EP0849355B1 - Composants de lavage et de nettoyage sous forme de poudre - Google Patents

Composants de lavage et de nettoyage sous forme de poudre Download PDF

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Publication number
EP0849355B1
EP0849355B1 EP97121407A EP97121407A EP0849355B1 EP 0849355 B1 EP0849355 B1 EP 0849355B1 EP 97121407 A EP97121407 A EP 97121407A EP 97121407 A EP97121407 A EP 97121407A EP 0849355 B1 EP0849355 B1 EP 0849355B1
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EP
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Prior art keywords
weight
acid
alkaline silicate
cleaning
cleaning detergents
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97121407A
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German (de)
English (en)
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EP0849355A2 (fr
EP0849355A3 (fr
Inventor
Günther Dr. Schimmel
Harald Dr. Bauer
Josef Holz
Volker Thewes
Richard Dr. Mertens
Peter Dr. Hardt
Matthias Dr. Berghahn
Thomas Dr. Müller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
clariant Produkte Deutschland GmbH
Evonik Operations GmbH
Original Assignee
Clariant GmbH
Stockhausen GmbH and Co KG
Chemische Fabrik Stockhausen GmbH
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
Priority claimed from DE19719888A external-priority patent/DE19719888A1/de
Application filed by Clariant GmbH, Stockhausen GmbH and Co KG, Chemische Fabrik Stockhausen GmbH filed Critical Clariant GmbH
Publication of EP0849355A2 publication Critical patent/EP0849355A2/fr
Publication of EP0849355A3 publication Critical patent/EP0849355A3/fr
Application granted granted Critical
Publication of EP0849355B1 publication Critical patent/EP0849355B1/fr
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • 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
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • 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
    • C11D3/3788—Graft polymers

