Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/82—Compounds containing silicon
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
  • C11D17/065—High-density particulate detergent compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

• the present invention relates to granular detergent compositions of high bulk density having good washing performance and good powder properties, and a process for preparing them.
• EP 219 328A discloses a granular low-phosphate detergent composition prepared by spray-drying a slurry to give a base powder containing a low to moderate level of sodium tripolyphosphate builder and low levels of inorganic salts, and then postdosing 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.
• EP 270 240A (Unilever), published on 8 June 1988, discloses a spray-dried zero-phosphate base powder having a particle porosity of less than 0.40 and containing anionic surfactant, optional nonionic surfactant, aluminosilicate builder, polymeric polycarboxylate and a low or zero level of electrolyte, preferably sodium carbonate. If desired, sodium sulphate or other solids of small particle size and high bulk density may be postdosed to the spray-dried powder to give compositions of very high bulk density.
• EP 229 671A discloses postdosing a crystalline alkaline inorganic salt, for example, sodium carbonate, to a spray-dried base powder to produce a high bulk density product.
• GB 1 517 713 (Unilever), which discloses a process in which a detergent powder produced by spray-drying or pan granulation is spheronised and granulated in a "marumerizer” (Trade Mark) with some increase in bulk density.
• JP 61 069897A discloses a process in which a spray-dried detergent powder containing surfactant and builder is subjected successively to pulverising and granulating treatments in a high-speed mixer/granulator, 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 required in order to prevent the composition from forming into large balls or cakes:
• the examples of spray-dried starting powders described in the Kao specification contain very high levels of surfactant (45 wt%) and relatively low levels of builder salts, and are likely to have a high tendency towards caking and balling.
• EP 220 024A (Procter & Gamble) is also concerned with the densification of a spray-dried powder containing a high level (30-85 wt%) of anionic surfactant.
• the powder is compacted and granulated, inorganic builder (sodium tripolyphosphate, or sodium aluminosilicate and sodium carbonate) being added before compaction.
• inorganic builder sodium tripolyphosphate, or sodium aluminosilicate and sodium carbonate
• detergent compositions of high bulk density can be prepared by granulating a spray-dried or dry-mixed powder in a high-speed mixer/granulator, if necessary after pulverisation, without the need for an "agent for improving surface properties" or similar pulverulent material, if the initial powder is correctly formulated, especially with regard to the amount of surfactant and the ratio of surfactant to builder present.
• the present invention provides a granular detergent composition or component therefor having a bulk density of at least 650 g/litre, which comprises:
• the present invention provides 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:
• the first aspect of the invention is a dense granular detergent powder combining high bulk density, good powder properties and excellent washing and cleaning performance, that can be prepared easily and conveniently by the process that is also the subject of the present invention.
• the detergent composition of the invention owes its combination of excellent properties and ready processability to a moderate content of surfactant, at least part of which is anionic, and a relatively high level of sodium aluminosilicate builder.
• the present inventors have found that when the absolute amounts of aluminosilicate builder and surfactant in a powder, and the ratio of one to the other, are suitably chosen, that powder may be granulated in a high-speed mixer/granulator without the need for the use of an "agent for improving surface properties" during the granulation step as prescribed by JP 61 069897A (Kao).
• the resulting dense granulate has good flow properties and is at least equal in washing and cleaning performance and cold water dispersability to the compositions described in the Kao specification which contain substantially higher levels of surfactant.
• the aluminosilicate builder present in the compoistions of the invention may be crystalline or amorphous or a mixture thereof, and has the general formula 0.8-1.5 Na20.Al2O3.0.8-6 SiO2.
• aluminosilicates contain 1.5-3.5 SiO2 units (in the formula above) and have a particle size of not more than about 100 microns, preferably not more than about 20 microns. Both amorphous and crystalline aluminosilicates can be made readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
• Crystalline aluminosilicates are preferred for use in the present invention. Suitable materials are described, for example, in GB 1 473 201 (Henkel) and GB 1 429 143 (Procter & Gamble).
• the preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
• Especially preferred for use in the present invention is Type 4A zeolite.
• the ratio of aluminosilicate builder (anhydrous basis) to total non-soap surfactant in the compositions of the invention is preferably within the range of from 1.2:1 to 1.8:1.
• the non-soap surfactant present consists at least partially of anionic surfactant.
• 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.
• the starting powder may contain nonionic surfactant, preferably in a minor amount.
• 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.
• the surfactant component of the compositions of the invention may be constituted by 10 to 35 wt% of anionic surfactant and 0 to 10 wt% of nonionic surfactant.
• non-soap surfactant for example, cationic, zwitterionic, amphoteric or semipolar surfactants, may also be present if desired.
