EP0323659B1 - Verfahren zur Herstellung eines Reinigungsproduktes in Granulatform - Google Patents

Verfahren zur Herstellung eines Reinigungsproduktes in Granulatform Download PDF

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Publication number
EP0323659B1
EP0323659B1 EP88202736A EP88202736A EP0323659B1 EP 0323659 B1 EP0323659 B1 EP 0323659B1 EP 88202736 A EP88202736 A EP 88202736A EP 88202736 A EP88202736 A EP 88202736A EP 0323659 B1 EP0323659 B1 EP 0323659B1
Authority
EP
European Patent Office
Prior art keywords
granulising
particles
binder
dusty
detergent
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 - Lifetime
Application number
EP88202736A
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English (en)
French (fr)
Other versions
EP0323659B2 (de
EP0323659A3 (en
EP0323659A2 (de
Inventor
Linda-Lou Huiskes-Taal
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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Filing date
Publication date
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0323659A2 publication Critical patent/EP0323659A2/de
Publication of EP0323659A3 publication Critical patent/EP0323659A3/en
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives thereof
    • 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
    • C11D13/00—Making of soap or soap solutions in general; Apparatus therefor
    • C11D13/14—Shaping
    • C11D13/20—Shaping in the form of small particles, e.g. powder or flakes
    • 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
    • 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
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/06—Inorganic compounds
    • C11D9/08—Water-soluble compounds
    • C11D9/10—Salts
    • 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/225—Polymers
    • 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/26—Organic compounds, e.g. vitamins containing oxygen
    • C11D9/262—Organic compounds, e.g. vitamins containing oxygen containing carbohydrates

