EP0609303B1 - Detergent liquide concentre pour surfaces dures - Google Patents

Detergent liquide concentre pour surfaces dures Download PDF

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Publication number
EP0609303B1
EP0609303B1 EP92921604A EP92921604A EP0609303B1 EP 0609303 B1 EP0609303 B1 EP 0609303B1 EP 92921604 A EP92921604 A EP 92921604A EP 92921604 A EP92921604 A EP 92921604A EP 0609303 B1 EP0609303 B1 EP 0609303B1
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EP
European Patent Office
Prior art keywords
acid
weight
anionic
active agents
concentrate
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
EP92921604A
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German (de)
English (en)
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EP0609303A1 (fr
Inventor
Dimitrios Ouzounis
Christian Nitsch
Peter Daute
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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.)
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Publication of EP0609303A1 publication Critical patent/EP0609303A1/fr
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • Liquid all-purpose detergents for household and commercial use have taken their place in the past decade because they are easy and straightforward to use.
  • the agents are usually marketed as preferably aqueous concentrates. They can already be identified as such, i.e. Apply undiluted, on a damp absorbent cloth of any texture or a sponge, with which the hard surfaces made of metal, painted wood, plastic, ceramic products such as porcelain, tiles, tiles and the like, are wiped away, thereby removing dust, greasy dirt and stains. It is desired that this surface treatment in turn does not leave any detergent stains and strips behind and does not require any aftertreatment, for example with a cloth soaked in clear water, that is to say moist.
  • Such liquid all-purpose cleaning agents generally consist of concentrated solutions of various anionic surfactant mixtures, but mixtures of anionic and nonionic surfactants are also known. Among other things, you will described in DE 28 40 463, EP 71 411 and DE 39 43 070.
  • the present invention thus relates to a liquid detergent concentrate for hard surfaces based on aqueous solutions of nonionic surfactants, optionally together with other anionic and / or nonionic surfactants, organic and / or inorganic builders, water-soluble solvents or solubilizers, and other usual constituents of such detergents, which thereby characterized in that it is a nonionic surfactant of about 1.0 to 30, preferably about 2.0 to 15,% by weight, based on the total concentrate, of an alkoxylation product of carboxylic acids containing OH groups and / or their derivatives (polyol alkoxylates) contains, with 30 - 85 wt .-%, preferably 30 - 65 wt .-% ethylene oxide or propylene oxide.
  • the epoxides of unsaturated oils and fats have been known for a long time and are inexpensive to produce on an industrial scale.
  • Their reaction with hydrogen or protic compounds such as water, alcohols or carboxylic acids leads to polyols which, depending on the fatty acid composition of the starting materials, carry a hydroxy group in the 9- or 10-position of the fatty alkyl chain.
  • polyunsaturated fatty acids several hydroxyl groups per fatty acid chain are obtained depending on the number and position of the double bonds. These can then be reacted with ethylene oxide and / or propylene oxide to give mostly liquid alkoxylates (polyol alkoxylates).
  • the polyol alkoxylates can preferably be used as the sole active ingredient, but also in combination with any other known surfactants of the sulfonate and / or sulfate type, and preferably with fatty alkyl glucosides, dialkyl sulfosuccinates and Glycerol monoalkyl ethers can be used.
  • Their share in the total mixture can be about 50 to 80, preferably 50 to 65% by weight.
  • the surfactants of the sulfonate type are alkylbenzenesulfonates (C9 ⁇ 15-alkyl), mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonating group, into consideration.
  • alkanesulfonates which can be obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins.
  • esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonic acids from hydrogenated methyl or ethyl esters of coconut, palm kernel or tallow fatty acid.
  • the preferred surfactants of the sulfate type for ecological reasons are the sulfuric acid monoesters of primary C12-C18, preferably C12-C14 fatty alcohols (e.g. from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and those of corresponding secondary alcohols.
  • Sulfated fatty acid alkanolamides, fatty acid monoglycerides or reaction products of 1-5 moles of ethylene oxide with primary or secondary fatty alcohols are also suitable.
