EP0628627B1 - Wasserlöslicher, wasserenthärtender Builder - Google Patents

Wasserlöslicher, wasserenthärtender Builder Download PDF

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Publication number
EP0628627B1
EP0628627B1 EP94108688A EP94108688A EP0628627B1 EP 0628627 B1 EP0628627 B1 EP 0628627B1 EP 94108688 A EP94108688 A EP 94108688A EP 94108688 A EP94108688 A EP 94108688A EP 0628627 B1 EP0628627 B1 EP 0628627B1
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Prior art keywords
weight
water
polymer
softening
softening builder
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EP94108688A
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English (en)
French (fr)
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EP0628627A1 (de
Inventor
Guido Dr. Wäschenbach
Manfred Müller
Harald Ahnsorge
Wolfgang Dr. Ussat
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Reckitt Benckiser NV
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Joh A Benckiser GmbH
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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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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 water-soluble, predominantly organic, water-softening builder.
  • DE 36 14 779 discloses a granular, phosphate-free water softener for softening wash liquors and also as an additive to detergents, which consists of 50-60% by weight of finely crystalline zeolite, 3-5% by weight sodium salt of a polyacrylic acid, polymethacrylic acid or acrylic acid-maleic acid Copolymers, 4-15% by weight sodium citrate, 4-12% by weight sodium carbonate and optionally up to 2% by weight sodium carboxymethyl cellulose.
  • DE 40 22 005 discloses a mild detergent which, as the only builder, contains a combination of a water-soluble citrate with a polyacrylate or a polymer of acrylic acid and maleic acid.
  • DE 36 03 471 discloses a low-phosphorus or phosphorus-free washing and / or cleaning agent which contains a surfactant, an inorganic and / or organic builder and at least one colloidal layered silicate, and additionally at least one water-soluble calcium and / or magnesium salt and polyacrylic acid .
  • DE 39 31 871 describes a granular, phosphate-free water softening agent containing 50-70% by weight of finely crystalline zeolite, 2-10% by weight of a layered silicate, 5-15% by weight of the sodium salt of a (co) polymeric carboxylic acid and 1-10% by weight % Sodium sulfate.
  • DE 39 43 019 discloses a granular detergent additive containing 20-45% by weight of a layered silicate, 15-50% by weight of a finely crystalline, synthetic zeolite, 0-15% by weight of a sulfate, carbonate of the phosphate, 0-8% by weight the sodium salt of a homopolymeric or copolymeric (meth) acrylic acid, 0-2% by weight of cellulose ether, 0-20% by weight of nonionic surfactants from the class of polyglycol ethers.
  • a similar spray-dried composition is disclosed in DE 40 09 618.
  • FR-PS 1 599 547 discloses a composition for inhibiting scale formation by alkaline earth metal salts in aqueous systems, comprising a carboxylic acid such as citric acid and a water-soluble organic polymer such as an acrylic acid polymer or copolymer.
  • CH-PS 577 937 discloses an agent in tablet form for preventing limescale, containing either citric acid and additions of acetylsalicylic acid and / or boric acid and / or nicotinic acid or nicotinic acid.
  • the applicant has set itself the task of providing a water softener in an easily manageable, well metered form.
  • a water-soluble, water-softening builder in the form of a tablet, the tablet having a specific composition which, on the one hand, makes the tablet easy to handle, on the other hand, a rapid dissolution of the tablet in the wash liquor is guaranteed.
