbonate) and compacted under high pressure using a roll compactor (~chilsonatox~; the compacted material, after removal of oversize material and fines, is then granulated using convantional apparatus, for example, a fluidised bed, tumble mixer, or rotating drum or pan.
EP 158 419A (Hashimura) published October 16, 1985, disclosPs the preparation of a detergent powder by mixing a majox proportion of soda ash (preferably 70 to 85 wt~ of the mixture) and a minor proportion of surfactan~ (wholly or predominantly nonionic) in a high-speed mixer/granulator.
~L 3 2 2 r~
~ 4 - C.3261 It has now been found that spray-dried powders containing moderate or high levels of water-soluble crystalline inorganic salts, including sodium tripolyphosphate and/or sodium carbonate, can be granulated and densified in a high-speed mixer/granulator, if necessary after pulverisation, without the need for an "agent for improving surface properties" or similar pulverulent material, even when high levels of anionic surfactant are present.
DEFINITION OF THE INVENTION
The present invention provides a process for the preparation of a granular detergen~ composition or component having a bulk density of at least 650 g/litre, which comprises the step of treating a particulate starting material comprising:
(a) from 12 to 70 wt% of non-soap detergent-active material, and (b) at least lS wt~ of water-soluble crystalline inorganic salts, including sodium tripolyphosphate and/or sodium carbonate, the weight ratio of (b) to (a) being at least 0.4:1, and optionally other detergent components to 100 wt%, in a high-speed mixer/granulator having both a stirring action and a cutting action, in the absence of a finely divided particu~ate agent for improving surface properties, whereby granulation and densification to a bulk density of at least 650 g/litre are effected.
~ 3 ~
- 5 - C.3261 DETAILED DESCRIPTION OF T~E INVENTION
The invention is concerned with a process for the preparation of a detergent powder combining high bulk density, good powder properties and excellent washing and c]eaning performance.
The present inventors have found that a detergent base powder prepared by any suitable method and containing substantial levels of water-soluble crystalline inorganic salts may be processed in a high-speed mixer/granulator, without the need for the use of an ~ayent for improving surface properties" during the granulation step as prescribed by JP 61 069897A (Kao), to give a dense granulate having good flow properties, even if relatively high levels of anionic surfactant are present. The product is characterised by an especially narrow particle size distribution, and in particular by a very small proportion of oversize material, giving good and rapid cold water dispersability and low insoluhle~.
The starting ~owder A preferred starting powder has a ratio of total water~soluble crystalline inorganic salts (b) to total non-soap surfactant la~ within the range of from 0.4:1 to 9:1, more preferably from 0.4:1 to 5:1. An especially preferred range for the xatio of ~b) to (a) is from 1~1 3 0 t:o 5 1 r Preferably the starting powder contains a total of from 15 to 70 wt~ of water-soluble crystalline inorganic salts. A5 well as sodium tripolyphosphate and sodium carbonate, examples of such salts include sodium 1 322 ~
- 6 - C.3261 sulphate, sodium ortho- and pyrophosphates, and crystalline sodium silicates, that is to say, sodium silicates having a ratio (SiO2 to Na20) < 1, such as sodium orthosilicate and sodium metasilicate. The alkaline and neutral silicates of higher ratio commonly used in detergent compositions are not to be regarded as crystalline.
According to a preferred embodiment of the invention, the starting powder contains from 15 to 50 wt%, more preferably from 20 to 40 wt4, of sodium tripolyphosphate.
The non-soap surfactant present in the starting powder preferably consists at least partially of anionic surfactant. Suitable anionic surfactants will be well known to those skilled in the art, and include linear alkylbenzene sulphonates, particularly sodium linear alkylbenzenesulphonates having an alkyl chain length of C8-C15; primary and secondary alkyl sulphates, particularly sodium C12-C15 primary alcohol sulphates;
alkyl ether sulphates; alpha-olefin and internal olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; fatty acid ester sulphonates; and combinations thereof.
If desired, the starting powder may contain nonionic surfactant. Nonionic surfactants too will be well known to those skilled in the art, and include 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~
2 ~
- 7 - C.3261 Suitably the surfactant component of the starting powder may be constituted by from 0 to 70%, preferably from 8 to 60 wt%, of anionic surfactant, and from 0 to 20%, preferably from 0 to 10%, by weight of nonionic surfactant.
Other types of non-soap surfactant, for example, cationic, zwitterionic, amphoteric or semipolar surfactants, may also be present if desired. Many suitable detergent-active compounds are available and are fully described in the literature, for example, in r'Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
If desired, soap may also be present, to provide foam control and additional detergency and builder power;
soap is not included in the 12 to 70~ figure for the surfactant content ~uoted previously.
The starting powder may be prepared by any suitable tower or non-tower method, for example, spray-drying or dry mixing. The invention is especially useful for the densification of a spray-dried powder.
If desired, at least part of the water-soluble crystalline inorganic salt to be included in ~he final product may be admixed to the remainder of the starting powder in the high-speed mixer/granulator itself. In this embodiment of the invention, the percentages and ratios ~pecified above should be based on the total material introduced into the high-speed mixer/granulator, including the added salt.
2~
- 8 - C.3261 Thus it is within the scope of the present invention to introduce into the high-spe~d mixer/granulator a starting powder, prepared for example by spray-dryin~, ~ontaining less than the amount of water-soluble crystalline inorganic salt specified above, and then to admix with that powder, in the high-spPed mixer/granulator, sufficient water-soluble crystalline inorganic salt to bring the salt percentage (b) and the ratio (b) to (a) up to the specified level.
Similarly, it is within the scope of the invention to add surfactant, or indeed any other component, in the high-speed mixer/granulator provided that the final composition is as specified above, and provided that the component so added is not a finely divided ~a~ent for improving surface properties" as described in JP 61 069897A (Kao) published April 10, 1986, disclosed previously. Thus, in the process of the invention, any component other than a finely divided particulate solid having a particle si~e of less than 100 microns may be added to the hiqh-speed mixer/granu:Lator prior to granulation.
One procedure according to the invention includes the step of admixing at least one inorganic or organic salt having a particle size of at least 100 microns with the remainder of ~he starting pow~er in the high-speed mixer/granulator. If the salt is water-soluble, inorganic and crystalline, it should be included within the percentages and ratios specified above which relate to the total amount of such salts in the material subjected to granulation in the high-speed mixer/granulator.
~L322~
- 9 ~ C.3261 Salts that may conveniently be incorporated by this method include borax, sodium bicarbonate, sodium silicate, sodium tripolyphosphate, sodium carbonate, sodium perborate, sodium percarbonate, sodium citrate, sodium nitrilotriacetate, sodium succinate, sodium sulphate and combinations of these. These salts can give various benefits: for example, borax and sodium bicarbonate a.re buffers ~iving mild products of low in-wash pH.
The process In the process of the invention, granulation is effected by means of a high-speed mixer/granulator having both a stirring action and a cutting action. PrefPrably the stirrer and the cutter may be operated independently of one another, and at separately variable speeds~ Such a mixer is capable of combining a high energy stirring input with a cutting action, but can also be used to provide other, gentler stirring regimes with or without the cutter in operatio.n. It is thus a highly versatile and flexible piece of apparatus.
A preferred type of high-speed mixer/granulator for use in the process of the invention is bowl-shaped and preferably has a substantially vertical stirrer axis.
Especially preferred are mixers of the Fukae (Trade Mark) v' FS-G series manufactured by Fukae Powtech Kogyo Co., Japan; this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cuttex positioned on a si~e wall.
The stirrer and cutter may be operated independently of one another, and at separately variable speeds.
: .
~ 3~27i'~
- 10 - C.3261 Other similar mixers found to be suitable for use in the pxocess of the invention are the Diosna (Trade Mark) V series ex Dierks & Sohne, Germany; and the Pharma Matrix ~Trade Mark) ex T K Fielder Ltd., England. Other similar mi~ers believed to be suitable for use in the process of the invention include the Fuji (Trade Mark) VG-C series ex Fuji Sangyo Co., Japan; and the Roto (Trade Mark) ex Zanchetta & Co srl, Italy.
Another mixer found to be suitable for use in the process of the invention is the Ladige ~Trade Mark) FM
series batch mixer ex Morton Machine Co. Ltd., Scotland.
This differs from the mixers mentioned above in that its stirrer has a horizontal axis.
As indicated above, the use of a high-speed mixer/granulator is essential in the process of the invention to effect granulation and densification. If desired, the mixer may also be used for a pretreatment step before granulation is carried out.