  • the fatty alkyl glucosides that can be used here are understood to mean compounds with an average of less than two glucose units per fatty alkyl radical, in particular those with 1 to 1.4 glucose units.
  • the fatty alkyl radical has 10 to 18, in particular essentially 12 to 14, carbon atoms.
  • “Fatty alkyl” is understood to mean the rest of the fatty alcohols which are produced by hydrogenation of natural fatty acids and which are wholly or predominantly saturated or which also comprise unsaturated portions.
  • the dialkyl sulfosuccinates are alkali metal, ammonium or substituted ammonium salts and can be derived from a C7, C8 or C9 alcohol, which can be linear or branched, or from any mixture thereof.
  • the preferred material is the straight chain and branched Di-octylsulfosuccinate.
  • the dialkyl sulfosuccinates were prepared by customary methods, for example by esterification of maleic acid and subsequent sulfonation with bisulfite.
  • anionic surfactants can be present in the form of their alkali, alkaline earth and ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the sodium salts are mostly preferred for reasons of cost.
  • the glycerol monoalkyl ethers are compounds of the general formula in which R stands for an alkyl radical with 1 to 22, preferably 8 to 18, carbon atoms, n for a number in the range 0 to 20, preferably 0 to 10 and x + y for a number in the range 0 to 60, preferably 0 to 30 stand, as well as mixtures of several such compounds.
  • glycerol monoalkyl ethers can advantageously be prepared by combining excess glycerol in a reaction kettle with sodium hydroxide solution and heating under a nitrogen atmosphere, with water being distilled off. The batch is stirred for several hours. Then this reaction product is reacted with fatty alcohol sulfate, sodium salt or fatty alcohol polyethylene glycol ether sulfate, sodium salt, and the reaction mixture is heated for a few more hours. The raw product is washed several times with water. Residual water in the organic phase is removed under reduced pressure. The glycerol monoalkyl ethers (GE) thus obtained can then, if appropriate in the presence of a catalyst (e.g. Na methylate), be reacted with ethylene oxide in a pressure vessel under a nitrogen atmosphere at elevated temperature.
  • a catalyst e.g. Na methylate
  • the cleaning agent concentrates according to the invention can furthermore act as alkalis in their entirety inorganic or organic compounds, as well as inorganic or organic complexing agents are used, which are preferably in the form of their alkali or amine salts, in particular the sodium and potassium salts.
  • the alkali hydroxides also belong to the framework substances here.
  • inorganic substances which can optionally be added to the agents according to the invention are, for example, bicarbonates, carbonates, borates, silicates or polyphosphates such as pentasodium triphosphate, pyrophosphates or orthophosphates.
  • bicarbonates carbonates, borates, silicates or polyphosphates
  • pentasodium triphosphate pyrophosphates or orthophosphates.
  • the latter salts containing phosphorus ions should not be used for ecological reasons.
  • the organic complexing agents of the aminopolycarboxylic acid type include, among others, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylene diamine triacetic acid.
  • polyphosphonic acids methylene diphosphonic acids, 1-hydroxyethane-1,1-diphosphonic acid, propane-1,1,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, copolymers of vinylphosphonic acid and acrylic acid, ethane-1 , 2, dicarboxy-1,2-diphosphonic acid, ethane-1,2-dicarboxy-1,2-dihydroxydiphosphonic acid, phosphonosuccinic acid, 1-aminoethane-1,2-diphosphonic acid, aminotri- (methylenephosphonic acid), methylamino- or ethylamino-di- (methylenephosphonic acid) and ethylenediaminetetra (m
  • carboxylic acids are often, if not exclusively, proposed as examples of N- or P-free and therefore preferred mono- or polyvalent carboxylic acids or their salts as builder substances.
  • a large number of these carboxylic acids have a complexing ability for calcium. These include e.g. As citric acid, tartaric acid, benzene hexacarboxylic acid, tetrahydrofuran tetracarboxylic acid, gluconic acid, glutaric acid, succinic acid, adipic acid, polyacrylic acids and copolymers or mixtures thereof.
  • aqueous use solutions at application concentrations of usually about 1 to 20, preferably about 5-15 g / l water or aqueous solution have a pH in the range of 7.0-10.5, preferably 7.0-9.5, can be added to regulate the pH by adding small amounts of acidic and / or or alkaline components, also as a buffer.
  • Suitable acidic substances are conventional inorganic or organic acids or acidic salts, such as hydrochloric acid or sulfuric acid, lactic acid, polycarboxylic acids, such as. B. citric acid, tartaric acid, glutaric acid, succinic acid, adipic acid or mixtures thereof and the like.
