EP0430603A2 - Detergent composition - Google Patents
Detergent composition Download PDFInfo
- Publication number
- EP0430603A2 EP0430603A2 EP19900312779 EP90312779A EP0430603A2 EP 0430603 A2 EP0430603 A2 EP 0430603A2 EP 19900312779 EP19900312779 EP 19900312779 EP 90312779 A EP90312779 A EP 90312779A EP 0430603 A2 EP0430603 A2 EP 0430603A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- filler
- composition
- detergent active
- anionic detergent
- particulate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 80
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 239000000945 filler Substances 0.000 claims abstract description 63
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 4
- 239000008247 solid mixture Substances 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 2
- 239000011872 intimate mixture Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000011236 particulate material Substances 0.000 claims description 2
- 239000011369 resultant mixture Substances 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims 2
- 150000005323 carbonate salts Chemical class 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 26
- 235000019198 oils Nutrition 0.000 description 26
- 239000000843 powder Substances 0.000 description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 18
- 239000000463 material Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 235000017550 sodium carbonate Nutrition 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- -1 nonionic Chemical group 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 150000004996 alkyl benzenes Chemical class 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- OBMBUODDCOAJQP-UHFFFAOYSA-N 2-chloro-4-phenylquinoline Chemical compound C=12C=CC=CC2=NC(Cl)=CC=1C1=CC=CC=C1 OBMBUODDCOAJQP-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000001924 fatty-acyl group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000012243 magnesium silicates Nutrition 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229940071207 sesquicarbonate Drugs 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing 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
- C11D17/0034—Fixed on a solid conventional detergent ingredient
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
Definitions
- This invention relates to the particulate detergent compositions containing relatively high levels of detergent active and furthermore where the detergent comprises a high level of anionic detergent, at least 30% by weight of the composition.
- Such compositions may in particular be suitable for cleaning fabrics, although they may be intended for other uses.
- This invention also relates to the production of such compositions.
- Detergent compositions containing lower levels of anionic detergent active are commonplace, and are often prepared by spray drying as is well known. At first sight it might be supposed that there would be no difficulty in making compositions with higher concentrations of anionic detergent because many anionic detergent active materials can be prepared in more or less solid form consisting of substantially pure anionic detergent, or at least containing a very high percentage of anionic detergent.
- US 4213874 discloses the production of aluminosilicates which have an oil absorbtion of at least 75ml/100gram. It is disclosed that they may be used to absorb nonionic detergents in detergent products.
- US 4707290, GB 1485371 and GB 1591518 disclose the use of absorbent solids to act as carriers for nonionic detergents.
- Nonionic detergents are a different problem to anionic detergents in that the nonionic materials are generally liquids (which need to be made into solid form) whereby anionic detergents are generally solids in their own right.
- this invention provides a particulate detergent composition, the particles of which contain at least 30% by weight of anionic detergent active and also contain a particulate filler with an oil absorption value of at least 100ml/100g, this filler being distributed within the particles of the composition in intimate mixture with the detergent active, the amount of the particulate filler being such that the weight ratio of the filler to anionic detergent active lies in the range from 1:10 to 1:1, more preferably 1:8 to 2:3.
- This ratio range signifies that the amount of filler is not greater than the amount of anionic detergent active.
- the filler has a mean particle size not greater than 20 micrometres.
- the invention provides a process of preparing a detergent composition which process comprises incorporating a particulate filler into a fluid or semi-solid composition containing anionic detergent active so that the filler is intimately mixed with the anionic detergent, which particulate filler has an oil absorbtion value in excess of 100ml/100gram, and forming the resultant mixture into a particulate composition with the filler distributed within the particles of the composition, the amounts of anionic detergent active and filler being such that the composition contains at least 30 wt% of anionic detergent and has a weight ratio of filler to detergent active ranging from 1:10 to 1:1.
- the present invention contains particulate filler with an oil absorption value which is equal to, or exceeds, a minimum value.
- the oil absorption value of the filler is to be determined by the following test which is in accordance with British Standard 3483 : Part B7 : 1982.
- the test for oil absorption is performed by placing a weighed sample of the test powder on a plate and then adding linseed oil from a burette. The oil is added a few drops at a time. After each addition the powder is mixed vigorously with the oil using a palette knife. Addition of oil is continued until a paste of smooth consistency is formed. The paste should just spread without cracking or crumbling.
- the oil absorption value is expressed as the volume (ml) of oil absorbed per 100 gram of powder.
- a detergent composition according to the invention may be marketed directly as a washing product. Alternatively it can be mixed with other particulate material to form a finished product.
- a particulate detergent composition according to the invention may be mixed with a second particulate composition which contains other constituents of a final detergent composition, such as detergency builders.
- a second composition which contains other constituents of a final detergent composition, such as detergency builders.