For example, it is within the scope of the invention, as previously indicated, for one or more further ingredients to be admixed with an otherwise premixed powder prepared elsewhere ~for example, by spray-drying~. A sui~able stirring/cutting regime and residence time may be chosen in accordance with the materials to be mixed.
Another possible pretreatment that may be carried out in the high speed mixer~granulator is pulverisation;
whether or not this is necessary depends, among other things, on the method of preparation of the starting powder and its free moisture content. Powders prepared by spray-drying, for example, are more likely to require 13 2 2 rl ~ ~
11 - C.32~1 pulverisation than powders prepared by dry~mixing.
Again, the flexibility of the apparatus allows a suitable stirring/cutting regime to be chosen: generally relatively high speeds for both stirrer and cutter. A
relatively short re~idence time (for example, 2-4 minutes for a 35 kg batch3 is generally sufficient.
The essential feature of the process of the invention i5 the granulation step, during which densification to the very high values of at least 650 g/litre, preferably at least 700 g/litre occurs, giving a dense, granular product of very uniform particle size and generally spherical particle shape.
Granulation is effected by running the mixer at a relatively high speed using both stirrer and cutter; a relatively short residence time (for example, 5-8 minutes for a 35 kg batch) i5 generally sufficient. The final bulk density can be controlled by choice of residence time, and it has been found that the powder properties of the resulting granulate are not optimum unless the bulk density has been allowed to rise to at least 650 g/litre.
The presence of a liquid binder is necessary for successful granulation. The amount of binder added preferably does not exceed that needed to bring the free moisture content of the composition above abou~ 6 wt%, since higher levels may lead to a deterioration in th~
flow properti~s of the final granulate. If necessary, binder, preferably water, may be added beore or during granulation, but ome starting powders will inh~rently Gontain sufficient moisture. If a liquid binder is to be added, it may be sprayed in while the mixer is running. In one preferred mode of operation, the mixer r~
- 12 - C.3261 is fi~st operated at a relatively slow speed while binder is added, before increasing the speed of the mixer to effect granulation.
If the starting powder has a sufficient free moisture content to render the addition of a binder unnecessary, pulverisation (i~ required) and granulation need not be regarded as separate process steps but as one single operation. Indeed, it is not, in that case, necessary to decide in advance whether or not pulverisation is required: the mixer may simply be allowed to do what is necessary, since the mixer conditions required are generally substantially the same for pulverisation and for granulation.
According to a preferred embodiment of the invention, granulation is carried out at a controlled temperature somewhat above ambient, preferably above 30C. The optim~m temperature is apparently formulation-~ependent, but appears generally to lie within the range of from 30 to 45C, preferably about 35C.
It is an essential feature of the present invention that during granulation no "agent for improving surface properties" as defined in the above-mentioned JP 51 06~897 (Kao) published April 10, 1986, be present. When processing a formulation having a relatively high ra~io of aluminosilicate builder to surfactant, in accordance with the present invention, the use of a finely divi~ed particulate material such as fine sodium aluminosilicate during the granulation step is not only unnecessary but can with some formulations make granulation more difficult, or even impossible.
~ ~2 ' ~
- 13 - C.3261 The optional flow aid In accordance with a preferred embodiment of the invention, a finely divided particulate flow aid may be admixed with the granular material after granulation is complete. Advantageously, flow aid is added while the granulate is still in the high-speed mixer/granulator, and the mixer is operated at a slow speed for a further short period. No further granulation occurs at this stage. It is also within the scope of the invention to add the flow aid to the granulate after removing the latter to different apparatus.
This embodiment of the invention should be distinguished from the prior art process of JP 61 069897A
(Kao), mentioned above, in which an "agent for improving surface properties", which can be fine sodium aluminosilicate, is present during the granulation stage itself. It is within the scope of the present invention to add a particulate flow aid aftex granulation is complete, but, as explained above, it is essential to the invention that no finely divided particulate "agent for improving surface properties" be prlesent during granulation. The addition of ~ flow aid after ~5 granulation is complete can have an additional bPneficial ef*ect on the properties of the granulate, regardless of the formulation, whereas the presence of this type of mat~rial during the granulation step in the process of the invention makes processing more difficult.
The preferred granulation temperature of from 30 to 45C, preferably about 3S~C, may also be maintained during the subsequent admixture of a flow aid.
~3~27~
- 14 - C.3261 The flow aid is a finely divided particulate material. The preferred average particle size is 0.1 to 20 microns, more preferably 1 to 10 microns.
According to one preferred embodiment of the invention, the flow aid is finely divided amorphous sodium aluminosilicate, as described and claimed in our copending application of even date (Case C.32363. A
suitable material is available commercially from Crosfield Chemicals Ltd, Warrington, Cheshire, England, under the trade mark Alusil. This material is !~
effective in improving flow properties even at very low levels, and also has the effect of increasing bulk density. It is therefore possible to adjust bulk density by appropriate choice of the level of amorphous sodium aluminosilicate added after granulation.
Amorphous sodium aluminosilicate is advantageously used in an amount of from 0.2 to 5.0 wt%, based on the starting powder, more preferably from 0.5 to 3.0 wt%.
Another preferred flow aid is finely divided crystalline s~dium aluminosilicate. The crystalline aluminosilicates discussed previously in the context of builders are also suitable for use as flow aids. They are, however, less weight-effective than the amorphous material and are suitably used in an amount of from 3.0 to 12.0 wt%, more preferably from 4.0 to lO.0 wt~.
If desired, both crystalline and amorphous sodium aluminosilicates may be used, together or sequentially, as flow aids.
~322~ ~
- 15 - C.3261 Other flow aids suitable for use in the process of the invention include precipitated silica, for example, Neosyl (Trade Mark), and precipitated calcium silicate, for example, Microcal (Trade Mark), both commercially available fro~ Crosfield Chemicals Ltd, Warrington, Cheshire, England.
The final ~ranulate The final granulate has a bulk density of at least 650 g/litre and preferably at least 700 g/litre. It is also characterised by an especially low particle porosity, preferably not exceeding 0.25 and more preferably not exceeding 0.20, which distinguishes it from even the densest powders prepared by spray-drying alone.
The final granulate may be used as a complete detergent composition in its own right. Alternatively, it may be admixed with other components or mixtures prepared separately, and may form a major or minor part of a final product~ Generally, any add.itional ingredients such as enzymes, bleach and perfume that are not suitable for undergoing the granulation process and the steps that precede it may be a~mixed to the granulate to make a final product.
In one preferred embodiment of the invention, for example, a detergent base powder is prepared by spxay-drying an aqueous slurry of heat-insensitive and compatible ingredients; if desired, other ingredients may then be admixed as dis~ussed above; and the resulting powder is densified and granulated in accordance with the process of the invention. Yet further ingredients may i desired be admixed after ~32~7~l~
- 16 - C.3261 granulation; the densified granulate may typically constitute from 40 to 100 wt% of a final product.
In another embodiment of the invention, the densified granulate prepared in accordance with the present invention is an "adjunct'l comprising a relatively high level of detergent-active material on an inorganic carrier; and this may be admixed in a minor amount with other ingredients to form a final product.
The invention is further illustrated by the following non-limiting Examples, in which parts and percentages are by weight unless otherwise stated.
~ 3 2 ~
- 17 - C.3261 EXAMPLES
In the Examples which follow, the following abbreviations are used.
LAS: sodium linear alkylbenzene sulphonate NI: nonionic surfactant ~ethoxylated alcohol) NSD: total non-soap detergent STP: sodium tripolyphosphate Carbonate: sodium carbonate Sulphate: sodium sulphate Silicat.e: sodium alkaline silicate g: good Alu: Alusil (Trade Mark) N, finely divided amorphous sodium aluminosilicate Zeo: Zeolite 4A (Wessalith (Trade Mark? ex Degussa) 13 2 2 ~
- 18 - C.3261 E~am~les 1 ~ 2 Powders containing sodium tripolyphosphate and sodium sulphate were prepared by spray-drying aqueous slurries to the formulations (weight %) shown in Table lo Table 1 Example 1 2 LAS 12.2 9.7 NI 8.1 2.8 NSD (a) 20.3 12.5 STP 42.7 42.5 Sulphate 10.2 14.8 Salts (b) 52.9 57.3 Soap _ ~ g Silicate 10.2 10.0 Minors 2.4 2.8 Water 14.2 12.5 (b):(a) 2.6 4.6 - -20 kg batches of each powder were densified in a Fukae (~rade Mark) high-speea mixer/granulator, process conditions and resulting powder properties being shown in Table 2. In Example 1, the powder was initially subjected to a 2-3 minute warming up period, at a low stirrer speed ~50 rpmj and without the cutter running, until the temperature had reached about 30-35C. This was followed by pulverisation (optional), then binder addition talso~optional~, then granulation, followed finally by addition of flow aid.