  • alkaline builders If the content of alkaline builders is not sufficient to regulate the pH, organic or inorganic compounds such as z.
  • organic or inorganic compounds such as z.
  • solubilizers individually or as a mixture with one another, can be incorporated, for which purpose, in addition to the water-soluble organic solvents, such as, in particular, low molecular weight aliphatic alcohols having 1-4 carbon atoms, also the so-called hydrotropic substances of the lower alkylarylsulfonate type, for example toluene, xylene or Cumene sulfonates or short chain alkyl sulfates such as octyl sulfate belong. They can also be in the form of their sodium and / or potassium and / or alkylamino salts.
  • water-soluble organic solvents such as, in particular, low molecular weight aliphatic alcohols having 1-4 carbon atoms
  • hydrotropic substances of the lower alkylarylsulfonate type for example toluene, xylene or Cumene sulfonates or short chain alkyl sulfates such as octyl sulfate belong
  • Water-soluble organic solvents can also be used as solubilizers, in particular those with boiling points above 75 ° C., for example the ethers from the same or different polyhydric alcohols or the partial ethers from polyhydric alcohols. These include, for example, di- or triethylene glycol polyglycerols and the partial ethers of ethylene glycol, propylene glycol, butylene glycol or glycerol with aliphatic monohydric alcohols containing 1 to 6 carbon atoms in the molecule.
  • ketones such as acetone, methyl ethyl ketone and aliphatic, cycloaliphatic and aromatic hydrocarbons, and also the terpene alcohols.
  • the weight ratio of surfactant to solvent or solubilizer can be 1: 0 to 1: 2, preferably 1: 0.05 to 1: 1.
  • the claimed agents may contain additives to colorants, fragrances and preservatives as other usual constituents.
  • a frame formulation of the concentrates according to the invention can thus have a total of approximately the following basic composition: Components % By weight Polyol alkoxylates: 1.0 to 30, preferably 2.0 to 15 Other surfactants: 0 to 80, preferably 50 to 80 Framework substances: 0 to 10, preferably 1.5 to 5 Surfactants: Solvents / Solubilizers: 1: 0 to 1: 2, preferably 1: 0.05 to 1: 1 Dyes / fragrances / preservatives: small quantities Water: Rest of 100 each
  • the cleaning agent to be tested was placed on an artificially soiled plastic surface.
  • a detergent with 10 wt .-% surfactant a mixture of petroleum jelly (R) , fatty acid glycerol esters and pigments was used as test soiling.
  • the test area of 26 x 28 cm was evenly coated with 2 g of the artificial soiling with the aid of a surface coater.
  • the test area was coated with 10 ml of the cleaning agent solution. After ten wiping movements with a plastic sponge, the cleaned test area was kept under running water and the loose dirt was removed.
  • the cleaning effect ie the whiteness of the plastic surface cleaned in this way, was determined using a Microcolor color difference measuring device from Dr. Measured for a long time.
  • a powerful standard formulation which falls under the scope of protection of the patent specification DE 28 40 463, served as a comparison: 8% by weight of alkylbenzenesulfonate, Na salt 2% by weight adduct of C 12/14 alkyl epoxide + ethylene glycol + 10 mol ethylene oxide 2% by weight Na gluconate 0.1% by weight of polyethylene glycol with a molecular weight of approx. 600,000 (Polyox WSR 205 (R) from UCC) Rest of water
  • the cleaning performance of the formulations given in the following examples was based on the cleaning performance of the above standard formulations, this being set to 100%.
  • the pH of the formulations was adjusted to about 7.0 either with sodium hydroxide solution or with citric acid as required.
  • Formula No. 4th 5 6 7 8th 9 10th 11 Verb from Example 1 8th % 6% 4% 2% - - - - Verb from example 2 - - - - 8th % 6% 4% 2% C 12/14 alkyl glucoside (DP 1.4) 2% 4% 6% 8th % 2% 4% 6% 8th % Na gluconate 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2%
  • a high cleaning performance is also obtained if, instead of sodium gluconate, a polycarboxylate with an average molecular weight of approx. 3000 (Sokalan ES 9911 (R) , from BASF) is used as a builder. This is illustrated by the recipes below.
  • Formula No. 12th 13 14 15 16 Verb from Example 1 8th % 8th % 8th % 8th % 8th % 8th % C 12/14 alkyl glucoside, (DP 1.4) 2% 2% 2% 2% 2% 2% Polycarboxylate MG approx. 3000 - 1 % 2% 3% 5% water Rest ⁇ Cleaning performance in% 124 132 128 129 124
  • Formula No. 27 28 29 Compound from example 1 8th % 6% 4% Na gluconate 2% 2% 2% C 12/14 monoalkylglycerol ether + 8 EO 2% 4% 6% water Rest ⁇ Cleaning performance in% 123 124 115

