EP0185660B1 - Suspension aqueuse, stabilisee a base de zeolithe - Google Patents

Suspension aqueuse, stabilisee a base de zeolithe Download PDF

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Publication number
EP0185660B1
EP0185660B1 EP84903064A EP84903064A EP0185660B1 EP 0185660 B1 EP0185660 B1 EP 0185660B1 EP 84903064 A EP84903064 A EP 84903064A EP 84903064 A EP84903064 A EP 84903064A EP 0185660 B1 EP0185660 B1 EP 0185660B1
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EP
European Patent Office
Prior art keywords
suspension
zeolite
weight
suspensions
acid
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
Application number
EP84903064A
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German (de)
English (en)
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EP0185660A1 (fr
Inventor
Elmar Wilms
Karl-Dieter Herold
Rainer Salz
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Priority claimed from DE19833330220 external-priority patent/DE3330220A1/de
Priority claimed from DE19843423351 external-priority patent/DE3423351A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT84903064T priority Critical patent/ATE32328T1/de
Publication of EP0185660A1 publication Critical patent/EP0185660A1/fr
Application granted granted Critical
Publication of EP0185660B1 publication Critical patent/EP0185660B1/fr
Expired legal-status Critical Current

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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
    • C11D3/02—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
    • C11D3/02—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
    • C11D3/1286—Stabilised aqueous aluminosilicate suspensions