~3227~
- 19 - C.3261 Table 2 1 2(a) 2Ib) Pulverisation:
Time (min) 4 0.5 0-5 Stirrer speed lrpm) 180 180 180 Cutter speed (rpm~ 3000 1000 1000 Binder lwater)~
Amount (wt %) 4 0.5 O.S
Addition time (min) 1 0.5 0.5 Stirrer speed (rpm) 100 100 100 Cutter speed ~rpm) 3000 3000 3000 Granulation:
Time (min) 15 7 6 Stirrer speed (rpm) 140 140 140 Cutter speed (rpm) 2700 3000 3000 Flow aid:
Zeo or Alu Alu Alu Zeo Amount (wt ~) 2 1.5 5 Addition time (min) Stirrer speed (rpm~ 90 90 90 Cutter speed (rpm) 300 300 300 ______________,__ _________~_____ _._.____ Yield`<1700 ~m (wt %) 95 93 97 Average particle size ~m) 689 ~55 480 Bulk density (g/litre) 854 840 780 Dynamic flow rate (ml/s~ 109 92 61 Compressibility ~v/v) 7.6 7 12 Particle porosity~0,20 <0.20 <0.20 Comparison of Examples 2(a) and 2lb) shows the greater weight-effec~iveness of Alusil as flow aid.
132~7~
- 20 - C.32~1 Examples 3 to 5 Powders containing sodium tripolyphosphate as the sole water-soluble crystalline inorganic salt were prepared by spray-drying aqueous slurries to the formulations (weight %~ shown in Table 3.
Table 3 10 Examp].e 3 4 5 LAS 48.625.3 26.4 NI - 2.4 2.6 NSD (a) 48.627.7 29.0 STP 26.742.5 45.9 Salts (b) 26.742.5 45.9 Silicate 15,511.0 10.0 Minors 1.52.9 2.9 Water 7.715.9 12.2 (b):(a) 0.551.5 1.6 ~ 20 kg batches o~ each powder were densified in a ~ ~ Fukae (Trade Mark~ high speed mixer/granulator as described in Examples l and 2, process con~itions and resulting powder properties beîng shown in TabIes 4 and 5.
' ' ' ' .. . .
13227~aL
- 21 - C.3261 able 4 3 5(a)5(b) Pulverisation:
Time (min) 3 0.50.5 Stirrer ~peed (rpm) 300 180 180 Cutter speed (rpm) 3000 3000 3000 Binder (water~:
~nount (wt %) 2 none none Addition time tmin) Stirrer speed (rpm) 100 Cutter speed (rpm) ~3000 Granulation:
Time (min) 5 5 6 Stirrer speed (rpm) 275 140 140 Cutter speed (rpm) 3000 2700 2700 Flow aid:
Zeo. or Alu. Alu Alu Zeo Amount (wt %) 1 1.5 5 Addition time (min) Stirrer speed (rpm) 90 90 90 Cutter speed (rpm) 0 300 300 Yield <1700 ~m ~wt ~) 80 94 93 ~verage particle size t~m)693 528 389 Bulk density (g/litre~ 673 720 820 Dynamic flow rate (ml/s) 134 ~3 96 Compressibility l~/v) 3.5 14 11 Particle porosity<0.20 <0.20 ~0.20 ~5 ~322~
- 22 - C.3261 Table 5 4(a) 4(b) 5 Pulverisation:
Time tmin) 0.5 0.5 Stirrer speed (rpm) 180 180 Cutter speed lrpm) 3000 3000 Binder (water):
Amount (wt %) 1 0.5 Addition time (min) 0.5 0.5 Stirrer speed (rpm) 100 100 Cutter speed (rpm) 3000 3000 Granulation:
Time (min) 4 4 Stirrer speed (rpm) 140 140 Cutter speed (rpm) 2700 2700 Flow aid:
Zeo. or Alu. Alu Alu Amount (wt g) 2.5 2.5 ~ Addition time (min) ;~ ~ 25 Stirrer speed (rpm) 90 90 Cutter speed (rpm) 300 300 Yield C1700 ~m (wt %)95 96 30 Average particle size (~m~5dl 608 Bulk density (g/litre)830 770 Dynamic flow rate (ml/s)86 B9 Comprassibility t%v/v~ 9 11 35 Particle porosity<0.20 <0.20 ~22~
- 23 - C.3261 Examples 6 to 8 Powders containing sodium tripolyphosphate, sodium carbonate and sodium sulphate were prepared to the formulations ~weight ~) shown in Table 6.
Table_6 Example 6 7 8 LAS 28.0 15.0 15.5 NI - 3.0 1.5 NSD (a) 28~0 18.0 17.0 STP 27.0 30.0 26.0 Carbonate 5.0 10.0 18.9 Sulphate 15.0 lS.0 17.2 Salts (b) 47.0 55.0 62.
20 Soap - 6.0 Silicate 8,0 9.0 9OO
Calcite 5.0 Minors 1.0 1.0 1.4 Water 11.0 11.0 9.8 ~b):(a) 107 3~0 3.7 The powders were prepared by spray-drying aqueous slurries. However, the sodium carbonate in the powder of Example 6 was not incorporated via the slurry ~t postdosed in the Fukae mixer.
20 kg batches of each powder were densified in a Fukae (Trade Mark) ~igh~speed mixer/granulator as described in Examplés 1 and 2, proce~s conditions and resulting powder properties being shown in Table 7.
~227~
~ 24 - C.3261 Ta~b~e 7 Pulverisation:
Time (min) Stirrer speed (rpm) 300 300 Cutter speed (~pm) 3000 3000 Binder (water):
Amount (wt %)0.5 Addition time (min) 2 Stirrer speed (rpm) 100 100 Cutter speed (rpm) 3000 3000 Granulation:
Time tmin) 4 4 Stirrer speed (rpm) 225 200 Cutter speed (rpm) 3000 3000 Flow aid:
Zeo. or Alu. Alu Alu Amount (wt %) Addition time (min) Stirrer spsed ~rpm) 90 90 Cutter speed (rpm) 0 0 Yiald ~1700 ~m Iwt ~) g g Average partîcle size l~m) 743 582 :
Bulk density (g/litre~ 906 800 Dynamic flow rate (ml/s) 133 120 Compressibility (%v/v) 3.5 7.0 Par icle poro~ity<0.20 ~0.20 ~22~
- 25 - C.3261 Table 8 8(a) 8(b~ 8(c) 5 Pulverisation: none none none Time (min) - - -Stirrer speed (rpm) - -Cutter speed (rpm) - - -Binder (water):
Amount (wt ~) 1.5 1~5 Addition time ~min)0.5 0.5 0~5 Stirrer speed (rpm)lO0 100 100 Cutter speed (rpm) 3000 3000 3000 Gramllation:
Time (min) 10 7 7 Stirrer speed (rpm) 140 140 140 Cutter speed (rpm) 2700 2700 2700 Flow aid:
~eo or Alu Alu Alu Alu Amount (wt %)1.5 1.5 Addition time (min3 0O5 0.5 Stirrer speed:(rpm) 90 90 90 Cutter speed (rpm) 300 300 300 Yield <1700 ~m (wt %l 94-5 9~ 9 : 30 Bulk density (g/litre~ 920 870 760 Dynamic flow rate (ml/s) g g g Compressibility (%v/v~ g g g Particle porosity~0.20 ~0.20 <0.20 ~32~
- 26 - C.3261 Examples 9 and 10 Powders containin~ sodium tripolyphosphate and sodium carbonate were prepared, by spray-drying aqueous slurries, to the formulations (weight %) shown in Table 9, and densified in the Fukae mixer as in previous Examples, as shown in Table 10.
Table 9 Example 9 10 LAS 38.0 22.7 NI 2.1 NSD (a) 38.0 24.8 STP 21.0 37.1 Carbonate 22.0 17,5 Salts (b) 43.0 54.6 2~
Silicate 12.0 9.3 Minors 1.0 1.0 Water 6.0 10.3 25 (b):(a~ 1.1 2.2 ~227~
- 27 - C.3261 Table 10 5 Pulverisation:
Time (min) 3 3 Stirrer speed (rpm) 300 300 Cutter speed (rpm) 3000 3000 ~inder (water):
Amount (wt ~ 2 Addition time (min) Stirrer speed (rpm) 100 100 Cutter speed (rpm) 3000 3000 Granulation:
Time (min) 5 5 Stirrer speed (rpm) 275 275 Cutter speed (rpm) 3000 3000 Flow aid:
Zeo or Alu Alu Alu : Amount (wt ~) 1 1 ~ Addition time (min) : 25 Stirrer speea (rpm) 90 90 Cutter speed (rpm) 0 0 Yield <1700 ~m (wt %)80 90 30 ~ Average particle size (~m) 810 566 Bulk density (g/litre) 746 801 Dynamic flow rate (ml/s) 137 . 122 Compressibility (~vlv) 3.0 10 Particle porosity ~0.20 <0O20 ~2 2J~
- 28 - C.3261 Example 11 A powder containing sodium tripolyphosphate, sodium sulphate and borax was prepared to the formulation (weight %~ shown in Table 11.
