EP0355551B1 - Agent de lavage et de nettoyage sous forme de pâte et son procédé de préparation - Google Patents

Agent de lavage et de nettoyage sous forme de pâte et son procédé de préparation Download PDF

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Publication number
EP0355551B1
EP0355551B1 EP89114540A EP89114540A EP0355551B1 EP 0355551 B1 EP0355551 B1 EP 0355551B1 EP 89114540 A EP89114540 A EP 89114540A EP 89114540 A EP89114540 A EP 89114540A EP 0355551 B1 EP0355551 B1 EP 0355551B1
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EP
European Patent Office
Prior art keywords
disalt
detergent
paste
alkyl glycoside
weight
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
EP89114540A
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German (de)
English (en)
Other versions
EP0355551A3 (en
EP0355551A2 (fr
Inventor
Brigitte Giesen
Alfred Dr. Meffert
Andreas Dr. Syldatk
Ingo Wegener
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
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Publication of EP0355551A2 publication Critical patent/EP0355551A2/fr
Publication of EP0355551A3 publication Critical patent/EP0355551A3/de
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Publication of EP0355551B1 publication Critical patent/EP0355551B1/fr
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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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0089—Pearlescent compositions; Opacifying agents
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides

Definitions

  • the invention relates to a pasty detergent and cleaning agent on an aqueous basis, which is suitable both for textile washing and for cleaning objects with hard surfaces, in particular for manual cleaning of dishes.
  • a viscous detergent concentrate which contains at least one nonionic surfactant and at least two anionic surfactants and an organic solvent is known from EP 0 243 685 A2.
  • This detergent concentrate which contains ethoxylated alcohols or ethoxylated alkylphenols as nonionic surfactants and alkylbenzenesulfonates, alkyl ether sulfates and alkanesulfonates as anionic surfactants, can be diluted with water. It is particularly suitable for the manual cleaning of dishes.
  • a paste-like detergent containing builders for cleaning textiles, dishes and hard surfaces which, in addition to a synthetic anionic surfactant of the fatty alcohol sulfate type, contains common builder substances, such as, for. B. sodium tripolyphosphate, and free alkanolamine.
  • US Pat. No. 3,219,656 discloses the glycosides of long-chain aliphatic alcohols, in particular the fatty alkyl glucosides. These fatty alkyl glycosides belong to the type of nonionic surfactants. They are non-ionic with others and anionic surfactants can be combined and are therefore suitable for use in washing and cleaning agents. A particular advantage of alkyl glycosides is their biodegradability. From US Pat. No.
  • the alkyl glycosides which can be used as surfactants can be represented by the structural formula RO (G) x , where R is an aliphatic radical with at least 8 carbon atoms, in particular the radical of a primary alcohol and very particularly a fatty alkyl or fatty alkenyl radical with 8 to 22, preferably 12 to 18 carbon atoms.
  • R is an aliphatic radical with at least 8 carbon atoms, in particular the radical of a primary alcohol and very particularly a fatty alkyl or fatty alkenyl radical with 8 to 22, preferably 12 to 18 carbon atoms.
  • the symbol (G) in the formula stands for a glycose unit, with glucose being preferred because of the technical availability on the one hand and the good reactivity on the other hand.
  • the index number x is any number between 1 and 10, which indicates the degree of oligomerization, ie the distribution of monoglycosides and oligoglycosides.
  • the value x for a special alkyl glycoside process product as an analytically determined arithmetic quantity is usually a fractional number .
  • the alkyl glycosides are represented by the formula RO (G) x , the percentage of fatty alcohol is neglected. In principle, this fatty alcohol portion can largely be controlled by gentle distillative treatment of the alkyl glycoside, ie the excess fatty alcohol resulting from the reaction can be removed from the product except for residual values that are less than 1% total.
  • alkylbenzene sulfonate As anionic co-surfactants, alkylbenzene sulfonate, soap, zwitterionic surfactants, amphoteric surfactants, alkane sulfonates, alpha-olefin sulfonates, alkyl sulfates, alkyl polyglycol ether sulfates and paraffin sulfonates and mixtures thereof are mentioned in particular.
  • the surfactant compositions described here are suitable for the production of products which foam strongly when used, such as, for example, manual dishwashing detergents and shampoos.
  • the surface-active properties of the salts of the alpha-sulfonated fatty acids, in particular the sodium disalts, are from "The Journal of the American Oil Chemists' Society", (1954), vol. 31, pages 13 ff and from vol. 34 (1957), Pages 100 ff known.
  • Textile detergents are known from German patent applications DE 21 44 592 B2 and DE 21 61 726 B2 which, in addition to the usual nonionic and / or anionic surfactants, contain the alkali metal salts of alpha-sulfonated saturated fatty acids with 14 to 20 carbon atoms.
  • These sodium disalts are regarded as builder substances and are combined either alone or together with other customary builder substances with the usual surfactants mentioned.
  • Belgian patent 661 860 describes liquid or pasty mixtures of nonionic surfactants of the ethoxylated fatty alcohol type and the ⁇ -sulfofatty acid disalts of C1al- to C12-fatty acids. These mixtures have a lower viscosity than the original solutions or pastes of the nonionic ethoxylate surfactants.
  • European patent application 0 327 684 A2 describes a process for washing textiles in conventional washing machines, the at least predominant part of the surfactants, if appropriate together with other customary detergent constituents, in the form of a largely dimensionally stable paste at room temperature directly to the dry or moistened textile in the washing machine.
