EP0536110B1 - Procede pour fabriquer des granules tensio-actifs - Google Patents

Procede pour fabriquer des granules tensio-actifs Download PDF

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Publication number
EP0536110B1
EP0536110B1 EP89911804A EP89911804A EP0536110B1 EP 0536110 B1 EP0536110 B1 EP 0536110B1 EP 89911804 A EP89911804 A EP 89911804A EP 89911804 A EP89911804 A EP 89911804A EP 0536110 B1 EP0536110 B1 EP 0536110B1
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Prior art keywords
water
weight
solids
gel phase
granulates
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German (de)
English (en)
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EP0536110A1 (fr
Inventor
Elmar Wilms
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite 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
    • 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 invention relates to a process of surfactant-containing granules which, despite their high content of nonionic surfactants and adsorbed water, are free-flowing, have a high bulk density and a very homogeneous grain spectrum.
  • the granules can be obtained by a comparatively simple mixing process and do not require subsequent drying. They can be used directly as detergents or cleaning agents or as additional powder components in composite detergents and cleaning agents.
  • Granules containing carrier substances and liquid or pasty nonionic surfactants adsorbed thereon are known. Methods have been developed for their production in which the liquid or melted nonionic surfactant is sprayed onto a previously spray-dried powder or mixed with a powdery carrier substance under granulating conditions. Such methods are known for example from German patent application DE-A-28 37 504.
  • water-soluble salts such as phosphates, silicates, borates or perborates or salt mixtures prepared beforehand in a certain manner, for example those made from sodium triphosphate and sodium silicate or from sodium carbonate and sodium bicarbonate, as well as water-insoluble compounds, for example zeolites, bentonites and Silicon dioxide (Aerosil) and mixtures of the substances mentioned.
  • zeolites zeolites, bentonites and Silicon dioxide (Aerosil) and mixtures of the substances mentioned.
  • Mixtures of water-soluble and water-insoluble Backing materials were used.
  • DE 32 06 265 describes phosphate-free carrier grains which consist of 25 or 52% sodium carbonate or hydrogen carbonate, 10 to 50% zeolite, 0 to 18% sodium carbonate and 1 to 20% bentonite or 0.05 to 2% polyacrylate.
  • DE 34 44 960-A1 discloses a granular adsorbent which is able to absorb high proportions of liquid to pasty detergent constituents, in particular nonionic surfactants, and (based on anhydrous substance) from 60 to 80% by weight of zeolite, 0.1 to 8% by weight .-% sodium silicate, 3 to 15 wt .-% of homo- or copolymers of acrylic acid, methacrylic acid and / or maleic acid, 8 to 18 wt .-% water and optionally up to 5 wt .-% of nonionic surfactants and by spray drying is available.
  • EP 149 264 teaches that commercially available spray-dried zeolites and their mixtures with inorganic salts, such as sodium sulfate, can be used for the same purpose, the grain size and the bulk density of these spray products being within the usual range.
  • powdery precursors for example finely crystalline zeolites or crystalline, water-soluble carrier salts
  • treats them with liquid or melted nonionic surfactants under granulating conditions ie with the powder particles being glued and cemented into larger granules, usually granules with a very uneven grain spectrum and reduced pouring properties are obtained.
  • the absorption capacity of such granules for nonionic surfactants is considerably lower than that of sprayed carrier grains.
  • nonionic surfactants of the polyglycol ether derivative type is the formation of highly viscous gels if they are mixed with water in a ratio of NT: water such as 5: 1 to 1: 2.
  • Such gels arise e.g. B. if nonionic surfactants are incorporated into the detergent slurry before spray drying. There they lead to a considerable increase in viscosity and thus put a strain on the spray drying process, since water is first added in order to reduce the viscosity and this has to be evaporated again in the subsequent drying process with increased effort.
  • the gels also form in the wash liquor when dissolving wash pastes containing high levels of nonionic surfactants.
  • tough chunks of mucus can form, which dissolve only very slowly or, if they sink to the bottom, not at all in the wash liquor. They can also form on the surface of detergent particles with nonionic surfactants adsorbed thereon, for example on the above-mentioned carrier grains, if these carrier grains or their mixtures with other detergents are dissolved in water.
  • the gels deteriorate the detergent behavior of the detergents, ie considerable amounts of detergent can remain undissolved in the dosing chambers of the washing machines. The tendency of the nonionic surfactants to form gels is therefore considered undesirable in specialist circles, and efforts are concentrated on preventing their formation in detergent production as well as in use as far as possible.