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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)
  • Detergent Compositions (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Claims (3)

  1. Détergent liquide concentré pour surfaces à base de solutions aqueuses de tensioactifs non ioniques, éventuellement conjointement avec d'autres tensioactifs anioniques et/ou non ioniques, de substances d'ossature organiques et/ou minérales, de solvants solubles dans l'eau ou d'agents de solubilisation ainsi que d'autres composants usuels des détergents de ce type, caractérisé en ce qu'il contient comme tensioactif non ionique de 1,0 à 30,0 % en poids, de préférence de 2,0 à 15 % en poids, rapportés au concentré total, d'un produit d'alcoxylation d'acides carboxyliques contenant des groupes OH et/ou de leurs dérivés ayant 30-85 % en poids, de préférence 30-65 % en poids d'oxyde d'éthylène ou d'oxyde de propylène.
  2. Agent selon la revendication 1, caractérisé en ce qu'il contient comme autres tensioactifs anioniques et/ou non ioniques, des tensioactifs anioniques du type sulfonate et/ou sulfate, des glucosides d'alkyl gras, des sulfosuccinates ainsi que des monoalkyléthers de glycérol.
  3. Agent selon les revendications 1 et 2, caractérisé en ce que le rapport de poids des produits d'alcoxylation d'acides carboxyliques contenant des groupe OH et/ou leurs dérivés, aux autres tensioactifs anioniques et/ou non ioniques va d'environ 1 à 100 jusqu' à environ 100 à 1, de préférence d'environ 1 à 10 à environ 10 à 1.
EP92921604A 1991-10-23 1992-10-14 Detergent liquide concentre pour surfaces dures Expired - Lifetime EP0609303B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4134973 1991-10-23
DE4134973A DE4134973A1 (de) 1991-10-23 1991-10-23 Fluessiges reinigungsmittelkonzentrat fuer harte oberflaechen
PCT/EP1992/002369 WO1993008248A1 (fr) 1991-10-23 1992-10-14 Detergent liquide concentre pour surfaces dures

Publications (2)

Publication Number Publication Date
EP0609303A1 EP0609303A1 (fr) 1994-08-10
EP0609303B1 true EP0609303B1 (fr) 1995-09-06

Family

ID=6443252

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EP92921604A Expired - Lifetime EP0609303B1 (fr) 1991-10-23 1992-10-14 Detergent liquide concentre pour surfaces dures

Country Status (5)

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EP (1) EP0609303B1 (fr)
AT (1) ATE127513T1 (fr)
DE (2) DE4134973A1 (fr)
ES (1) ES2076040T3 (fr)
WO (1) WO1993008248A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69325589T2 (de) 1992-11-03 2000-01-27 The Procter & Gamble Co., Cincinnati Reinigen mit kurzkettigen tensiden
DE19502454A1 (de) * 1995-01-27 1996-08-01 Henkel Kgaa Flüssigwaschmittel
DE19643857A1 (de) * 1996-10-30 1998-05-07 Henkel Kgaa Verwendung biologisch abbaubarer Alkoxylierungsprodukte zum Reinigen von Bohrlöchern, Bohrgeräten oder Bohrklein
EP2631289B1 (fr) * 2012-02-24 2018-06-13 Henkel AG & Co. KGaA Détergent liquide pour lessive comprenant des capsules II

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3923394A1 (de) * 1989-07-14 1991-01-17 Henkel Kgaa Alkoxylierungsprodukte von oh-gruppenhaltigen carbonsaeurederivaten und/oder carbonsaeuren

Also Published As

Publication number Publication date
EP0609303A1 (fr) 1994-08-10
DE4134973A1 (de) 1993-04-29
DE59203602D1 (de) 1995-10-12
WO1993008248A1 (fr) 1993-04-29
ES2076040T3 (es) 1995-10-16
ATE127513T1 (de) 1995-09-15

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