  • the alkyl glycosides and the alpha-sulfofatty acid disalts are also mentioned there.
  • the invention relates to a pasty washing and cleaning agent which contains nonionic and anionic surfactants and the viscous to largely dimensionally stable pasty agents such as viscous liquids, flowable gels, flowable pastes and pasty masses which have a viscosity (measured according to Höppler at 20 ° C.
  • the viscosity (measured by Höppler at 20 ° C or Brookfield Helipath at 20 ° C and 4 revolutions / min.) Is generally in the range from about 1000 to 200,000, preferably 2000 to 100,000 and especially at 5000 to 90,000 mPas.
  • the flowable to viscous pastes are further characterized by a minimum dissolution rate to be determined under certain test conditions as follows: To determine the dissolution rate, 1 g of the pasty product is placed as a coherent mass in a beaker of 250 ml, tall shape, diameter about 5.5 cm, and with 100 ml Water at a temperature of 20 ⁇ 2 ° C.
  • a magnetic stir bar of 3 cm in length is placed in the beaker, and the contents of the beaker are then stirred at the specified temperature at a speed of 500 revolutions per minute. The time is measured until the paste has completely dissolved or finely dispersed.
  • the pastes according to the invention dissolve completely in at most 10 minutes, ie a homogeneous, cloudy, slightly pearlescent solution or suspension is formed. This complete disappearance of the paste-like consistency and the fine dispersion occur after only 2 to 5 minutes.
  • Typical representatives of the alkyl glycosides which have the properties of a nonionic surfactant are those whose aliphatic radical represents a typical fatty alkyl radical, for example octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl.
  • Particularly suitable alkyl glycosides contain a coconut fatty alkyl residue, ie mixtures with essentially dodecyl and tetradecyl.
  • the sugar component in the alkyl glucoside can, in principle, from conventional aldoses or ketoses, such as. B. glucose, fructose, mannose, galactose, talose, gulose, allose, old rose, idose, arabinose, xylose, lyxose and ribose. Because of the glucose available in large quantities and their good reactivity, the alkyl glucosides are particularly preferred. It is a particular advantage of the alkyl glycosides in the form of the fatty alkyl glucosides that they are made entirely from renewable raw materials, namely fat on the one hand and sugars or starches on the other hand.
  • alkyl glycosides whose alkyl radical is derived from synthetic primary alcohols in particular the so-called oxo alcohols, ie. H. those primary alkanols, which have a certain percentage of branched isomers.
  • alkylglycosides of this type are less preferred in the present case, since it is precisely an object of the invention that both essential components of the agent according to the invention are produced from natural, renewable raw materials.
  • the alpha-sulfofatty acid disalts (hereinafter referred to briefly as disalts) which can be used according to the invention can be prepared in a manner known per se by sulfonating fatty acids, combined with subsequent bleaching and conversion into the salts. Particularly light-colored and odorlessly neutral disalts are obtained by sulfonating the corresponding purified fatty acid methyl ester, with the subsequent steps of bleaching and saponifying the ester group and converting them to the disalt. Cations, preferably the cations of the alkali metals, in particular of sodium, are suitable for salt formation. However, the magnesium salts can also be used according to the invention. Disalts with the ammonium cation and with cations derived from mono-, di- and triethanolamine are also suitable.
  • both the alkyl glycosides and the disalts are expediently used in the form of aqueous pastes as starting materials, the concentration of the alkyl glycoside pastes in the range from 50 to 70% by weight and the concentration of the disalting pastes in the range of 20 to 35 wt .-% is.
  • a typical example of an alkyl glycoside paste is that made from coconut fatty alcohols with a C12 / C14 ratio of about 3: 1 coconut alkyl glucoside with the degree of oligomerization 1.3 and in a concentration of about 60% by weight.
  • a typical disalt paste contains a sulfofatty acid disalt based on C16 / C18 fatty acid, made from tallow fatty acid, in a concentration of about 28 wt .-%.
  • Pasty detergents and cleaning agents according to the invention contain alkyl glycoside and disalt as essential components of the surfactant combination.
  • the term “essentially” is understood to mean that, according to a first and also preferred embodiment, the agent according to the invention consists only of the alkyl glycoside and the disalt and water.
  • the ratio of alkyl glycoside to disalt is preferably 8: 1 to 1: 1.
  • the total amount of alkyl glycoside and disalt in the composition according to the invention is preferably 10 to 50, in particular 15 to 35,% by weight.
  • the agent according to the invention contains, as a further constituent, a soap which preferably corresponds at most to the amount of the disalt and which likewise preferably has the same fatty acid base. It has been found that such soap components do not impair the washing and cleaning properties, so that the soap component can be present as a cheap diluent.
  • a soap component as an additional constituent of the agent according to the invention, the technical disalts, which generally still contain soaps due to the incomplete sulfonation of the starting materials, can also be used directly as technical products.
  • the agent according to the invention can also contain conventional thickeners.
  • Suitable thickeners are primarily natural polymer compounds or their derivatives, in particular derivatives of cellulose and starch such as.
  • the agents according to the invention can also contain additives of paste-like detergents and cleaning agents which are customary per se, in the present case primarily fragrances and dyes, water-soluble or water-insoluble builder substances, Enzymes and pH regulators can be understood.