- Admixing the composition in accordance with the invention would then serve to increase the overall proportion of detergent active.
- admixing a composition in accordance with this invention did not increase the overall proportion of detergent active - for instance by achieving beneficial physical properties or by enhancing overall production from available process plant.
- compositions in accordance with this invention may be accomplished by conventional routes for the manufacture of particulate detergent compositions with a high level of detergent active, provided there is a stage when the detergent active is in a fluid or semi-solid form.
- the particulate filler is mixed with the detergent active at this stage and leads to an improvement in the properties of the particulate composition which is produced. In some instances a particulate state would not be achieved without the filler.
- the filler can be mixed with the acid form of the detergent active before neutralization.
- the filler may even be used as a base to neutralise the acid form of the detergent active, i.e. part of the material used as filler may serve to effect neutralisation. Another possibility is to neutralise the active and mix the filler with the resulting neutralised paste before this becomes solid.
- a fluid or semi-solid mixture containing the detergent active and the filler may be dried to solidify it, for example by means of a drum dryer.
- a viscous dough may be produced with a formulation such that the dough can be extruded but will then solidify into a hard solid which can be comminuted to desired particle size.
- compositions of this invention is by neutralizing an acid form of an anionic detergent active with an alkali metal oxide, hydroxide or carbonate (which may be a true carbonate, bicarbonate or sesquicarbonate) to produce a viscous dough, mixing the particulate filler with this dough, allowing the dough to harden to a solid and comminuting the solid.
- Neutralization may be effected in the presence of little or no added water.
- the amount of water added is not more than 10%, more preferably not more than 5%, by weight based on the total weight of acid detergent and carbonate.
- Such neutralization and admixing of filler can be carried out in various types of high shear mixer.
- One possibility is a Z-blade mixer
- another possibility is a cavity transfer mixer whose use as a chemical reactor is disclosed in our European patent application 194812
- yet another possibility is a twin screw extruder.
- Other intensive mixers which may be used consist of vessels which contain rotating blades for mixing and high speed knives for dispersing, manufactured for example by Lödige (Trade Mark) ex Morton Machine Co Ltd, Scotland.
- detergent active may also be mixed in.
- some preneutralised detergent active or nonionic detergent active may be mixed in.
- a surface coating of a flow-improving aid which may itself be a particulate solid having the oil absorption property required for the filler used in this invention.
- a surface coating is conventional. The examples below demonstrate that it does not, by itself, achieve the results achieved by the invention.
- compositions according to this invention must contain at least 30% by weight of active detergent. Preferably they contain more, e.g. at least 40% or even at least 55%.
- the amount of detergent active present may range as high as 90% by weight of the composition.
- anionic detergent actives may be utilized, selected from the conventional categories of anionic, nonionic, cationic and amphoteric.
- anionic detergent active predominates; even if detergent active from another category is present the anionic detergent active may itself provide 30%, 40% or even 55% or more of the composition.
- anionic detergent actives useful in this invention are: linear and branched alkyl benzene sulphonates, alkane sulphonates, secondary alcohol sulphates, primary alcohol sulphates, alpha olefin sulphonates, alkyl ether sulphates, fatty acyl ester sulphonates, and mixtures of these.
- the invention is particularly applicable when at least part of the detergent active is alkyl benzene sulphonate, or a mixture thereof with fatty acyl ester sulphonate or primary alcohol sulphate.
- the filler should have an oil absorbency, measured according to the test stated, of at least 100ml/100g. Preferably it is higher such as at least 150ml/100g, better at least 200ml/100g and most preferably at least 300ml/100g.
- the filler may be water soluble but is more likely to be water insoluble.
- the mean particle size of the filler is not over 20 micrometres, better not over 10 micrometres.
- a small particle size is especially desirable for an insoluble filler, since it facilitates rinsing the filler away after a detergent composition has been used. Small particle size increases the speed of dissolution of a soluble filler.
- An alternative way to state desirable particle size is that the particle size distribution includes substantially no particles larger than 50 micrometres. These particles however will generally be aggregates of smaller particles, typically having a size in the range from 5 to 200 nanometres and predominantly (or even wholly) in the narrower range 10 nanometres to 100 nanometres. Such smaller particles can be distinguished by electron microscopy.
- Suitable inorganic materials tend to be finely divided solids obtained by precipitation.
- Materials can be produced in such form include silica, aluminosilicates, calcium silicates, magnesium silicates and calcium carbonate.
- Other materials which can be suitable, subject to testing their oil absorbency, are diatomaceous earths and finely divided cellulosic fillers.
- the amount of filler included in the composition will generally range from 3% to 50% by weight, usually 5% to 40%.
- detergent active and specified filler may be included in addition to the detergent active and specified filler, for example detergency builder, alkaline salts or other filler of lesser oil absorbency. A small quantity of moisture will almost always be present.