Table 11 LAS 28.0 NSD ~a) 28.0 STP ~7 o Sulphate 19~7 Borax 10.0 Salts (b) 56.7 Polyacrylate polymer 4.5 Minors 0.8 Water 10.0 (b):(a) 2.0-~
The powder was prapared by spray-drying an aqueous : s7urry of all the ingredients except the borax. 9.0 kg of spray-dried base powder and 1.0 kg of borax were mixed and granulatedjdensified in the Fukae mixer, process conditions and resulting powder properties being shown in : : Table 12~
:~ 3 ~
- 29 - C.3261 Table 12 Mixing:
Time (min~ 5 Stirrer speed (rpm~ 200 Cutter speed (rpm~ 0 Binder (water):
Amount (wt %) Addition time (min) Stirrer speed (rpm) 300 Cuttex speed (rpm~ 3000 Granulation:
Time ~min) 9 Stirrer speed (rpm) 300 Cuttex speed (rpm) 3000 Breakdown of oversize:
Time (min) 1.5 Stirrer speed (rpm) 75 Cutter speed (rpm) 3000 .
Flow a1d:
Zeo or Alu Alu Amount jwt ~) 1 Addition time Imin) O . 5 Stirrer speed IrPm) 75 Cutter speed (rpm) 0 Di~charge:
Time (min) 0.5 Stirrer speed (rpm) 75 Cutter speed (rpm) 0 ~ 3 2 ~
- 30 - C.3261 During granulation the temperature rose from an initial 20C to about 40-45C. It was not necessary to cool the mixer.
The properties of the densified granulate were as follows:
Yiela <1700 ~m (wt %)82.l Average particle size (~m) 583 lD ~3u~X den~ity l~litre) ~B7 Dynamic flow rate (ml/s) l40 Compress ibiL ity ~v /v 1 4 . 7 Particle porosity <0O20 The product was a mild detergent powder giving a pH
(l wt~ a~ueous solution1 f 9-~
,
- 7 - C.3261 Suitably the surfactant component of the starting powder may be constituted by from 0 to 70%, preferably from 8 to 60 wt%, of anionic surfactant, and from 0 to 20%, preferably from 0 to 10%, by weight of nonionic surfactant.
Other types of non-soap surfactant, for example, cationic, zwitterionic, amphoteric or semipolar surfactants, may also be present if desired. Many suitable detergent-active compounds are available and are fully described in the literature, for example, in r'Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
If desired, soap may also be present, to provide foam control and additional detergency and builder power;
soap is not included in the 12 to 70~ figure for the surfactant content ~uoted previously.
The starting powder may be prepared by any suitable tower or non-tower method, for example, spray-drying or dry mixing. The invention is especially useful for the densification of a spray-dried powder.
If desired, at least part of the water-soluble crystalline inorganic salt to be included in ~he final product may be admixed to the remainder of the starting powder in the high-speed mixer/granulator itself. In this embodiment of the invention, the percentages and ratios ~pecified above should be based on the total material introduced into the high-speed mixer/granulator, including the added salt.
2~
- 8 - C.3261 Thus it is within the scope of the present invention to introduce into the high-spe~d mixer/granulator a starting powder, prepared for example by spray-dryin~, ~ontaining less than the amount of water-soluble crystalline inorganic salt specified above, and then to admix with that powder, in the high-spPed mixer/granulator, sufficient water-soluble crystalline inorganic salt to bring the salt percentage (b) and the ratio (b) to (a) up to the specified level.
Similarly, it is within the scope of the invention to add surfactant, or indeed any other component, in the high-speed mixer/granulator provided that the final composition is as specified above, and provided that the component so added is not a finely divided ~a~ent for improving surface properties" as described in JP 61 069897A (Kao) published April 10, 1986, disclosed previously. Thus, in the process of the invention, any component other than a finely divided particulate solid having a particle si~e of less than 100 microns may be added to the hiqh-speed mixer/granu:Lator prior to granulation.
One procedure according to the invention includes the step of admixing at least one inorganic or organic salt having a particle size of at least 100 microns with the remainder of ~he starting pow~er in the high-speed mixer/granulator. If the salt is water-soluble, inorganic and crystalline, it should be included within the percentages and ratios specified above which relate to the total amount of such salts in the material subjected to granulation in the high-speed mixer/granulator.
~L322~
- 9 ~ C.3261 Salts that may conveniently be incorporated by this method include borax, sodium bicarbonate, sodium silicate, sodium tripolyphosphate, sodium carbonate, sodium perborate, sodium percarbonate, sodium citrate, sodium nitrilotriacetate, sodium succinate, sodium sulphate and combinations of these. These salts can give various benefits: for example, borax and sodium bicarbonate a.re buffers ~iving mild products of low in-wash pH.
The process In the process of the invention, granulation is effected by means of a high-speed mixer/granulator having both a stirring action and a cutting action. PrefPrably the stirrer and the cutter may be operated independently of one another, and at separately variable speeds~ Such a mixer is capable of combining a high energy stirring input with a cutting action, but can also be used to provide other, gentler stirring regimes with or without the cutter in operatio.n. It is thus a highly versatile and flexible piece of apparatus.
A preferred type of high-speed mixer/granulator for use in the process of the invention is bowl-shaped and preferably has a substantially vertical stirrer axis.
Especially preferred are mixers of the Fukae (Trade Mark) v' FS-G series manufactured by Fukae Powtech Kogyo Co., Japan; this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cuttex positioned on a si~e wall.
The stirrer and cutter may be operated independently of one another, and at separately variable speeds.
: .
~ 3~27i'~
- 10 - C.3261 Other similar mixers found to be suitable for use in the pxocess of the invention are the Diosna (Trade Mark) V series ex Dierks & Sohne, Germany; and the Pharma Matrix ~Trade Mark) ex T K Fielder Ltd., England. Other similar mi~ers believed to be suitable for use in the process of the invention include the Fuji (Trade Mark) VG-C series ex Fuji Sangyo Co., Japan; and the Roto (Trade Mark) ex Zanchetta & Co srl, Italy.
Another mixer found to be suitable for use in the process of the invention is the Ladige ~Trade Mark) FM
series batch mixer ex Morton Machine Co. Ltd., Scotland.
This differs from the mixers mentioned above in that its stirrer has a horizontal axis.
As indicated above, the use of a high-speed mixer/granulator is essential in the process of the invention to effect granulation and densification. If desired, the mixer may also be used for a pretreatment step before granulation is carried out.
For example, it is within the scope of the invention, as previously indicated, for one or more further ingredients to be admixed with an otherwise premixed powder prepared elsewhere ~for example, by spray-drying~. A sui~able stirring/cutting regime and residence time may be chosen in accordance with the materials to be mixed.
Another possible pretreatment that may be carried out in the high speed mixer~granulator is pulverisation;
whether or not this is necessary depends, among other things, on the method of preparation of the starting powder and its free moisture content. Powders prepared by spray-drying, for example, are more likely to require 13 2 2 rl ~ ~
11 - C.32~1 pulverisation than powders prepared by dry~mixing.
Again, the flexibility of the apparatus allows a suitable stirring/cutting regime to be chosen: generally relatively high speeds for both stirrer and cutter. A
relatively short re~idence time (for example, 2-4 minutes for a 35 kg batch3 is generally sufficient.
The essential feature of the process of the invention i5 the granulation step, during which densification to the very high values of at least 650 g/litre, preferably at least 700 g/litre occurs, giving a dense, granular product of very uniform particle size and generally spherical particle shape.
Granulation is effected by running the mixer at a relatively high speed using both stirrer and cutter; a relatively short residence time (for example, 5-8 minutes for a 35 kg batch) i5 generally sufficient. The final bulk density can be controlled by choice of residence time, and it has been found that the powder properties of the resulting granulate are not optimum unless the bulk density has been allowed to rise to at least 650 g/litre.