Definitions

  • the present invention relates to a method for preparing a granular detergent material. More in particular, it relates to a method for preparing said granules from a dusty detergent component, such as soap, builders, e.g. sodium tripolyphosphate, surfactants, e.g. alkyl benzene sulphonate, soda ash, and corrosion inhibitors, such as disilicate.
  • a dusty detergent component such as soap, builders, e.g. sodium tripolyphosphate, surfactants, e.g. alkyl benzene sulphonate, soda ash, and corrosion inhibitors, such as disilicate.
  • Soap is a common ingredient of detergent powder compositions. It may be included as a detergent active, a builder or a foam suppressor. It may be added to a slurry which is subsequently spray-dried, or dry-mixed with other particulate ingredients, including composite particles which are themselves the product of a spray-drying process.
  • soap When supplied as a raw material for incorporating in such compositions, soap is often in the form of a fine dusty powder. As well as being messy in the handling, such powders have a tendency to cause respiratory tract irritation in those working with them.
  • US-A-3,761,549 and US-A-3,588,950 describe a process of making non-dusty granulates by means of gas fluidisation in a rotating drum.
  • Granules which, it is said, can be made in this way include those with a core of potassium soap coated with sodium soap, a core of a strong caustic detergent coated with a mild caustic detergent or a core of potassium soap with a coating of metasilicate.
  • the core is formed by interactions during the fluidisation process and the coating is applied by spraying-on the coating as a liquid.
  • non-dusting soap granulates are formed by mixing soap dust with fatty acid and an alkaline material which saponifies the acid.
  • the resultant particles consist of two kinds of soaps.
  • DE-A-2,340,882 provides a process for preparing a detergent composition, in which a spray-dried granule is wetted and subsequently coated with a builder salt.
  • CA-A-1,056,687 refers to a process for agglomerating detergent material by coating a mixtures of constituents (including sodium tripolyphosphate) with an alkaline detergent salt in the presence of water.
  • US-A-4,207,197 relates to a process for preparing an agglomerated granular detergent composition, wherein one or more inorganic particulate components are mixed with an agglomerating agent.
  • EP-A-075,250 discloses a process for preparing a metasilicate containing granule coated with tripolyphosphate.
  • US-A-3,329,616 relates to a process for preparing a detergent composition, wherein particles consisting of a builder salt are coated with a surfactant in the presence of water as a binder.
  • non-dusting granules of a detergent component may be made in a simplified process, optionally in mixture with a wide variety of other materials.
  • the detergent component can be worked into a substantially non-dusty form from a pre-mix comprising:
  • This pre-mix is used to prepare a granular detergent material having a core of granulising particles coated with a detergent component and a binder, comprising up to 40% by weight of the detergent component and from 1 to 10% by weight of the binder.
  • the dusty detergent component and the granulising particles are admixed intimately and the resultant product is then admixed with the binder to form said pre-mix. Mixing of the pre-mix then continues until the granular detergent material is formed.
  • the present invention provides a method for preparing a granular detergent material having a core of a granulising particle coated with a mixture of a dusty detergent component and a binder, which detergent material contains up to 40 % by weight of said dusty detergent component and from 1 to 10 % by weight of said binder, said method consisting of the steps of:
  • the physical structure of the granular detergent material obtained by the method according to the invention can vary. However, it is believed that the granulising particles are coated with the detergent component and the binder.
  • This granular detergent material is considerably less dusty than, for instance, known fine soap powders, yet the process defined above for its production is more cost-effective than extrusion techniques.
  • granulating as an adjective is used to refer to components which are capable of being processed to form compositions comprising granules.
  • granulising is used to refer to particles which are capable of acting on other substances, during processing, to transform those substances into granules.
  • the granules obtained are, by themselves, suitable for incorporation in complete detergent powder compositions which also comprise one or more synthetic detergent actives selected from anionic, nonionic, cationic, zwitterionic or amphoteric surfactants.
  • These complete compositions preferably also contain other ingredients usual in such powders, for example detergency builders (i.e. substances which sequester and/or precipitate calcium ions contributing to water hardness), soil-suspending and anti-redeposition agents, corrosion inhibitors, buffers, bleaches (including low-temperature systems comprising a bleach precursor and an activator therefor), enzymes, enzyme stabilisers, lather boosters or foam depressors, dyes, pigments, fluorescers and perfumes etc.
  • detergency builders i.e. substances which sequester and/or precipitate calcium ions contributing to water hardness
  • soil-suspending and anti-redeposition agents e.e. substances which sequester and/or precipitate calcium ions contributing to water hardness
  • Soap-containing complete detergent powder compositions for which soap-containing granules according to the present invention are well suited to formulating include those generically and specifically described in patent specification EP-A-117,568.
  • the base mixture also contains the granulising particles.
  • the granulising particles should be of one or more substances which are usual ingredients in detergent powders such as recited in the preceding paragraph.
  • One preferred class of granulising particles comprises neutral and alkaline salts of alkali metal cations and organic or inorganic anions, into which class fall many of the aforementioned "usual ingredients" (which will be mentioned in more detail hereinbelow).
  • especially preferred salts are the alkali metal metasilicates (preferably hydrated), for example sodium metasilicate 5 aq. which is a corrosion inhibi- tor/alkaline buffer.
  • granulising particles whether salts or otherwise, as a general rule it is preferred that they should not be too pervious to water, which is why the salts should be hydrated.
  • the granulising particles should also be capable of surviving without fragmentation in the mixing apparatus used (vide infra).
  • the dusty detergent component may, in principle, be any usual detergent component.
  • the process of the invention is particularly suited for soap; builders like sodium tripolyphosphate, zeolite or polyacrylates; surfactants, such as alkyl benzene sulphonate; soda ash; and corrosion inhibitors, such as disilicate. Especially good results are obtained for dusty soap powders.
  • the detergent component may be of any kind, provided it is compatible with the binder, the granulising particles and the mixing apparatus. On the latter point, it is believed to be important that it should not soften too much or melt with the heat of mixing, although some softening may aid the granulation process.
  • it will be added to the mixer in the form of the known fine dusty powders, in order to convert it to a more acceptable form. However, in some circumstances it may be possible to add them as larger particles or even lumps, depending on the type of mixer, the kind of detergent component and the working temperature.
  • soaps which are capable of producing extremely good quality granules by this invention are tallow and hardened fish/rape soaps. In the case of softer soaps, better results may be obtained if the mixture is cooled during processing.
