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WO1990005175A1 - Procede de fabrication de granules de haute densite contenant de la zeolithe - Google Patents

Procede de fabrication de granules de haute densite contenant de la zeolithe Download PDF

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Publication number
WO1990005175A1
WO1990005175A1 PCT/EP1989/001312 EP8901312W WO9005175A1 WO 1990005175 A1 WO1990005175 A1 WO 1990005175A1 EP 8901312 W EP8901312 W EP 8901312W WO 9005175 A1 WO9005175 A1 WO 9005175A1
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WO
WIPO (PCT)
Prior art keywords
weight
zeolite
water
granules
parts
Prior art date
Application number
PCT/EP1989/001312
Other languages
German (de)
English (en)
Inventor
Jochen Jacobs
Ulrich Jahnke
Franz-Josef Carduck
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to KR1019900701431A priority Critical patent/KR900701992A/ko
Publication of WO1990005175A1 publication Critical patent/WO1990005175A1/fr
Priority to DK086891A priority patent/DK86891A/da

Links

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
    • C11D3/37—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

  • the present invention relates to a new production process for zeolite-containing granules with a pronounced adsorption capacity for liquid to waxy active substances.
  • the granules are characterized by a high density, i. H. a bulk density between 750 and 1 000 g / 1 (grams per liter) and are suitable for use in detergents and cleaning agents.
  • DE-A-33 16 513 discloses granules containing fine powdered zeolites and salts of (co) polymeric carboxylic acids produced by spray drying aqueous slurries. They have a bulk density of only 560 - 610 g / 1. A teaching of the content that such granules can be used as carrier material for liquid to waxy detergent components is not to be found in this document.
  • DE-A-34 44 960 describes granules which contain zeolites, salts of (co) polymeric carboxylic acids and additionally small amounts of alkali metal silicates and serve as carrier material for liquid detergent components, in particular nonionics.
  • the bulk density of these granules produced by spray drying is a maximum of 700 g / 1 and is preferably between 500 and 650 g / 1.
  • Document EP-A-149 264 teaches that commercially available spray-dried zeolites or mixtures thereof with inorganic salts, such as sodium sulfate, can be used for the same purpose.
  • the bulk density of this spray pro products is in the range of 400 - 600 g / 1.
  • From EP-A-21 267 agglomerates containing zeolites and alkali metal silicates are known which have a bulk density of 300-700 g / l.
  • a dry premix of zeolite and alkali metal silicate (mixing ratio 1: 1 to 1: 8) is sprayed with water in a granulator and agglomerated, whereupon the excess water to a residual proportion of less than 5% by weight. -% is removed by drying.
  • the granules are also suitable for adsorbing liquid detergent components, in particular from Nonionics.
  • the main disadvantage is their high content of strongly alkaline-reacting alkali silicates, which severely limits their use in neutral to weakly alkaline-reacting detergents suitable for sensitive textiles and furthermore reduces the proportion of zeolite capable of ion exchange.
  • bulk densities of over 700 g / 1 cannot be achieved.
  • the invention relates to a process for the production of granules containing fine crystalline zeolite, sodium or potassium salts of polymeric or copolymeric carboxylic acids and water, characterized in that (a) in a first mixing stage a homogeneous, powdery mixture of zeolite and the salt of the (co) polymeric carboxylic acid, agglomerating this mixture (b) in a second mixing and granulation stage and (c) the agglomerate obtained until a free-flowing mixture is reached Granules with a bulk density of 750-1000 g / 1 after-rocket.
  • the granules which are produced by the process according to the invention generally contain (based on anhydrous substance) 60-80% by weight of zeolite, 2-15% by weight of a sodium salt of (co) polymeric carboxylic acids and 15 25% by weight of water, including the water bound to the zeolite.
  • water-free zeolite is understood to mean a sodium zeolite dewatered at the annealing temperature.