  • the polymers to be used as softeners in accordance with the invention in combination with citrate and / or citric acid are known substances.
  • Maleic acid / acrylic acid copolymers and preferably biodegradable polymers, in particular those based on peptides, are suitable for this.
  • Such peptide-based polymers are, for example, the Cygnus products from Cygnus Corporation.
  • Serine-N-N-diacetic acid derivatives suitable as builders are described in EP 287 885.
  • Maleic acid / acrylic acid copolymers suitable as builders are commercially available under various Sokalan brands, for example a maleic acid / acrylic acid copolymer, sodium salt, under the "Sokalan CP 5" brand.
  • An essential component of the builder tablets according to the invention is the polyethylene glycol, which should be present in an amount of 0.5-6% by weight, preferably 1-3% by weight.
  • Suitable polyethylene glycols are the polyethylene glycols (1000-6000), in particular polyethylene glycol (4000-6000). These polyethylene glycols act as tableting aids. That polyethylene glycol as a tabletting aid was known. However, it was surprisingly found that while there were difficulties in dissolving other tableting aids, the polyethylene glycols mentioned are particularly suitable for the purpose according to the invention.
  • a polyethylene glycol with a low degree of ethoxylation for example polyethylene glycol 200, is not suitable as a tabletting agent, but is suitable as a dust-binding agent and as such can also be present in the tablet according to the invention in a small amount, for example in an amount of 0.5-5% by weight.
  • the tablet according to the invention should contain a disintegrant.
  • An insoluble polyvinylpyrrolidone which can be present in an amount of 1-20% by weight, preferably 7-12% by weight, is suitable as such.
  • a polyvinylpyrrolidone suitable for this purpose is commercially available under the "Sokalan HP 50" brand.
  • the builder combination (A) it is particularly preferred in the builder combination (A) to use partially neutralized, acidic polymer as component (a) citric acid and / or as component (b) and as a further auxiliary carbonate and / or bicarbonate, for example sodium carbonate, sodium hydrogen carbonate and / or potassium carbonate, which in combination with the aforementioned acidic component serves as a disintegrant.
  • the carbonate / bicarbonate can be used in amounts of 5-30% by weight.
  • the builders mentioned in combination (A) according to the invention are preferably the only builders in the tablet.
  • Zeolites are preferably not used, although the tablet may optionally contain 5-20% by weight of a layered silicate, which makes the builder particularly suitable for hard water with high proportions of magnesium hardness.
  • cellulose derivatives such as methylhydroxyethyl cellulose, or paraffin oil can also be used in small quantities.
  • a preferred builder tablet according to the present invention contains: 16-40% by weight, preferably 18-35% by weight trisodium citrate, 14-21% by weight, preferably 17-19% by weight citric acid, 20-40% by weight, preferably 30-36% by weight maleic acid / acrylic acid Copolymer, Na salt and / or polymer based on peptides, 2-5% by weight polyethylene glycol (4000-6000) 15-30% by weight carbonate / bicarbonate 1-2% by weight polyvinylpyrrolidone
  • the builder tablet according to the invention has particular advantages when used with colorful textiles. It ensures very good color retention and avoids color transfer.
  • a builder tablet was pressed from the following components: Maleic acid / acrylic acid copolymer, granules (Sokalan ® CP 45), pH 4 30% Trisodium citrate 19% Citric acid 18% sodium 30% Paraffin oil 0.2% Polyethylene glycol (1500) 2.8% 100.0% ⁇