  • the invention relates to a process for the production of free-flowing granules with a high bulk density, containing nonionic surfactants from the class of polyglycol ether derivatives and finely divided, water-insoluble and, if appropriate, water-soluble solids and water, characterized in that (A) the nonionic surfactant is mixed with water which, if appropriate a part, but less than 50 wt .-% of the total amount of water-insoluble or water-soluble solids in dispersed or dissolved form, mixed until a viscous gel phase is formed, whereupon (B) the water-insoluble or water-soluble solids, optionally the most of the remaining amount, mixed in solid, powdery form and mechanically processed until the formation of granules, the weight ratio of nonionic surfactant and water to total solids present (calculated as anhydrous substance) being 25: 75 to 65 35.
  • the weight ratio of nonionic surfactant and water in the gel phase (A) to total solids present (calculated as anhydrous substance) is 30:70 to 60:40.
  • 0 to 40% by weight, preferably 0 to 30% by weight .-% and in particular 5 to 25 wt .-% of the total solids used as an aqueous solution and / or aqueous dispersion in the formation of the gel phase (A) and the remaining main amount is added as a dry powder in the granulation phase (B) and granulated.
  • Suitable nonionic surfactants are alkoxylation products with 10 to 20 carbon atoms in the hydrophobic radical and 3 to 20 glycol ether groups. These include ethoxylation products of alcohols, vicinal diols, amines, thioalcohols, fatty acid amides and fatty acids. Alkylphenol polyglycol ethers with 5 to 12 carbon atoms in the alkyl radical and 3 to 15 ethylene glycol ether groups can also be used. The ethoxylates mentioned can also contain glycol ether groups derived from propylene oxide, for example as block groups or in statistical distribution. Finally, block polymers of ethylene oxide and propylene oxide, which are commercially available under the name Pluronics, are also suitable.
  • liquid to pasty nonionic surfactants derived from alcohols with 12 to 18 carbon atoms are preferred. These alcohols can be saturated or linearly olefinically unsaturated or methyl-branched in the 2-position (oxo radical). Examples of these are C12 ⁇ 18 coconut alcohol with 3 to 12 EO, C16 ⁇ 18 tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO and ethoxylation products of corresponding chain and EO distribution available from other native fatty alcohol mixtures. From the series of ethoxylated oxo alcohols, for example, those of the composition C12 ⁇ 15 with 3 to 10 EO and C14 - C15 with 5 to 12 EO are suitable.
  • Mixtures of low and highly ethoxylated alcohols are distinguished by an increased detergency against both greasy and mineral soiling, for example those made from tallow alcohol with 3 to 6 EO and tallow alcohol with 12 to 16 EO or C13 ⁇ 15 oxo alcohol with 3 to 5 EO and C12 ⁇ 14 oxo alcohol with 8 to 12 EO.
  • Ethoxylates which contain EO groups and PO groups are also suitable, e.g. B. C12 ⁇ 18 alcohols of the formula R- (PO) a - (EO) b or R- (EO) b - (PO) c , in which a numbers from 1 to 3, b such from 3 to 20 and c those from 1 to 10 (b greater than a or c) mean.
  • Preferred solids are water-insoluble compounds and their mixtures with water-soluble salts. In a further preferred version, at least 50% by weight of the solids consist of finely divided water-insoluble solids.
  • Silicic acid and silicates preferably zeolites and layered silicates (bentonites) and mixtures thereof are suitable as finely divided, water-insoluble solids (constituent of the granulation phase B and optionally the gel phase A).
  • Their grain size is preferably less than 100 »m, in particular less than 50» m.
  • Suitable zeolites are those of the zeolite A type. Mixtures of zeolite NaA and NaX can also be used, the proportion of the zeolite NaX in such mixtures advantageously being less than 30%, in particular less than 20%. Suitable zeolites have no particles larger than 30 »m and consist at least 80% of particles smaller than 10» m. Their average particle size (volume distribution, measurement method: Coulter Counter) is 1 to 10 »m. Their calcium binding capacity, which is determined according to the information in DE 24 12 837, is in the range from 100 to 200 mg CaO / g.
  • Suitable layered silicates are of natural and synthetic origin, such as those used for. B. from DE 23 34 899 B2, EP 26 529 A1 and DE 35 26 405 A1 are known. Their usability as carrier material is not limited to a special composition or structural formula.
  • Usable representatives of this class are also the salts of organic polyacids or polymeric acids, such as sodium nitrilotriacetate, sodium citrate, sodium carboxymethyl cellulose, sodium polyacrylate and the sodium salts of copolymers of acrylic acid and maleic acid.
  • Such salts generally cause a very strong increase in viscosity in aqueous solution with increasing concentration. They are preferably used together with water-insoluble solids. In this case, their proportion, based on the total solids present, can be up to 50% by weight, preferably up to 35% by weight.