Definitions

  • the invention relates to a stabilized, aqueous suspension of synthetically produced zeolite of type A, a process for the production of this suspension on an industrial scale and the use of the suspension for the production of low-phosphate and phosphate-free powdered detergents and cleaning agents.
  • type A synthetic zeolites in particular NaA zeolite
  • sodium tripolyphosphate in detergents and cleaning agents has become increasingly important in recent years.
  • Numerous zeolite-containing detergents with low-phosphate and phosphate-free formulations have already appeared on the market.
  • zeolite A as a novel water-insoluble detergent component on an industrial scale has also led to new developments in detergent technology;
  • the processing of the zeolite as a storage-stable, free-flowing suspension with the highest possible zeolite content should be emphasized here.
  • zeolite-containing detergents in particular using stabilized zeolite suspensions, see above Koch, Seifen- ⁇ le-Fette-Wwachs, 106 (1980), pages 321 to 324.
  • the stabilizers of DE-OS-25 27 388 together with a stabilizing aid from the group of non-surfactant organic and inorganic water-soluble salts with molecular weights below 1,000, z. B. sodium sulfate, sodium citrate, sodium tripolyphosphate, sodium carbonate, etc. used; this gives greater flexibility in adapting the viscosity of the suspensions to the storage and processing conditions.
  • German Offenlegungsschrift 30 21 295 recommends the use of nitrilotriacetate sodium salt; on the other hand, water glass solutions, gel-like aluminum oxides or silicon oxides, soaps of chain length C 5 -C 22 , or sodium salts of the type of washing alkalis, including sodium hydroxide, are described in Japanese laid-open patent applications 54 064 504, 55 127 499, 57 034 017, 57 061 615 and 57 067 697 proposed.
  • the requirements for the properties of the zeolite suspensions depend to a certain extent on the type of washing and cleaning agents for which they are to be used; However, it has been found that, in order to be usable on an industrial scale, the zeolite suspensions should have the following individual properties: stability in the widest possible temperature range, which ranges from room temperature or below to at least 70 ° C .; a sediment, if it arises after prolonged storage, must be able to be stirred up again using technical stirrers; the viscosity should remain low even in the lower temperature range, i. H.
  • the proportions of the stabilizer system consisting of the suspension stabilizer and the stabilizing aid in the suspension according to the invention are preferably in the range from 0.5 to 5% by weight. Amounts of 1 to 3% by weight and in particular those of 1.5 to 2.5% by weight, based in each case on the stabilized aqueous zeolite suspension, are particularly preferred. Within these quantitative ranges, the ratio of the nonionic surfactant to the anionic sulfate surfactant is in the range from 5: 1 to 1: 5, and preferably in the range from 3: 1 to 1: 1.
  • the suspension according to the invention is low-viscosity over the entire temperature range from room temperature to 80 ° C. and can be stirred and pumped without problems.
  • Room temperature is understood here to mean the temperatures in the storage and processing rooms, which fluctuate between 15 and 25 ° C, depending on the season. Even after storage for several days in this temperature range, in particular at elevated temperatures of 50 to 70 ° C., only a slight, soft sediment is formed which can be easily stirred up again.
  • the suspension according to the invention also shows excellent rheological properties, which are characterized above all by a narrow viscosity range and by perfect flow behavior.
  • the zeolite suspension In some technical processing equipment for zeolite suspensions for the production of powder detergents, the zeolite suspension must be warmed up, i.e. H. above room temperature. It is then crucial for usability that the suspension remains stable over a longer period of time at elevated temperature and does not disintegrate.
  • the pH value of the aqueous zeolite suspension which is at pH 11 to 14, is not significantly changed by the stabilizer system according to the invention consisting of nonionic surfactant and anionic sulfate surfactant.
  • the pH fluctuations caused by the free alkali present in industrial production have a significantly reduced influence on the stability of the suspension when the stabilizer system according to the invention is used.
  • the further reduction in viscosity is achieved by a targeted lowering of the pH by adjusting the suspensions to a pH of less than 12, in particular from 9 to 11, and adjusting this pH by adding an acidic salt.
  • the addition of acidic salt is generally in the range from 0.2 to 3% by weight, based on the finished suspension in which this salt is then present as a neutral salt.
  • the stabilizer system according to the invention has no negative influence on the calcium binding capacity of the zeolite.
  • the stabilizer system according to the invention consists of a mixture of detergent substances known per se;
  • the zeolite suspension stabilized with it is therefore not only useful for the production of a large number of detergents and cleaning agents, but these detergent active substances reaching the finished detergents and cleaning agents via the zeolite suspension make a contribution to the washing and cleaning success of the finished product .
  • the neutral salts formed from the acidic salts are also generally used as components of detergents and cleaning agents.
  • Aqueous zeolite suspensions with an addition of dispersants from the group of the water-soluble nonionic surfactants and the synthetic organic surfactants of the sulfonate type are known from US Pat. No. 3,254,034 (Dwyer et al). These known zeolite suspensions are used to exchange the sodium cations for the cations of the rare earths and then to process the exchanged zeolites into catalysts. In these known suspensions, which are constantly moved, special storage stability is not important; It is important, however, that only readily soluble compounds which can be easily separated off again after the cation exchange by filtration can be considered as organic additives.