  • Granules with a content of 62-75% by weight, in particular 65-70% by weight of zeolite (calculated as anhydrous) and 4-12% by weight, in particular 5-10% by weight of Na salt (co- ) polymeric carboxylic acids (water content: difference up to 100% by weight) are preferred.
  • the granules For the production of the granules, it is expedient to start from spray-dried, finely powdered zeolite, which generally has a water content of 17-25% by weight, preferably 19-22% by weight.
  • This water includes constitutional water and adhering moisture.
  • 70-95 parts by weight, preferably 75-93 parts by weight and in particular 80-90 parts by weight of this water-containing zeolite are mixed in a mixing device with 2-12 parts by weight, preferably 4-10 parts by weight. parts and in particular 5 - 8 parts by weight of the sodium salt of the polymeric or copoly eric carboxylic acid combined into a homogeneous powder mixture.
  • agglomeration 15-25 parts by weight, preferably 18-23 parts by weight of water are mixed in with constant further mixing.
  • the water is preferably sprayed onto the powder mixture kept in motion by means of nozzles and mechanically processed until granular agglomerates are formed.
  • the still moist but already free-flowing agglomerate is then dried, for example with hot flowing air or with hot combustion gases, the drying being carried out until the water added in the granulation stage to a proportion of less than 5% by weight. divide, preferably less than 3 parts by weight.
  • further water components that were originally introduced with the zeolite or a (co) polymeric salt which is not used anhydrous can be removed during drying.
  • Such "over-dried" granules can have application-technical advantages, for example when added to detergents which contain active ingredients which are sensitive to moisture.
  • the dewatering of the zeolite should preferably not be driven below a water content of 18% by weight in order to avoid a reduction in activity.
  • the water content of the granules is expediently in a range in which the water-binding capacity of the zeolite is largely saturated, ie in which the zeolite has a total water content of 19-22% by weight (including constitutional water).
  • 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 of 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 in accordance with DE 24 12 837 and is based on anhydrous substance, is in the range from 100 to 200 mg CaO / g.
  • Examples of the homopolymeric and / or copolymeric carboxylic acids contained in the granules, in the present case as water-soluble salts, of which the sodium salts are preferred, are polyacrylic acid, polymethacrylic acid and polymaleic acid, copolymers of acrylic acid with methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether , further with vinyl esters, such as vinyl acetate or vinyl propionate, Acryla id, Methacryla id and with ethylene, propylene or styrene.
  • copolymeric acids in which one of the components has no acid function, the proportion thereof in the interest of sufficient water solubility is not more than 50 mol percent, preferably less than 30 mol percent.
  • Copolymers of acrylic acid or methacrylic acid with maleic acid as described in more detail in EP 25 551 B1, for example, have proven to be particularly suitable. These are copolymers which contain 50 to 90% by weight of acrylic acid or methacrylic acid and 50 to 10% by weight of maleic acid. Copolymers in which 45 to 85% by weight of acrylic acid and 55 to 15% by weight of maleic acid are present are particularly preferred.
  • the molecular weight of the homo- or copolymeric polycarboxylates is generally 2,000 to 150,000, preferably 5,000 to 100,000.
  • salts of (co) polymeric carboxylic acids in powder form often contain 5 to 15% by weight of moisture. This proportion of water is included in the calculation of the water balance, or the amount of water introduced into the pelletizing stage can be reduced by this proportion.
  • the proportion of salts in the preparation of the compositions or in the composition of the finished granules is based on anhydrous salt.
  • the granulation can be carried out batchwise or continuously in conventional mixing and granulating devices.
  • B. pelletizers which consist of a horizontally arranged or inclined to the horizontal, cylindrical containers, in the longitudinal axis of which a shaft equipped with mixing tools and conveying blades rotates. The water can be supplied by spray nozzles mounted in the wall or on the hollow shaft.