  • water-soluble salts can also be used or used instead of the aforementioned polyanionic salts, which can be characterized as strongly polar, are essentially mono-anionic or dianionic and have only a small concentration in aqueous solution with increasing concentration Cause an increase in viscosity.
  • Typical representatives of this class are sodium sulfate, sodium carbonate, sodium acetate, sodium nitrate and sodium chloride as well as corresponding potassium salts.
  • their proportion, based on the total solids present can be at most 35% by weight, preferably at most 25% by weight and in particular less than 20% by weight.
  • anionic, zwitterionic, ampholytic or cationic surfactants can be added to the gel phase as solids.
  • suitable anionic surfactants are soaps derived from saturated or monounsaturated C12 ⁇ 22 fatty acids, alkylbenzenesulfonates with a linear C9 ⁇ 13 alkyl group, salts of alpha sulfofatty acids derived from saturated or monounsaturated C12 ⁇ 18 fatty acids and their esters with saturated C1 ⁇ 3 alcohols, C12 ⁇ 18 alkanesulfonates, C12 ⁇ 18 olefin sulfonates and C12 ⁇ 18 alkyl sulfates or alkyl ether sulfates, the surfactants mentioned preferably being in the form of Na salts.
  • the proportion of these surfactants can be up to 25% by weight, preferably up to 15% by weight, of the solids.
  • the weight ratio of nonionic surfactant to anionic surfactant should not be less than 3: 2 and should preferably be less than 2: 1. Higher proportions of anionic surfactants can impair the formation of the gel phase or hinder the conversion of the gel phase into granular, free-flowing granules.
  • solids can be incorporated into the gel phase (A) or added in the granulation phase (B), which are usually contained in small amounts in detergents and cleaning agents, such as optical brighteners, graying inhibitors, complexing agents, dyes, pigments, enzymes, defoamers and fragrances. Their proportion is generally less than 1% by weight, which is why they do not adversely affect the conversion of the gel phase into the granules.
  • detergents and cleaning agents such as optical brighteners, graying inhibitors, complexing agents, dyes, pigments, enzymes, defoamers and fragrances.
  • Their proportion is generally less than 1% by weight, which is why they do not adversely affect the conversion of the gel phase into the granules.
  • the nonionic surfactant is expediently not only mixed with water, although this is fundamentally possible, but an aqueous solution or dispersion is preferably used which already contains part of the total solids or solid mixtures to be used. If zeolite is used as a solid, the preparation of the gel phase is preferably based on a stabilized aqueous dispersion (master batch) as described in DE 25 27 388.
  • Such dispersions which are obtained as water-moist filter cakes in the zeolite synthesis, usually contain 35 to 55% by weight, preferably 40 to 50% by weight, of zeolite, calculated as anhydrous active substance (ie dewatered at the annealing temperature), 0.5 to 5 % By weight, preferably 1 to 4% by weight, of a dispersion stabilizer, in particular a nonionic surfactant, and water (difference up to 100%).
  • aqueous solutions of alkali silicates e.g. B. water glass solutions
  • anionic surfactants or mixtures of such solutions can be used to form the gel phase.
  • the granules can be produced in conventional mixing and granulating devices, for example in cylindrical, horizontally or inclinedly arranged mixers with an axial, rotatable shaft, to which stirring and mixing elements are attached. You can add the nonionic surfactant and add the water or a water-containing solid mixture and mix until gel formation or in reverse order. With further mixing, the dry, powdery solid component is then added to the gel formed and the mixing is continued until the desired granules have formed.
  • the gelling of the gel phase (A) often takes some time, for example 10 to 30 seconds, to reach the maximum viscosity, in many cases it is also possible to work in such a way that the powdery solid component is placed in the mixer and immediately before prepared, still flowable gel phase is added and the mixing also continues until the formation of free-flowing granules.
  • the variants mentioned can be carried out batchwise or continuously. In the discontinuous mode of operation, it is fundamentally possible and preferred to add the solids completely and not in portions over a longer period of time, which simplifies the method of operation.
  • the mixing and granulation can be carried out at room temperature, for example at 15 to 30 ° C. It is not necessary to heat or cool during processing.
  • the granules are formed spontaneously and require no special measures other than stirring or mixing.
  • the time until the formation of the uniform granules depends to a certain extent on the total amount of solids, in particular, however from the proportion of powdery solids added and is from 30 to 3 minutes for solids additions of 35 to 50% by weight, based on the finished granules.
