WO1997013831A1 - Additif de lessive - Google Patents

Additif de lessive Download PDF

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Publication number
WO1997013831A1
WO1997013831A1 PCT/EP1996/004337 EP9604337W WO9713831A1 WO 1997013831 A1 WO1997013831 A1 WO 1997013831A1 EP 9604337 W EP9604337 W EP 9604337W WO 9713831 A1 WO9713831 A1 WO 9713831A1
Authority
WO
WIPO (PCT)
Prior art keywords
detergent
surfactant
agglomerate
detergent additive
optical brightener
Prior art date
Application number
PCT/EP1996/004337
Other languages
German (de)
English (en)
Inventor
Norbert Schall
Wolfgang Heininger
Rüdiger Hirsch
Original Assignee
Süd-Chemie AG
Dalli-Werke Wäsche- und Körperpflege GmbH & Co. KG
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 Süd-Chemie AG, Dalli-Werke Wäsche- und Körperpflege GmbH & Co. KG filed Critical Süd-Chemie AG
Priority to JP09514693A priority Critical patent/JP2000512320A/ja
Priority to EP96934551A priority patent/EP0856046B1/fr
Priority to AT96934551T priority patent/ATE234912T1/de
Priority to DE59610244T priority patent/DE59610244D1/de
Publication of WO1997013831A1 publication Critical patent/WO1997013831A1/fr

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
    • C11D3/02—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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents

Definitions

  • the invention relates to a detergent additive which contains at least one swellable layered silicate and further additive components.
  • DE-A-34 34 854 describes a process for producing a granular, free-flowing detergent component which contains inorganic carrier substances (in particular sodium aluminosilicates of the zeolite A type), surfactants and optical brighteners.
  • inorganic carrier substances in particular sodium aluminosilicates of the zeolite A type
  • surfactants in particular sodium aluminosilicates of the zeolite A type
  • optical brighteners inorganic carrier substances (in particular sodium aluminosilicates of the zeolite A type), surfactants and optical brighteners.
  • Zeolites are not swellable layer silicates.
  • WO 94/05 761 describes a process for producing a detergent with a high bulk density and good solubility, using non-swellable silicates (eg zeolites), surfactants and optical brighteners.
  • WO 89/08 695 describes a stabilized particulate composition for use in detergents which contains optical brighteners or enzymes. The particles are protected by a bentonite coating. Separated particles contain bleach, surfactants or builders.
  • DE-A-35 26 405 describes layered silicates with limited swelling capacity, and their use in detergents and cleaners, which also contain surfactants and optical brighteners.
  • the layered silicates are synthetic aluminosilicates.
  • Detergents which contain sodium aluminosilicates, such as zeolites, that is to say non-swellable silicates, and optical brighteners and surfactants are also known from other references.
  • DE-C-3 424 987 describes the production of detergent concentrates with high bulk density, which do not contain sodium sulfate as a setting agent.
  • a basic powder is produced by spray drying, which contains the usual detergent ingredients, such as surfactants, carboxymethyl cellulose (CMC), sodium polyphosphate, zeolite A, water glass, optical brighteners includes.
  • the base powder obtained which has a low bulk density and is free of sodium sulfate, is sprayed with other nonionic surfactant to increase the bulk density and dry-mixed with a separately produced granulate with a high bulk density.
  • the optical brightener is exposed to contact, especially oxidation, by other detergent components.
  • a problem is the incorporation of optical brighteners in detergent concentrates with a high bulk density.
  • the optical brightener was either processed in the spray product or it was subsequently mixed as a powder in the tower product (spray product). If the optical brightener is not separated from the bleaching agents also contained in the detergent, such as sodium perborate, but especially sodium percarbonate, by a coating (coating) produced in the production or by the presence of diluting, spatially separating and water-absorbing adjusting agents, op ⁇ table brighteners are oxidized. The bleaching potential consumed in this way is therefore no longer available for the subsequent bleaching action in the wash liquor.
  • the oxidation product of the optical brightener can be colored yellow be, whereby the detergent shows a yellow tint on the one hand, and on the other hand draws the yellow oxidation product of the brightener noun onto the washing textiles, which leads to an impairment of the aesthetic aspect, especially in the case of white laundry.
  • the oxidation of the optical brightener preceding Ent stehung of active oxygen in the detergent powder is a Reak ⁇ tion renberichtzusupplementary ⁇ of 'washing powder contained bleaches, especially when percarbonate is contained as a bleaching agent.
  • TAED tetraacetylethylenediamine
  • the detergent agglomerates of high bulk density generally have poor dispersibility; this can be improved by adding dispersants and disintegrants, which swell in contact with water and blow up or loosen the agglomerates, which leads to improved solubility and availability of the active components.
  • dispersants and disintegrants which swell in contact with water and blow up or loosen the agglomerates, which leads to improved solubility and availability of the active components.
  • Brightener spotting is the result of prolonged contact of undissolved, brightener-containing agglomerate with the laundry. Through the direct. Contact of locally over-concentrated optical brightener is transferred to the tissue at the contact point in undesirable, high concentrations, locally limited. This is particularly visible in the presence of UV light in the form of slight stains and represents an impairment of the aesthetic aspect.
  • the detergent agglomerates should therefore contain disintegrants so that they are blasted in contact with the wash liquor, as a result of which the optical brightener is homogeneous dissolved in the wash liquor and direct contact of the detergent agglomerates with the laundry is avoided.
  • the object of the invention was to provide a detergent additive in agglomerate form (granulate form) which contains at least one swellable layered silicate and an optical brightener which, with good mechanical stability, disintegrates well in water and in which the optical brightener is present in a homogeneous distribution and against Oxidation is protected by the oxidizing agent contained in the detergent.
  • the invention relates to a detergent additive in agglomerate form, which is characterized in that it contains at least one swellable layered silicate, an optical brightener and a surfactant.
  • the surfactant helps to at least partially distribute the optical brightener homogeneously between the layers of the layered silicate, since the layer expansion in the X-ray diffraction diagram of the dried product is from about 1.05 to 1.30 nm to about 1.35 up to 1.85 nm is observed.
  • the detergent additive preferably contains an alkali carbonate.
  • the detergent additive according to the invention preferably contains
  • the swellable layered silicate is preferably a natural or synthetic clay mineral.
  • the swellable clay mineral is preferably montmorillonite, beidellite, saponite or hectorite.
  • the montmorillonite can be used in the sodium or calcium form or in the form of a calcium montmorillonite ion-exchanged with soda. Synthetically produced clay minerals from the group mentioned above can also be used.
  • the layered silicate is preferably used in an amount of 10 to 50% by weight, in particular 30 to 50% by weight.
  • the swellable layered silicates have the property of intercalating polar agents between the silicate lamellae under internal crystalline swelling, which is noticeable at higher concentrations in an increase in the layer spacing.
  • the surfactant is preferably selected from the group of anionic and nonionic surfactants, the nonionic surfactant preferably being a mixture of fatty alcohol ethoxylates of various degrees of ethoxylation.
  • the fatty alcohol ethoxylates have the formula:
  • R is a hydrocarbon radical with 10 to 18, in particular their 12 to 18 carbon atoms, EO an ethylene oxide group and y a number from 2 to 20, in particular from 3 to 10.
  • R is a hydrocarbon radical with 10 to 18, in particular their 12 to 18 carbon atoms
  • EO an ethylene oxide group
  • y a number from 2 to 20, in particular from 3 to 10.
  • Significantly prepared mixtures of fatty alcohol ethoxylates of different degrees of ethoxylation can also be used.
  • the nonionic surfactants in which the optical brighteners, in particular of the stilbene type, are soluble, promote their transport between the lamellae of the swellable layered silicate.
  • the optical brighteners are intercalated between the lamellae of the layered silicate and thus protected from the reaction with other detergent components.
  • the layered silicates in granular form intercalated with surfactants and optical brighteners swell in water and release the surfactants and optical brighteners of the solution in water.
  • the optical brighteners and the surfactants are therefore fully available in the washing process. Due to the swelling effect of the layered silicate agglomerate in water, the agglomerates are blown up and distributed in the water, as a result of which "brightener spotting" is avoided.
  • the alkali carbonate which is used in particular in the form of sodium carbonate, fulfills several functions:
  • the layered silicate is agglomerated with the surfactant, a soft agglomerate is obtained which becomes sticky with increasing surfactant content and which is not free-flowing and not capable of ensiling.
  • the presence of the sodium carbonate improves the mechanical stability of the agglomerate and reduces its stickiness.
  • the sodium carbonate in the detergent is desirable for adjusting the alkalinity and as a builder component.
  • the alkali carbonate is preferably used in amounts of approximately 10 to 40% by weight, in particular approximately 12 to 30% by weight.
  • the layered silicate is agglomerated with the surfactant, a soft agglomerate is obtained which becomes sticky with increasing surfactant content and which is not free-flowing and not capable of ensiling.