  • two mixers connected in series can be used, the dry premix being produced in the first mixer and the pelletizing being carried out with the addition of water in the second mixer.
  • Continuous work is also possible in a mixer, the powder streams being combined and homogenized in a first mixing section and the mixture being treated with water and agglomerating in a subsequent mixing section in a subsequent mixing section.
  • the drying can be carried out by introducing hot gases in a third mixing section z.
  • coarse and fine particles are sieved. The coarse fractions are ground and mixed into the product, fine fractions or dust are returned to the granulation.
  • the granules have a bulk density of 750-1000 g / 1, usually that of 800-950 g / 1. Due to their tight packing and their small pore volume, their absorption capacity for liquid or pasty detergent components, especially nonionics, is somewhat reduced compared to specifically lighter carrier grains, but is still 15 to a maximum of 20% by weight without any appreciable impairment of the free-flowing properties. This In view of the high packing density, the surprisingly high adsorption capacity is completely sufficient for the usual fields of application, in particular for use as a mixture component in detergents and cleaning agents.
  • the granules can be impregnated with any liquid or paste-like or fat-like detergent constituents which cannot be incorporated into conventional powdery or granular detergents or cleaning agents in other ways or only with a loss of activity.
  • foam inhibitors in particular paraffin hydrocarbons, silicones, silicone resins and bis-acylalkylenediamines derived from long-chain fatty acids and mixtures thereof.
  • Further adsorbable active ingredients are fatty acid alkylolamides and cationic plasticizers, such as quaternary ammonium salts containing long-chain fatty residues, and also fat-dissolving solvents, such as terpenes.
  • the granules are preferably used as carrier grains for nonionic surfactants. This is another aspect of the invention.
  • 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, thio alcohols, fatty acid amides and fatty acids. Alkylphenol polyglycol ethers with 5 to 12 carbon atoms in the alkyl radical and 3 to 10 ethylene glycol ether groups are also useful. Block polymers of ethylene oxide and propylene oxide, which are commercially available under the name Pluronics, are also suitable. Furthermore, alkyl glycosides or alkyl polyglycosides as well as their mixtures with the ⁇ thoxylation products mentioned can be used »
  • Preferred nonionics which can be adsorbed on the granulate and together with it are in the form of a free-flowing mixture, are derived from alcohols having 12 to 18 carbon atoms which are saturated or olefinically unsaturated, linear or methyl in 2-position branches (oxo residue) can be.
  • Their reaction products with ethylene oxide (EO) or propylene oxide (PO) are water-soluble or water-dispersible mixtures of compounds with different degrees of alkoxylation, the number of EO or PO groups given below being statistical Corresponds to the mean.
  • ethoxylated fatty alcohols examples include C12-I8 "coconut alcohols with 3 to 12 EO, Ci5_i8 ⁇ tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO as well as ethoxylation products of appropriate chain and EO distribution available from other native fatty alcohol mixtures.
  • Aus In the series of ethoxylated oxo alcohols for example, those with the composition C 2-15 + 5 to 10 EO and C14-C15 + 6 to 12 EO are suitable.
  • Mixtures are characterized by low and high levels of detergency against both greasy and mineral soiling highly ethoxylated alcohols, for example those made from tallow alcohol + 3 to 6 EO and tallow alcohol + 12 to 16 EO or Ci3_i5-0xoalkohol + 5 EO and Ci2-i4-0xoalcohol + 8 to 12 EO.
  • Ethylates which contain EO groups and PO groups are also suitable, for.
  • the liquid, optionally heated, additives, in particular nonionics, can be applied to the granules by admixing, preferably spraying, the carrier material advantageously being kept in motion by suitable mixing devices. Further treatment of the granular adsorbate is not necessary. However, allowing the product to rest for several hours at high contents of the applied liquid material can be expedient since its diffusion into the interior of the grain takes some time. The treatment of the granules with the liquid additives leads to a further increase in the bulk density, which can rise to values of over 1,000 g / l.