  • the binder is any substance capable of bonding the fine detergent component particles to form and maintain granules thereof and to enable them to coat the granulising particles. Thus, it should be compatible with the detergent component and with the granulising particles. It should also possess a "setting property", either alone or by interaction with the detergent component. Especially useful are aqueous-based binders, in which the detergent component is at least partly soluble, for example aqueous solutions of sugars, polyacrylate polymers or neutral waterglass, the latter being most preferred, or water. Generally, these substances will be used at aqueous concentrations at which the liquid is viscous and 'sticky'. Thus, for example, waterglasses may be in solutions from about 25% to about 50% by weight, typically around 34% by weight. It is also possible to utilise gums.
  • the binder may also contain other ingredients such as dyes, optical brighteners.
  • ingredients mentioned above in respect of complete detergent powder compositions are the synthetic anionic, nonionic, cationic, zwitterionic and amphoteric surfactants. These will be well known to those skilled in the art and, for example, may be selected from the classes, sub-classes and individual agents described in "Surface Active Agents", Vol. I by Schwartz & Perry (Interscience 1949) and “Surface Active Agents", Vol. II by Schwartz, Perry and Berch (Interscience 1958).
  • the preferred but optional other ingredients of the complete composition are the "usual ingredients". Most important of these are the detergency builders. Those which are crystalline, and in some cases amorphous, inorganic or non-polymeric organic salts may either be added to the complete detergent powder composition and/or constitute the granulising particles.
  • This class includes water-soluble alkali metal phosphates, triphosphates, polyphosphates, silicates, borates, and also carbonates. Specific examples of such salts are sodium and potassium triphosphates, pyrophosphates, orthophosphates, hexametaphosphates, tetraborates, neutral silicates and carbonates.
  • aluminosilicate is an amorphous water-insoluble hydrated compound of the formula Na x (Al0 2 .Si0 2 )y, wherein x is a number from 1.0 to 1.2 and y is 1, said amorphous material being further characterised by an Mg ++ exchange capacity of from 50 mg eq. CaC0 3 /g to about 150 mg eq. CaC0 3 /g and a particle diameter of from about 0.01 micron to about 5 microns.
  • This ion exchange builder is more fully described in GB-A-1 470 250.
  • a second such water-insoluble synthetic aluminosilicate ion exchage material is crystalline and has the formula Na z [(A10 2 ) Y (Si0 2 )] xH 2 0, wherein z and y are integers of at least 6; the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264, said aluminosilicate ion exchange material having a particle size diameter from about 0.1 micron to about 100 microns; a calcium ion exchange capacity on an anhydrous basis of at least about 200 milligrams equivalent of CaC0 3 hardness per gram; and a calcium ion exchange rate on an anhydrous basis of at least about 2 gralns/gallon/minute/gram.
  • These synthetic aluminosilicates are more fully described in GB-A-1 429 143.
  • Suitable organic builder salts in this class are:
  • alkali metal salts of ethane-2-carboxy-1,1-diphosphonic acid hydrox- ymethane diphosphonic acid, carboxyl diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,2-triphosphonic acid, propane-1,1,3,3-tetraphosphonic acid, propane-1,1,2,3,- tetraphosphonic acid, and propane-1,2,2,3-tetraphosphonic acid.
  • alkylmalonates, alkylsuccinates, alkylsulphocarboxylates and carboxymethyloxymalonates include the salts of the free acids or of esters thereof.
  • Other polycarboxylate builders which can be used satisfactorily, include water-soluble salts of mellitic acid, citric acid, and carboxymethyloxy succinic acid and salts of polymers of itaconic acid and maleic acid.
  • polystyrene builders are the water-soluble salts of polycarboxylate polymers and copolymers as described in U.S. Patent specification No. 3 308 067.
  • oxygen bleaches such as alkali metal peroxygen compounds (perborates, percarbonates, etc.) as well as activators therefor.
  • activators A large number of such activators is known, but one preferred agent in the context of this invention, especially as the granulising particles, is N,N,N',N'- tetraacetyl ethylenediamine, otherwise known as TAED.
  • the method for preparing the granular detergent material, according to the invention as described above, may be applied, using any mixing apparatus according to the scale intended but the Lodige (Trade Mark) batch-type of mixers, for example the FKM-range, are especially preferred.
  • Lodige Trade Mark
  • the dusty detergent component and the granulising particles should to be admixed for about half to about 5 minutes (typically about 3); the binder is then added in an amount which by simple trial and error will be found to yield the best formed particles with minimum lumps present.
  • a good guide is to add the binder slowly until the mix just takes on a slightly wet appearance. Below this concentration there is an increasing tendency for the granules to form imperfectly. Above this level, there is a progressive tendency for the mixture to stick to the knives of the mixer and eventually form lumps which contaminate the final product.
  • mixing is continued for at least 3 minutes, most preferably for 5 or even 10 minutes, the best results being obtained after about 15 minutes or more.
  • the binder is added in an amount of about 1 to about 10% by weight, but we have found that in most situations the optimum is in the range from about 5 to about 7%. Generally speaking, the more dusty detergent component is present, the more binder is needed. It is possible to granulate up to 40% by weight of detergent component in the total composition by this method, but normally this will be from about 25 to about 38%. In most situations, the balance of the pre-mix will consist only of the granulising particles, but optionally small amounts of other components may also be present.
  • Granulising particles may be chosen from amongst a very wide range of particle sizes.
  • average particle size means the diameter value in which 50% of the particles are larger and 50% are smaller. Of course, the particles will not be as small as the fine dusty detergent component referred to previously. In general, the average particle size will be from about 75 ⁇ .m to about 4,000 ⁇ m, preferably from about 250 ⁇ m to about 2,500 ⁇ m.
  • compositions were prepared by mixing of soap and granulising particles for three minutes in a Lodige M 20 (a batch-type of mixer), followed by addition of the binder and continued mixing for a further 15 minutes. In all cases the resulting product was a granular mixture. The products had the consistency shown. All amounts are percentages by weight.
  • Examples 1-3 were repeated, using as the dusty detergent component a mixture of : the granulising particles : binder :
  • a free-flowing mixture of granular particles was obtained having excellent powder properties.
  • Examples 1-3 were repeated, using dusty sodium tripolyphosphate (20.1%), sodium metasilicate.5 aq. (77.9%) as granulising particles and a 34% solution of sodium waterglass (2.0%) as binder. Granules having good powder properties were obtained.
  • Examples 1-3 were repeated, using dusty alkylbenzene sulphonate (26.0%), sodium tripolyphosphate particles (72.5%) as granulising particles and a 34% solution of sodium waterglass (1.5%) as binder. Granules having good powder properties were obtained.
  • Examples 1-3 were repeated, using dusty soda ash (15.0%), sodium metasilicate.5 aq. particles (79.1%) as granulising particles and a 34% solution of waterglass (5-7%) as binder. The properties of the granules obtained were good.
  • Examples 1-3 were repeated, using dusty sodium disilicate (20.0%), STP granules (78.0%) as granulising particles and water (2.0%) as binder.
  • the granules obtained had good powder properties.