  • the nonionic surfactant defined above is generally in amounts of 0.2 to 3% by weight and the stabilizing aid in accordance with a) and / or b) as defined above in amounts of 0.2 to 3 wt .-% present, the total amount of nonionic surfactant and stabilizing aid in the range 0.5 to 5 wt .-%, based on the stabilized zeolite suspension.
  • the maximum amounts mentioned in order to achieve the improved viscosity and storage properties, it is not necessary to add the maximum amounts mentioned; rather, total quantities of up to 2.5% by weight are sufficient for most further processing purposes.
  • the pH of aqueous zeolite suspensions which do not contain a stabilizer or a stabilizer which does not influence the pH is from pH 11 to pH 14, i.e. H. there is an excess of alkali. This alkali excess is often welcomed for further processing into detergents and cleaning agents because it enters the final detergent product as an alkali reserve. If the pH value is lowered by the further addition of the acid salt, the corresponding neutral salts are formed which, when the acid salts are selected appropriately, are also considered to be typical detergent and cleaning agent constituents because they impart advantageous properties to the finished product.
  • German Offenlegungsschrift 25 14 399 proposes adding acid to the suspension of a large-scale zeolite to lower the pH to 8.5 to 11 before the subsequent drying to a zeolite powder, in order to avoid excessive agglomeration of the zeolite -Avoid particles during drying and the formation of oversize (grit).
  • German Offenlegungsschrift 27 04 310 a production method for zeolite NaA is described, in which prior to increasing the volume / time - yield operates with an increased alkali content and the alkali excess after the crystallization step by washing with water or the addition of free acid removed .
  • German Offenlegungsschrift 26 52 409 recommends adding acid or an acid salt to the freshly prepared zeolite suspension to such an extent that the pH does not drop below 9.0. This measure improves the buffering capacity of the zeolite.
  • the references mentioned also explain that special precautions must be taken when admixing the acid so that there is no local over-concentration of acid and the acid-sensitive zeolite structure is not destroyed.
  • German Offenlegungsschrift 26 15 698 describes the addition of a non-surfactant, organic or inorganic low molecular weight salt as a stabilization aid to a stabilized zeolite suspension, but also the European patent application EP-A-870 describes the improvement of the rheological properties of zeolite suspensions the addition of sodium sulfate neutral salt is known, but this prior art, either as a single document or together, does not suggest adding an acidic salt for targeted pH adjustment to an aqueous zeolite suspension already stabilized by a stabilizer system comprising a nonionic and a sulfate surfactant , and so to arrive at the desired narrow range of low viscosity, which is not very temperature-dependent.
  • the constituents of the stabilizer system of the anionic sulfate surfactants according to a) are preferably the sulfuric acid monoester of a primary C 12 -C 18 alkanol in the form of the water-soluble salt, and as sulfate surfactant according to b) preferably the sulfuric acid monoester of a primary C 12 -C 1S - reacted with ethylene oxide Alkanol, also in the form of the water-soluble salt, used.
  • the degree of ethoxylation of the sulfate surfactants according to b) is generally on average 1 to 15 moles of ethylene oxide per mole of the alkanol, preferably 1 to 4 moles of ethylene oxide.
  • the C 12 -C 1S fatty alcohols which can be prepared from natural fats are particularly preferred.
  • Derivatives of this type combine the particularly good stabilizing properties with those of perfect biodegradability and good accessibility from natural renewable raw materials.
  • Typical representatives of the sulfate surfactants used according to the invention are, for example, the products tallow alcohol sulfate (TAS) (where "tallow alcohol” stands for the hydrogenated tallow fat-alcohol mixture of the chain length range C 14 -C 18 ); Lauryl alcohol sulfate; Coconut alcohol sulfate (KOAS) (where "coconut alcohol” stands for the C t2 / C t8 cut from natural coconut fatty alcohol ); Lauryl alcohol ether sulfate (LAES) (made from a C 12 / C 14 fatty alcohol reacted with 2 to 3 moles of ethylene oxide); coconut / tallow alcohol sulfate (made from coconut and tallow alcohol in a 1: 1 ratio); Cetyl / stearyl alcohol sulfate (Applicant's Lanette E product); Tallow alcohol 2EO sulfate.
  • TAS tallow alcohol sulfate
  • tallow alcohol stands for the hydrogenated
  • the practically water-insoluble nonionic surfactants used as suspension stabilizers are compounds whose cloud point, when determined according to method DIN 53917 in aqueous butyl diglycol solution, is 90 ° C. and below, preferably 85 ° C. and below .
  • These nonionic surfactants are described in detail in German Offenlegungsschriften 25 27 388 and 26 15 698. Typical representatives for these practically water-insoluble nonionic surfactants, which are known as have proven particularly useful, e.g. B.
  • the compounds tallow alcohol polyglycol ether with 5 moles of ethylene oxide (TA 5EO); Coconut alcohol (C 12 -C 1S cut ) polyglycol ether with 4 moles of ethylene oxide; Oleyl alcohol polyglycol ether with 5 moles of ethylene oxide; Oleyl / cetyl alcohol polyglycol ether with 7 moles of EO (made from an alcohol mixture with an iodine number of 50 to 55); C 14 -C 15 oxo alcohol polyglycol ether with 4 moles of EO; Nonylphenol polyglycol ether with 5 moles of ethylene oxide.
  • TA 5EO ethylene oxide
  • Oleyl alcohol polyglycol ether with 5 moles of ethylene oxide Oleyl / cetyl alcohol polyglycol ether with 7 moles of EO (made from an alcohol mixture with an iodine number of 50 to 55
  • the amount of the acid salt is generally in the range from 0.2 to 3% by weight, based on the finished suspension. In individual cases, the additional quantities can also be above or below these range limits. In any case, the amount of acid salt added depends on the pH of the moist zeolite filter cake or the zeolite suspension at the end of the zeolite production process. The pH value is therefore not only dependent on the choice of the zeolite production process, but also on the degree of washing out of the zeolite with water.