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Developing Agents For Electrophotography (AREA)

Description

  • Gegenstand der Erfindung ist ein wasserlöslicher, vorwiegend organischer, wasserenthärtender Builder.
  • Die DE 36 14 779 offenbart ein granulares, phosphatfreies Wasserenthärtungsmittel zum Enthärten von Waschlaugen als auch als Zusatz zu Waschmitteln, welches aus 50-60 Gew.% feinkristallinem Zeolith, 3-5 Gew.% Natriumsalz eines Polyacrylsäure-, Polymethacrylsäure- oder Acrylsäure-Maleinsäure-Copolymeren, 4-15 Gew.% Natriumcitrat, 4-12 Gew.% Natriumcarbonat und gegebenenfalls bis zu 2 Gew.% Natrium-Carboxymethylcellulose besteht.
  • In der DE 40 22 005 wird ein Feinwaschmittel offenbart, welches als einzigen Builder eine Kombination aus einem wasserlöslichen Citrat mit einem Polyacrylat oder einem Polymer aus Acrylsäure und Maleinsäure enthält.
  • Die DE 36 03 471 offenbart ein phosphorarmes, bzw. phosphorfreies Wasch- und/oder Reinigungsmittel, welches ein Tensid, einen anorganischen und/oder organischen Builder und mindestens ein kolloidales Schichtsilikat enthält, sowie zusätzlich mindestens ein wasserlösliches Kalzium- und/oder Magnesiumsalz und Polyacrylsäure.
  • Die DE 39 31 871 beschreibt ein granulares, phosphatfreies Wasserenthärtungsmittel enthaltend 50-70 Gew.% feinkristallinen Zeolith, 2-10 Gew.% eines Schichtsilikates, 5-15 Gew.% des Natriumsalzes einer (Co-)polymeren Carbonsäure und 1-10 Gew.% Natriumsulfat.
  • Die DE 39 43 019 offenbart ein granulares Waschmitteladditiv enthaltend 20-45 Gew.% eines Schichtsilikates, 15-50 Gew.% eines feinkristallinen, synthetischen Zeoliths, 0-15 Gew.% eines Sulfats, Carbonats der Phosphats, 0-8 Gew.% des Natriumsalzes einer homopolymeren, bzw. copolymeren (Meth-)acrylsäure, 0-2 Gew.% an Celluloseether, 0-20 Gew.% an nichtionischen Tensiden aus der Klasse der Polyglykolether. Eine ähnliche sprühgetrocknete Zusammensetzung wird in der DE 40 09 618 offenbart.
  • Die FR-PS 1 599 547 offenbart eine Zusammensetzung zur Inhibierung der Kesselsteinbildung durch Erdalkalisalze in wässrigen Systemen, enthaltend eine Carbonsäure wie beispielsweise Zitronensäure und ein wasserlösliches organisches Polymer wie beispielsweise ein Acrylsäurepolymer oder -copolymer.
  • Die CH-PS 577 937 offenbart ein Mittel in Tablettenform zur Verhinderung von Kalkansatz, enthaltend entweder Zitronensäure und Zusätze von Acetylsalizylsäure und/oder Borsäure und/oder Nikotinsäure oder Nikotinsäure.
  • Es ist dem Fachmann bekannt und durch den zitierten Stand der Technik dokumentiert, daß Waschmitteladditive und insbesondere Wasserenthärter bislang in möglichst kleinteiliger, vorzugsweise Pulverform, allenfalls in Granulatform angeboten werden, da die Meinung bestand, daß nur dadurch die erforderliche schnelle Löslichkeit eines Wasserenthärters gewährleistet werden kann.
  • Die Anmelderin hat sich zur Aufgabe gesetzt, einen Wasserenthärter in leicht handhabbarer, gut dosierbarer Form zur Verfügung zu stellen.
  • Erfindungsgemäß wird dies durch einen wasserlöslichen, wasserenthärtenden Builder in Form einer Tablette erreicht, wobei die Tablette eine bestimmte Zusammensetzung aufweist, die einerseits eine gute Handhabbarkeit der Tablette, andererseits eine schnelle Auflösung der Tablette in der Waschlauge gewährleistet.
  • Der erfindungsgemäße wasserlösliche, wasserenthärtende Builder in Form einer Tablette besteht aus
    • A) 60-98 Gew.% einer Kombination aus
      • a) Citrat und/oder Citronensäure und
      • b) einem als Enthärter wirksamen Polymer
      in einem Gewichtsverhältnis von a:b von 70:30 bis 50:50, vorzugsweise 65:35 bis 55:45,
    • B) 0,5-6 Gew.% Polyethylenglykol
    • C) 0-38 Gew.% weiterer Hilfsstoffe.
  • Die erfindungsgemäß in Kombination mit Citrat und/oder Citronensäure einzusetzenden, als Enthärter wirksamen Polymeren sind bekannte Substanzen. Hierfür eignen sich Maleinsäure/Acrylsäure-Copolymerisate und vorzugsweise biologisch abbaubare Polymere, insbesondere solche auf Peptid-Basis. Solche Polymere auf Peptid-Basis sind beispielsweise die Cygnus-Produkte der Cygnus Corporation. Als Builder geeignete Serin-N-N-Diessigsäurederivate werden in der EP 287 885 beschrieben.