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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)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (8)

1. Verfahren zur Herstellung eines Reinigungsmittels in Granulatform mit einem Kern aus einem granulierenden Teilchen, beschichtet mit einem Gemisch aus einer staubförmigen Waschmittelkomponente und einem Bindemittel, wobei der Waschmittelstoff bis zu 40 Gew.-% der staubförmigen Waschmittelkomponente und 1 bis 10 Gew.-% des Bindemittels enthält, wobei das Verfahren aus den Schritten besteht:
(a) anfängliches Anmischen für etwa 0,5 bis 5 Minuten von granulierenden Teilchen und der staubförmigen Waschmittelkomponente, gefolgt von Anmischen des Bindemittels damit und
(b) Fortführen des Mischens der so erhaltenen Vormischungszusammensetzung für mindestens 3 Minuten.
2. Verfahren nach Anspruch 1, wobei das fortführende Mischen der Vormischungszusammensetzung für mindestens 5 Minuten ausgeführt wird.
3. Verfahren nach Anspruch 1 oder 2, wobei die staubförmige Waschmittelkomponente ausgewählt ist aus Seife, anionischen Tensiden, Buildern, kalzinierter Soda oder Korrosionsinhibitoren.
4. Verfahren nach Anspruch 1 oder 2, wobei die staubförmige Waschmittelkomponente Seife ist.
5. Verfahren nach Anspruch 1 oder 2, wobei das Bindemittel eine wässerige Lösung von entweder neutralem Wasserglas und/oder einem Polyacrylatpolymer oder Wasser umfaßt.
6. Verfahren nach Anspruch 1 und 2, wobei das granulierende Teilchen Kristalle eines Salzes von einem Alkalimetallkation und einem organischen oder anorganischen Anion umfaßt.
7. Verfahren nach Anspruch 6, wobei die Kristalle ausgewählt sind aus Alkalimetallmetasilicaten und Alkalimetallorthophosphaten, Pyrophosphaten und Tripolyphosphaten und Gemischen davon.
8. Verfahren nach einem der Ansprüche 1 bis 7, wobei die granulierenden Teilchen eine durchschnittliche Teilchengröße im Bereich von 75 um bis 4000 um aufweisen.
EP88202736A 1987-12-11 1988-11-30 Verfahren zur Herstellung eines Reinigungsproduktes in Granulatform Expired - Lifetime EP0323659B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8728959 1987-12-11
GB878728959A GB8728959D0 (en) 1987-12-11 1987-12-11 Soap based compositions