Definitions

  • the invention relates to a powder detergent and cleaning agent component, a method for their manufacture and their use.
  • washing and cleaning agents contain a variety of ingredients, one Perform a number of different functions. Important for the quality of such washing and Detergent is both the type and amount of ingredients used and the type and the order in which these ingredients are combined.
  • the main components in modern laundry detergents include surfactants, Bleach, washing alkalis and the so-called builders.
  • the main components for detergents and dishwashing detergents are primarily builders, bleach, alkalis, Dispersants and enzymes.
  • An ideal builder for textile detergents fulfills a number of functions and carries, for example significantly to water softening. In addition, it should have the highest possible carrying capacity for liquid components and sufficient buffering of the wash liquor enable.
  • NaTPP sodium tripolyphosphate
  • zeolites A and P crystalline silicates
  • SKS-6 sodium tripolyphosphate
  • Water softening (removal or binding of calcium causing water hardness and / or magnesium ions) is carried out with the aforementioned builders in different ways Way.
  • the sodium tripolyphosphate dissolves and forms with the calcium and magnesium ions soluble complexes that do not interfere with the washing process.
  • the zeolites and the layered silicates form with the calcium and magnesium ions insoluble complexes.
  • the zeolites significantly increase the amount of insoluble Preserve complexes. These particles present as a solid in the wash liquor must be kept in suspension by additional detergent ingredients do not deposit on the textile fiber. The same applies to other (solid) dirt particles and any precipitated components of water hardness.
  • Detergents for the automatic cleaning of dishes also need components included, which are able to keep the detached dirt in suspension and the To prevent re-depositing on the wash ware.
  • Suitable additional detergent ingredients are the so-called cobuilders, which are also known as Polyelectrolyte compounds are called. These include citric acid, nitrilotriacetic acid, Homopolymers and copolymers of acrylic acid, polyaspartic acid and starch oxidation products. The aforementioned ingredients can also be found in detergents and dishwashing detergents deploy.
  • polycarboxylates which are polymers with a molecular weight from about 2,000 to 100,000. They consist of different carboxylic acids and the corresponding monomers. In powder detergents and Also in dishwashing detergents, they are usually in the form of their neutral sodium salts, solid or in aqueous solution.
  • the amounts of builder are usually 10 to 40% by weight and that of cobuilders usually 1 to 10% by weight, based on the total amount of powdered laundry detergent.
  • the quantities added in a similar order of magnitude.
  • Powdered laundry detergents that contain crystalline silicates as builders usually require lower amounts of cobuilders than those containing only zeolite A as a builder.
  • zeolite A cannot be used in dishwashing detergents because of its insolubility only soluble components come into question here.
  • the quality or the mode of action of such a builder / cobuilder system for textile detergents can be measured, for example, with the so-called secondary washing behavior.
  • the secondary washing behavior indicates in particular to what extent such a builder / cobuilder system is able to prevent deposits on the laundry fibers.
  • the washed fabric is ashed and the amount of ash is determined gravimetrically.
  • the mode of action of the aforementioned builder / cobuilder systems can be used for dishwashing detergents with regard to the re-soiling of already cleaned dishes by visual sampling be recorded quantitatively with the help of a grading system.
  • the sodium polycarboxylates are used in the washing powder production introduced both as an aqueous solution and in powder form.
  • the aqueous Solution sprayed on the other solid detergent components to make a total free-flowing Get product.
  • This is a component with particularly good absorbency Layered silicate SKS-6 from Hoechst AG, Frankfurt am Main, which is capable of a good one To ensure that the washing powder flows freely.
  • the object of the invention is therefore to provide a composition make, with which the aforementioned disadvantages can be overcome and with the excellent Washing and cleaning results, in particular with regard to the secondary washing ability, can be achieved.