- compositions and comparative compositions were prepared using a standard procedure as follows.
- Linear alkyl benzene sulphonic acid with an average C13 alkyl chain length was charged to a Z-blade mixer. Temperature was maintained at 80°C. Sodium carbonate was added over ten minutes with continuous mixing during which time carbon dioxide was evolved. A particulate filler was then added over a period of 15 minutes and mixing continued for 5 minutes.
- the dough produced by this procedure was removed from the mixer and cut into pellets. These were allowed to cool to ambient temperature, hardening as they did so.
- the pellets were milled into a powder. This was mixed with 2% by weight of a conventional flow aid which coated the surfaces of the powder particles.
- the mean particle size, bulk density and dynamic flow rate of the resulting powders were tested. Their content of sodium alkyl benzene sulphonate was checked analytically and found to be approximately 60% by weight, except in Example 5 where the content was approximately 52% by weight.
- the dynamic flow rate, in ml/s, was measured using a cylindrical glass tube having an internal diameter of 35mm and a length of 600mm. The tube was securely clamped with its longitudinal axis vertical. Its lower end was terminated by means of a smooth cone of polyvinyl chloride having an internal angle of 15° and a lower outlet orifice of diameter 22.5mm. A beam sensor was positioned 150mm above the outlet, and a second beam sensor was positioned 250mm above the first sensor.
- the outlet orifice was temporarily closed, for example, by covering with a piece of card, and powder was poured into the top of the cylinder until the powder level was about 100mm above the upper sensor. The outlet was then opened and the time t (seconds) taken for the powder level to fall from the upper sensor to the lower sensor was measured electronically. The result is the tube volume between the sensors, divided by the time measured.
- Caking resistance of the particles and their hardness after exposure to air was tested by the following procedure: The powder was spread in a thin layer in a dish and exposed to atmosphere at 37°C and 70% relative humidity. After exposure for one week the powder was graded for feel. Also a sample of the powder which had been exposed was compressed under a standard load in a 2cm diameter cylindrical die to form a pellet. The hardness of the material in this pellet was tested with a cone penetrometer. The cone had an angle of 9° 10′ and was applied under 100 gram load for 10 seconds.
- compositions of these examples and comparative examples are set out in Tables 1 and 2 below.
- comparative example A an increased quantity of sodium carbonate was used rather than a separate particulate filler.
- the sodium carbonate was added over a period of 15 minutes in view of the greater quantity used.
- Sodium primary alcohol sulphate paste or sodium alkyl benzene sulphonate paste was charged to a Z-blade mixer. Temperature was maintained at 80°C. Sodium carbonate was added over five minutes with continuous mixing. A particulate filler was then added over a period of 15 minutes and mixing continued for 5 minutes.
- the dough produced by this procedure was removed from the mixer and cut into pellets. These were dried and allowed to cool to ambient temperature, hardening as they did so. Excepting pellets from Example E, which could not be milled as they were too soft, the pellets were milled into a powder. This was mixed with 2% by weight of a conventional flow aid (Alusil ET).
- Examples 7 and E are an instance where a particulate solid was not achieved without the filler.
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- 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
Description
- This invention relates to the particulate detergent compositions containing relatively high levels of detergent active and furthermore where the detergent comprises a high level of anionic detergent, at least 30% by weight of the composition. Such compositions may in particular be suitable for cleaning fabrics, although they may be intended for other uses. This invention also relates to the production of such compositions.
- Detergent compositions containing lower levels of anionic detergent active are commonplace, and are often prepared by spray drying as is well known. At first sight it might be supposed that there would be no difficulty in making compositions with higher concentrations of anionic detergent because many anionic detergent active materials can be prepared in more or less solid form consisting of substantially pure anionic detergent, or at least containing a very high percentage of anionic detergent.
- However, such materials tend to be sticky and to cake together whereas products which are suitable for retail sale are required not to be sticky and to be free flowing. A sticky solid with a tendency to cake is of course inconvenient during manufacture as well as at the time of use.
- In fact it is difficult to produce a particulate solid which both contains a high proportion of detergent active and also has satisfactory properties for use as part or the whole of a product suitable for retail sale.
- US 4515707 (Brooks) discloses a procedure in which anionic detergent acid is neutralized and mixed with a powdered ingredient to produce a powder which is described as dry. This is used subsequently as a raw material for the production of detergent bars. The powdered ingredients which are referred to can be made with varying absorbencies and the document does not disclose materials of unusual absorbency.
- US 4213874 (Williams et al) discloses the production of aluminosilicates which have an oil absorbtion of at least 75ml/100gram. It is disclosed that they may be used to absorb nonionic detergents in detergent products. US 4707290, GB 1485371 and GB 1591518 disclose the use of absorbent solids to act as carriers for nonionic detergents. Nonionic detergents are a different problem to anionic detergents in that the nonionic materials are generally liquids (which need to be made into solid form) whereby anionic detergents are generally solids in their own right.