The presence of a liquid binder is necessary for successful granulation. The amount of binder added preferably does not exceed that needed to bring the free moisture content of the composition above abou~ 6 wt%, since higher levels may lead to a deterioration in th~
flow properti~s of the final granulate. If necessary, binder, preferably water, may be added beore or during granulation, but ome starting powders will inh~rently Gontain sufficient moisture. If a liquid binder is to be added, it may be sprayed in while the mixer is running. In one preferred mode of operation, the mixer r~
- 12 - C.3261 is fi~st operated at a relatively slow speed while binder is added, before increasing the speed of the mixer to effect granulation.
If the starting powder has a sufficient free moisture content to render the addition of a binder unnecessary, pulverisation (i~ required) and granulation need not be regarded as separate process steps but as one single operation. Indeed, it is not, in that case, necessary to decide in advance whether or not pulverisation is required: the mixer may simply be allowed to do what is necessary, since the mixer conditions required are generally substantially the same for pulverisation and for granulation.
According to a preferred embodiment of the invention, granulation is carried out at a controlled temperature somewhat above ambient, preferably above 30C. The optim~m temperature is apparently formulation-~ependent, but appears generally to lie within the range of from 30 to 45C, preferably about 35C.
It is an essential feature of the present invention that during granulation no "agent for improving surface properties" as defined in the above-mentioned JP 51 06~897 (Kao) published April 10, 1986, be present. When processing a formulation having a relatively high ra~io of aluminosilicate builder to surfactant, in accordance with the present invention, the use of a finely divi~ed particulate material such as fine sodium aluminosilicate during the granulation step is not only unnecessary but can with some formulations make granulation more difficult, or even impossible.
~ ~2 ' ~
- 13 - C.3261 The optional flow aid In accordance with a preferred embodiment of the invention, a finely divided particulate flow aid may be admixed with the granular material after granulation is complete. Advantageously, flow aid is added while the granulate is still in the high-speed mixer/granulator, and the mixer is operated at a slow speed for a further short period. No further granulation occurs at this stage. It is also within the scope of the invention to add the flow aid to the granulate after removing the latter to different apparatus.
This embodiment of the invention should be distinguished from the prior art process of JP 61 069897A
(Kao), mentioned above, in which an "agent for improving surface properties", which can be fine sodium aluminosilicate, is present during the granulation stage itself. It is within the scope of the present invention to add a particulate flow aid aftex granulation is complete, but, as explained above, it is essential to the invention that no finely divided particulate "agent for improving surface properties" be prlesent during granulation. The addition of ~ flow aid after ~5 granulation is complete can have an additional bPneficial ef*ect on the properties of the granulate, regardless of the formulation, whereas the presence of this type of mat~rial during the granulation step in the process of the invention makes processing more difficult.
The preferred granulation temperature of from 30 to 45C, preferably about 3S~C, may also be maintained during the subsequent admixture of a flow aid.
~3~27~
- 14 - C.3261 The flow aid is a finely divided particulate material. The preferred average particle size is 0.1 to 20 microns, more preferably 1 to 10 microns.
According to one preferred embodiment of the invention, the flow aid is finely divided amorphous sodium aluminosilicate, as described and claimed in our copending application of even date (Case C.32363. A
suitable material is available commercially from Crosfield Chemicals Ltd, Warrington, Cheshire, England, under the trade mark Alusil. This material is !~
effective in improving flow properties even at very low levels, and also has the effect of increasing bulk density. It is therefore possible to adjust bulk density by appropriate choice of the level of amorphous sodium aluminosilicate added after granulation.
Amorphous sodium aluminosilicate is advantageously used in an amount of from 0.2 to 5.0 wt%, based on the starting powder, more preferably from 0.5 to 3.0 wt%.
Another preferred flow aid is finely divided crystalline s~dium aluminosilicate. The crystalline aluminosilicates discussed previously in the context of builders are also suitable for use as flow aids. They are, however, less weight-effective than the amorphous material and are suitably used in an amount of from 3.0 to 12.0 wt%, more preferably from 4.0 to lO.0 wt~.
If desired, both crystalline and amorphous sodium aluminosilicates may be used, together or sequentially, as flow aids.
~322~ ~
- 15 - C.3261 Other flow aids suitable for use in the process of the invention include precipitated silica, for example, Neosyl (Trade Mark), and precipitated calcium silicate, for example, Microcal (Trade Mark), both commercially available fro~ Crosfield Chemicals Ltd, Warrington, Cheshire, England.
The final ~ranulate The final granulate has a bulk density of at least 650 g/litre and preferably at least 700 g/litre. It is also characterised by an especially low particle porosity, preferably not exceeding 0.25 and more preferably not exceeding 0.20, which distinguishes it from even the densest powders prepared by spray-drying alone.
The final granulate may be used as a complete detergent composition in its own right. Alternatively, it may be admixed with other components or mixtures prepared separately, and may form a major or minor part of a final product~ Generally, any add.itional ingredients such as enzymes, bleach and perfume that are not suitable for undergoing the granulation process and the steps that precede it may be a~mixed to the granulate to make a final product.
In one preferred embodiment of the invention, for example, a detergent base powder is prepared by spxay-drying an aqueous slurry of heat-insensitive and compatible ingredients; if desired, other ingredients may then be admixed as dis~ussed above; and the resulting powder is densified and granulated in accordance with the process of the invention. Yet further ingredients may i desired be admixed after ~32~7~l~
- 16 - C.3261 granulation; the densified granulate may typically constitute from 40 to 100 wt% of a final product.
In another embodiment of the invention, the densified granulate prepared in accordance with the present invention is an "adjunct'l comprising a relatively high level of detergent-active material on an inorganic carrier; and this may be admixed in a minor amount with other ingredients to form a final product.
The invention is further illustrated by the following non-limiting Examples, in which parts and percentages are by weight unless otherwise stated.
~ 3 2 ~
- 17 - C.3261 EXAMPLES
In the Examples which follow, the following abbreviations are used.
LAS: sodium linear alkylbenzene sulphonate NI: nonionic surfactant ~ethoxylated alcohol) NSD: total non-soap detergent STP: sodium tripolyphosphate Carbonate: sodium carbonate Sulphate: sodium sulphate Silicat.e: sodium alkaline silicate g: good Alu: Alusil (Trade Mark) N, finely divided amorphous sodium aluminosilicate Zeo: Zeolite 4A (Wessalith (Trade Mark? ex Degussa) 13 2 2 ~
- 18 - C.3261 E~am~les 1 ~ 2 Powders containing sodium tripolyphosphate and sodium sulphate were prepared by spray-drying aqueous slurries to the formulations (weight %) shown in Table lo Table 1 Example 1 2 LAS 12.2 9.7 NI 8.1 2.8 NSD (a) 20.3 12.5 STP 42.7 42.5 Sulphate 10.2 14.8 Salts (b) 52.9 57.3 Soap _ ~ g Silicate 10.2 10.0 Minors 2.4 2.8 Water 14.2 12.5 (b):(a) 2.6 4.6 - -20 kg batches of each powder were densified in a Fukae (~rade Mark) high-speea mixer/granulator, process conditions and resulting powder properties being shown in Table 2. In Example 1, the powder was initially subjected to a 2-3 minute warming up period, at a low stirrer speed ~50 rpmj and without the cutter running, until the temperature had reached about 30-35C. This was followed by pulverisation (optional), then binder addition talso~optional~, then granulation, followed finally by addition of flow aid.
~3227~
- 19 - C.3261 Table 2 1 2(a) 2Ib) Pulverisation:
Time (min) 4 0.5 0-5 Stirrer speed lrpm) 180 180 180 Cutter speed (rpm~ 3000 1000 1000 Binder lwater)~
Amount (wt %) 4 0.5 O.S
Addition time (min) 1 0.5 0.5 Stirrer speed (rpm) 100 100 100 Cutter speed ~rpm) 3000 3000 3000 Granulation:
Time (min) 15 7 6 Stirrer speed (rpm) 140 140 140 Cutter speed (rpm) 2700 3000 3000 Flow aid:
Zeo or Alu Alu Alu Zeo Amount (wt ~) 2 1.5 5 Addition time (min) Stirrer speed (rpm~ 90 90 90 Cutter speed (rpm) 300 300 300 ______________,__ _________~_____ _._.____ Yield`<1700 ~m (wt %) 95 93 97 Average particle size ~m) 689 ~55 480 Bulk density (g/litre) 854 840 780 Dynamic flow rate (ml/s~ 109 92 61 Compressibility ~v/v) 7.6 7 12 Particle porosity~0,20 <0.20 <0.20 Comparison of Examples 2(a) and 2lb) shows the greater weight-effec~iveness of Alusil as flow aid.