  • a powder detergent component characterized in that it is a reaction product of an alkaline silicate and an acidic polycarboxylate.
  • the weight ratio of alkaline silicate to acidic polycarboxylate is preferably (40 to 1): 1.
  • the weight ratio of alkaline silicate to acidic polycarboxylate is particularly preferred (20 to 2): 1.
  • the powdered detergent and cleaning agent component preferably contains 50 to 98 % By weight of alkaline silicate and 2 to 50% by weight of a copolymer of 10 to 70% by weight Maleic acid, 20 to 85% by weight acrylic acid and / or methacrylic acid, 1 to 50% by weight Vinyl acetate and 0 to 10% by weight of further monomers with a degree of neutralization of 0 up to 70%.
  • the alkaline silicate is preferably an amorphous sodium silicate.
  • the alkaline silicate is particularly preferably a crystalline one Sodium silicate.
  • the alkaline silicate is particularly preferably a crystalline one Sodium silicate.
  • the further elements and / or connections are preferably aluminum, Titanium, iron, calcium, magnesium and / or their compounds.
  • the above object is also achieved by a method for producing a powder Detergent and cleaning agent component, characterized in that apply an acidic polycarboxylate solution to an alkaline silicate.
  • the acidic polycarboxylate solution is preferably brought into a solid mixer, the one Contains liquid injection device based on the alkaline silicate.
  • reaction product of alkaline sodium silicate and acidic polycarboxylate solution is preferred at temperatures of 40 to 150 ° C for a time of 5 to 120 minutes dried.
  • the invention also relates to the use of the powdery form according to the invention Detergent and cleaning agent component for the production of detergents.
  • the powdered detergent and cleaning agent component according to the invention is preferred used for the production of detergents using the dry mix method.
  • the invention also relates to the use of the powdery form according to the invention Detergent and detergent component for the production of detergent compositions.
  • the powdered detergent and cleaning agent component according to the invention is preferred for the production of detergent compositions for cleaning hard Surfaces used.
  • the invention also relates to the use of the powdery form according to the invention Detergent and detergent component for the manufacture of dishwashing detergent compositions.
  • the powdered detergent and cleaning agent component according to the invention is preferred for the preparation of dishwasher detergent compositions for machine cleaning used by dishes.
  • the powder detergent component according to the invention are non-neutralized and / or partially neutralized acid group-containing polycarboxylates neutralized polymers containing acid groups.
  • These include the homopolymers of acrylic acid or methacrylic acid or their copolymers with further ethylenically unsaturated monomers such as acrolein, dimethylacrylic acid, Ethyl acrylic acid, vinyl acetic acid, allylacetic acid, maleic acid, fumaric acid, Itaconic acid, meth (allysulfonic acid), vinylsulfonic acid, styrene sulfonic acid, acrylamidomethyl propane sulfonic acid, and monomers containing phosphoric acid groups, such as, for example Vinylphosphonic acid, allylphosphonic acid and acrylamidomethylpropanephosphonic acid and their salts and hydroxyethyl (meth) acrylate sulfates, allyl alcohol sulfates and phosphates.
  • ethylenically unsaturated monomers such as acrolein, dimethylacrylic acid, Ethyl acrylic acid, vinyl acetic acid, allylacetic acid,
  • Graft polymers of monosaccharides, oligosaccharides, polysaccharides and modified polysaccharides, as described in DE-A-40 03 172 and DE-A-44 15 623, are also suitable for the use according to the invention.
  • the graft polymers described in EP-A-0 457 025 with proteins of animal and vegetable origin, in particular also with modified proteins, are also well suited for the use according to the invention.
  • polyaspartic acids or their derivatives in or not partially neutralized form are polyaspartic acids or their derivatives in or not partially neutralized form.
  • the polyaspartic acids usually fall in the form of their alkali metal or ammonium salt. From this you can get the non-neutralized or only partially neutralized products by adding appropriate amounts of organic or inorganic acids and, if necessary, separating them of the resulting salts.
  • Such products can also be achieved through the thermal conversion of maleic acid and ammonia or by the condensation of aspartic acid and the subsequent hydrolysis of the resulting polysuccinimide.