  • the grains can optionally also be dusted with finely divided powders or coated on the surface.
  • Suitable powdering agents have a grain size of 0.001 to at most 0.1 mm, preferably less than 0.05 mm and can be in proportions of 0.03 to 3, preferably 0.05 mm to 2% by weight, based on the adsorbent loaded with additive.
  • finely powdered zeolites, silica airgel (Aerosil ( R )), colorless or colored pigments such as titanium dioxide are suitable. in the in general, however, such an aftertreatment is superfluous, especially since it does not improve the solution properties.
  • the detergent additives can be combined and mixed in a known manner with the granular or powdered detergent, for example a tower spray powder and its mixtures with other powder components, such as persalts, enzyme granules, bleach activators or defoamers.
  • a tower spray powder and its mixtures with other powder components, such as persalts, enzyme granules, bleach activators or defoamers.
  • the detergents mixed together generally contain 10 to 40% by weight of the additive according to the invention.
  • the granules according to the invention have a different grain structure than those which are produced by conventional granulation processes. This can also be demonstrated by electron micrographs. If, as is customary in conventional granulation processes, the powdered zeolite is placed in the mixer and a solution of the (co) polymeric salt is sprayed on, granules are formed which do not differ externally from the products according to the invention, except that their bulk density is significantly reduced.
  • the images obtained with the scanning electron microscope show sections through two different granules at a magnification of 1: 2 500 (Figs. 1 and 2) and 1: 5 000 (Figs. 3 and 4). Both grains have the same qualitative and quantitative composition as in Example 1.
  • Figures 1 and 3 show a grain in the production of which the spray-dried zeolite was sprayed in a mixer with a 25% strength by weight aqueous solution of the copolymeric salt, granulated and then dried.
  • Figures 2 and 4 show the grain structure of the spiels 1 manufactured product. The arrangement of the cubic zeolite particles in Figures 1 and 3 is completely random. Large pores alternate with strongly bonded, irregularly structured aggregates. In Figures 2 and 4 the zeolite cubes are packed much more densely and uniformly. Individual parts are reminiscent of a structure comparable to a pavement or masonry. The pore size is also significantly reduced.
  • the granulation was carried out in a mixing granulator, consisting of a horizontally arranged cylindrical mixer with a rotating shaft (Lödige type) rotating in the central axis, equipped with mixing elements, with a capacity of 130 liters and a knife mill connected to it, operated at a speed of 1200 to 1500 rpm .
  • 69.5 parts by weight of a synthetic, finely crystalline, spray-dried NaA r type zeolite containing 20 parts by weight of bound water were mixed with 8.8 parts by weight of powdered sodium salt of an acrylic acid-maleic acid copolymer (moisture content 8 wt .-%) mixed to a homogeneous powder mixture.
  • the copolymer (Sokalan ( R ) CP5 from BASF, Ludwigshafen) had a molecular weight of approximately 70,000. After the mixing, which took about 20 seconds, 21.7 parts by weight of water were sprayed in over 90 seconds by means of nozzles and the mixture was granulated for a further 3 minutes with constant mixing. The granules leaving the mixer were dried in a fluidized bed with hot, flowing dry gases.
  • the final product had the following composition:
  • the bulk density of the granules was 900 g / 1.
  • the granules were sprayed in a spray mixer with a liquid, nonionic surfactant heated to 40 ° C., consisting of a 1: 4 mixture of coconut and tallow alcohol reacted with 5 mol EO. After standing for 1 hour, the Adsorbate the following bulk weights:
  • the granules treated with the nonionic surfactant were free-flowing and had a perfect wash-in capacity, both as unblended powder and mixed with a powdery household detergent in a ratio of 1: 4.