  • the presence of the sodium carbonate improves the mechanical stability of the agglomerate and reduces its stickiness.
  • the sodium carbonate in the detergent is desirable for adjusting the alkalinity and as a builder component.
  • the alkali carbonate is preferably used in amounts of approximately 10 to 40% by weight, in particular approximately 12 to 30% by weight.
  • the optical brightener is preferably a stilbene derivative.
  • benzoxazole, coumarin and pyrazoline derivatives can also be used. These products generally have an anionic dye residue, which is why it was surprising that they are embedded between the negatively charged layers of the swellable layered silicate.
  • Suitable optical brighteners are, for example
  • Cyanuric acid chloride diaminostilbene (a) Cyanuric acid chloride diaminostilbene (CCDAS), in which R can have the following meanings:
  • the agglomerate particles of the detergent additive are preferably coated with synthetic zeolite, which improves the flowability of the agglomerate particles.
  • the coating with zeolite further improves the whiteness of the agglomerate.
  • the agglomerate preferably has a bulk density of more than about 700 g / liter and, owing to this high bulk density, is compatible with highly concentrated detergents at high density.
  • the invention further relates to a process for the production of the detergent additive described above in agglomerate form, which is characterized in that (a) the optical brightener (s) is added as an aqueous slurry simultaneously with the surfactant (s) gives the layered silicate (s) or (b) dissolves at least part of the optical brightener (s) in the surfactant (s) beforehand and adds the solution to the layered silicate (s).
  • the swellable layered silicate is preferably mixed with the alkali metal carbonate before the addition of the optical brightener / surfactant.
  • the powder components can, for example, in an intensive mixer, e.g. are mixed together in an Eirich mixer.
  • the optical brightener (preferably as an aqueous dispersion) and the surfactant are then sprayed simultaneously or in succession to the powder component while swirling. This forms an agglomerate which is powdered with the zeolite at a low mixing speed.
  • the resulting agglomerate is sieved and surface-coated by adding further zeolite (in particular zeolite P) in powder form to reduce the stickiness and to improve the whiteness.
  • the agglomerate obtained is readily dispersible in water.
  • the optical brightener is protected against oxidation and is fully available after the agglomerate has dissolved in the wash liquor. Due to the presence of the layer silicate swellable in water, no "brightener spotting" occurs.
  • the agglomerate can be subsequently added to the detergents produced in brightener-free production plants, so that the additives were not contaminated with brighteners.
  • the invention further relates to a detergent containing the detergent additive described above in addition to conventional detergent components such as anionic and nonionic surfactants, builders (builders), polymers (co-builders), graying inhibitors, bleaching agents and bleach activators , Enzymes, foam inhibitors, fragrances and / or dyes.
  • conventional detergent components such as anionic and nonionic surfactants, builders (builders), polymers (co-builders), graying inhibitors, bleaching agents and bleach activators , Enzymes, foam inhibitors, fragrances and / or dyes.
  • the powdered layered silicate and the powdered sodium carbonate are premixed intensively. With intensive swirling of the powder mixture, the surfactant or a solution of the surfactant is added. At the same time, the optical brightener or a mixture of different optical brighteners is added as an aqueous dispersion (slurry). Alternatively, a solution of the optical brightener in a surfactant solution can be added to the powder mixture.
  • the mixture agglomerates at a water content of about 20 to 30% by weight, based on the total mixture.
  • an agglomerate is obtained which is dried in a suitable dryer, preferably in a fluidized bed dryer, to a residual water content of about 2 to 15% by weight, preferably of about 5 to 10% by weight becomes.
  • the agglomerate obtained is sieved using a sieving machine to a particle size of approximately 0.2 to 2.5 mm, preferably 0.5 to 1.7 mm.
  • the fraction ⁇ 0.2 mm is returned to the agglomeration.
  • the resulting coarse grain is crushed with a roller crusher and placed on the screening plant again.
  • the optical brightener in powder form is first dissolved in the surfactant.
  • the weight ratio between surfactant and optical brightener can be 15: 2 to 4:10, preferably 10: 3 to 10: 8.
  • the solution or dispersion of the optical brightener in the surfactant is added to the powder with intensive stirring, at the same time further portions of the optical brightener are added in an aqueous dispersion.
  • an agglomerate forms, which is somewhat sticky due to the presence of the surfactant and therefore tends to stick.
  • a synthetic zeolite By adding about 0.5 to 5% by weight of a synthetic zeolite during the last 30 seconds of the agglomeration process, the tackiness of the agglomerate is reduced to such an extent that the agglomerate can be dried in a fluidized bed and sieved off as described.
  • the sieved agglomerate is placed in a drum mixer (for example in a drum mixer from Telschig) or in a granulating plate. Then about 3 to 15% by weight, preferably about 5 to 10% by weight, of synthetic zeolite in fine-grained form are added.
  • the average particle size of this powder should preferably be ⁇ 20 ⁇ m, in particular approximately 3 to 10 ⁇ m.
  • the detergent additive produced according to the described method has the following additional advantages:
  • the bulk density is greater than 700 g / liter, so that it is compatible with detergents with a high bulk density. Due to the swelling effect of the layer silicate contained in the detergent additive, the agglomerates rapidly disintegrate in water. No brightener spotting is observed on the laundry.
  • the active components surfactant and optical brightener are fully available in the detergent.
  • the presence of layered silicate and alkali carbonate makes the agglomerate mechanically stable. The agglomerate can be subsequently added to the detergent, so that essential parts of the detergent production system are not contaminated with optical brighteners.
  • a detergent additive was produced according to the following recipe:
  • Bentonite (Laundrosil ® DGA, Süd-Chemie AG) 40% by weight
  • Zeolite P 10% by weight 800 g of component A and 310.4 g of component B were placed in an Eirich intensive mixer type R02 (filling 3-5 liters, power 2.7 kW) and mixed for 1 minute. Then component C was added during mixing, followed by addition of components D and E. A yellow tinted agglomerate having a water content of 18% by weight was obtained. This agglomerate was dried in a drying cabinet to a residual moisture of 6% by weight of water. Then the grain fraction was sieved 0.2 to 1.7 mm.
  • the sieved agglomerate was then mixed with 10% by weight of Zeolith P and mixed in a granulating plate.
  • the surface of the agglomerate was coated with zeolite powder, whereby a white agglomerate was obtained.
  • nonionic surfactant component C
  • the breakdown of brighteners A and B is significantly less, and there is no annoying yellow tint of the detergent due to oxidation products.
  • Example 1 As an alternative to Example 1, components A and B were mixed in an Eirich mixer. A solution of 134 g Tinopal ® DMS-X hc (powder form) in 438 g of component C (surfactant) was prepared, which during the mixing process to Mi ⁇ ⁇ chung of component A and B is added. Component E was then added as a slurry. A yellow-tinted agglomerate was also obtained, which was further processed as in Example 1.
  • the stabilization of brightener A occurs regardless of whether it has been incorporated into the detergent additive as a slurry in water (Example 1) or in nonionic surfactant (Example 2).
  • a detergent additive was produced according to the following recipe:
  • Bentonite (Laundrosil ® DGA, Süd-Chemie AG) 42 wt.
  • Example 2 As in Example 1, 840 g of component A and 424 g of component B were premixed in an Eirich intensive mixer for about one minute. A mixture of components E (140 g) and F (36 g) was then added. Then 180 g of component C and 180 g of component D (premixed) were added.
  • the agglomerate obtained was sieved to a grain size of 0.2 mm to 2.0 mm.
  • the sieved agglomerate was then mixed again with 5% by weight of zeolite P and mixed in a granulating plate, the surface of the agglomerate being coated with zeolite powder, as a result of which a white agglomerate was obtained.
  • this detergent contains:
  • Brightener A breaks down much more slowly when using the detergent additive than when used in the spray product.
  • the detergent remains white.