  • the acidic salt is added in solid form or in the form of a concentrated aqueous solution in small portions with stirring.
  • Acid salts which can be used according to the invention are primarily inorganic acid salts, in particular the acid salts of sulfuric acid, carbonic acid, phosphoric acid and polyphosphoric acids, boric acid and silica.
  • Usable, although less preferred, are the acidic salts of polyvalent organic acids, such as. B. citric acid, diglycolic acid, gluconic acid, polyacrylic acid, nitrilotriacetic acid, hydroxyethane diphosphonic acid and analogous hydroxyalkane or aminoalkane polyphosphonic acids.
  • Acid salts of other inorganic and organic acids are also suitable; however, those acidic salts are preferred which are present after the partial neutralization as such neutral salts which play an advantageous role in building up the detergent and cleaning agent or during the washing or cleaning process.
  • Acid salts are accordingly the salts of polyvalent acids which have at least one alkali or ammonium cation and react with the alkali in the aqueous zeolite suspension with partial neutralization.
  • the zeolite A used according to the invention can be prepared by numerous known processes by hydrothermal synthesis from sodium silicate and sodium aluminate solutions or from destructured kaolin and sodium hydroxide.
  • a number of processes have become known for the industrial production of zeolite A for detergent purposes, in which the zeolite A crystals are formed with rounded corners and edges and the formation of oversize (grit) is avoided by specific process parameters.
  • Such methods are described, for example, in German Offenlegungsschriften 24 47 021, 25 17 218, 25 33 614, 26 51 419, 28 51 420, 26 51 436, 26 51 437, 26 51 445, 26 51 485, 27 04 310, 27 34 296, 29 41 636, 30 11 834. 30 21 370.
  • zeolite A is generally obtained as a moist filter cake with about 50 to 60% water content. Because of its thixotropic properties, this filter cake can be easily stirred immediately after production and mixed directly with the suspension stabilizer.
  • the suspensions according to the invention can be prepared by simply mixing the components.
  • the aqueous suspension of the zeolite which is still moist and undried from its production, is preferably used by converting the moist filter cake obtained after separating the mother liquor and washing with water into a flowable suspension by stirring. A further addition of water is generally not necessary.
  • the stabilizers are used in the case of nonionic surfactants in undiluted form and in the case of anionic sulfate surfactants in the form of the commercially available technical aqueous concentrates of the sodium salts or as granules, flakes or pasta.
  • the acidic salts are usually added in powder form.
  • the amount of water additionally introduced with paste-like concentrates is small in quantity, so that it does not significantly influence the zeolite concentration in the stabilized suspension.
  • the suspensions according to the invention can be prepared with zeolite concentrations of at least 20% by weight; however, for economic reasons, i.e. H. at z. B. to save transport and energy costs, set the water content in the suspensions as low as possible. For example, efforts will be made to adjust the zeolite content to values above 40% by weight and, if possible, to values around 50% by weight.
  • the suspensions according to the invention are generally prepared at elevated temperatures, ie. H. at approx. 50 ° C, which speeds up the mixing process.
  • an already dried zeolite powder can also be used for the production of the suspensions according to the invention if the zeolite filter cake which is still moist from the production is not available.
  • the stabilized zeolite suspensions are used as a liquid raw material according to the usual manufacturing processes for such agents.
  • the use of the stabilized zeolite suspensions for the production of powdered detergents by the method of hot spray drying is of particular technical importance, the so-called slurry batch being produced with the zeolite suspension and then converted into a detergent powder in the usual manner in spray towers.
  • the suspension according to the invention can also be converted into a spray-dried powder as such or after the addition of further detergent substances. It was found as a special property of the spray-dried suspension that the resulting powder product can be stirred up again with water to form a stable suspension, which increases the practical application possibilities for the suspension according to the invention.
  • Stabilizer system composed of nonionic surfactant and anionic sulfate surfactant
  • the Brookfield viscosity was determined: 20 revolutions per minute; Spindle depending on the viscosity range.
  • the viscosity behavior of the suspension according to the invention extends practically over the entire temperature range.
  • Example 1 describe bench tests of three suspensions according to the invention in comparison to a known suspension (see Example 1).
  • the stored suspensions are based on the criteria of sedimentation, i.e. H. Sediment formation, and sediment consistency assessed.
  • the storage tests were carried out at room temperature, 35 ° C, 50 ° C and 70 ° C.
  • the viscosity of the suspensions was also measured at these temperatures before storage; no change in viscosity was observed during the storage period in the case of the completely homogeneous suspensions and in the case of the again stirred suspensions with a soft sediment consistency.
  • TA 5 EO and TAS have the meanings given in Example 1.
  • KOAS coconut oil alcohol sulfate sodium salt (C 14 -C 18 cut ).
  • LAES lauryl alcohol (C 12 / C 14 ) ether sulfate sodium salt (with approx. 2 mol EO).
  • Stabilizer system consisting of nonionic surfactant and anionic sulfate surfactant and with the addition of an acidic salt
  • the stabilized suspension had the following composition:
  • the Brookfield viscosity was determined: 20 revolutions per minute; Spindle depending on the viscosity range.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Saccharide Compounds (AREA)