- It is known to apply powdered materials to the surface of a particulate solid to reduce stickiness and enhance its abilities to flow as a powder. This however is merely a surface treatment.
- We have now found that the flow properties and caking resistance of detergent powders containing a high level of anionic detergent can be improved by incorporating a particulate filler with a relatively high oil absorption value.
- Accordingly, in a first aspect, this invention provides a particulate detergent composition, the particles of which contain at least 30% by weight of anionic detergent active and also contain a particulate filler with an oil absorption value of at least 100ml/100g, this filler being distributed within the particles of the composition in intimate mixture with the detergent active, the amount of the particulate filler being such that the weight ratio of the filler to anionic detergent active lies in the range from 1:10 to 1:1, more preferably 1:8 to 2:3.
- This ratio range signifies that the amount of filler is not greater than the amount of anionic detergent active.
- It is preferred that the filler has a mean particle size not greater than 20 micrometres.
- In a second aspect the invention provides a process of preparing a detergent composition which process comprises incorporating a particulate filler into a fluid or semi-solid composition containing anionic detergent active so that the filler is intimately mixed with the anionic detergent, which particulate filler has an oil absorbtion value in excess of 100ml/100gram, and forming the resultant mixture into a particulate composition with the filler distributed within the particles of the composition, the amounts of anionic detergent active and filler being such that the composition contains at least 30 wt% of anionic detergent and has a weight ratio of filler to detergent active ranging from 1:10 to 1:1.
- As stated above, the present invention contains particulate filler with an oil absorption value which is equal to, or exceeds, a minimum value.
- The oil absorption value of the filler is to be determined by the following test which is in accordance with British Standard 3483 : Part B7 : 1982. The test for oil absorption is performed by placing a weighed sample of the test powder on a plate and then adding linseed oil from a burette. The oil is added a few drops at a time. After each addition the powder is mixed vigorously with the oil using a palette knife. Addition of oil is continued until a paste of smooth consistency is formed. The paste should just spread without cracking or crumbling. The oil absorption value is expressed as the volume (ml) of oil absorbed per 100 gram of powder.
- A detergent composition according to the invention may be marketed directly as a washing product. Alternatively it can be mixed with other particulate material to form a finished product. In particular, a particulate detergent composition according to the invention may be mixed with a second particulate composition which contains other constituents of a final detergent composition, such as detergency builders. There are various possibilities for such a second composition. It might contain no detergent active or very little. It might contain a substantial quantity of detergent active but nevertheless a lower proportion than in a composition according to this invention which is mixed with it. Admixing the composition in accordance with the invention would then serve to increase the overall proportion of detergent active. There could even be a commercial advantage in circumstances where admixing a composition in accordance with this invention did not increase the overall proportion of detergent active - for instance by achieving beneficial physical properties or by enhancing overall production from available process plant.
- Production of compositions in accordance with this invention may be accomplished by conventional routes for the manufacture of particulate detergent compositions with a high level of detergent active, provided there is a stage when the detergent active is in a fluid or semi-solid form. The particulate filler is mixed with the detergent active at this stage and leads to an improvement in the properties of the particulate composition which is produced. In some instances a particulate state would not be achieved without the filler.
- If the overall process entails neutralization, the filler can be mixed with the acid form of the detergent active before neutralization. The filler may even be used as a base to neutralise the acid form of the detergent active, i.e. part of the material used as filler may serve to effect neutralisation. Another possibility is to neutralise the active and mix the filler with the resulting neutralised paste before this becomes solid.
- A fluid or semi-solid mixture containing the detergent active and the filler may be dried to solidify it, for example by means of a drum dryer. A viscous dough may be produced with a formulation such that the dough can be extruded but will then solidify into a hard solid which can be comminuted to desired particle size.
- One preferred method of producing compositions of this invention is by neutralizing an acid form of an anionic detergent active with an alkali metal oxide, hydroxide or carbonate (which may be a true carbonate, bicarbonate or sesquicarbonate) to produce a viscous dough, mixing the particulate filler with this dough, allowing the dough to harden to a solid and comminuting the solid. Neutralization may be effected in the presence of little or no added water. Alternatively there may be some deliberate addition of water: this can lead to a solid which is already in equilibrium with atmospheric humidity. Generally, the amount of water added (if any) is not more than 10%, more preferably not more than 5%, by weight based on the total weight of acid detergent and carbonate.
- Such neutralization and admixing of filler can be carried out in various types of high shear mixer. One possibility is a Z-blade mixer, another possibility is a cavity transfer mixer whose use as a chemical reactor is disclosed in our European patent application 194812, yet another possibility is a twin screw extruder. Other intensive mixers which may be used consist of vessels which contain rotating blades for mixing and high speed knives for dispersing, manufactured for example by Lödige (Trade Mark) ex Morton Machine Co Ltd, Scotland.