• suitable detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
• soap may also be present, to provide foam control and additional detergency and builder power; soap is not included in the 17 to 35% figure for the total surfactant content of the compositions of the invention.
• compositions of the invention preferably do not contain more than 5 wt% of phosphate builders, and are more preferably substantially free of phosphate builders.
• the particulate starting composition may be prepared by any suitable tower or non-tower method, for example, spray-drying or dry-mixing. If desired, the particulate starting material may be prepared at least partially by mixing in the high-speed mixer/granulator itself. The particulate starting material may consist at least partially of a spray-dried powder.
• 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 additional ingredients such as enzymes, bleach and perfume that are not suitable for undergoing the granulation process may be admixed to the granulate to make a final product.
• a detergent base powder is prepared by spray-drying an aqueous slurry of heat-insensitive and compatible ingredients; if desired, other ingredients may then be admixed; and the resulting powder is densified and granulated to give a product in accordance with the present invention. Yet further ingredients may if desired be admixed after granulation; the densified granulate of the invention may typically constitute from 40 to 100 wt% of a final product.
• a detergent base powder is prepared by dry mixing one or more raw materials and/or one or more premixes of raw materials, in the high-speed mixer/granulator itself or in other apparatus, and is then densified and granulated to give a product in accordance with the present invention. Again, further ingredients may if desired be added after granulation.
• the granulate prepared in accordance with the present invention is an "adjunct" 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.
• a particulate starting material (detergent base powder) prepared by any suitable method is granulated in a high-speed mixer/granulator to increase its bulk density and simultaneously to improve its powder properties.
• the process of the invention provides a route for the production of very dense granular detergent compositions, having excellent cleaning performance, containing low to moderate levels of anionic surfactant and high levels of aluminosilicate builder.
• a preferred starting powder comprises:
• granulation is effected by means of a high-speed mixer/granulator having both a stirring action and a cutting action.
• 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 operation. 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.
• mixers of the Fukae (Trade Mark) FS-G series manufactured by Fukae Powtech Kogyo Co., Japan are 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 cutter positioned on a side wall.
• the stirrer and cutter may be operated independently of one another, and at separately variable speeds.
• Another mixer found to be suitable for use in the process of the invention is the Lödige (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.
• the use of a high-speed mixer/granulator is essential in the process of the invention to effect granulation and densification.
• the mixer may also be used for a pretreatment step before granulation is carried out.
• the particulate starting material prefferably be prepared at least in part by mixing in the high-speed mixer/granulator.
• a dry-mixed starting powder may be prepared from its raw materials in the high-speed mixer/granulator; or one or more further ingredients may be admixed with an otherwise premixed powder prepared elsewhere (for example, by spray-drying).
• a suitable stirring/cutting regime and residence time may be chosen in accordance with the materials to be mixed.
• pulverisation 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 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 residence time (for example, 2-4 minutes for a 35 kg batch) is generally sufficient.
• the essential feature of the process of the invention is 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) is 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.
• binder preferably water
• binder may be added before or during granulation, but some starting powders will inherently contain sufficient moisture.
• a liquid binder it may be sprayed in while the mixer is running. In one preferred mode of operation, the mixer is first operated at a relatively slow speed while binder is added, before increasing the speed of the mixer to effect granulation.
• pulverisation if required
• 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.
• granulation is carried out at a controlled temperature somewhat above ambient, preferably above 30°C.
• the optimum temperature is apparently formulation-dependent, but appears generally to lie within the range of from 30 to 45°C, preferably about 35°C.
• a finely divided particulate flow aid may be admixed with the granular material after granulation is complete.
• 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 after granulation is complete, but, as explained above, it is essential to the invention that no finely divided particulate "agent for improving surface properties" be present during granulation. The addition of a flow aid after granulation is complete can have an additional beneficial effect on the properties of the granulate, regardless of the formulation, whereas the presence of this type of material during the granulation step in the process of the invention makes processing more difficult.
• the preferred granulation temperature of from 30 to 45°C, preferably about 35°C, may also be maintained during the subsequent admixture of a flow aid.
• 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.
• the flow aid is finely divided amorphous sodium aluminosilicate, as described and claimed in our copending application of even date (Case C.3236).
• 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 sodium 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 10.0 wt%.
• both crystalline and amorphous sodium aluminosilicates may be used, together or sequentially, as flow aids.
• 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 from Crosfield Chemicals Ltd, Warrington, Cheshire, England.