  • it is a particular advantage of the agents according to the invention that, owing to their very low intrinsic odor and their appealing appearance, they can do without fragrances and dyes.
  • the agent itself already has a white pearlescent, without the need, as is generally required, to add a special pearlescent agent.
  • the agent according to the invention contains additional builder substances, there are preferably ecologically harmless substances such as. B. citric acid and its salts or zeolite A, into consideration.
  • the agent according to the invention can be used both for the manual cleaning of objects with hard surfaces, for example dishes, and for washing textiles by hand or in the washing machine at low temperatures from room temperature to about 60 ° C., with a focus on 30 - 40 ° wash can be used.
  • the paste-like agent is characterized by good storage stability and simple metering;
  • the agent is either squeezed out of soft plastic bottles or tubular bags as a pasty strand or as a highly viscous liquid, or removed from containers with larger openings with a spatula or a spoon, whereby the amount to be removed, for example with a teaspoon or tablespoon, can also be removed in a simple manner can use as a dosage measure.
  • Round or square cans or boxes made of sheet metal, plastic or coated cardboard with simple lids for closing are suitable as containers with larger openings.
  • the agents according to the invention can be prepared in a manner known per se by mixing the alkyl glycoside and the disalt, preferably in the form of concentrated aqueous pastes, in the desired ratio and the desired concentration and viscosity, optionally by adding water and / or a Thickener, so that the concentration in the range of 10 to 50 wt .-% of the total amount of alkyl glycoside and disalt, preferably 15 to 35 wt .-%, and the viscosity (measured by Höppler at 20 ° C or Brookfield Helipath at 20 ° C and 4 revolutions / min.) in the range of about 1000 to 200,000, preferably 2000 to 100,000, and in particular 5000 to 90,000, and where appropriate the pH of the mixtures (based on the measurement of a 10% solution) if necessary by adding a regulator to an approximately neutral value.
  • Suitable pH regulators are system and environmentally compatible acids, such as citric acid, tartaric acid, glycolic acid, malic acid, technical mixtures of succinic
  • alkyl glycoside was a 58.7% aqueous paste of a coconut fatty alkyl glucoside with a C12 / C14 distribution of about 3: 1 and a degree of oligomerization of 1.3 and as the sodium salt of alpha-sulfo-C16 / C18 tallow fatty acid as disalt as 28% aqueous paste used.
  • the paste-like agent was prepared by mixing 13.5 g of the alkyl glycoside and 4.5 of the disalt, in each case based on the anhydrous substance, and adding 1.0% by weight of carboxymethyl cellulose in powder form, and the paste was added by adding citric acid adjusted to pH 7.2.
  • the viscosity of the paste produced in this way (according to Höppler, 20 ° C.) was found to be 27,960.
  • the paste-like composition was dissolved in a concentration of 1 g / l in water at 45 ° C. This dosage corresponds approximately to the amount of one teaspoon per 5 l of water.
  • Beef tallow (approx. 1.7 g per plate) was used as the standard soil (see H.-J. Lehmenn, Fette, Seifen, Anstrichstoff, 74 , (1972), pages 163 to 165).
  • Maximum number of plates in water of 16 ° dH 17.
  • the reflectance values of the washed textile samples were determined and an average value was calculated. A value of 44.4 was determined; Initial value 26. A similar washing test at room temperature gave the reflectance value 40.9.
  • Example 1 The alkyl glycoside of Example 1 was used; the corresponding magnesium salt was used as the disalz instead of the sodium salt from Example 1. Otherwise, a paste with 18% surfactant content was produced as in Example 1, but in an alkyl glycoside: disalt ratio of 3: 2.
  • the water used had a hardness of 16 ° dH.
  • the determination of the dishwashing capacity resulted in the number of 17 plates.
  • the washability with this paste was refined as in Example 1 in a launderometer with test rags made of polyester / cotton and a standard soiling from dust / skin fat was determined. The reflectance value 42 was measured. Additions of neutral salts such as sodium sulfate or builder substances such as sodium triphosphate had an effect-increasing influence.
  • Example C a paste of the following composition was prepared: 23% by weight coconut alcohol sulfate, 1.0% by weight triethanolamine, 24.5% by weight sodium triphosphate, 6.0% % Soda, 1.1% carboxymethyl cellulose, 2.5% sodium sulfate, balance water.
  • this paste Based on its surfactant content of coconut alcohol sulfate, this paste had 23% by weight of active surfactants. The paste was white and no longer flowable, the viscosity, determined according to Brookfield in Helipath at room temperature (RVF), was 350,000 mPas.
  • composition according to the invention had the composition 10% by weight of alkyl glycoside as in Example 1, 8% by weight sodium disalt as in Example 1, 2.0 wt% carboxymethyl cellulose Rest of water.
  • the agent according to the invention was evenly distributed in 2 minutes and 10 seconds to form a cloudy, slightly pearlescent cleaning liquor, the known agent required 12 minutes and 30 seconds for this.
  • the dishwashing capacity was measured at 1 g / l of the two products in water at 45 ° C.
  • Means according to the invention 16 plates at 3 ° dH, 15 plates at 16 ° dH.
  • Known means 12 plates at 3 ° dH, 3 plates at 16 ° dH.
  • the washability was determined in a launderometer at 40 ° C., dosage 3 g / l, water hardness 16 ° dH, liquor ratio 1:30, with the test soiling already given in example 1. The same average reflectance value of 42 was found for both pastes.
  • the known formulation performs significantly worse than the formulation according to the invention because of the lower dishwashing capacity and the poorer dissolving behavior and because of its content of undesired sodium triphosphate.