132~7~
- 20 - C.32~1 Examples 3 to 5 Powders containing sodium tripolyphosphate as the sole water-soluble crystalline inorganic salt were prepared by spray-drying aqueous slurries to the formulations (weight %~ shown in Table 3.
Table 3 10 Examp].e 3 4 5 LAS 48.625.3 26.4 NI - 2.4 2.6 NSD (a) 48.627.7 29.0 STP 26.742.5 45.9 Salts (b) 26.742.5 45.9 Silicate 15,511.0 10.0 Minors 1.52.9 2.9 Water 7.715.9 12.2 (b):(a) 0.551.5 1.6 ~ 20 kg batches o~ each powder were densified in a ~ ~ Fukae (Trade Mark~ high speed mixer/granulator as described in Examples l and 2, process con~itions and resulting powder properties beîng shown in TabIes 4 and 5.
' ' ' ' .. . .
13227~aL
- 21 - C.3261 able 4 3 5(a)5(b) Pulverisation:
Time (min) 3 0.50.5 Stirrer ~peed (rpm) 300 180 180 Cutter speed (rpm) 3000 3000 3000 Binder (water~:
~nount (wt %) 2 none none Addition time tmin) Stirrer speed (rpm) 100 Cutter speed (rpm) ~3000 Granulation:
Time (min) 5 5 6 Stirrer speed (rpm) 275 140 140 Cutter speed (rpm) 3000 2700 2700 Flow aid:
Zeo. or Alu. Alu Alu Zeo Amount (wt %) 1 1.5 5 Addition time (min) Stirrer speed (rpm) 90 90 90 Cutter speed (rpm) 0 300 300 Yield <1700 ~m ~wt ~) 80 94 93 ~verage particle size t~m)693 528 389 Bulk density (g/litre~ 673 720 820 Dynamic flow rate (ml/s) 134 ~3 96 Compressibility l~/v) 3.5 14 11 Particle porosity<0.20 <0.20 ~0.20 ~5 ~322~
- 22 - C.3261 Table 5 4(a) 4(b) 5 Pulverisation:
Time tmin) 0.5 0.5 Stirrer speed (rpm) 180 180 Cutter speed lrpm) 3000 3000 Binder (water):
Amount (wt %) 1 0.5 Addition time (min) 0.5 0.5 Stirrer speed (rpm) 100 100 Cutter speed (rpm) 3000 3000 Granulation:
Time (min) 4 4 Stirrer speed (rpm) 140 140 Cutter speed (rpm) 2700 2700 Flow aid:
Zeo. or Alu. Alu Alu Amount (wt g) 2.5 2.5 ~ Addition time (min) ;~ ~ 25 Stirrer speed (rpm) 90 90 Cutter speed (rpm) 300 300 Yield C1700 ~m (wt %)95 96 30 Average particle size (~m~5dl 608 Bulk density (g/litre)830 770 Dynamic flow rate (ml/s)86 B9 Comprassibility t%v/v~ 9 11 35 Particle porosity<0.20 <0.20 ~22~
- 23 - C.3261 Examples 6 to 8 Powders containing sodium tripolyphosphate, sodium carbonate and sodium sulphate were prepared to the formulations ~weight ~) shown in Table 6.
Table_6 Example 6 7 8 LAS 28.0 15.0 15.5 NI - 3.0 1.5 NSD (a) 28~0 18.0 17.0 STP 27.0 30.0 26.0 Carbonate 5.0 10.0 18.9 Sulphate 15.0 lS.0 17.2 Salts (b) 47.0 55.0 62.
20 Soap - 6.0 Silicate 8,0 9.0 9OO
Calcite 5.0 Minors 1.0 1.0 1.4 Water 11.0 11.0 9.8 ~b):(a) 107 3~0 3.7 The powders were prepared by spray-drying aqueous slurries. However, the sodium carbonate in the powder of Example 6 was not incorporated via the slurry ~t postdosed in the Fukae mixer.
20 kg batches of each powder were densified in a Fukae (Trade Mark) ~igh~speed mixer/granulator as described in Examplés 1 and 2, proce~s conditions and resulting powder properties being shown in Table 7.
~227~
~ 24 - C.3261 Ta~b~e 7 Pulverisation:
Time (min) Stirrer speed (rpm) 300 300 Cutter speed (~pm) 3000 3000 Binder (water):
Amount (wt %)0.5 Addition time (min) 2 Stirrer speed (rpm) 100 100 Cutter speed (rpm) 3000 3000 Granulation:
Time tmin) 4 4 Stirrer speed (rpm) 225 200 Cutter speed (rpm) 3000 3000 Flow aid:
Zeo. or Alu. Alu Alu Amount (wt %) Addition time (min) Stirrer spsed ~rpm) 90 90 Cutter speed (rpm) 0 0 Yiald ~1700 ~m Iwt ~) g g Average partîcle size l~m) 743 582 :
Bulk density (g/litre~ 906 800 Dynamic flow rate (ml/s) 133 120 Compressibility (%v/v) 3.5 7.0 Par icle poro~ity<0.20 ~0.20 ~22~
- 25 - C.3261 Table 8 8(a) 8(b~ 8(c) 5 Pulverisation: none none none Time (min) - - -Stirrer speed (rpm) - -Cutter speed (rpm) - - -Binder (water):
Amount (wt ~) 1.5 1~5 Addition time ~min)0.5 0.5 0~5 Stirrer speed (rpm)lO0 100 100 Cutter speed (rpm) 3000 3000 3000 Gramllation:
Time (min) 10 7 7 Stirrer speed (rpm) 140 140 140 Cutter speed (rpm) 2700 2700 2700 Flow aid:
~eo or Alu Alu Alu Alu Amount (wt %)1.5 1.5 Addition time (min3 0O5 0.5 Stirrer speed:(rpm) 90 90 90 Cutter speed (rpm) 300 300 300 Yield <1700 ~m (wt %l 94-5 9~ 9 : 30 Bulk density (g/litre~ 920 870 760 Dynamic flow rate (ml/s) g g g Compressibility (%v/v~ g g g Particle porosity~0.20 ~0.20 <0.20 ~32~
- 26 - C.3261 Examples 9 and 10 Powders containin~ sodium tripolyphosphate and sodium carbonate were prepared, by spray-drying aqueous slurries, to the formulations (weight %) shown in Table 9, and densified in the Fukae mixer as in previous Examples, as shown in Table 10.
Table 9 Example 9 10 LAS 38.0 22.7 NI 2.1 NSD (a) 38.0 24.8 STP 21.0 37.1 Carbonate 22.0 17,5 Salts (b) 43.0 54.6 2~
Silicate 12.0 9.3 Minors 1.0 1.0 Water 6.0 10.3 25 (b):(a~ 1.1 2.2 ~227~
- 27 - C.3261 Table 10 5 Pulverisation:
Time (min) 3 3 Stirrer speed (rpm) 300 300 Cutter speed (rpm) 3000 3000 ~inder (water):
Amount (wt ~ 2 Addition time (min) Stirrer speed (rpm) 100 100 Cutter speed (rpm) 3000 3000 Granulation:
Time (min) 5 5 Stirrer speed (rpm) 275 275 Cutter speed (rpm) 3000 3000 Flow aid:
Zeo or Alu Alu Alu : Amount (wt ~) 1 1 ~ Addition time (min) : 25 Stirrer speea (rpm) 90 90 Cutter speed (rpm) 0 0 Yield <1700 ~m (wt %)80 90 30 ~ Average particle size (~m) 810 566 Bulk density (g/litre) 746 801 Dynamic flow rate (ml/s) 137 . 122 Compressibility (~vlv) 3.0 10 Particle porosity ~0.20 <0O20 ~2 2J~
- 28 - C.3261 Example 11 A powder containing sodium tripolyphosphate, sodium sulphate and borax was prepared to the formulation (weight %~ shown in Table 11.
Table 11 LAS 28.0 NSD ~a) 28.0 STP ~7 o Sulphate 19~7 Borax 10.0 Salts (b) 56.7 Polyacrylate polymer 4.5 Minors 0.8 Water 10.0 (b):(a) 2.0-~
The powder was prapared by spray-drying an aqueous : s7urry of all the ingredients except the borax. 9.0 kg of spray-dried base powder and 1.0 kg of borax were mixed and granulatedjdensified in the Fukae mixer, process conditions and resulting powder properties being shown in : : Table 12~
:~ 3 ~
- 29 - C.3261 Table 12 Mixing:
Time (min~ 5 Stirrer speed (rpm~ 200 Cutter speed (rpm~ 0 Binder (water):
Amount (wt %) Addition time (min) Stirrer speed (rpm) 300 Cuttex speed (rpm~ 3000 Granulation:
Time ~min) 9 Stirrer speed (rpm) 300 Cuttex speed (rpm) 3000 Breakdown of oversize:
Time (min) 1.5 Stirrer speed (rpm) 75 Cutter speed (rpm) 3000 .