  • the manufacture of such products is for example in DE-A-36 26 672, DE-A-43 07 114, DE-A-44 27 287, EP-A-0 612 784, EP-A-0 644 257 and PCT / WO 92/14753.
  • Particularly suitable for the production of the powdered washing and Detergent components are graft polymers of acrylic acid, methacrylic acid, maleic acid and further ethylenically unsaturated monomers on salts of polyaspartic acid, as they usually occur in the hydrolysis of the polysuccinimide described above.
  • the otherwise necessary addition of acid to produce the only partially neutralized Form of polyaspartic acid can be dispensed with.
  • the amount of polyaspartate is usually chosen so that the degree of neutralization of all carboxyl groups incorporated in the polymer 80%, preferably 60%, does not exceed.
  • copolymers are prepared by the following examples, polymer 1 to polymer 5 described.
  • thermometer and metering devices 150 g of maleic anhydride, 200 g of sodium hydroxide solution (50 wt .-%), 360 g of water and 0.01 g of ammonium iron sulfate (Mohr's salt) and heated to 90 ° C with stirring.
  • 275 g of acrylic acid in 200 g of water and 100 g of sodium hydroxide solution (50% by weight) and a second solution of 1.5 g sodium persulfate and 15 g hydrogen peroxide (35% by weight) in 75 g of water.
  • the total time of metering is 4 hours.
  • the mixture is stirred for one hour under reflux and distilled then about 420 g of water.
  • a viscous solution with a dry matter content is obtained of about 55% by weight, a pH of 4.8 and a Brookfield viscosity of 55,000 mPa * s at 20 ° C.
  • the weight average molecular weight, determined by means of gel permeation chromatography, is 21,000 g / mol.
  • the mixture is stirred for one hour and then about 300 g of water are distilled off. you obtains a viscous, brown product with a dry matter content of about 55% by weight, a pH of 5.0 and a Brookfield viscosity of 84,000 mPa * s at 20 ° C.
  • the Weight-average molecular weight, determined by means of gel permeation chromatography, is 60,000 g / mol.
  • Examples 1 to 8 below describe the preparation of the powdery form according to the invention Detergent and detergent component and their application.
  • the powders have a significantly reduced alkalinity compared to pure SKS-6, as shown in Figure 1 from the representation of the reserve alkalinity (titration curve of 2 g of product with In HCl).
  • the reserve alkalinity indicates how much acid is required to lower a substance to a certain pH above 5.
  • Production of the washing and cleaning agent component according to the invention each using 2 kg of SKS-6 powder example Amount of polycarboxylate solution pH of the moist component after drying flowability % H 2 O % Active ingredient Cobuilder wet dried 1 222 11.66 3.5 5.6 15 23 2 500 11.59 5.5 11.5 11 28 3 1140 11.4 8th 22 11 270
  • Powdery textile detergents are produced in accordance with Examples 4 and 5, but instead of pure SKS-6 a mixture of SKS-6 and the powdery detergent and cleaning agent component SKS-6 / polycarboxylate in accordance with Example 3 is used.
  • SKS-6 powdery detergent and cleaning agent component
  • Example 3 powdery detergent and cleaning agent component
  • Examples 4 and 6 and 5 and 7 are the same and therefore placed side by side (Table 2).
  • the detergents from Examples 4 to 7 are subjected to a washing test and tested for their Secondary washing effect checked. This is done by using 5 standard fabrics together 4.5 kg of ballast tissue are washed 25 times and after every fifth wash by ashing of the standard tissue, the inorganic tissue deposits are determined. The Results are shown in Table 3.
  • Examples 9 and 10 below relate to the production and testing of a Dishwashing composition.
  • Example 9 The detergent additive used in Example 9 is one according to Table 1, Example 3. Its composition corresponds approximately to the sum of SKS-6 and sodium polycarboxylate in example 10.
  • the washing and cleaning agent component according to the invention in the present dishwashing agent formulation Example 9 is particularly high Cleaning ability off (test according to DIN 44990). It is particularly suitable for burned and to remove protein-containing food residues and tea stains. In addition, it has a pronounced Dispersion behavior, especially towards fiber-containing food residues.
  • the detergent and cleaning agent component according to the invention prevents Present dishwashing detergent glass and decor damage.