  • Als Builder geeignete Maleinsäure/Acrylsäure-Copolymerisate sind unter verschiedenen Sokalan-Marken im Handel, beispielsweise ein Maleinsäure/Acrylsäure-Copolymerisat, Natriumsalz, unter der Marke "Sokalan CP 5".
  • Ein wesentlicher Bestandteil der erfindungsgemäßen Buildertabletten stellt das Polyethylenglykol dar, welches in einer Menge von 0,5-6 Gew.%, vorzugsweise 1-3 Gew.%, anwesend sein sollte. Als geeignete Polyethylenglykole sind die Polyethylenglykole (1000-6000) zu nennen, insbesondere Polyethylenglykol (4000-6000). Diese Polyethylenglykole wirken als Tablettierungshilfsmittel. Daß Polyethylenglykol als Tablettierungshilfsmittel brauchbar ist, war bekannt. Jedoch ergab sich überraschenderweise, daß, während bei anderen Tablettierungshilfsmitteln Auflösungsschwierigkeiten sich ergaben, die genannten Polyethylenglykole für den erfindungsgemäßen Zweck vorzüglich geeignet sind.
  • Ein Polyethylenglykol mit niederem Ethoxylierungsgrad, beispielsweise Polyethylenglykol 200, eignet sich nicht als Tablettierungsmittel, wohl aber als Staubbindemittel und kann als solches in der erfindungsgemäßen Tablette ebenfalls in geringer Menge, beispielsweise in einer Menge von 0,5-5 Gew.%, anwesend sein.
  • Die erfindungsgemäße Tablette sollte ein Sprengmittel enthalten. Als solches eignet sich ein unlösliches Polyvinylpyrrolidon, welches in einer Menge von 1-20 Gew.%, vorzugsweise 7-12 Gew.%, vorliegen kann. Ein für diesen Zweck geeignetes Polyvinylpyrrolidon ist unter der Marke "Sokalan HP 50" im Handel.
  • Es wird jedoch besonders bevorzugt in der Builderkombination (A) als Komponente (a) Citronensäure und/oder als Komponente (b) teilneutralisiertes, sauer wirkendes Polymer einzusetzen und als weiteren Hilfsstoff Carbonat und/oder Bicarbonat, beispielsweise Natriumcarbonat, Natriumhydrogencarbonat und/oder Kaliumcarbonat, welches in Kombination mit der vorerwähnten sauren Komponente als Sprengmittel dient. Das Carbonat/Bicarbonat kann in Mengen von 5-30 Gew.% eingesetzt werden.
  • Vorzugsweise stellen die in der erfindungemäßen Kombination (A) genannten Builder die einzigen Builder in der Tablette dar. Zeolithe werden vorzugsweise nicht mitverwendet, obwohl gegebenenfalls die Tablette 5-20 Gew.% eines Schichtsilikates enthalten kann, was den Builder besonders geeignet macht für hartes Wasser mit hohen Anteilen Magnesiumhärte.
  • Als weitere Hilfsmittel zusätzlich zu den bereits genannten können beispielsweise Cellulosederivate, wie Methylhydroxyethylcellulose, oder Paraffinöl in geringen Mengen mitverwendet werden.
  • Eine bevorzugte Builder-Tablette gemäß vorliegender Erfindung enthält:
    16-40 Gew.%, vorzugsweise 18-35 Gew.% Trinatriumcitrat, 14-21 Gew.%, vorzugsweise 17-19 Gew.% Citronensäure, 20-40 Gew.%, vorzugsweise 30-36 Gew.% Maleinsäure/Acrylsäure-Copolymerisat, Na-Salz und/oder Polymer auf Peptidbasis, 2-5 Gew.% Polyethylenglykol (4000-6000) 15-30 Gew.% Carbonat/Bicarbonat 1-2 Gew.% Polyvinylpyrrolidon
  • Die erfindungsgemäße Buildertablette besitzt besondere Vorteile bei Anwendung mit bunten Textilien. Sie gewährleistet hierbei sehr guteFarberhaltung und vermeidet eine Farbübertragung.
  • Außerdem wirkt sie einer Vergrauung bei weißen Textilien entgegen, verringert den Wäscheverschleiß und die Knitterbildung der Wäsche, erhält die natürliche Weichheit der Textilien durch deutliche Inkrustationsverminderung und verringert den Gewebeschrumpf insbesonders bei der Heißwäsche (60 - 95°C) von Baumwolltextilien.
    Figure imgb0001
    • Beispiel 10:
  • Aus folgenden Bestandteilen wurde eine Builder-Tablette gepreßt:
    Maleinsäure/Acrylsäure-Copolymerisat, Granulat (Sokalan ® CP 45), pH 4 30 %
    Trinatriumcitrat 19 %
    Citronensäure 18 %
    Natriumcarbonat 30 %
    Paraffinöl 0,2 %
    Polyethylenglykol (1500) 2,8%
    100,0 % ¯
    Figure imgb0002