- If production is by a route which entails neutralization of the acid form of an anionic detergent active, other detergent active may also be mixed in. For example some preneutralised detergent active or nonionic detergent active may be mixed in.
- When the powder has been made it may be given a surface coating of a flow-improving aid which may itself be a particulate solid having the oil absorption property required for the filler used in this invention. Use of such materials as a surface coating is conventional. The examples below demonstrate that it does not, by itself, achieve the results achieved by the invention.
-
- As mentioned above compositions according to this invention must contain at least 30% by weight of active detergent. Preferably they contain more, e.g. at least 40% or even at least 55%. The amount of detergent active present may range as high as 90% by weight of the composition.
- Various detergent actives may be utilized, selected from the conventional categories of anionic, nonionic, cationic and amphoteric. Preferably anionic detergent active predominates; even if detergent active from another category is present the anionic detergent active may itself provide 30%, 40% or even 55% or more of the composition.
- Specific examples of anionic detergent actives useful in this invention are: linear and branched alkyl benzene sulphonates, alkane sulphonates, secondary alcohol sulphates, primary alcohol sulphates, alpha olefin sulphonates, alkyl ether sulphates, fatty acyl ester sulphonates, and mixtures of these. The invention is particularly applicable when at least part of the detergent active is alkyl benzene sulphonate, or a mixture thereof with fatty acyl ester sulphonate or primary alcohol sulphate.
- As stated above the filler should have an oil absorbency, measured according to the test stated, of at least 100ml/100g. Preferably it is higher such as at least 150ml/100g, better at least 200ml/100g and most preferably at least 300ml/100g.
- The filler may be water soluble but is more likely to be water insoluble.
- Preferably the mean particle size of the filler is not over 20 micrometres, better not over 10 micrometres. A small particle size is especially desirable for an insoluble filler, since it facilitates rinsing the filler away after a detergent composition has been used. Small particle size increases the speed of dissolution of a soluble filler. An alternative way to state desirable particle size is that the particle size distribution includes substantially no particles larger than 50 micrometres. These particles however will generally be aggregates of smaller particles, typically having a size in the range from 5 to 200 nanometres and predominantly (or even wholly) in the narrower range 10 nanometres to 100 nanometres. Such smaller particles can be distinguished by electron microscopy.
- A variety of materials are available with suitable particle size and oil absorbency. Suitable inorganic materials tend to be finely divided solids obtained by precipitation. Materials can be produced in such form include silica, aluminosilicates, calcium silicates, magnesium silicates and calcium carbonate. Other materials which can be suitable, subject to testing their oil absorbency, are diatomaceous earths and finely divided cellulosic fillers.
- The amount of filler included in the composition will generally range from 3% to 50% by weight, usually 5% to 40%.
- Other materials may be included in addition to the detergent active and specified filler, for example detergency builder, alkaline salts or other filler of lesser oil absorbency. A small quantity of moisture will almost always be present.
- A number of compositions and comparative compositions were prepared using a standard procedure as follows.
- Linear alkyl benzene sulphonic acid with an average C₁₃ alkyl chain length was charged to a Z-blade mixer. Temperature was maintained at 80°C. Sodium carbonate was added over ten minutes with continuous mixing during which time carbon dioxide was evolved. A particulate filler was then added over a period of 15 minutes and mixing continued for 5 minutes.
- The dough produced by this procedure was removed from the mixer and cut into pellets. These were allowed to cool to ambient temperature, hardening as they did so. The pellets were milled into a powder. This was mixed with 2% by weight of a conventional flow aid which coated the surfaces of the powder particles.
- The mean particle size, bulk density and dynamic flow rate of the resulting powders were tested. Their content of sodium alkyl benzene sulphonate was checked analytically and found to be approximately 60% by weight, except in Example 5 where the content was approximately 52% by weight. The dynamic flow rate, in ml/s, was measured using a cylindrical glass tube having an internal diameter of 35mm and a length of 600mm. The tube was securely clamped with its longitudinal axis vertical. Its lower end was terminated by means of a smooth cone of polyvinyl chloride having an internal angle of 15° and a lower outlet orifice of diameter 22.5mm. A beam sensor was positioned 150mm above the outlet, and a second beam sensor was positioned 250mm above the first sensor.
- To determine the dynamic flow rate of a powder sample, the outlet orifice was temporarily closed, for example, by covering with a piece of card, and powder was poured into the top of the cylinder until the powder level was about 100mm above the upper sensor. The outlet was then opened and the time t (seconds) taken for the powder level to fall from the upper sensor to the lower sensor was measured electronically. The result is the tube volume between the sensors, divided by the time measured.