Publications (4)

Publication Number Publication Date
EP0323659A2 EP0323659A2 (de) 1989-07-12
EP0323659A3 EP0323659A3 (en) 1990-10-24
EP0323659B1 true EP0323659B1 (de) 1995-01-11
EP0323659B2 EP0323659B2 (de) 1998-02-25

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ID=10628354

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Application Number Title Priority Date Filing Date
EP88202736A Expired - Lifetime EP0323659B2 (de) 1987-12-11 1988-11-30 Verfahren zur Herstellung eines Reinigungsproduktes in Granulatform

Country Status (8)

Country Link
EP (1) EP0323659B2 (de)
AU (1) AU615239B2 (de)
DE (1) DE3852754T3 (de)
ES (1) ES2067467T5 (de)
FI (1) FI885665A (de)
GB (1) GB8728959D0 (de)
NZ (1) NZ227224A (de)
ZA (1) ZA889240B (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2636036B2 (ja) * 1989-03-06 1997-07-30 花王株式会社 高密度洗剤粒子の連続造粒方法及び装置
EP0612843A1 (de) * 1993-02-22 1994-08-31 Unilever N.V. Körnige saure Reiniger
US5703027A (en) * 1994-11-29 1997-12-30 The Procter & Gamble Company Monomeric rich silicate system in automatic dishwashing composition with improved glass etching
ATE183773T1 (de) * 1995-07-06 1999-09-15 Henkel Kgaa Von staub- und feinanteilen freie granulare wasch- und reinigungsmittel hoher schüttdichte
GB2343191A (en) * 1998-10-30 2000-05-03 Procter & Gamble Low dusting components for detergent compositions

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1813701A (en) * 1927-10-20 1931-07-07 Alden Speare S Sons Co Detergent
US3329616A (en) * 1963-07-31 1967-07-04 Monsanto Co Process for preparing detergents
JPS5229761B2 (de) * 1972-08-17 1977-08-04
CA1056687A (en) * 1976-04-08 1979-06-19 Conn Chem Limited Process for the manufacture of a dishwashing detergent
US4207197A (en) * 1978-08-09 1980-06-10 The Procter & Gamble Company Agglomeration process for making granular detergents
DE3136986A1 (de) * 1981-09-17 1983-03-31 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung eines granulierten rohmaterials fuer reinigungsmittel
EP0108429A1 (de) * 1982-09-07 1984-05-16 THE PROCTER & GAMBLE COMPANY Körniges Detergens ein Pyrophosphat und ein Polyacrylat-Polymer enthaltend

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Publication number Publication date
EP0323659B2 (de) 1998-02-25
AU2667488A (en) 1989-06-15
DE3852754T2 (de) 1995-05-18
NZ227224A (en) 1991-07-26
ES2067467T3 (es) 1995-04-01
GB8728959D0 (en) 1988-01-27
FI885665A0 (fi) 1988-12-07
FI885665A (fi) 1989-06-12
EP0323659A3 (en) 1990-10-24
ZA889240B (en) 1990-08-29
EP0323659A2 (de) 1989-07-12
DE3852754T3 (de) 1998-07-02
DE3852754D1 (de) 1995-02-23
ES2067467T5 (es) 1998-05-16
AU615239B2 (en) 1991-09-26

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