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (22)

  1. Constituant de détergents et de produits de nettoyage en poudre, caractérisé en ce qu'il contient un produit de réaction d'un silicate alcalin et d'un polycarboxylate acide.
  2. Constituant de détergents et de produits de nettoyage en poudre selon la revendication 1, caractérisé en ce que le rapport en masse du silicate alcalin au polycarboxylate acide est de (40 à 1) : 1.
  3. Constituant de détergents et de produits de nettoyage en poudre selon la revendication 1 ou 2, caractérisé en ce que le rapport en masse du silicate alcalin au polycarboxylate acide est de (20 à 2) : 1.
  4. Constituant de détergents et de produits de nettoyage en poudre selon l'une ou plusieurs des revendications 1 à 3, caractérisé en ce que l'on utilise comme polycarboxylate un homopolymère et/ou un copolymère d'acide acrylique, d'acide méthacrylique, d'acide maléique, de poly(acide aspartique), d'acide saccharique et/ou d'autres monomères, non neutralisé ou seulement partiellement neutralisé.
  5. Constituant de détergents et de produits de nettoyage en poudre selon l'une ou plusieurs des revendications 1 à 4, caractérisé en ce qu'il contient de 50 à 98 % en masse de silicate alcalin et de 2 à 50 % en masse d'un copolymère constitué de 10 à 70 % en masse d'acide maléique, de 20 à 85 % en masse d'acide acrylique et/ou d'acide méthacrylique, de 1 à 50 % en masse d'acétate de vinyle et de 0 à 10 % en masse d'autres monomères avec un degré de neutralisation de 0 à 70 %.
  6. Constituant de détergents et de produits de nettoyage en poudre selon l'une ou plusieurs des revendications 1 à 5, caractérisé en ce que le silicate alcalin est un silicate de formule xM2O ySiO2 zH2O avec un rapport molaire de SiO2 à M2O de (1 à 3,5) : 1, où z = 0 à 4 et M = Na et/ou K, qui peut contenir jusqu'à 1 % en masse d'autres éléments et/ou composés.
  7. Constituant de détergents et de produits de nettoyage en poudre selon l'une ou plusieurs des revendications 1 à 6, caractérisé en ce que le silicate alcalin est un silicate de sodium amorphe.
  8. Constituant de détergents et de produits de nettoyage en poudre selon l'une ou plusieurs des revendications 1 à 6, caractérisé en ce que le silicate alcalin est un silicate de sodium cristallin.
  9. Constituant de détergents et de produits de nettoyage en poudre selon la revendication 8, caractérisé en ce que le silicate alcalin est un phyllosilicate de sodium cristallin.
  10. Constituant de détergents et de produits de nettoyage en poudre selon l'une ou plusieurs des revendications 6 à 9, caractérisé en ce que les autres éléments et/ou composés sont l'aluminium, le titane, le fer, le calcium, le magnésium et/ou leurs composés.
  11. Procédé de préparation d'un constituant de détergents et de produits de nettoyage en poudre, caractérisé en ce que l'on applique une solution de polycarboxylate acide sur un silicate alcalin.
  12. Procédé selon la revendication 11, caractérisé en ce que l'on applique 2 à 60 parties en masse de solution de polycarboxylate acide sur 100 parties en masse de silicate alcalin.
  13. Procédé selon la revendication 11 ou 12, caractérisé en ce que l'on applique 10 à 40 parties en masse de solution de polycarboxylate acide sur 100 parties en masse de silicate alcalin.
  14. Procédé selon l'une ou plusieurs des revendications 11 à 13, caractérisé en ce que l'on utilise comme solution de polycarboxylate un homopolymère et/ou un copolymère d'acide acrylique, d'acide méthacrylique, d'acide maléique, de poly(acide aspartique), d'acide saccharique et/ou d'autres monomères, non neutralisé ou seulement partiellement neutralisé.
  15. Procédé selon l'une ou plusieurs des revendications 11 à 14, caractérisé en ce que l'on applique la solution de polycarboxylate sur le silicate alcalin dans un mélangeur de produits solides contenant un dispositif de pulvérisation d'un liquide.
  16. Procédé selon l'une ou plusieurs des revendications 11 à 15, caractérisé en ce que l'on sèche le produit de réaction du silicate alcalin et de la solution de polycarboxylate acide à des températures de 40 à 150°C pendant un temps de 5 à 120 minutes.
  17. Utilisation du constituant de détergents et de produits de nettoyage en poudre selon au moins l'une des revendications 1 à 10 ou préparé par le procédé des revendications 11 à 16 pour la préparation de détergents.
  18. Utilisation du constituant de détergents et de produits de nettoyage en poudre selon au moins l'une des revendications 1 à 10 ou préparé par le procédé des revendications 11 à 16 pour la préparation de détergents en poudre selon le procédé de mélange à sec.
  19. Utilisation du constituant de détergents et de produits de nettoyage en poudre selon au moins l'une des revendications 1 à 10 ou préparé par le procédé des revendications 11 à 16 pour la préparation de compositions de produits de nettoyage.
  20. Utilisation du constituant de détergents et de produits de nettoyage en poudre selon au moins l'une des revendications 1 à 10 ou préparé par le procédé des revendications 11 à 16 pour la préparation de compositions de produits de nettoyage pour le nettoyage de surfaces dures.
  21. Utilisation du constituant de détergents et de produits de nettoyage en poudre selon au moins l'une des revendications 1 à 10 ou préparé par le procédé des revendications 11 à 16 pour la préparation de compositions détergentes pour la vaisselle.
  22. Utilisation du constituant de détergents et de produits de nettoyage en poudre selon au moins l'une des revendications 1 à 10 ou préparé par le procédé des revendications 11 à 16 pour la préparation de compositions détergentes pour la vaisselle pour le lavage de la vaisselle à la machine.
EP97121407A 1996-12-21 1997-12-05 Composants de lavage et de nettoyage sous forme de poudre Expired - Lifetime EP0849355B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19653949 1996-12-21
DE19653949 1996-12-21
DE19719888 1997-05-12
DE19719888A DE19719888A1 (de) 1996-12-21 1997-05-12 Pulverförmige Wasch- und Reinigungsmittel-Komponente

