EP0425804B1 - Additif granulaire contenant un agent tensioactif pour détergent et agent de nettoyage avec des propriétés de rinçage améliorées - Google Patents

Additif granulaire contenant un agent tensioactif pour détergent et agent de nettoyage avec des propriétés de rinçage améliorées Download PDF

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Publication number
EP0425804B1
EP0425804B1 EP90117749A EP90117749A EP0425804B1 EP 0425804 B1 EP0425804 B1 EP 0425804B1 EP 90117749 A EP90117749 A EP 90117749A EP 90117749 A EP90117749 A EP 90117749A EP 0425804 B1 EP0425804 B1 EP 0425804B1
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EP
European Patent Office
Prior art keywords
weight
additive
component
granular
water
Prior art date
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Expired - Lifetime
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EP90117749A
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German (de)
English (en)
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EP0425804A2 (fr
EP0425804A3 (en
Inventor
Lothar Pioch
Wolfgang Dr. Seiter
Adolf Wiche
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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
    • 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
    • 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
    • C11D3/16—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

Definitions

  • the invention relates to a granular detergent additive consisting of an adsorbent with high adsorption capacity and liquid non-ionic surfactants adsorbed thereon or melting when heated.
  • the additive is suitable for use in phosphate-free or low-phosphate detergents and cleaning agents which, after mixing with the additive, have a very good wash-in behavior, i.e. they do not form undissolved residues in the washing machines of washing machines.
  • nonionic surfactants have a very high cleaning ability, which makes them particularly suitable for use in cold detergents or 60 ° C. detergents.
  • their proportion cannot be increased significantly beyond 8 to 10 percent by weight in the generally customary production of detergents by spray drying, since this would otherwise result in excessive smoke formation in the exhaust air from the spray towers and inadequate pouring properties of the spray powder. Processes have therefore been developed in which the liquid or melted nonionic surfactant is mixed onto the previously spray-dried powder or sprayed onto a carrier substance.
  • Loose in particular spray-dried phosphates, borates or Perborate, sodium aluminosilicate (zeolite), silicon dioxide (Aerosil) or salt mixtures previously prepared in a certain way, e.g. B. proposed from sodium carbonate and sodium bicarbonate, but all known agents have certain disadvantages. Phosphates are often undesirable because of their eutrophic properties. Borates or perborates have only a limited absorption capacity for liquid substances, which also applies to finely powdered zeolites, while special adsorbents, such as diatomaceous earth and aerosil, do not contribute to the washing action as inert components.
  • Absorbent carrier grains which consist of several components and are usually produced by spray drying, are e.g. B. from US 3 849 327, US 3 886 098 and US 3 838 027 and US 4 269 722 (DE 27 42 683) known.
  • these carrier grains developed especially for the adsorption of nonionic surfactants, contain considerable amounts of phosphates, which limits their possible uses.
  • Phosphate-free carrier grains are known from DE 32 06 265. They consist of 25 to 52% sodium carbonate or hydrogen carbonate, 10 to 50% zeolite, 0 to 18% sodium silicate and 1 to 20% bentonite or 0.05 to 2% polyacrylate.
  • the high proportion of carbonate favors the formation of calcium carbonate in hard water and thus the formation of incrustations on the textile fiber or the heating elements in the washing machine.
  • the absorption capacity of the carrier grains cited above is limited. With proportions of more than 25% by weight of mixed liquid or sticky nonionic surfactants, the free-flowing properties of the products decrease considerably and are unsatisfactory above 30% by weight.
  • 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) 60 to 80% by weight zeolite, 0.1 to 8% by weight.
  • % Sodium silicate 3 to 15% by weight of homo- or copolymers of acrylic acid, methacrylic acid and / or maleic acid, 8 to 18% by weight of water and optionally up to 5% by weight of nonionic surfactants and obtainable by spray drying is.
  • the adsorbent (I) has an average particle size of 0.2 to 1.2 mm, the portion with a particle size of less than 0.05 mm not more than 2 percent by weight and the portion with a particle size of more than 2 mm more than 5 wt .-% and the bulk density of the detergent additive is 500 to 750 g / l.
  • Phosphate-free is understood to mean an agent which contains less than 0.1% of inorganic phosphorus.
  • the layered silicates can contain hydrogen, alkali and alkaline earth ions, in particular Na + and Ca ++ .
  • the amount of water of hydration is usually in the range from 8 to 20% by weight and depends on the state of swelling or the type of processing.
  • the particle size is in the range from 0.05 to 25 ⁇ m, usually less than 10 ⁇ m.
  • Useful sheet silicates are known, for example, from US 3,966,629, US 4,062,647 (DE 23 34 899-B2), EP 26 529 A1 and EP 28 432 A1.
  • Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
  • the layered silicate content of the adsorbent (I) is 2 to 10% by weight, preferably 3 to 7% by weight.