Claims (9)

  1. Wasserlöslicher, wasserenthärtender Builder in Form einer Tablette bestehend aus
    A) 60-98 Gew.% einer Kombination aus
    a) Citrat und/oder Citronensäure und
    b) einem als Enthärter wirksamen Polymer
    in einem Gewichtsverhältnis von a:b von 70:30 bis 50:50, vorzugsweise 65:35 bis 55:45,
    B) 0,5-6 Gew.% Polyethylenglykol
    C) 0-38 Gew.% weiterer Hilfsstoffe.
  2. Wasserenthärtender Builder nach Anspruch 1, dadurch gekennzeichnet, daß das Polymer ein biologisch abbaubares Polymer auf Peptid-Basis ist.
  3. Wasserenthärtender Builder nach Anspruch 1, dadurch gekennzeichnet, daß das Polymer ein Maleinsäure/Acrylsäure Copolymerisat ist.
  4. Wasserenthärtender Builder nach einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß als Komponente (a) Citronensäure und/oder als Komponente (b) teilneutralisiertes, sauer wirkendes Polymer eingesetzt werden und als Komponente (C) Carbonat und/oder Bicarbonat als Sprengmittel.
  5. Wasserenthärtender Builder nach einem der vorgehenden Ansprüche , dadurch gekennzeichnet, daß er 1-3 Gew.% Polyethylenglykol (1.000-6.000) enthält.
  6. Wasserenthärtender Builder nach einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß er als weiteren Hilfsstoff 0,5-5 Gew.% Polyethylenglykol (200) als Staubbindemittel enthält.
  7. Wasserenthärtender Builder nach einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß er als weiteren Hilfsstoff 1-20 Gew.% eines unlöslichen Polyvinylpyrrolidons als Sprengmittel enthält.
  8. Wasserenthärtender Builder nach einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß er als weiteren Hilfsstoff 5-20 Gew.% eines Schichtsilikats enthält.
  9. Wasserenthärtender Builder nach einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß er
    a1) 16-40 Gew.%, vorzugsweise 18-35 Gew.% Trinatriumcitrat,
    a2) 14-21 Gew.%, vorzugsweise 17-19 Gew.% Citronensäure,
    b) 20-40 Gew.%, vorzugsweise 30-36 Gew.% Maleinsäure/Acrylsäure-Copolymerisat, Na-Salz und/oder Polymer auf Peptidbasis,
    2-5 Gew.% Polyethylenglykol (4000-6000)
    15-30 Gew.% Carbonat/Bicarbonat
    1-2 Gew.% Polyvinylpyrrolidon enthält.
EP94108688A 1993-06-07 1994-06-07 Wasserlöslicher, wasserenthärtender Builder Expired - Lifetime EP0628627B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI9430037T SI0628627T1 (en) 1993-06-07 1994-06-07 Water-soluble, water softening builder