Flow a1d:
Zeo or Alu Alu Amount jwt ~) 1 Addition time Imin) O . 5 Stirrer speed IrPm) 75 Cutter speed (rpm) 0 Di~charge:
Time (min) 0.5 Stirrer speed (rpm) 75 Cutter speed (rpm) 0 ~ 3 2 ~
- 30 - C.3261 During granulation the temperature rose from an initial 20C to about 40-45C. It was not necessary to cool the mixer.
The properties of the densified granulate were as follows:
Yiela <1700 ~m (wt %)82.l Average particle size (~m) 583 lD ~3u~X den~ity l~litre) ~B7 Dynamic flow rate (ml/s) l40 Compress ibiL ity ~v /v 1 4 . 7 Particle porosity <0O20 The product was a mild detergent powder giving a pH
(l wt~ a~ueous solution1 f 9-~
,
Claims (16)
1. A process for the preparation of a granular detergent composition or component having a bulk density of at least 650 g/litre, which comprises the step of treating a particulate starting material comprising:
(a) from 12 to 70 wt% of non-soap detergent-active material, and (b) at least 15 wt% of water-soluble crystalline inorganic salts, including sodium tripolyphosphate and/or sodium carbonate, the weight ratio of (b) to (a) being at least 0.4:1, and optionally other detergent components to 100 wt%, in a high-speed mixer/granulator having both a stirring action and a cutting action, in the absence of a finely divided particulate agent for improving surface properties, whereby granulation and densification to a bulk density of at least 650 g/litre are effected.
(a) from 12 to 70 wt% of non-soap detergent-active material, and (b) at least 15 wt% of water-soluble crystalline inorganic salts, including sodium tripolyphosphate and/or sodium carbonate, the weight ratio of (b) to (a) being at least 0.4:1, and optionally other detergent components to 100 wt%, in a high-speed mixer/granulator having both a stirring action and a cutting action, in the absence of a finely divided particulate agent for improving surface properties, whereby granulation and densification to a bulk density of at least 650 g/litre are effected.
2. A process as claimed in claim 1, wherein granulation is carried out in a bowl-type high-speed mixer/granulator having a substantially vertical stirrer axis.
- 32 - C.3261 US
- 32 - C.3261 US
3. A process as claimed in claim 1, wherein the particulate starting material consists at least partially of a spray-dried powder.
4. A process as claimed in claim 1, wherein the particulate starting material has a ratio of (b) to (a) within the range of from 0.4:1 to 9:1.
5. A process as claimed in claim 1, wherein the particulate starting material has a ratio of (b) to (a) within the range of from 0.4:1 to 5:1.
6. A process as claimed in claim 1, wherein the particulate starting material has a ratio of (b) to (a) within the range of from 1:1 to 5:1.
7. A process as claimed in claim 1, wherein the particulate starting material comprises from 15 to 70 wt%
of water-soluble crystalline inorganic salts including sodium tripolyphosphate and/or sodium carbonate.
- 33 - C.3261 US
of water-soluble crystalline inorganic salts including sodium tripolyphosphate and/or sodium carbonate.
- 33 - C.3261 US
8. A process as claimed in claim 1, wherein the particulate starting material comprises from 15 to 50 wt%
of sodium tripolyphosphate.
of sodium tripolyphosphate.
9. A process as claimed in claim 1, wherein the non-soap detergent-active material of the particulate starting material consists at least partially of anionic detergent-active material.
10. A process as claimed in claim 1, wherein the particulate starting material is prepared by a process including the step of admixing at least one inorganic or organic salt having a particle size of at least 100 microns with the remainder of the particulate starting material in the high-speed mixer/granulator.
11. A process as claimed in claim 10, wherein the salt is selected from the group consisting of borax, sodium bicarbonate, sodium silicate, sodium tripolyphosphate, sodium carbonate, sodium perborate, sodium percarbonate, sodium citrate, sodium nitrilotriacetate, sodium succinate, sodium sulphate and combinations thereof.
12. A process as claimed in claim 1, which further comprises the step of admixing a finely divided particulate flow aid to the granular material after granulation is complete.
- 34 - C.3261 US
- 34 - C.3261 US
13. A process as claimed in claim 12, wherein the flow aid is amorphous sodium aluminosilicate and is added in an amount of from 0.2 to 5.0 wt%, based on the total composition.
14. A process as claimed in claim 12, wherein the flow aid is finely divided crystalline sodium aluminosilicate and is added in an amount of from 3.0 to 12.0 wt% based on the total composition.
15. A detergent composition or component therefor, prepared by a process as claimed in claim 1 and having a particle porosity of less than 0.25.
16. A detergent composition or component therefor, prepared by a process as claimed in claim 1 and having a particle porosity of less than 0.20.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8817386.9 | 1988-07-21 | ||
| GB888817386A GB8817386D0 (en) | 1988-07-21 | 1988-07-21 | Detergent compositions & process for preparing them |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1322704C true CA1322704C (en) | 1993-10-05 |
Family
ID=10640869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000597591A Expired - Fee Related CA1322704C (en) | 1988-07-21 | 1989-04-24 | Detergent compositions and process for preparing them |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0351937B2 (en) |
| JP (1) | JP2644038B2 (en) |
| KR (2) | KR920004462B1 (en) |
| AU (1) | AU611556B2 (en) |
| BR (1) | BR8902006A (en) |
| CA (1) | CA1322704C (en) |
| DE (1) | DE68912983T3 (en) |
| ES (1) | ES2049320T5 (en) |
| GB (2) | GB8817386D0 (en) |
| HK (1) | HK86594A (en) |
| IN (2) | IN170472B (en) |
| MY (1) | MY105051A (en) |
| PH (1) | PH26823A (en) |
| TR (1) | TR25923A (en) |
| ZA (2) | ZA893186B (en) |
Families Citing this family (42)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8926718D0 (en) * | 1989-11-27 | 1990-01-17 | Unilever Plc | Process for the preparation of detergent compositions |
| GB9008013D0 (en) * | 1990-04-09 | 1990-06-06 | Unilever Plc | High bulk density granular detergent compositions and process for preparing them |
| GB9012613D0 (en) * | 1990-06-06 | 1990-07-25 | Unilever Plc | Soap powder compositions |
| CA2027518A1 (en) * | 1990-10-03 | 1992-04-04 | Richard L. Tadsen | Process for preparing high density detergent compositions containing particulate ph sensitive surfactant |
| DE4216774A1 (en) * | 1992-05-21 | 1993-11-25 | Henkel Kgaa | Process for the continuous production of a granular washing and / or cleaning agent |
| US5691294A (en) * | 1993-03-30 | 1997-11-25 | The Procter & Gamble Company | Flow aids for detergent powders comprising sodium aluminosilicate and hydrophobic silica |
| USH1604H (en) * | 1993-06-25 | 1996-11-05 | Welch; Robert G. | Process for continuous production of high density detergent agglomerates in a single mixer/densifier |
| AU673926B2 (en) * | 1993-07-13 | 1996-11-28 | Colgate-Palmolive Company, The | Process for preparing detergent composition having high bulk density |
| US5968891A (en) * | 1993-07-13 | 1999-10-19 | Colgate-Palmolive Co. | Process for preparing detergent composition having high bulk density |
| US5733862A (en) * | 1993-08-27 | 1998-03-31 | The Procter & Gamble Company | Process for making a high density detergent composition from a sufactant paste containing a non-aqueous binder |
| US5486303A (en) * | 1993-08-27 | 1996-01-23 | The Procter & Gamble Company | Process for making high density detergent agglomerates using an anhydrous powder additive |
| EP0643129A1 (en) * | 1993-09-07 | 1995-03-15 | The Procter & Gamble Company | Process for preparing detergent compositions |
| US5565137A (en) * | 1994-05-20 | 1996-10-15 | The Proctor & Gamble Co. | Process for making a high density detergent composition from starting detergent ingredients |