Claims (8)

  1. Produit pâteux de lavage et de nettoyage, renfermant des tensioactifs non ioniques et anioniques et des agents pâteux fort visqueux, coulants à largement indéformables, tels des liquides visqueux, des gels coulants, des pâtes coulantes et des masses pâteuses, qui possèdent une viscosité (déterminée selon Höppler à 20 °C ou selon Brookfield Helipath à 20 °C et 4 tours/min) comprise dans l'intervalle d'environ 1000 à 200 000 mPa.s, caractérisé en ce qu'il renferme essentiellement une association de tensioactifs constituée d'un alkylglucoside comme surfactif non ionique et d'un acide gras alphasulfonique-sel neutre comme agent de surface anionique à base aqueuse, avec un rapport des ingrédients entre l'alkylglucoside et le sel neutre compris entre 10:1 et 1:3 et avec une vitesse de désagrégation minimale d'au moins 10 min pour 1 g du produit dans 100 ml d'eau, à une température de 20 ± 2 °C, selon la méthode d'essai spécifiée dans la description.
  2. Produit selon la revendication 1, caractérisé en ce que le rapport des ingrédients entre l'alkylglucoside et l'acide gras alphasulfonique-sel neutre est compris entre 8:1 et 1:1.
  3. Produit selon la revendication 1 ou 2, caractérisé en ce que la quantité totale de l'alkylglucoside et de l'acide gras alphasulfonique-sel neutre atteint 10 à 15 % en poids, de préférence 15 à 35 % en poids.
  4. Produit selon l'une des revendications 1 à 3, caractérisé en ce qu'il renferme, comme autre constituant, un savon dans une proportion correspondant au maximum à la quantité de l'acide gras alphasulfonique-sel neutre.
  5. Produit selon l'une des revendications 1 à 4, caractérisé en ce qu'il renferme un épaississant, de préférence de la carboxyméthylcellulose, dans une proportion permettant d'obtenir une consistance visqueuse-coulante à pâteuse-solide.
  6. Produit selon l'une des revendications 1 à 4, caractérisé en ce qu'il présente un pH (déterminé dans une solution à 10 %) à peu près neutre.
  7. Produit selon l'une des revendications 1 à 6, caractérisé en ce qu'il renferme des quantités secondaires d'additifs usuels pour les pâtes de produits de lavage et de nettoyage, du type des matières colorantes et odoriférantes, enzymes, sels électrolytiques, adjuvants et régulateurs de pH.
  8. Procédé de fabrication de produits conformes aux revendications 3 à 7, caractérisé en ce que l'on mélange ensemble l'alkylglucoside et le sel neutre, sous la forme de pâtes aqueuses concentrées, la concentration des pâtes d'alkylglucoside étant comprise dans la plage de 50 à 70 % en poids et celle des pâtes de sel neutre se situant dans l'intervalle de 20 à 35 % en poids, et en ajustant la concentration de la quantité totale de l'alkylglucoside et du sel neutre à 10 à 50 % en poids, de préférence à 15 à 35 % en poids, le cas échéant par adjonction d'eau et éventuellement d'un épaississant, et la viscosité (déterminée selon Höppler à 20 °C ou selon Brookfield Helipath à 20 °C et 4 tours/min) dans la plage s'étendant d'environ 1000 à 200 000 mPa.s, de préférence 2000 à 100 0000 mPa.s, en particulier 5000 à 90 000, ainsi que, le cas échéant, le pH à un pH à peu près neutre (déterminé dans une solution à 10 %) par adjonction d'un régulateur.
EP89114540A 1988-08-16 1989-08-07 Agent de lavage et de nettoyage sous forme de pâte et son procédé de préparation Expired - Lifetime EP0355551B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3827778A DE3827778A1 (de) 1988-08-16 1988-08-16 Pastenfoermiges wasch- und reinigungsmittel und verfahren zur herstellung
DE3827778 1988-08-16