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4318902A DE4318902C2 (de) 1993-06-07 1993-06-07 Wasserlösliches, wasserenthärtendes Mittel
DE4318902 1993-06-07

Publications (2)

Publication Number Publication Date
EP0628627A1 EP0628627A1 (de) 1994-12-14
EP0628627B1 true EP0628627B1 (de) 1997-03-12

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EP (1) EP0628627B1 (de)
AT (1) ATE150081T1 (de)
DE (2) DE4318902C2 (de)
DK (1) DK0628627T3 (de)
ES (1) ES2098820T3 (de)
GR (1) GR3023207T3 (de)
SI (1) SI0628627T1 (de)

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DE4404279A1 (de) * 1994-02-10 1995-08-17 Henkel Kgaa Tablette mit Buildersubstanzen
EP0736595A1 (de) * 1995-04-03 1996-10-09 The Procter & Gamble Company Zusammensetzungen zum Einweichen
DE19606765A1 (de) * 1996-02-23 1997-08-28 Henkel Kgaa Verfahren zur Herstellung von Geschirrspülmitteltabletten
DE19714657C1 (de) * 1997-04-09 1999-01-07 Benckiser Nv Wasserlöslicher, wasserenthärtender Builder
EP1004661A1 (de) 1998-11-11 2000-05-31 DALLI-WERKE WÄSCHE- und KÖRPERPFLEGE GmbH & Co. KG Verdichtetes Granulat, Herstellungsverfahren und Verwendung als Sprengmittel für gepresste Formkörper (2)
DE19858888A1 (de) * 1998-12-19 2000-06-21 Henkel Kgaa Verhinderung von Ablagerungen
DE19937428A1 (de) * 1999-08-07 2001-02-08 Henkel Kgaa Reinigungs- und Waschmittelformkörper
US20030104969A1 (en) 2000-05-11 2003-06-05 Caswell Debra Sue Laundry system having unitized dosing
DE10123621B4 (de) * 2001-05-15 2006-12-07 Henkel Kgaa Verfahren zur Herstellung einer Wasserenthärtertablette
GB2410496A (en) * 2004-01-31 2005-08-03 Reckitt Benckiser Nv Water softening tablets
GB0415316D0 (en) * 2004-07-08 2004-08-11 Reckitt Benckiser Nv Method of removing laundry ash
GB0415291D0 (en) * 2004-07-08 2004-08-11 Reckitt Benckiser Nv Method of removing laundry ash
DE102007059677A1 (de) * 2007-12-10 2009-06-25 Henkel Ag & Co. Kgaa Reinigungsmittel
CA2770869A1 (en) * 2009-09-02 2011-03-10 Unilever Plc Composition and process for treatment of a fabric
US8476219B2 (en) 2009-11-05 2013-07-02 The Procter & Gamble Company Laundry scent additive
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ES2098820T3 (es) 1997-05-01
EP0628627A1 (de) 1994-12-14
DE4318902C2 (de) 1996-10-24
ATE150081T1 (de) 1997-03-15
DK0628627T3 (da) 1997-08-25
SI0628627T1 (en) 1997-10-31
DE59402005D1 (de) 1997-04-17
GR3023207T3 (en) 1997-07-30
DE4318902A1 (de) 1994-12-08

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