• a detergent composition was prepared to the following composition by spray-drying an aqueous slurry to a free moisture content of substantially zero: parts Linear alkylbenzene sulphonate 24.0 Nonionic surfactant 2.0 Soap 1.0 Zeolite (anhydr.) 38.0 Water bound with zeolite 10.84 Sodium silicate 4.0 Acrylate/maleate copolymer 2.0 Minor ingredients 2.0 Sodium carbonate 10.0 94.64
• Example 2 20 kg of the spray-dried powder used in Example 1 were introduced into a Fukae (Trade Mark) FS-30 high-speed mixer/granulator, and pulverised for 4 minutes. Water (0.8 kg) was then added and the mixture granulated over a period of 4 minutes, while the temperature was maintained at about 35°C. A sample (Example 2) was removed from the mixer and its powder properties determined: these are shown in Table 1 below.
• Alusil (Trade Mark) finely divided amorphous sodium aluminosilicate (0.2 kg) was then admixed.
• the physical properties of the resulting powder (Example 3) are shown in Table 1 below, from which the beneficial effect on flow and bulk density of adding a flow aid after granulation is complete is apparent.
• the presence of the Alusil did result in an increase in the content of fine particles ⁇ 180 microns, but not to an unacceptable level.
• Example 1 20 kg of the spray-dried powder used in Example 1 were introduced into the Fukae high-speed mixer/granulator, and pulverised for 4 minutes.
• Alusil Trade Mark
• Finely divided amorphous sodium aluminosilicate 0.2 kg
• Water 0.8 kg
• the mixture granulated over a period of 4 minutes, while the temperature was maintained at about 35°C.
• Physical properties of the resulting powder are shown in Table 1 below, from which the detrimental effect of adding Alusil before granulation are apparent. It will be noted that the increase in fines content is significantly greater when the Alusil is added before granulation.
• Example 2 A Bulk density (g/l) 688 740 670 Dynamic flow rate (ml/s) 109 120 60 Particle size (microns) 550 480 380 Fines content (wt% of particles ⁇ 180 microns) 0 10 22 Particle porosity 0.1 0.1 not measured
• This Example describes an attempt to carry out the process of the invention using a different spray-dried formulation containing a high level of anionic surfactant and a relatively low level of sodium aluminosilicate.
• the formulation was as follows: parts Spary-dried base Linear alkylbenzene sulphonate 26.0 Primary alcohol sulphate 8.0 Nonionic surfactant 1.0 Soap 3.0 Zeolite (anhydrous) 14.8 Water bound with zeolite 4.2 Sodium silicate 6.0 Sodium carbonate (light soda ash) 5.0 Sodium sulphate 4.0 Acrylate/maleate copolymer 1.0 Free moisture 4.0 Postdosed Zeolite (hydrated)* 5.0 Sodium carbonate (granular) 15.0 Nonionic surfactant 3.0 100.00 *equivalent to 3.9 parts of anhydrous zeolite
• the ratio of zeolite (anhydrous) to non-soap surfactant (0.53) was less than 0.9:1.
• the spray-dried base powder (7.7 kg) was placed in a Diosna (Trade Mark) bowl-type high-speed mixer/granulator, the 5.0 parts (0.3 kg) of nonionic surfactant were sprayed on, and the 15 parts (1.5 kg) of granular soda ash and the 5 parts (0.5 kg) of zeolite were added. Pulverisation at a stirrer speed of 196 rpm and a cutter speed of 3000 rpm was attempted for 1 minute, but the mixture overgranulated to form large lumps, and overheated.
• Diosna Trade Mark
• Example 4 35 kg of the spray-dried powder used in Example 1 were introduced into a Lödige (Trade Mark) FM series high-speed mixer/granulator, and pulverised for 4 minutes. Water (1.1 kg, 3.5%) was then sprayed in while the mixer continued to run at the same speed, then the mixer was allowed to run for a further 3 minutes while the temperature was maintained at about 35°C. During this period granulation occurred. A sample (Example 4) was removed from the mixer and its powder properties determined: these are shown in Table 2 below.
• Example 2 28.8 kg of the spray-dried powder used in Example 1 were introduced into a Lödige (Trade Mark) FM series high-speed mixer/granulator, and pulverised for 4 minutes. Alusil (Trade Mark) finely divided amorphous sodium aluminosilicate (1.2 kg) was then introduced into the mixer. Water (1.1 kg, 3.5%) was sprayed in while the mixer continued to run, then the mixer was allowed to run for a further 3 minutes while the temperature was maintained at about 35°C. During this period granulation occurred. Physical properties of the resulting powder are shown in Table 2 below.
• This Example describes an attempt to carry out the process of the invention in the Lödige mixer using a spray-dried formulation, similar to that used in Comparative Example B, containing a high level of anionic surfactant and a relatively low level of sodium aluminosilicate.