  • the component (c) consists of a homopolymeric and / or copolymeric carboxylic acid in the form of the sodium salt.
  • Suitable homopolymers are polyacrylic acid and polymethacrylic acid.
  • Suitable copolymers are those of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid or methacrylic acid with maleic acid, as described, for example, in EP 25 551-B1, have proven particularly suitable. It is about copolymers containing 40 to 90% by weight of acrylic acid or methacrylic acid and 60 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 homopolymers or copolymers is generally 1,000 to 150,000, preferably 1,500 to 100,000. Their proportion of the composition is 2.5 to 10% by weight and preferably 3 to 8% by weight.
  • Optional component (d) is sodium sulfate, the proportion of which, calculated on anhydrous salt, is 0 to 10% by weight, preferably 0 to 8% by weight.
  • sodium sulfate, calculated as an anhydrous salt can improve both the granule properties and the flushing behavior. It also increases the bulk density of the product, which is often desired.
  • the adsorbent (I) can contain small amounts of surface-active compounds, which can be added during the production and processing of the synthetic zeolites in order to increase the stability of the aqueous zeolite dispersions (master batch) .
  • Such additives which are introduced into the compositions with the zeolite, are described in DE 25 27 388-B2.
  • These can be nonionic surfactants containing polyglycol ether groups, for example primary alcohols having 12 to 18 carbon atoms reacted with 2 to 7 mol of ethylene oxide.
  • the proportion of stabilizers introduced into the composition via such zeolite dispersions can be, for example, 0.5 to 3% by weight. This proportion, insofar as it consists of nonionic surfactant, is added to component (II) in the overall balance.
  • the water content of the adsorbent (I) depends on the drying conditions.
  • the one at a drying temperature of 145 ° C Removable water content is about 8 to 18 wt .-%, usually 10 to 16 wt .-%.
  • Other amounts of water bound by the zeolite or layered silicate that are released at higher temperatures are not included in this amount. If these are taken into account by calcining the zeolite or layered silicate at temperatures of 800 ° C., the total water content of the compositions is 12 to 25% by weight.
  • the average grain size of the adsorbent (I) is usually 0.2 to 1.2 mm, the fraction of the grains being below 0.1 mm not more than 3% by weight and being above 1.8 mm to 2.4 mm no more than 20% by weight.
  • At least 80% by weight, in particular at least 90% by weight, of the grains preferably have a size of 0.2 to 2.0 mm, the proportion of the grains between 0.1 and 0.05 mm not more than 2% by weight .-%, in particular less than 1 wt .-% and the proportion of grains between 1.6 to 2.4 mm is not more than 15 wt .-%, in particular not more than 10 wt .-%. Larger proportions of fine grain generally lead to a deterioration in the induction behavior and should therefore be avoided. Larger proportions of coarse grain cause a lower bulk density and make the product appear visually inconsistent, but are otherwise not disadvantageous.
  • the bulk density of the adsorbent (I) is 400 to 700 g / l, usually 450 to 650 g / l in the presence of sodium sulfate and 400 to 650 g / l, usually 450 to 600 g / l in the absence of sodium sulfate.
  • the agent consists essentially of rounded grains, which have a very good flow behavior. This very good flow behavior is still present even after the grains have been impregnated with large proportions of liquid, semi-liquid or solid nonionic surfactants (II).
  • the amount these adsorbed components can be 5 to 35% by weight, preferably 10 to 30% by weight, based on the adsorbate.
  • the adsorbent (I) is preferably produced by spray drying an aqueous, liquid to pasty batch (slurry) by means of heated gases (combustion gases) in conventional drying towers. Since the combustion air, which is widely used as a dry gas, contains comparatively high proportions of carbon dioxide, it may be advantageous to add small amounts of sodium hydroxide to the slurry before spraying, in order to counteract a pH reduction by a corresponding excess of alkali. The recommended proportions of NaOH are usually between 0.1 and 1% by weight.
  • the minor constituents that can also be added to the agents during production include dyes or color pigments with which the intrinsic color of individual active ingredients, in particular of the layered silicate, can be covered.
  • the liquid to pasty nonionic surfactants (II) bound to the adsorbent (I) from the class of the polyglycol ethers are preferably derived from alcohols having 10 to 22, in particular 12 to 18, carbon atoms. These alcohols can be saturated or olefinically unsaturated, linear or methyl-branched in the 2-position (oxo radical).
  • 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 in technical alkoxylates corresponds to the statistical mean and is generally 2 to 25.
  • ethoxylated fatty alcohols examples include C 12-18 coco alcohols with 3 to 12 EO, C 16-18 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.
  • ethoxylated oxo alcohols are, for example, those of the composition C 13-15 oxo alcohol + 3 to 5 EO and C 12-14 oxo alcohol + 8 to 12 EO.
  • Agents in which the adsorbed nonionic surfactants have both long hydrophobic residues and higher degrees of ethoxylation have particularly favorable flushing properties.