Claims (11)

1. Suspension aqueuse stabilisée à base de zéolithe, consistant en une zéolithe de type A obtenue industriellement, de l'eau et un système stabilisant, comprenant un agent tensio-actif non-ionique pratiquement insoluble dans l'eau en tant qu'agent stabilisant de la suspension ainsi qu'un adjuvant de stabilisation, caracterisée en ce que l'adjuvant de stabilisation consiste en un agent tensio-actif anionique sulfaté choisi dans le groupe formé par:
a) les mono esters sulfuriques d'alcools primaires à chaîne droite ou ramifiée dont la longueur de chaîne est de C10-C20, de préférence C12-C18 ou les mono esters sulfuriques d'alcools secondaires à chaîne droite ou ramifiée dont la longueur de chaîne est de C10 à C20 sous forme de sels solubles dans l'eau,
b) les produits réactionnels sulfatés des alcools primaires ou secondaires selon a) avec l'oxyde d'éthylène ou des alcanolamides d'acides gras sulfatés ou des monoglycérides d'acides gras sulfatés, sous forme de sels solubles dans l'eau,

ou les mélanges de a) et b).
2. Suspension selon la revendication 1, caractérisée en ce qu'elle contient le système stabilisant en quantité allant de 0,5 à 5 % en poids, de préférence de 1 à 3 % en poids et en particulier de 1,5 à 2,5 % en poids.
3. Suspension selon la revendication 1 ou la revendication 2, caractérisée en ce que le rapport entre l'agent tensio-actif non-ionique constituant l'agent stabilisant de la suspension, et l'agent tensio-actif anionique sulfaté constituant l'adjuvant de stabilisation se situe dans la zone de 5/1 à 1/5, de préférence de 3/1 à 1/1.
4. Suspension selon l'une quelconque des revendications 1 à 3, caractérisée en ce que l'agent tensio-actif non ionique est présent en quantités allant de 0,2 à 3 % en poids et l'adjuvant de stabilisation selon a) et/ou b) en quantités allant de 0,2 à 3 % en poids, pour une quantité totale de 0,5 à 5 % en poids de système stabilisant.
5. Suspension selon l'une quelconque des revendications 1 à 4, caractérisée en ce que la suspension présente une valeur de pH inférieure à 12, en particulier de 9 à 11 et en ce que ce pH est ajusté par addition d'un sel acide.
6. Suspension selon l'une quelconque des revendications 1 à 5, caractérisée en ce que la quantité de sel acide ajoutée rapportée à la suspension totale se chiffre à 0,2 à 3 % en poids.
7. Suspension selon l'une des revendications 1 à 6, caractérisée en ce qu'elle contient en tant qu'agent tensio actif anionique sulfaté selon a) le mono ester sulfurique d'un alcanol primaire en C12-C18 sous forme de sel soluble dans l'eau, ou selon b) le mono ester sulfurique d'un alcanol primaire en C12-C18 ayant réagi en particulier avec 1 à 4 moles d'oxyde d'éthylène, également sous forme de sel soluble dans l'eau.
8. Suspension selon l'une quelconque des revendications 1 à 7, caractérisée en ce qu'elle contient en tant qu'agent tensio actif anionique sulfaté selon a) le mono ester sulfurique d'un alcool gras en C12-C18 sous forme de sel de sodium ou selon b) l'hemi-ester sulfurique d'un alcool gras en C12-C18 ayant réagi en particulier avec 1 à 4 moles d'oxyde d'éthylène, également sous forme de sel de sodium.
9. Suspension selon l'une quelconque des revendications 1 à 8, caractérisée en ce que l'on ajoute en tant que sel acide, en particulier un sel choisi dans le groupe formé par les sels acides de l'acide sulfurique, l'acide carbonique, l'acide phosphorique, les acides polyphosphoriques, l'acide borique et l'acide silicique.
10. Procédé pour l'obtention d'une suspension selon l'une quelconque des revendications 1 à 9, caractérisé en ce que l'on agite le tourteau de filtration de zéolithe encore humide provenant de sa préparation et l'on ajoute l'agent stabilisant sous une forme non-diluée ou en tant que concentré aqueux.
11. Utilisation des suspensions selon l'une quelconque des revendications 1 à 9 pour l'obtention d'agent de nettoyage ou de lavage pulvérulents selon des méthodes connues en soi, en particulier selon la méthode de dessication par pulvérisation à chaud d'un mélange de départ liquide obtenu avec la suspension.
EP84903064A 1983-08-22 1984-08-13 Suspension aqueuse, stabilisee a base de zeolithe Expired EP0185660B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84903064T ATE32328T1 (de) 1983-08-22 1984-08-13 Stabilisierte, waessrige zeolith-suspension.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19833330220 DE3330220A1 (de) 1983-08-22 1983-08-22 Stabilisierte, waessrige zeolith-suspension
DE3330220 1983-08-22
DE19843423351 DE3423351A1 (de) 1984-06-25 1984-06-25 Stabilisierte, waessrige zeolith-suspension
DE3423351 1984-06-25