  • the granulation time increases exponentially and takes 10 to 15 minutes for solids contents of 65 to 75% by weight. In general, higher solids contents than 75% by weight are not necessary and in many cases are not appropriate either. Furthermore, it is neither necessary nor advantageous to continue mixing after the formation of uniform, free-flowing granules.
  • the procedure is expediently such that granulation is continued until the bulk density of the granules has reached a maximum.
  • This maximum is also characterized by an optimal grain structure and flowability and can be determined by a simple preliminary test if necessary. This state is easily recognizable visually, since the granules appear particularly uniform in the mixer and trickle easily and no material adheres to the mixer wall or the mixing tools. At the same time, this condition is characterized by a minimal power requirement for operating the mixer and can also be easily determined in this way.
  • the granules can be removed from the mixer without residue and removed from the outflow opening.
  • the inside wall of the empty mixer and the mixing tools are usually bare afterwards. This effect is extremely surprising, especially when you recall the initial stage when the gel sticks to the tools and the mixer shaft as a tough, pasty or lumpy mass.
  • the granules produced in the manner indicated are extremely free-flowing and generally do not require any aftertreatment or drying. If a lower water content of the granules is desirable, for example if they are to be mixed further with moisture-sensitive components or powder mixtures, drying can also be connected. This drying can take place, for example, in a fluidized bed dryer. In this case it is not necessary to use heated air. Furthermore, the resulting or the after-dried granules can also be dusted or coated with other powdery constituents, such as finely divided silica or pigments (including colored ones).
  • other powdery constituents such as finely divided silica or pigments (including colored ones).
  • the method offers further advantages in that it permits the gentle processing of those substances which lose their effect when spray-dried or which interact with other substances.
  • the decomposable or ineffective additives include enzymes, bleaching agents, bleach activators, foam inhibitors and fragrances. Mixtures of zeolite and alkali silicate, which react during spray drying to form coarse-grained and poorly redispersible agglomerates, can be processed well together without these disadvantages.
  • both a laboratory mixer with a capacity of 2 liters and a mixer (type: Lödige) with a capacity of 135 liters were used. Both mixers consisted of a cylindrical, horizontally arranged container with an axially arranged shaft equipped with mixing blades. Their rotation speed was 300 rpm in the laboratory mixer and 120 rpm in the large mixer. With regard to the mode of operation, the time required for granulation and the properties of the granules, there were no significant differences in the two test series. In the following examples, “GT” stands for parts by weight, "sec” for seconds. 1.
  • the increase in bulk density (in g / l) as a function of the granulation time in seconds after adding the dry zeolite was as follows: sec 20th 30th 40 50 60 70 80 100 g / l 650 730 790 835 875 900 900 840 After 50 seconds, the granules were already free-flowing. Up to a mixing time of 70 seconds, ie until the maximum is reached Bulk density, the flowability increased still further. After mixing for a long time, the granules softened and clumped, at the same time the bulk density decreased again and the energy requirement of the mixer increased. The granules obtained after mixing times of 60 seconds had the following grain spectrum, determined by sieve analysis.
  • the granules obtained after a granulation time of 50 seconds had a bulk density of 660 g / l. 3.
  • the granules produced with the addition of 50 pbw of spray-dried zeolite within 50 seconds had a bulk density of 840 g / l. 4.
  • a gel obtained by mixing 20 pbw of the fatty alcohol ethoxylate used in Example 1, 20 pbw of aqueous zeolite dispersion and 10 pbw of a water glass solution (Na2O: SiO2 1: 3.3, water content 65.5% by weight) was granulated with the addition of 50 pbw of spray-dried zeolite over the course of 60 seconds.
  • the free-flowing granules which disintegrate quickly in water and show no signs of agglomerate formation, had a bulk density of 850 g / l. 7.
  • aqueous surfactant slurry containing 31% by weight of a mixture of alpha-sulfofatty acid methyl ester (Na salt) and alpha-sulfofatty acid (di-Na salt) from saturated C16 ⁇ 18 fatty acids (Mixing ratio mono-Na salt to di-Na salt 4: 1), a gel was prepared.
  • Example 1 was repeated in a granulating mixer (Lödige mixer (R) ) with a capacity of 135 liters in such a way that the mixer was first filled with the spray-dried zeolite powder.
  • the fatty alcohol ethoxylate was premixed with the aqueous zeolite dispersion and the gel which formed was transferred to the granulating mixer in the flowable state within 10-15 seconds.