Publications (3)

Publication Number Publication Date
EP0355551A2 EP0355551A2 (fr) 1990-02-28
EP0355551A3 EP0355551A3 (en) 1990-04-11
EP0355551B1 true EP0355551B1 (fr) 1993-12-15

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EP89114540A Expired - Lifetime EP0355551B1 (fr) 1988-08-16 1989-08-07 Agent de lavage et de nettoyage sous forme de pâte et son procédé de préparation
EP89908974A Pending EP0429493A1 (fr) 1988-08-16 1989-08-07 Agent de lavage et de rin age pateux et procede pour sa fabrication

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EP89908974A Pending EP0429493A1 (fr) 1988-08-16 1989-08-07 Agent de lavage et de rin age pateux et procede pour sa fabrication

Country Status (9)

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US (1) US5200115A (fr)
EP (2) EP0355551B1 (fr)
JP (1) JPH04500082A (fr)
KR (1) KR960015369B1 (fr)
CN (1) CN1040389A (fr)
AU (1) AU4042389A (fr)
BR (1) BR8907607A (fr)
DE (2) DE3827778A1 (fr)
WO (1) WO1990002163A1 (fr)

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ES2667168T3 (es) * 2014-02-04 2018-05-09 Basf Se Composiciones acuosas de tensioactivo
EP3246384A1 (fr) * 2016-05-18 2017-11-22 Basf Se Compositions de tensioactifs aqueux
EP3966302A1 (fr) * 2019-05-07 2022-03-16 Basf Se Compositions tensioactives aqueuses et pains de savon

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Also Published As

Publication number Publication date
BR8907607A (pt) 1991-07-30
EP0355551A3 (en) 1990-04-11
KR960015369B1 (ko) 1996-11-11
KR900701989A (ko) 1990-12-05
EP0429493A1 (fr) 1991-06-05
DE3827778A1 (de) 1990-02-22
EP0355551A2 (fr) 1990-02-28
US5200115A (en) 1993-04-06
WO1990002163A1 (fr) 1990-03-08
CN1040389A (zh) 1990-03-14
JPH04500082A (ja) 1992-01-09
AU4042389A (en) 1990-03-23
DE58906421D1 (de) 1994-01-27

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