  • nonionic surfactants that can be bound to the adsorbent are ethoxylated alkylamines, ethoxylated fatty acid ethanolamides and ethoxylated fatty acid ethanolamides and ethoxylated vicinal diols, which can contain the same number of carbon atoms and the same number of EO groups in the glycol ether residue as the aforementioned alcohol ethoxylates .
  • Preferred compounds are ethoxylated C 12-18 fatty amines, ethoxylated C 12-18 -1,2-diols with 1 to 5 EO groups, which act as detergency boosters and can be bound to the adsorbent (I) alone or as a mixture with alcohol ethoxylates .
  • detergent constituents can also be bound to the adsorbent.
  • these include sensitive substances such as enzymes, biocides, fragrances, bleach activators, softeners, optical brighteners and anionic or cationic surfactants. They can be mixed with the adsorbents after they have been dissolved or dispersed in water or organic solvents or the liquid or molten nonionic surfactants. These substances penetrate into the porous grain together with the solvent or dispersant and are thus protected against interactions with other powder components.
  • the adsorbent (I) can be impregnated with the nonionic surfactants or other constituents to be adsorbed in a manner known per se by spraying the granules kept in motion with the liquid or melted nonionic surfactants or mixtures containing surfactants. Conventional spray mixing devices and granulating drums are suitable for this.
  • the adsorbents (I) run comparatively quickly and completely, so that free-flowing adsorbates (additives) are produced in one operation without aftertreatment or rest.
  • the impregnation process also leads to an increase in the bulk density to values of 500 to 800 g / l, depending on the type and amount of the starting materials.
  • the granular additives impregnated with the nonionic surfactants or with the mixtures of nonionic surfactant and additive are usually mixed in any ratio with further powdery to granular detergents or detergent components, such as are obtainable for example by spray drying or granulation.
  • their good flowability and their high grain stability are of great advantage, since an undesirable formation of abrasion and dust is avoided.
  • the powder mixtures are in turn stable in storage and do not tend to clump or exude the nonionic surfactant.
  • they are very easy to flush in compared to known mixtures, which is particularly surprising since the additive according to the invention itself has only a moderately good to poor flushing behavior. It was therefore not to be expected that the additive according to the invention would not only not impair the induction behavior of conventional detergents and cleaning agents, but would in many cases even improve them and would make their use in washing machines possible in the first place.
  • the proportion of additive in such washing and cleaning agents is usually 5 to 40% by weight, preferably 10 to 35% by weight and in particular 15 to 30% by weight, based on the finished mixture.
  • These detergents and cleaning agents to be mixed with the additive can be produced in the customary manner, ie by spray drying or granulation, and can contain customary detergent components, such as surfactants, builder substances, sequestering agents, neutral salts, polymers, optical brighteners, etc., and further granular mixture components, such as bleaching agents , Bleach activators, enzymes, defoamers and fragrance carriers.
  • the powder components can be mixed continuously or discontinuously in conventional mixing devices and, because of the favorable grain properties of the additives according to the invention, presents no problems.
  • the zeolite used had a calcium binding capacity of 165 mg CaO / g and an average particle size of 3 ⁇ m, with no proportions above 20 ⁇ m. It was used as an aqueous dispersion containing 48% by weight of anhydrous zeolite, 1.5% by weight of component (s) and 50.5% by weight of water.
  • the product Laundrosil (R) DG-A (treated with soda solution) was used as layered silicate.
  • a copolymer of acrylic acid and maleic acid with a molecular weight of 70,000 (Sokalan (R) ) in the form of the sodium salt was used as the polycarboxylic acid.
  • the sodium hydroxide was used as 50% sodium hydroxide solution.
  • the slurry which had a temperature of 70 ° C. and a viscosity of 10,400 mPa ⁇ s, was sprayed at a pressure of 40 bar in a tower in which combustion gases at a temperature of 185 ° C. (measured in the ring channel) were directed towards the spray product.
  • the outlet temperature of the dry gas was 58 ° C.
  • the granular adsorbent leaving the spray tower contained f2) 19.55 GT water.
  • the liter weight was 490 g / l.
  • (V1) was a granular, spray-dried zeolite NaA and (V2) one made according to DE 34 44 960 Backing material (free of layered silicate) used and processed in the same way.
  • the additive was very free-flowing and had a wash-in grade of B 1 before the impregnation process.
  • 2 test series were carried out, namely with the additive after impregnation, but without the addition of a detergent and after mixing 25 parts of the impregnated additive with 50 parts of tower spray powder and 25 parts of perborate (term "with detergent").
  • the atomization pressure in the nozzle area was 40 bar.
  • the counter-current heating gas had a temperature of 223 ° C in the ring channel and 60 ° C in the area of the nozzle level.
  • the flushability was determined with grade B 10.
  • the liter weight was 530 g / l with the following particle size distribution: mm 2.4 to 1.6 to 0.8 to 0.4 up to 0.2 to 0.1 less than 0.1 % By weight 0 2nd 42 46 10th 0