- Caking resistance of the particles and their hardness after exposure to air was tested by the following procedure: The powder was spread in a thin layer in a dish and exposed to atmosphere at 37°C and 70% relative humidity. After exposure for one week the powder was graded for feel. Also a sample of the powder which had been exposed was compressed under a standard load in a 2cm diameter cylindrical die to form a pellet. The hardness of the material in this pellet was tested with a cone penetrometer. The cone had an angle of 9° 10′ and was applied under 100 gram load for 10 seconds.
- The compositions of these examples and comparative examples are set out in Tables 1 and 2 below. In the case of comparative example A an increased quantity of sodium carbonate was used rather than a separate particulate filler. In other words a part of the sodium carbonate, having an oil absorption value of 63ml/100g, constituted the particulate filler. In this comparative example the sodium carbonate was added over a period of 15 minutes in view of the greater quantity used.
- The various solids were nominally dry, which in practice means that they contained a small percentage of absorbed moisture.
TABLE 1 Components Charged in the Z-blade Mixer (Kg) I II III IV V A B C Alkyl benzene sulphonic acid (1) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Sodium carbonate (2) 0.2 0.2 0.2 0.4 1.0 0.8 0.2 0.2 Water 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Socal U3 (3) 0.6 - - - - - - - Alusil ET (4) - 0.6 - - - - - - Microsil GP (5) - - 0.6 0.4 0.12 - - - Kaolin (6) - - - - - - 0.6 - Durcal 40 (7) - - - - - - - 0.6 (1) Sulphonated Dobane 113, ex Shell (1) Sulphonated Dobane 113, ex Shell (2) Light Soda Ash, ex ICI (2) Light Soda Ash, ex ICI (3) Calcium Carbonated, ex Solvay (3) Calcium Carbonate, ex Solvay (4) Aluminosilicate, ex J Crosfield and Sons (4) Aluminosilicate, ex J Crosfield and Sons (5) Silica, ex J Crossfield and Sons (5) Silica, ex J Crosfield and Sons (6) Speswhite grade, ex English China Clays (6) Speswhite grade, ex English China Clays (7) Calcium Carbonate, ex Sturge. (7) Calcium Carbonate, ex Sturge. TABLE 2 Properties of Materials Produced I II III IV V A B C Mean particle size (µm) 515 505 465 485 510 500 515 525 Bulk density (Kg/m³) 668 652 654 664 700 676 668 650 Dynamic flow rate (ml/sec) 75 80 96 96 90 75 75 70 Penetration of compact pellet after exposure (mm) 14 6.8 2.4 3.5 4.2 19 20 22 Feel of the powder after exposure* S MS MC MC MC VS VS VS Oil absorption value of the filler (ml/100g) 120 200 330 330 330 63** 51 25 * S = Soft, MS = Moderately Soft, MC = Moderately Crisp, VS = Very Soft ** Oil absorption value of the light soda ash. - It can be seen that below an oil absorption value of 100ml/100g the properties of the powder are not much affected by the oil absorption value of the filler whereas considerable improvements are observed at higher oil absorption values.
- In each case the conventional flow aid used to provide a surface coating on the particles was Alusil ET. The inferior results with the comparative examples demonstrate that a conventional dusting or surface coating with a flow aid does not itself achieve the benefit of this invention.
- These Examples commence using pastes, i.e. previously neutralised detergent active. The procedure was as follows.
- Sodium primary alcohol sulphate paste or sodium alkyl benzene sulphonate paste was charged to a Z-blade mixer. Temperature was maintained at 80°C. Sodium carbonate was added over five minutes with continuous mixing. A particulate filler was then added over a period of 15 minutes and mixing continued for 5 minutes.
- The dough produced by this procedure was removed from the mixer and cut into pellets. These were dried and allowed to cool to ambient temperature, hardening as they did so. Excepting pellets from Example E, which could not be milled as they were too soft, the pellets were milled into a powder. This was mixed with 2% by weight of a conventional flow aid (Alusil ET).
- The physical properties were determined as for Examples 1-5. The active contents were measured analytically and are shown in Table 4.