Publications (2)

Publication Number Publication Date
EP0185660A1 EP0185660A1 (fr) 1986-07-02
EP0185660B1 true EP0185660B1 (fr) 1988-02-03

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US (1) US4529541A (fr)
EP (1) EP0185660B1 (fr)
KR (1) KR850001800A (fr)
AT (1) ATE32328T1 (fr)
AU (1) AU3215784A (fr)
DE (1) DE3469159D1 (fr)
ES (1) ES535309A0 (fr)
FI (1) FI853339A0 (fr)
IT (1) IT1176619B (fr)
WO (1) WO1985001039A1 (fr)

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DE4203789A1 (de) * 1992-02-10 1993-08-12 Henkel Kgaa Verfahren zur stabilisierung von waessrigen zeolith-suspensionen
NZ259340A (en) * 1992-12-15 1996-05-28 Shell Int Research Surfactant composition and preparation containing a secondary alkyl sulphate and a zeolite
DE4303297A1 (de) * 1993-02-05 1994-08-11 Degussa Verfahren zur Verbesserung des Fließverhaltens von Zeolithpulvern
EP0693549A1 (fr) 1994-07-19 1996-01-24 The Procter & Gamble Company Compositions d'activateurs de blanchiment solides
GB2296919A (en) * 1995-01-12 1996-07-17 Procter & Gamble Detergent composition
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AT335035B (de) * 1974-10-10 1977-02-25 Henkel & Cie Gmbh Stabile suspensionen wasserunloslicher, zum binden von calciumionen befahigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln
US4409136A (en) * 1977-01-31 1983-10-11 Colgate Palmolive Company Molecular sieve zeolite-built detergent paste
GB2015488B (en) * 1978-03-02 1982-09-22 Unilever Ltd Stabilised sodium aluminosilicate suspensions
US4264466A (en) * 1980-02-14 1981-04-28 The Procter & Gamble Company Mulls containing chain structure clay suspension aids
US4405483A (en) * 1982-04-27 1983-09-20 The Procter & Gamble Company Stable liquid detergents containing aluminosilicate ion exchange material
US4545919A (en) * 1982-08-31 1985-10-08 Ciba-Geigy Corporation Detergent composition for washing off dyeings obtained with fibre-reactive dyes and washing process comprising the use thereof

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ES8505550A1 (es) 1985-06-01
KR850001800A (ko) 1985-04-01
IT1176619B (it) 1987-08-18
ATE32328T1 (de) 1988-02-15
FI853339L (fi) 1985-08-30
EP0185660A1 (fr) 1986-07-02
AU3215784A (en) 1985-03-29
IT8422372A0 (it) 1984-08-21
FI853339A0 (fi) 1985-08-30
US4529541A (en) 1985-07-16
DE3469159D1 (en) 1988-03-10
ES535309A0 (es) 1985-06-01
WO1985001039A1 (fr) 1985-03-14

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