| US5496487A (en) * | 1994-08-26 | 1996-03-05 | The Procter & Gamble Company | Agglomeration process for making a detergent composition utilizing existing spray drying towers for conditioning detergent agglomerates |
| CA2157257C (en) * | 1994-09-12 | 1999-08-10 | Kazuhiko Endo | Semiconductor device with amorphous carbon layer and method of fabricating the same |
| US5516448A (en) * | 1994-09-20 | 1996-05-14 | The Procter & Gamble Company | Process for making a high density detergent composition which includes selected recycle streams for improved agglomerate |
| US5691297A (en) * | 1994-09-20 | 1997-11-25 | The Procter & Gamble Company | Process for making a high density detergent composition by controlling agglomeration within a dispersion index |
| US5489392A (en) * | 1994-09-20 | 1996-02-06 | The Procter & Gamble Company | Process for making a high density detergent composition in a single mixer/densifier with selected recycle streams for improved agglomerate properties |
| WO1996025482A1 (en) * | 1995-02-13 | 1996-08-22 | The Procter & Gamble Company | Process for producing detergent agglomerates in which particle size is controlled |
| US5574005A (en) * | 1995-03-07 | 1996-11-12 | The Procter & Gamble Company | Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties |
| US5569645A (en) * | 1995-04-24 | 1996-10-29 | The Procter & Gamble Company | Low dosage detergent composition containing optimum proportions of agglomerates and spray dried granules for improved flow properties |
| US6207635B1 (en) | 1995-05-31 | 2001-03-27 | The Procter & Gamble Company | Process for manufacture of high density detergent granules |
| US5707959A (en) * | 1995-05-31 | 1998-01-13 | The Procter & Gamble Company | Processes for making a granular detergent composition containing a crystalline builder |
| WO1997032003A1 (en) * | 1996-02-29 | 1997-09-04 | The Procter & Gamble Company | Process for manufacture of high density detergent granules |
| US5565422A (en) * | 1995-06-23 | 1996-10-15 | The Procter & Gamble Company | Process for preparing a free-flowing particulate detergent composition having improved solubility |
| US5554587A (en) * | 1995-08-15 | 1996-09-10 | The Procter & Gamble Company | Process for making high density detergent composition using conditioned air |
| US5665691A (en) * | 1995-10-04 | 1997-09-09 | The Procter & Gamble Company | Process for making a low density detergent composition by agglomeration with a hydrated salt |
| US5576285A (en) * | 1995-10-04 | 1996-11-19 | The Procter & Gamble Company | Process for making a low density detergent composition by agglomeration with an inorganic double salt |
| KR100394762B1 (en) * | 1996-02-13 | 2003-11-20 | 주식회사 엘지생활건강 | Concentrated powdery detergent composition with excellent long period storage stability |
| US5668099A (en) * | 1996-02-14 | 1997-09-16 | The Procter & Gamble Company | Process for making a low density detergent composition by agglomeration with an inorganic double salt |
| GB9604022D0 (en) * | 1996-02-26 | 1996-04-24 | Unilever Plc | Anionic detergent particles |
| CN1116400C (en) * | 1996-02-29 | 2003-07-30 | 普罗格特-甘布尔公司 | Process for mfg. high density detergent granules |
| BR9711966A (en) * | 1996-08-26 | 1999-08-24 | Procter & Gamble | Agglomeration process for the production of detergent compositions involving pre-mixing of modified polyamine polymers |
| EP0923637B1 (en) * | 1996-08-26 | 2001-10-17 | The Procter & Gamble Company | Spray drying process for producing detergent compositions involving premixing modified polyamine polymers |
| US5914307A (en) * | 1996-10-15 | 1999-06-22 | The Procter & Gamble Company | Process for making a high density detergent composition via post drying mixing/densification |
| GB9711359D0 (en) * | 1997-05-30 | 1997-07-30 | Unilever Plc | Detergent powder composition |
| GB9711350D0 (en) * | 1997-05-30 | 1997-07-30 | Unilever Plc | Granular detergent compositions and their production |
| HUP0002906A3 (en) | 1997-05-30 | 2003-02-28 | Unilever Nv | Free-flowing particulate detergent composition |
| GB9711356D0 (en) | 1997-05-30 | 1997-07-30 | Unilever Plc | Particulate detergent composition |
| WO1999011749A1 (en) * | 1997-08-28 | 1999-03-11 | The Procter & Gamble Company | Agglomeration process for producing a particulate modifier polyamine detergent admix |
| US6610645B2 (en) | 1998-03-06 | 2003-08-26 | Eugene Joseph Pancheri | Selected crystalline calcium carbonate builder for use in detergent compositions |
| GB0418918D0 (en) * | 2004-08-25 | 2004-09-29 | Unilever Plc | A particulate detergent composition, and packaging therefor |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1617109B2 (en) * | 1967-12-05 | 1973-04-19 | Großeinkaufs Gesellschaft deutscher Konsumgenossenschaften mbH, 2000 Harn bürg | PROCESS FOR THE PRODUCTION OF DUST-FREE AND RUBBLE-CAPABLE WASHING AND CLEANING AGENTS |
| GB1517713A (en) * | 1974-10-31 | 1978-07-12 | Unilever Ltd | Preparation of detergent formulations |
| JPH0631431B2 (en) * | 1985-06-27 | 1994-04-27 | ライオン株式会社 | Method for producing cleaning composition |
| JPH0631430B2 (en) * | 1985-05-29 | 1994-04-27 | ライオン株式会社 | Method for producing high bulk density granular detergent composition |
| DE3617756C2 (en) * | 1985-05-29 | 1995-01-19 | Lion Corp | A process for producing a high bulk density granular detergent composition |
| US4925585A (en) * | 1988-06-29 | 1990-05-15 | The Procter & Gamble Company | Detergent granules from cold dough using fine dispersion granulation |
-
1988
- 1988-07-21 GB GB888817386A patent/GB8817386D0/en active Pending
-
1989
- 1989-04-24 CA CA000597591A patent/CA1322704C/en not_active Expired - Fee Related
- 1989-04-27 EP EP89304210A patent/EP0351937B2/en not_active Expired - Lifetime
- 1989-04-27 DE DE68912983T patent/DE68912983T3/en not_active Expired - Lifetime
- 1989-04-27 ES ES89304210T patent/ES2049320T5/en not_active Expired - Lifetime
- 1989-04-27 AU AU33751/89A patent/AU611556B2/en not_active Ceased
- 1989-04-28 IN IN113/BOM/89A patent/IN170472B/en unknown
- 1989-04-28 MY MYPI89000581A patent/MY105051A/en unknown
- 1989-04-28 JP JP1111946A patent/JP2644038B2/en not_active Expired - Fee Related
- 1989-04-28 ZA ZA893186A patent/ZA893186B/en unknown
- 1989-04-28 KR KR1019890005623A patent/KR920004462B1/en not_active IP Right Cessation
- 1989-04-28 BR BR898902006A patent/BR8902006A/en not_active IP Right Cessation
- 1989-04-28 TR TR89/0322A patent/TR25923A/en unknown
- 1989-04-28 IN IN114/BOM/89A patent/IN169824B/en unknown
- 1989-04-28 PH PH38585A patent/PH26823A/en unknown
- 1989-05-03 GB GB898910087A patent/GB8910087D0/en active Pending
- 1989-07-21 KR KR1019890010340A patent/KR920000114B1/en not_active IP Right Cessation
- 1989-07-21 ZA ZA895578A patent/ZA895578B/en unknown
-
1994
- 1994-08-25 HK HK86594A patent/HK86594A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TR25923A (en) | 1993-09-17 |
| ES2049320T3 (en) | 1994-04-16 |
| PH26823A (en) | 1992-11-05 |
| ZA895578B (en) | 1991-03-27 |
| MY105051A (en) | 1994-07-30 |
| ES2049320T5 (en) | 2002-05-16 |
| DE68912983T2 (en) | 1994-06-01 |
| DE68912983D1 (en) | 1994-03-24 |
| JPH0241399A (en) | 1990-02-09 |
| BR8902006A (en) | 1990-04-10 |
| GB8910087D0 (en) | 1989-06-21 |
| AU611556B2 (en) | 1991-06-13 |
| EP0351937B2 (en) | 2001-12-12 |
| KR920000114B1 (en) | 1992-01-09 |
| EP0351937B1 (en) | 1994-02-09 |
| ZA893186B (en) | 1990-12-28 |
| HK86594A (en) | 1994-09-02 |
| DE68912983T3 (en) | 2002-04-04 |
| KR900001829A (en) | 1990-02-27 |
| KR900001836A (en) | 1990-02-27 |
| JP2644038B2 (en) | 1997-08-25 |
| KR920004462B1 (en) | 1992-06-05 |
| IN169824B (en) | 1991-12-28 |
| EP0351937A1 (en) | 1990-01-24 |
| GB8817386D0 (en) | 1988-08-24 |
| IN170472B (en) | 1992-03-28 |
| AU3375189A (en) | 1990-01-25 |
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