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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)

Abstract

On obtient des granulés de haute densité apparente, qui contiennent de la zéolithe en fins cristaux et des sels d'acides carboxyliques (co)polymères, en particulier des copolymères d'acide maléique-acide acrylique, de la manière suivante: on fabrique tout d'abord un premier mélange sec de zéolithe et de polycarboxylate que l'on transforme ensuite en granulés, en ajoutant de l'eau, avant de le sécher. Lesdits granulés contiennent entre 60 et 80 % en poids de zéolithe (% de la matière sans eau), entre 2 et 15 % en poids de polycarboxylate et entre 14 et 25 % en poids d'eau, y compris l'eau fixée à de la zéolithe.
PCT/EP1989/001312 1988-11-10 1989-11-02 Procede de fabrication de granules de haute densite contenant de la zeolithe WO1990005175A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1019900701431A KR900701992A (ko) 1988-11-10 1989-11-02 제올라이트 함유 고밀도 입상물의 제조방법
DK086891A DK86891A (da) 1988-11-10 1991-05-08 Fremgangsmaade til fremstilling af zeolitholdige granuler med hoej massefylde

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3838086A DE3838086A1 (de) 1988-11-10 1988-11-10 Verfahren zur herstellung zeolithhaltiger granulate hoher dichte
DEP3838086.2 1988-11-10

Publications (1)

Publication Number Publication Date
WO1990005175A1 true WO1990005175A1 (fr) 1990-05-17

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ID=6366852

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1989/001312 WO1990005175A1 (fr) 1988-11-10 1989-11-02 Procede de fabrication de granules de haute densite contenant de la zeolithe

Country Status (9)

Country Link
EP (2) EP0368137B1 (fr)
JP (1) JPH04501730A (fr)
KR (1) KR900701992A (fr)
DE (2) DE3838086A1 (fr)
DK (1) DK86891A (fr)
ES (1) ES2047091T3 (fr)
PT (1) PT92223B (fr)
TR (1) TR24018A (fr)
WO (1) WO1990005175A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0421664A2 (fr) * 1989-10-02 1991-04-10 Rohm And Haas Company Granulés contenant des polymères
WO1994004650A1 (fr) * 1992-08-24 1994-03-03 Henkel Kommanditgesellschaft Auf Aktien Adjuvants pour agents de lavage

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5108646A (en) * 1990-10-26 1992-04-28 The Procter & Gamble Company Process for agglomerating aluminosilicate or layered silicate detergent builders
DE4038609A1 (de) * 1990-12-04 1992-06-11 Henkel Kgaa Verfahren zur herstellung von zeolith-granulaten
DE4110510A1 (de) * 1991-03-30 1992-10-01 Henkel Kgaa Niederalkalische, chlor- und phosphatfreie maschinengeschirrspuelmittel in form von schwerpulvern und -granulaten
DE4125330A1 (de) * 1991-07-31 1993-02-04 Henkel Kgaa Verfahren zur herstellung von zeolith-granulaten
DE4137470A1 (de) * 1991-11-14 1993-05-19 Henkel Kgaa Verfahren zur herstellung niederalkalischer, aktivchlor- und phosphatfreier maschinengeschirrspuelmittel in form von schwergranulaten
DE4216774A1 (de) * 1992-05-21 1993-11-25 Henkel Kgaa Verfahren zur kontinuierlichen Herstellung eines granularen Wasch und/oder Reinigungsmittels
DE4229660A1 (de) * 1992-09-04 1994-03-10 Henkel Kgaa Wasch- und Reinigungsmittel mit Buildersubstanzen
EP0639638A1 (fr) * 1993-08-18 1995-02-22 The Procter & Gamble Company Procédé de préparation de compositions détergentes
DE19549411C2 (de) * 1994-02-11 1999-05-12 Degussa Zeolithgranulate
DE19504043C2 (de) * 1994-02-11 1998-07-09 Degussa Zeolithgranulate
DE19515256A1 (de) * 1995-04-26 1996-10-31 Degussa Zeolithgranulat, Verfahren zu seiner Herstellung und Verwendung
GB9820573D0 (en) * 1998-09-22 1998-11-11 Ind Zeolite Uk Ltd Water absorbing composition
DE19850100A1 (de) 1998-10-29 2000-05-04 Henkel Kgaa Polymer-Granulate durch Wirbelschichtgranulation
DE102005025656A1 (de) 2005-06-03 2006-12-07 IPK-Institut für Pflanzengenetik und Kulturpflanzenforschung Promotor zur epidermisspezifischen, pathogeninduzierbaren Transgenexpression in Pflanzen
JP5705525B2 (ja) * 2010-12-16 2015-04-22 花王株式会社 ゼオライト複合粒子群
EP3241889B1 (fr) * 2016-05-03 2019-03-20 The Procter and Gamble Company Composition de nettoyage