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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)

Claims (10)

  1. Additif en grains contenant des agents tensioactifs non ioniques, pour des détergents et des agents de lavage en grains manifestant un comportement de rinçage amélioré, constitué par un agent d'adsorption granulaire (I) et par des agents tensioactifs non ioniques (II) adsorbés sur ce dernier, le composant (I) présentant la composition ci-après rapportée à la substance anhydre:
    (a) de 50 à 75% en poids de zéolithe finement cristalline,
    (b) de 2 à 10% en poids d'un silicate stratifié,
    (c) de 2,5 à 10% en poids du sel de sodium d'un acide carboxylique (co)polymère,
    (d) de 0 à 10% en poids de sulfate de sodium,
    (e) de 0 à 3% en poids d'un agent tensioactif organique,
    (f) le reste étant de l'eau et des constituants mineurs,
    avec cette mesure que la fraction en agent tensioactif non ionique (II) s'élève de 5 à 35% en poids, rapportée à l'adsorbat.
  2. Agent selon la revendication 1, dans lequel le composant (I) présente une granulométrie moyenne de 0,2 à 1,2 mm, dans lequel la fraction dont la granulométrie est inférieure à 0,05 mm ne représente pas plus de 2% en poids et la fraction dont la granulométrie est supérieure à 2 mm ne représente pas plus de 5% en poids, la densité apparente de l'additif de détergent s'élevant de 500 à 750 g/l.
  3. Agent selon les revendications 1 et 2, dans lequel (a), rapporté au composant (I), est constitué par 60 à 72% en poids de zéolithe du type NaA, calculés comme substance anhydre.
  4. Agent selon l'une ou plusieurs des revendications 1 à 3, dans lequel (b), rapporté au composant (I), est présent dans des fractions de 3 à 7% en poids et est constitué par la montmorrilonite, l'hectorite ou la saponite.
  5. Agent selon l'une ou plusieurs des revendications 1 à 4, dans lequel (c), rapporté au composant (I), est constitué par 3 à 8% en poids d'un sel de sodium d'un acide polyacrylique, respectivement d'un copolymère d'acide acrylique-acide maléique.
  6. Agent selon l'une ou plusieurs des revendications 1 à 5, dans lequel la fraction (d), rapportée au composant (I), s'élève de 0 à 8% en poids.
  7. Agent selon l'une ou plusieurs des revendications 1 à 6, dans lequel l'agent tensioactif non ionique (II) dérive d'alcools gras et d'oxoalcools contenant de 12 à 18 atomes de carbone, et présente de 2 à 25 groupes d'étherglycols.
  8. Procédé pour la préparation des agents selon l'une ou plusieurs des revendications 1 à 7, caractérisé en ce que l'on sèche par pulvérisation une suspension aqueuse des constituants contenus dans le composant (I) et on imprègne le produit de granulation obtenu avec des agents tensioactifs non ioniques (II).
  9. Utilisation d'un agent selon l'une ou plusieurs des revendications 1 à 7, comme constituant de mélange dans des détergents et des agents de lavage granulaires.
  10. Utilisation selon la revendication 9, dans des fractions de 5 à 40% en poids, de préférence de 10 à 35% en poids rapportés au mélange prêt à l'emploi, comme constituant de mélange dans des détergents et des agents de lavage granulaires.
EP90117749A 1989-11-02 1990-09-14 Additif granulaire contenant un agent tensioactif pour détergent et agent de nettoyage avec des propriétés de rinçage améliorées Expired - Lifetime EP0425804B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3936405A DE3936405A1 (de) 1989-11-02 1989-11-02 Koerniges, nichtionische tenside enthaltendes additiv fuer wasch- und reinigungsmittel mit verbessertem einspuelverhalten
DE3936405 1989-11-02