• the formulation was as follows: parts Linear alkylbenzene sulphonate 26.0 Primary alcohol sulphate 8.0 Nonionic surfactant 1.0 Soap 3.0 Zeolite (anhydr.) 10.9 Water bound with zeolite 3.1 Sodium silicate 6.0 Sodium carbonate 5.0 Sodium sulphate 4.0 Acrylate/maleate copolymer 1.0 Free moisture 2.9 68.9
• the ratio of zeolite to non-soap surfactant (0.31) was less than 0.9:1.
• Example 1 Three powders were prepared by spray-drying the nominal composition shown in Example 1 to three different moisture contents, as shown in Table 3 below. Since the 38.0 parts of zeolite (anhydrous basis) in the formulation require 10.84 parts of water of hydration, the free moisture content of each powder is found by subtracting that figure from the total moisture content: it will be noted that the powder of Example 6 was overdried, while that of Example 8 contained 3.16 parts of free moisture.
• This Example describes a process in which an additional ingredient (sodium carbonate) was added to a spray-dried base powder in the mixer prior to pulverisation and granulation.
• the formulation was as follows: parts Spray-dried base Linear alkylbenzene sulphonate 24.0 Nonionic surfactant 2.0 Soap 1.0 Zeolite (anhydr.) 38.0 Water bound with zeolite 10.84 Sodium silicate 4.0 Acrylate/maleate copolymer 2.0 Minor ingredients 2.0 84.04 Added in mixer Sodium carbonate 10.0 94.04
• the properties of the resulting granulate were as follows: Bulk density (g/l) 780 Dynamic flow rate (ml/s) 133 Compressibility ( %v/v) 7 Particle size (microns) 839 Particle porosity 0.10
• the ratio of aluminosilicate to non-soap surfactant in the mixture subjected to granulation was 1.46.
• This Example describes a process in which the anionic surfactant was introduced in part via the spray-dried base powder and in part added to the base powder in the mixer prior to pulverisation and granulation.
• the formulation was as follows: parts Spray-dried base Linear alkylbenzene sulphonate 12.0 Nonionic surfactant 2.0 Soap 1.0 Zeolite (anhydr.) 38.0 Water bound with zeolite 10.84 Sodium carbonate (light soda ash) 10.0 Sodium silicate 4.0 Acrylate/maleate copolymer 2.0 Minor ingredients 2.0 81.84 Added in mixer Linear alkylbenzene sulphonate (powder) 12.0 93.84
• the properties of the resulting granulate were as follows: Bulk density (g/l) 714 Dynamic flow rate (ml/s) 55 Compressibility ( %v/v) 17 Particle size (microns) 712 Particle porosity ⁇ 0.20
• the ratio of aluminosilicate to non-soap surfactant in the mixture subjected to granulation was 1.46.
• the ratio of aluminosilicate to non-soap surfactant in this mixture was 1.46.
• the powder properties of the granulate before and after the addition of Alusil were as follows: 11 12 Bulk density (g/l) 750 810 Dynamic flow rate (ml/s) 80 96 Compressibility ( %v/v) 17.0 15.3 Particle size (microns) - 607 Particle porosity ⁇ 0.20 ⁇ 0.20
• Premix The ingredients listed under "Premix” were mixed for 2 minutes in the Fukae mixer at a stirrer speed of 80 rpm and a cutter speed of 2000 rpm. The nonionic surfactant was then added over a period of 1 minute, followed by water over a period of 2 minutes, while the mixer was operated at the same stirrer and cutter speeds. Granulation for 6 minutes at the same stirrer and cutter speeds followed, and finally the zeolite was added over a period of 2 minutes, still at the same stirrer and cutter speeds.
• the properties of the resulting granulate were as follows: Bulk density (g/l) 780 Dynamic flow rate (ml/s) 83 Compressibility (%v/v) 11.8 Particle size (microns) 477 Particle porosity 0.1
• the ratio of zeolite (anhydrous) to non-soap detergent-active material in the material subjected to granulation was 1.0.

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• 1988
  • 1988-04-29 GB GB888810193A patent/GB8810193D0/en active Pending
• 1989
  • 1989-04-24 CA CA000597593A patent/CA1336668C/en not_active Expired - Fee Related
  • 1989-04-27 DE DE68927745T patent/DE68927745T2/de not_active Revoked
  • 1989-04-27 ES ES89304242T patent/ES2097741T3/es not_active Expired - Lifetime
  • 1989-04-27 EP EP89304242A patent/EP0340013B1/de not_active Revoked
  • 1989-04-27 AU AU33750/89A patent/AU621611B2/en not_active Ceased
  • 1989-04-28 KR KR1019890005621A patent/KR950004824B1/ko not_active IP Right Cessation
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  • 1989-04-28 BR BR898902004A patent/BR8902004A/pt not_active IP Right Cessation
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  • 1989-04-28 JP JP1111945A patent/JPH0768553B2/ja not_active Expired - Fee Related
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