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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)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)

Abstract

L'invention concerne un additif de lessive sous forme d'agglomérat. Cet additif est caractérisé en ce qu'il contient au moins un silicate stratifié capable de gonflement, un azurant optique et un tensio-actif.
PCT/EP1996/004337 1995-10-12 1996-10-05 Additif de lessive WO1997013831A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP09514693A JP2000512320A (ja) 1996-10-05 1996-10-05 洗剤添加物
EP96934551A EP0856046B1 (fr) 1995-10-12 1996-10-05 Additif de lessive
AT96934551T ATE234912T1 (de) 1995-10-12 1996-10-05 Waschmittelzusatz
DE59610244T DE59610244D1 (de) 1995-10-12 1996-10-05 Waschmittelzusatz

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19538028A DE19538028A1 (de) 1995-10-12 1995-10-12 Waschmittelzusatz
DE19538028.2 1995-10-12

Publications (1)

Publication Number Publication Date
WO1997013831A1 true WO1997013831A1 (fr) 1997-04-17

Family

ID=7774674

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/004337 WO1997013831A1 (fr) 1995-10-12 1996-10-05 Additif de lessive

Country Status (5)

Country Link
EP (1) EP0856046B1 (fr)
AT (1) ATE234912T1 (fr)
DE (2) DE19538028A1 (fr)
ES (1) ES2193265T3 (fr)
WO (1) WO1997013831A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2339203A (en) * 1998-07-08 2000-01-19 Procter & Gamble A method of dipensing
US6365563B1 (en) 1997-09-17 2002-04-02 Ciba Specialty Chemicals Corporation Agglomerated antimicrobial detergent additive comprising swellable layered silicate and surfactant