Publications (3)

Publication Number Publication Date
EP0849355A2 EP0849355A2 (fr) 1998-06-24
EP0849355A3 EP0849355A3 (fr) 1999-12-15
EP0849355B1 true EP0849355B1 (fr) 2004-03-17

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EP97121407A Expired - Lifetime EP0849355B1 (fr) 1996-12-21 1997-12-05 Composants de lavage et de nettoyage sous forme de poudre

Country Status (11)

Country Link
US (1) US7256169B2 (fr)
EP (1) EP0849355B1 (fr)
JP (1) JP3258952B2 (fr)
CN (1) CN1186110A (fr)
CA (1) CA2226071C (fr)
CZ (1) CZ414697A3 (fr)
ES (1) ES2218632T3 (fr)
HU (1) HUP9702513A3 (fr)
NO (1) NO975974L (fr)
PL (1) PL323895A1 (fr)
TW (1) TW386109B (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19819187A1 (de) 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
DE19960744A1 (de) 1999-12-16 2001-07-05 Clariant Gmbh Granulares Alkalischichtsilicat-Compound
DE10056346A1 (de) * 2000-11-14 2002-05-16 Clariant Gmbh Builder-Zusammensetzung
DE10121051A1 (de) 2001-04-28 2002-10-31 Clariant Gmbh Builder-Zusammensetzung
DE10334047A1 (de) 2003-07-25 2005-02-24 Clariant Gmbh Adsorbat aus Schichtsilicat und seine Verwendung
KR100817687B1 (ko) * 2004-09-10 2008-03-27 주식회사 엘지생활건강 산성형태의 수용성 고분자와 유기산을 함유하는 저밀도분말세제 조성물 및 그의 제조방법
KR100751556B1 (ko) 2005-08-22 2007-08-22 주식회사 엘지생활건강 분말 세제 조성물 및 그 제조방법
KR101392380B1 (ko) * 2007-02-21 2014-05-07 주식회사 엘지생활건강 산성형태의 수용성 고분자를 함유하는 분말세제 입자 및그의 제조방법
US7999040B2 (en) * 2007-09-25 2011-08-16 Nanochem Solutions, Inc. Method of making graft copolymers from sodium poly(aspartate) and the resulting graft copolymer
EP2277982B1 (fr) 2009-07-17 2012-01-18 Clariant Finance (BVI) Limited Composition de nettoyage à changement de couleur
JP5385773B2 (ja) * 2009-12-22 2014-01-08 花王株式会社 衣料洗剤用高分子ビルダー
JP5628552B2 (ja) * 2010-04-30 2014-11-19 花王株式会社 アルカリ金属珪酸塩粒子