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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)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Medicinal Preparation (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Glanulating (AREA)
  • Colloid Chemistry (AREA)
  • Cosmetics (AREA)

Claims (10)

  1. Procédé de fabrication de granulés à bonne capacité à ruisseler à densité apparente élevée contenant des tensioactifs non ioniques de la classe des dérivés de polyglycoléthers ainsi que des solides finement divisés, insolubles dans l'eau et hydrosolubles le cas échéant et de l'eau, caractérisé en ce que (A) on mélange le tensioactif non ionique à l'eau qui contient une partie le cas échéant, en tout cas moins de 50 % de la quantité totale des solides insolubles ou hydrosolubles sous forme dispersée ou dissoute, jusqu'à formation d'une phase gel visqueuse, après quoi (B) on ajoute par mélange les solides insolubles dans l'eau ou hydrosolubles, le cas échéant la majorité de ces produits qui restent, sous forme de poudre, de solide et on traite mécaniquement pour former des granulés, la proportion pondérale du tensioactif non ionique et de l'eau au total des solides présents (calculé sous forme de substance anhydre) est le 25 : 75 à 65 : 35.
  2. Procédé selon la revendication 1, caractérisé en ce que la proportion du tensioactif et de l'eau dans la phase gel (A) au total des solides présents est de 30 : 70 à 60 : 40.
  3. Procédé selon la revendication 1 et 2, caractérisé en ce qu'on utilise 0 à 40 % en poids, de préférence de 0 à 30 % en poids et notamment 5 à 25 % en poids de la totalité des solides utilisés lors de la formation de la phase gel (A) et qu'on ajoute par mélange la majorité restante sous forme de poudre sèche dans la phase granulée (B).
  4. Procédé selon la revendication 3, caractérisé en ce qu'on utilise des solides insolubles dans l'eau d'une granulométrie inférieure à 100 »m, de préférence inférieure à 50 »m.
  5. Procédé selon la revendication 4, caractérisé en ce qu'on utilise comme solide insoluble de la zéolithe finement cristallisée , de la bentonite ou leurs mélanges.
  6. Procédé selon la revendication 1 à 4, caractérisé en ce qu'on mélange le mélange de la phase gel avec le solide en poudre jusqu'à ce que la densité apparente du granulé qui se forme ait atteint un maximum.
  7. Procédé selon l'une ou plusieurs des revendications 1 à 4, caractérisé en ce qu'on mélange le tensioactif non ionique à une dispersion aqueuse de zéolithe finement cristallisée en formant la phase gel, la dispersion aqueuse comprenant 35 à 55 % en poids de zéolithe, rapportée à la substance anhydre, 0,5 à 5 % en poids d'un tensioactif non ionique agissant comme stabilisant de la dispersion et 64,5 à 40 % d'eau.
  8. Granulés préparés selon l'une ou plusieurs des revendications 1 à 6.
  9. Granulés selon la revendication 8, caractérisé par une densité apparente de 600 à 1000 g/l, de préférence de 650 à 900 g/l.
  10. Produit lessiviel et nettoyant granulaire contenant des granulés selon les revendications 8 à 9.
EP89911804A 1988-10-21 1989-10-12 Procede pour fabriquer des granules tensio-actifs Expired - Lifetime EP0536110B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE3835918 1988-10-21
DE3835918A DE3835918A1 (de) 1988-10-21 1988-10-21 Verfahren zur herstellung von tensidhaltigen granulaten
PCT/EP1989/001206 WO1990004629A2 (fr) 1988-10-21 1989-10-12 Procede pour fabriquer des granules tensio-actifs