TABLE 3 Components charged in the Z-blade mixer VI D VII E Sodium primary alcohol sulphate paste (1) 1.0 1.0 - - Sodium alkyl benzene sulphonate paste (2) - - 1.0 1.0 Sodium carbonate (3) 0.25 0.4 0.45 0.6 Microsil GP (4) 0.15 - 0.15 - (1) Derived from coconut oil, active content 62%. (2) Derived from Dobane 113, ex Shell, active content 75%. (3) Light Soda Ash, ex ICI. (4) Silica, ex J Crosfield and Sons. TABLE 4 Properties of Materials Produced VI D VII E Moisture content after drying (%) 15.3 14.1 3.1 2.1 % Active 52 52 54 54 Mean particle size (um) 400 355 630 - (1) Bulk Density (Kg/m³) 560 585 680 - Dynamic flow rate (ml/sec) 80 75 90 - Penetration of compacted pellet after exposure (mm) 0.8 2.3 5.5 - Feel of the powder after exposure (3) C MS(2) MC - Oil absorption value of the filler (ml/100g) 330 63 330 63 (1) Could not be satisfactorily comminuted. (2) Formed some lumps. (3) C = Crisp, MC = Moderately Crisp, MS = Moderately Soft. - Once again it was apparent that incorporation of filler with high oil absorption value led to powders with enhanced physical properties. Examples 7 and E are an instance where a particulate solid was not achieved without the filler.
Claims (10)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB898926644A GB8926644D0 (en) | 1989-11-24 | 1989-11-24 | Detergent composition |
GB8926644 | 1989-11-24 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0430603A2 true EP0430603A2 (en) | 1991-06-05 |
EP0430603A3 EP0430603A3 (en) | 1991-11-27 |
EP0430603B1 EP0430603B1 (en) | 1995-01-25 |
Family
ID=10666891
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90312779A Revoked EP0430603B1 (en) | 1989-11-24 | 1990-11-23 | Detergent composition |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0430603B1 (en) |
JP (1) | JPH03177499A (en) |
AU (1) | AU629429B2 (en) |
BR (1) | BR9005872A (en) |
CA (1) | CA2030306C (en) |
DE (1) | DE69016374T2 (en) |
ES (1) | ES2067699T3 (en) |
GB (1) | GB8926644D0 (en) |
NO (1) | NO176405C (en) |
ZA (1) | ZA909423B (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0688861A1 (en) | 1994-06-22 | 1995-12-27 | SOCIETE FRANCAISE HOECHST Société anonyme dite: | Process for the preparation of anionic surfactant compositions in powder, bead or granular form and use of these compositions in cleaning and care products |
WO1996015214A1 (en) * | 1994-11-14 | 1996-05-23 | Henkel Kommanditgesellschaft Auf Aktien | Scouring powder having improved pourability and process for its preparation |
WO2000031223A1 (en) * | 1998-11-20 | 2000-06-02 | Unilever Plc | Granular detergent components and particulate detergent compositions containing them |
EP1111035A2 (en) * | 1999-12-21 | 2001-06-27 | Henkel Kommanditgesellschaft auf Aktien | Combination of active agents for incorporation in detergent compositions |
WO2014198034A1 (en) * | 2013-06-13 | 2014-12-18 | The Procter & Gamble Company | Granular laundry detergent |
WO2016145643A1 (en) * | 2015-03-19 | 2016-09-22 | The Procter & Gamble Company | Structured detergent particles and granular detergent compositions containing the same |
US9828569B2 (en) | 2013-06-13 | 2017-11-28 | The Procter & Gamble Company | Granular laundry detergent |
US10287531B2 (en) | 2013-07-18 | 2019-05-14 | Galaxy Surfactants Ltd. | Free-flowing, solid, high active alkyl ether sulfates |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB783223A (en) * | 1954-09-06 | 1957-09-18 | Degussa | Process for the production of moulded bodies of detergent sulphonates |
DE2542050A1 (en) * | 1974-09-27 | 1976-04-15 | Procter & Gamble | SPRAY-DRIED CALCIUM CARBONATE CONTAINING GRANULES |
FR2391274A1 (en) * | 1977-05-18 | 1978-12-15 | Unilever Nv | PRODUCTION OF PULVERULENT DETERGENT COMPOSITIONS BASED ON ALKALINE METAL CARBONATE AND CALCIUM CARBONATE |
FR2568584A1 (en) * | 1984-08-06 | 1986-02-07 | Kao Corp | HIGH DENSITY POWDER DETERGENT AND PROCESS FOR PREPARING THE SAME |
EP0345090A2 (en) * | 1988-06-03 | 1989-12-06 | Colgate-Palmolive Company | Process for manufacturing particulate detergent composition directly from in situ produced anionic detergent salt |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1042924B (en) * | 1974-09-27 | 1980-01-30 | Procter & Gamble | Phosphate free granules contg submicron calcium carbonate - and an alkali (bi) carbonate or sesquicarbonate, useful washing agent additives to ppte soluble calcium salts |
-
1989
- 1989-11-24 GB GB898926644A patent/GB8926644D0/en active Pending
-
1990