Family Cites Families (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1514A (en) * 1840-03-14 Machine for laying on veneers straight or curved
NL157021B (nl) 1973-11-15 1978-06-15 Degussa Werkwijze ter bereiding van polycarboxylaten met verbeterde biologische afbreekbaarheid.
US5175361A (en) 1981-09-28 1992-12-29 Basf Aktiengesellschaft Preparation of copolymers of monoethylenically unsaturated monocarboxylic acids and dicarboxylic acids
DE3626672A1 (de) 1986-08-07 1988-02-11 Bayer Ag Polyasparaginamidsaeure
CA2044151C (fr) * 1989-10-19 1996-01-09 Toshio Yanaki Materiau complexe mineral de polymere-silicate hydrophile, et utilisation
DE4003172A1 (de) 1990-02-03 1991-08-08 Basf Ag Pfropfcopolymerisate von monosacchariden, oligosacchariden, polysacchariden und modifizierten polysacchariden, verfahren zu ihrer herstellung und ihre verwendung
DE4008696A1 (de) 1990-03-17 1991-09-19 Basf Ag Verfahren zur herstellung von homo- und copolymerisaten monoethylenisch ungesaettigter dicarbonsaeuren und ihre verwendung
DE4016057A1 (de) 1990-05-18 1991-11-21 Man Nutzfahrzeuge Ag Pendelschranke am durchgang zum fahrgastraum von omnibussen mit rollstuhllift
GB9018157D0 (en) * 1990-08-17 1990-10-03 Procter & Gamble Detergent compositions
DE4034131C2 (de) * 1990-10-26 1999-08-26 Henkel Kgaa Gerüststoff für Waschmittel
US5221733A (en) 1991-02-22 1993-06-22 Donlar Corporation Manufacture of polyaspartic acids
US5315010A (en) 1991-02-22 1994-05-24 Donlar Corporation Polyaspartic acid manufacture
US5540855A (en) * 1991-04-23 1996-07-30 The Procter & Gamble Company Particulate detergent compositions
DE4221381C1 (de) 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Zuckern, Verfahren zu ihrer Herstellung und ihre Verwendung
US5576277A (en) * 1992-03-10 1996-11-19 The Procter & Gamble Company Granular detergent compositions
DE4300772C2 (de) 1993-01-14 1997-03-27 Stockhausen Chem Fab Gmbh Wasserlösliche, biologisch abbaubare Copolymere auf Basis von ungesättigten Mono- und Dicarbonsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung
US5610255A (en) 1993-02-22 1997-03-11 Bayer Ag Process for preparing polysuccinimide and polyaspartic acid
DE4307114A1 (de) 1993-03-06 1994-09-08 Basf Ag Verfahren zur Herstellung von Umsetzungsprodukten aus Polyasparaginsäureamid und Aminosäuren und ihre Verwendung
US5780410A (en) * 1993-07-14 1998-07-14 The Procter & Gamble Company Detergent compositions containing percarbonate and making processes thereof
EP0643129A1 (fr) * 1993-09-07 1995-03-15 The Procter & Gamble Company Procédé de préparation de compositions détergentes
US5698510A (en) * 1993-09-13 1997-12-16 The Procter & Gamble Company Process for making granular detergent compositions comprising nonionic surfactant
US5457176A (en) 1993-09-21 1995-10-10 Rohm And Haas Company Acid catalyzed process for preparing amino acid polymers
CA2132112A1 (fr) 1993-09-21 1995-03-22 David Elliott Adler Methode de catalysation acide pour l'obtention de polymeres d'acide amine
US5773400A (en) * 1993-12-10 1998-06-30 The Procter & Gamble Company Nil-phosphate granular detergent compositions which contain percarbonate and sulfate particles
US5972040A (en) * 1993-12-21 1999-10-26 The Procter & Gamble Company Detergent compositions containing percarbonate and amylase
US5883064A (en) * 1993-12-21 1999-03-16 The Procter & Gamble Company Protease containing dye transfer inhibiting composition
DE4343993A1 (de) 1993-12-22 1995-06-29 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Polyhydroxyverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4415623A1 (de) 1994-05-04 1995-11-09 Basf Ag Verwendung von Pfropfpolymerisaten von monoethylenisch ungesättigten Dicarbonsäuren auf hydrierten Sacchariden als Zusatz zu Wasch- und Reinigungsmitteln
USH1514H (en) * 1994-06-01 1996-01-02 The Procter & Gamble Company Detergent compositions with oleoyl sarcosinate and polymeric dispersing agent
DE4427287A1 (de) 1994-08-02 1996-02-08 Basf Ag Verfahren zur Herstellung von Polykondensaten der Asparaginsäure mit verbesserter biologischer Abbaubarkeit und ihre Verwendung
DE4439978A1 (de) 1994-11-09 1996-05-15 Stockhausen Chem Fab Gmbh Verfahren zur Herstellung von Terpolymeren
US5534179A (en) * 1995-02-03 1996-07-09 Procter & Gamble Detergent compositions comprising multiperacid-forming bleach activators
DE19516957C2 (de) * 1995-05-12 2000-07-13 Stockhausen Chem Fab Gmbh Wasserlösliche Copolymere und Verfahren zu ihrer Herstellung und ihre Verwendung
US5965507A (en) * 1995-06-08 1999-10-12 Procter & Gamble Company Cleaning compositions comprising chondroitinase
US5663133A (en) * 1995-11-06 1997-09-02 The Procter & Gamble Company Process for making automatic dishwashing composition containing diacyl peroxide
CA2248160C (fr) * 1996-03-08 2002-08-06 The Procter & Gamble Company Preparation de particules de sulfate alkyle secondaire possedant une meilleure solubilite

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CN1186110A (zh) 1998-07-01
HUP9702513A2 (hu) 1999-06-28
NO975974L (no) 1998-06-22
CA2226071A1 (fr) 1998-06-21
HU9702513D0 (en) 1998-03-02
CA2226071C (fr) 2003-01-07
JPH10251686A (ja) 1998-09-22
CZ414697A3 (cs) 1998-07-15
TW386109B (en) 2000-04-01
NO975974D0 (no) 1997-12-19
PL323895A1 (en) 1998-06-22
HUP9702513A3 (en) 2000-08-28
EP0849355A2 (fr) 1998-06-24
ES2218632T3 (es) 2004-11-16
EP0849355A3 (fr) 1999-12-15
JP3258952B2 (ja) 2002-02-18
US7256169B2 (en) 2007-08-14
US20040176268A1 (en) 2004-09-09

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