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0903401B1 (fr) * 1997-09-17 2003-08-06 Ciba SC Holding AG Additif antimicrobien pour détergents

Citations (6)

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DE2856087A1 (de) * 1978-12-23 1980-07-10 Henkel Kgaa Verfahren zur herstellung weisser, optische aufheller und kationenaustauschfaehige alumosilikate enthaltender, pulverfoermiger waschmittel
GB1572815A (en) * 1977-05-06 1980-08-06 Procter & Gamble Process for making detergent compositions
FR2500475A1 (fr) * 1981-02-26 1982-08-27 Colgate Palmolive Co Perles de base destinees a la fabrication de compositions detergentes, procede et melanges pour leur fabrication et compositions detergentes les contenant
DD220328A1 (de) * 1983-09-05 1985-03-27 Bitterfeld Chemie Waschhilfsmittel zur weissgradverstaerkung
WO1989008695A1 (fr) * 1988-03-14 1989-09-21 Novo-Nordisk A/S Composition particulaire stabilisee
WO1991014762A1 (fr) * 1990-03-26 1991-10-03 Henkel Kommanditgesellschaft Auf Aktien Additif d'avivage seche par pulverisation pour agents de lavage

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US4427410A (en) * 1974-09-06 1984-01-24 Colgate-Palmolive Company Fabric softening composition containing molecular sieve zeolite
DE3261394D1 (en) * 1981-01-21 1985-01-17 Unilever Plc Detergent compositions
DE3248022A1 (de) * 1982-12-24 1984-06-28 Henkel KGaA, 4000 Düsseldorf Spruehgetrocknetes mehrkomponenten-waschmittel
DE3434854A1 (de) * 1984-09-22 1986-04-03 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung einer koernigen, freifliessenden waschmittelkomponente
DE3526405A1 (de) * 1985-07-24 1987-02-05 Henkel Kgaa Schichtsilikate mit beschraenktem quellvermoegen, verfahren zu ihrer herstellung und ihre verwendung in wasch- und reinigungsmitteln
DE3717227A1 (de) * 1987-05-21 1988-12-01 Henkel Kgaa Phosphatfreies waschmittel mit reduzierter inkrustierungstendenz
DE3737071A1 (de) * 1987-10-31 1989-05-11 Henkel Kgaa Verwendung von aminethern als netzmittel fuer textilien
WO1992017404A1 (fr) * 1991-03-26 1992-10-15 Henkel Kommanditgesellschaft Auf Aktien Percarbonate de sodium stabilise
TR27586A (tr) * 1992-09-01 1995-06-13 Procter & Gamble Yüksek yogunlukla zerre deterjanin yapilmasi icin islem ve islem ile yapilan bilesimler.

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1572815A (en) * 1977-05-06 1980-08-06 Procter & Gamble Process for making detergent compositions
DE2856087A1 (de) * 1978-12-23 1980-07-10 Henkel Kgaa Verfahren zur herstellung weisser, optische aufheller und kationenaustauschfaehige alumosilikate enthaltender, pulverfoermiger waschmittel
FR2500475A1 (fr) * 1981-02-26 1982-08-27 Colgate Palmolive Co Perles de base destinees a la fabrication de compositions detergentes, procede et melanges pour leur fabrication et compositions detergentes les contenant
DD220328A1 (de) * 1983-09-05 1985-03-27 Bitterfeld Chemie Waschhilfsmittel zur weissgradverstaerkung
WO1989008695A1 (fr) * 1988-03-14 1989-09-21 Novo-Nordisk A/S Composition particulaire stabilisee
WO1991014762A1 (fr) * 1990-03-26 1991-10-03 Henkel Kommanditgesellschaft Auf Aktien Additif d'avivage seche par pulverisation pour agents de lavage

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8530, Derwent World Patents Index; Class D25, AN 85-177900, XP002025190 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6365563B1 (en) 1997-09-17 2002-04-02 Ciba Specialty Chemicals Corporation Agglomerated antimicrobial detergent additive comprising swellable layered silicate and surfactant
GB2339203A (en) * 1998-07-08 2000-01-19 Procter & Gamble A method of dipensing

Also Published As

Publication number Publication date
DE59610244D1 (de) 2003-04-24
EP0856046B1 (fr) 2003-03-19
DE19538028A1 (de) 1997-04-17
ES2193265T3 (es) 2003-11-01
ATE234912T1 (de) 2003-04-15
EP0856046A1 (fr) 1998-08-05

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