- 1990-11-20 CA CA002030306A patent/CA2030306C/en not_active Expired - Fee Related
- 1990-11-20 BR BR909005872A patent/BR9005872A/en not_active IP Right Cessation
- 1990-11-22 AU AU66899/90A patent/AU629429B2/en not_active Ceased
- 1990-11-22 JP JP2320525A patent/JPH03177499A/en active Pending
- 1990-11-23 DE DE69016374T patent/DE69016374T2/en not_active Revoked
- 1990-11-23 EP EP90312779A patent/EP0430603B1/en not_active Revoked
- 1990-11-23 ZA ZA909423A patent/ZA909423B/en unknown
- 1990-11-23 ES ES90312779T patent/ES2067699T3/en not_active Expired - Lifetime
- 1990-11-23 NO NO905080A patent/NO176405C/en not_active IP Right Cessation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB783223A (en) * | 1954-09-06 | 1957-09-18 | Degussa | Process for the production of moulded bodies of detergent sulphonates |
DE2542050A1 (en) * | 1974-09-27 | 1976-04-15 | Procter & Gamble | SPRAY-DRIED CALCIUM CARBONATE CONTAINING GRANULES |
FR2391274A1 (en) * | 1977-05-18 | 1978-12-15 | Unilever Nv | PRODUCTION OF PULVERULENT DETERGENT COMPOSITIONS BASED ON ALKALINE METAL CARBONATE AND CALCIUM CARBONATE |
FR2568584A1 (en) * | 1984-08-06 | 1986-02-07 | Kao Corp | HIGH DENSITY POWDER DETERGENT AND PROCESS FOR PREPARING THE SAME |
EP0345090A2 (en) * | 1988-06-03 | 1989-12-06 | Colgate-Palmolive Company | Process for manufacturing particulate detergent composition directly from in situ produced anionic detergent salt |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0688861A1 (en) | 1994-06-22 | 1995-12-27 | SOCIETE FRANCAISE HOECHST Société anonyme dite: | Process for the preparation of anionic surfactant compositions in powder, bead or granular form and use of these compositions in cleaning and care products |
FR2721616A1 (en) * | 1994-06-22 | 1995-12-29 | Hoechst France | Compositions of anionic surfactants in powder, pearls or granules, process for their preparation and their use in cleaning and maintenance products |
WO1996015214A1 (en) * | 1994-11-14 | 1996-05-23 | Henkel Kommanditgesellschaft Auf Aktien | Scouring powder having improved pourability and process for its preparation |
WO2000031223A1 (en) * | 1998-11-20 | 2000-06-02 | Unilever Plc | Granular detergent components and particulate detergent compositions containing them |
US6369020B1 (en) | 1998-11-20 | 2002-04-09 | Unilever Home & Personal Care Usa | Granular detergent components and particulate detergent compositions containing them |
EP1111035A2 (en) * | 1999-12-21 | 2001-06-27 | Henkel Kommanditgesellschaft auf Aktien | Combination of active agents for incorporation in detergent compositions |
EP1111035A3 (en) * | 1999-12-21 | 2003-04-23 | Henkel Kommanditgesellschaft auf Aktien | Combination of active agents for incorporation in detergent compositions |
WO2014198034A1 (en) * | 2013-06-13 | 2014-12-18 | The Procter & Gamble Company | Granular laundry detergent |
WO2014198128A1 (en) * | 2013-06-13 | 2014-12-18 | The Procter & Gamble Company | Granular laundry detergent |
US9828569B2 (en) | 2013-06-13 | 2017-11-28 | The Procter & Gamble Company | Granular laundry detergent |
US10287531B2 (en) | 2013-07-18 | 2019-05-14 | Galaxy Surfactants Ltd. | Free-flowing, solid, high active alkyl ether sulfates |
WO2016145643A1 (en) * | 2015-03-19 | 2016-09-22 | The Procter & Gamble Company | Structured detergent particles and granular detergent compositions containing the same |
Also Published As
Publication number | Publication date |
---|---|
NO905080L (en) | 1991-05-27 |
AU629429B2 (en) | 1992-10-01 |
JPH03177499A (en) | 1991-08-01 |
AU6689990A (en) | 1991-05-30 |
ZA909423B (en) | 1992-07-29 |
ES2067699T3 (en) | 1995-04-01 |
EP0430603A3 (en) | 1991-11-27 |
NO176405C (en) | 1995-03-29 |
BR9005872A (en) | 1991-09-24 |
NO905080D0 (en) | 1990-11-23 |
GB8926644D0 (en) | 1990-01-17 |
CA2030306A1 (en) | 1991-05-25 |
DE69016374D1 (en) | 1995-03-09 |
DE69016374T2 (en) | 1995-05-24 |
NO176405B (en) | 1994-12-19 |
CA2030306C (en) | 1998-12-22 |
EP0430603B1 (en) | 1995-01-25 |
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Opponent name: PROCTER & GAMBLE E.T.C. Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN |
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Effective date: 20020425 |
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NLR1 | Nl: opposition has been filed with the epo |
Opponent name: PROCTER & GAMBLE E.T.C. Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN |
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