Publications (2)

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EP0536110A1 EP0536110A1 (fr) 1993-04-14
EP0536110B1 true EP0536110B1 (fr) 1995-01-25

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EP89911804A Expired - Lifetime EP0536110B1 (fr) 1988-10-21 1989-10-12 Procede pour fabriquer des granules tensio-actifs
EP89118962A Pending EP0364881A3 (fr) 1988-10-21 1989-10-12 Préparation de granulés contenant des agents tensio-actifs

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EP89118962A Pending EP0364881A3 (fr) 1988-10-21 1989-10-12 Préparation de granulés contenant des agents tensio-actifs

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US (1) US5354493A (fr)
EP (2) EP0536110B1 (fr)
JP (1) JP2704020B2 (fr)
KR (1) KR970001224B1 (fr)
AT (1) ATE117718T1 (fr)
DE (2) DE3835918A1 (fr)
DK (1) DK71791A (fr)
ES (1) ES2067569T3 (fr)
PT (1) PT92060A (fr)
TR (1) TR24142A (fr)
WO (1) WO1990004629A2 (fr)

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3943019A1 (de) * 1989-12-27 1991-07-04 Henkel Kgaa Granulares, avivierend wirkendes waschmitteladditiv und verfahren zu seiner herstellung
KR0170424B1 (ko) * 1990-07-05 1999-01-15 호르스트 헤를레,요한 글라슬 세제 및 청정제용 표면 활성제 과립의 제조방법
US5108646A (en) * 1990-10-26 1992-04-28 The Procter & Gamble Company Process for agglomerating aluminosilicate or layered silicate detergent builders
DE4110510A1 (de) * 1991-03-30 1992-10-01 Henkel Kgaa Niederalkalische, chlor- und phosphatfreie maschinengeschirrspuelmittel in form von schwerpulvern und -granulaten
DE4127323A1 (de) * 1991-08-20 1993-02-25 Henkel Kgaa Verfahren zur herstellung von tensidgranulaten
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WO1990004629A2 (fr) 1990-05-03
ES2067569T3 (es) 1995-04-01
JP2704020B2 (ja) 1998-01-26
PT92060A (pt) 1990-04-30
TR24142A (tr) 1991-04-09
WO1990004629A3 (fr) 1991-05-30
EP0364881A3 (fr) 1990-06-06
DE3835918A1 (de) 1990-04-26
EP0536110A1 (fr) 1993-04-14
EP0364881A2 (fr) 1990-04-25
DE58908952D1 (de) 1995-03-09
ATE117718T1 (de) 1995-02-15
JPH04501129A (ja) 1992-02-27
KR900701988A (ko) 1990-12-05
US5354493A (en) 1994-10-11
DK71791D0 (da) 1991-04-19
KR970001224B1 (en) 1997-02-04
DK71791A (da) 1991-04-19

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