Publications (3)

Publication Number Publication Date
EP0425804A2 EP0425804A2 (fr) 1991-05-08
EP0425804A3 EP0425804A3 (en) 1991-07-03
EP0425804B1 true EP0425804B1 (fr) 1996-08-07

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ID=6392681

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90117749A Expired - Lifetime EP0425804B1 (fr) 1989-11-02 1990-09-14 Additif granulaire contenant un agent tensioactif pour détergent et agent de nettoyage avec des propriétés de rinçage améliorées

Country Status (4)

Country Link
EP (1) EP0425804B1 (fr)
AT (1) ATE141100T1 (fr)
DE (2) DE3936405A1 (fr)
ES (1) ES2090070T3 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4009618A1 (de) * 1990-03-26 1991-10-02 Henkel Kgaa Spruehgetrocknetes, avivierend wirkendes waschmitteladditiv
EP0477974B1 (fr) * 1990-09-28 1995-09-13 Kao Corporation Composition détergente non-ionique pulvérulente
AU649504B2 (en) * 1991-07-03 1994-05-26 Kao Corporation Nonionic powder detergent composition
DE4209435A1 (de) * 1992-03-24 1993-09-30 Henkel Kgaa Granulares, nichtionische Tenside enthaltendes, phosphatfreies Additiv für Wasch- und Reinigungsmittel
AU660101B2 (en) * 1992-08-07 1995-06-08 Colgate-Palmolive Company, The Heavy duty laundry detergent compositions of reduced dye transfer properties
TR27896A (tr) * 1993-08-05 1995-10-11 Colgate Palmolive Co Boya transferi özellikleri düsürülmüs agir is camasir deterjani bilesimleri.
DE4329064A1 (de) * 1993-08-28 1995-03-02 Henkel Kgaa Gerüststoffkomponente für Wasch- oder Reinigungsmittel
DE19500644B4 (de) * 1995-01-12 2010-09-09 Henkel Ag & Co. Kgaa Sprühgetrocknetes Waschmittel oder Komponente hierfür
GB2315768A (en) * 1996-08-01 1998-02-11 Procter & Gamble Detergent compositions
DE19728588A1 (de) * 1997-07-04 1999-01-07 Henkel Kgaa Schweres Waschmittelgranulat mit hoher Löslichkeit und verbessertem Fettauswaschvermögen
GB2339203A (en) * 1998-07-08 2000-01-19 Procter & Gamble A method of dipensing

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU549122B2 (en) * 1981-02-26 1986-01-16 Colgate-Palmolive Pty. Ltd. Spray dried base beads and detergent compositions
DE3444960A1 (de) * 1984-12-10 1986-06-12 Henkel KGaA, 4000 Düsseldorf Koerniges adsorptionsmittel
DE3818829A1 (de) * 1988-06-03 1989-12-14 Henkel Kgaa Koerniges adsorptionsmittel mit verbessertem einspuelverhalten
DE3822479A1 (de) * 1988-07-02 1990-02-08 Henkel Kgaa Waschmitteladditiv mit verbessertem einspuelverhalten

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Publication number Publication date
EP0425804A2 (fr) 1991-05-08
DE3936405A1 (de) 1991-05-08
ES2090070T3 (es) 1996-10-16
EP0425804A3 (en) 1991-07-03
DE59010440D1 (de) 1996-09-12
ATE141100T1 (de) 1996-08-15

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