Citations (7)

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Publication number Priority date Publication date Assignee Title
DE2412837A1 (de) 1973-04-13 1974-10-31 Henkel & Cie Gmbh Verfahren zum waschen und reinigen der oberflaechen von festen werkstoffen, insbesondere von textilien, sowie mittel zur durchfuehrung des verfahrens
EP0021267A1 (fr) 1979-06-18 1981-01-07 PQ Corporation Echangeur d'ions zéolitique aggloméré
EP0025551B1 (fr) 1979-09-13 1982-09-22 BASF Aktiengesellschaft Utilisation de copolymères d'acide (méth)acrylique et d'acide maléique comme inhibiteurs d'incrustation dans des produits de lavage
DE3316513A1 (de) 1983-05-06 1984-11-08 Joh. A. Benckiser Gmbh, 6700 Ludwigshafen Abriebfeste granulate auf basis von alkalialuminiumsilikat
EP0149264A1 (fr) 1983-11-09 1985-07-24 Unilever N.V. Adjonctions de particules stables à bon écoulement pour l'utilisation dans des compositions détergentes
DE3444960A1 (de) 1984-12-10 1986-06-12 Henkel KGaA, 4000 Düsseldorf Koerniges adsorptionsmittel
EP0243908A2 (fr) 1986-05-02 1987-11-04 Henkel Kommanditgesellschaft auf Aktien Produit granulaire, exempt de phosphate, pour adoucir l'eau

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA774818B (en) * 1976-08-17 1979-03-28 Colgate Palmolive Co Disintegrable detergent builder agglomerates

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2412837A1 (de) 1973-04-13 1974-10-31 Henkel & Cie Gmbh Verfahren zum waschen und reinigen der oberflaechen von festen werkstoffen, insbesondere von textilien, sowie mittel zur durchfuehrung des verfahrens
EP0021267A1 (fr) 1979-06-18 1981-01-07 PQ Corporation Echangeur d'ions zéolitique aggloméré
EP0025551B1 (fr) 1979-09-13 1982-09-22 BASF Aktiengesellschaft Utilisation de copolymères d'acide (méth)acrylique et d'acide maléique comme inhibiteurs d'incrustation dans des produits de lavage
DE3316513A1 (de) 1983-05-06 1984-11-08 Joh. A. Benckiser Gmbh, 6700 Ludwigshafen Abriebfeste granulate auf basis von alkalialuminiumsilikat
EP0149264A1 (fr) 1983-11-09 1985-07-24 Unilever N.V. Adjonctions de particules stables à bon écoulement pour l'utilisation dans des compositions détergentes
DE3444960A1 (de) 1984-12-10 1986-06-12 Henkel KGaA, 4000 Düsseldorf Koerniges adsorptionsmittel
EP0243908A2 (fr) 1986-05-02 1987-11-04 Henkel Kommanditgesellschaft auf Aktien Produit granulaire, exempt de phosphate, pour adoucir l'eau

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0421664A2 (fr) * 1989-10-02 1991-04-10 Rohm And Haas Company Granulés contenant des polymères
EP0421664A3 (en) * 1989-10-02 1991-12-18 Rohm And Haas Company Polymer-containing granulates
WO1994004650A1 (fr) * 1992-08-24 1994-03-03 Henkel Kommanditgesellschaft Auf Aktien Adjuvants pour agents de lavage

Also Published As

Publication number Publication date
DE3838086A1 (de) 1990-05-17
JPH04501730A (ja) 1992-03-26
ES2047091T3 (es) 1994-02-16
KR900701992A (ko) 1990-12-05
DK86891A (da) 1991-07-08
PT92223A (pt) 1990-05-31
EP0442923A1 (fr) 1991-08-28
DE58906639D1 (de) 1994-02-17
EP0368137A1 (fr) 1990-05-16
PT92223B (pt) 1995-07-06
TR24018A (tr) 1991-02-01
EP0368137B1 (fr) 1994-01-05
DK86891D0 (da) 1991-05-08

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