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WO1992015663A1 - Detergents - Google Patents

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Publication number
WO1992015663A1
WO1992015663A1 PCT/EP1992/000390 EP9200390W WO9215663A1 WO 1992015663 A1 WO1992015663 A1 WO 1992015663A1 EP 9200390 W EP9200390 W EP 9200390W WO 9215663 A1 WO9215663 A1 WO 9215663A1
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WO
WIPO (PCT)
Prior art keywords
zeolite
silicate
weight
alkali
silicates
Prior art date
Application number
PCT/EP1992/000390
Other languages
German (de)
English (en)
Inventor
Horst Upadek
Jörg Poethkow
Rainer Salz
Hans-Jürgen Riebe
Wolfgang Seiter
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6426447&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1992015663(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to DE59204203T priority Critical patent/DE59204203D1/de
Priority to EP92905355A priority patent/EP0574436B1/fr
Priority to JP50465492A priority patent/JPH06505045A/ja
Publication of WO1992015663A1 publication Critical patent/WO1992015663A1/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
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—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
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds

Definitions

  • the invention relates to a phosphate-free detergent based on zeolite and alkali silicate and a process for its production.
  • zeolite in particular zeolite NaA, and in particular mixtures of zeolite with alkali silicates and alkali metal carbonates and polymeric polycarboxylates were used as phosphate substitutes in washing and cleaning agents.
  • complexing agents such as the salts of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA) and phosphonic acids.
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • phosphonic acids phosphonic acids.
  • the mostly selective complexing agents have the task of eliminating heavy metal ions, which in trace amounts can have a very negative effect on the washing process, in particular on the bleaching process (Ullmann, 1987, Vol. 8, pp. 351 to 354) .
  • European patent application 291 869 (Henkel) describes phosphate-free builders combinations of zeolite and aminoalkane polyphosphonate and / or polymeric polycarboxylate and l-hydroxyethane-l, l-diphosphonate (HEDP), certain weight ratios of the last three components show a synergism with regard to the prevention of the formation of fiber incrustations.
  • Crystalline, layered sodium silicates have also been described as substitutes or as partial substitutes for phosphates and zeolites.
  • European patent application 164 514 discloses a phosphate-free builder combination which mainly contains crystalline sheet silicates of the formula (I) aMSi x ⁇ 2 + ⁇ * yH2 ⁇ , where M is sodium or water serstoff means, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • These layered silicates can be used as water softeners both separately and in detergents and cleaners together with other builders such as phosphates, zeolite, other silicates, phosphonates and polycarboxylates.
  • German patent application 24 12837 already describes detergents which, in combination with zeolite, contain various complexing agents such as polymeric polycarboxylates and phosphonates and alkaline framework substances which are not capable of complex formation, such as carbonates and silicates.
  • microcrystalline zeolites are preferably used, which are at least 80% by weight of particles between 10 and 0.01 ⁇ m in size and in particular between 8 and 0.1 ⁇ m.
  • washing and cleaning agents which contain 0.5 to 3% by weight of alkali silicate (calculated as a solid). These agents are produced either by a customary mixing process in which the solid silicates or a corresponding amount of a water glass solution are mixed together with the other main constituents, or by a spray drying process in which the slurry contains both zeolite and the corresponding amount of alkali silicate .
  • the alkali silicates serve as corrosion inhibitors.
  • a detergent is known from German patent application 26 56 009 (Colgate) which contains 12 to 25% by weight of zeolite, in particular of type 4A, 5 to 20% by weight of a sodium silicate having the composition a2 ⁇ : Si ⁇ 2 of 1: 1 to 1 : 3.2, in particular from 1: 2.0 to 1: 2.6, and contains a peroxy bleach.
  • undesired deposits of the water-insoluble zeolite particles on the laundry are to be prevented by 0.3 to 3% by weight of a polymer from the group carboxymethyl cellulose, lower alkyl cellulose, hydroxy-lower alkyl-lower alkyl cellulose, Polyvinyl alcohol, polyvinyl acetate and polyvinylpyrrolidone are used.
  • the zeolite has an average particle diameter of 0.5 to 12 ⁇ m, preferably 5 to 9 ⁇ m.
  • European patent application 10 247 (Henkel) describes a detergent which contains surfactants in conventional amounts, zeolite, alkali silicate and, if appropriate, a peroxy bleach.
  • the composition contains 20 to 65% by weight of a finely divided zeolite, as described in German patent application DE 24 12837, and 1 to 7% by weight of solid, powdered sodium silicate with the molar composition Na2 ⁇ : SiÜ2 of 1 : 2 to 1: 2.2.
  • the composition consists of a mixture of at least 2 powder constituents, the first of which is obtained by spray drying an aqueous slurry which contains the zeolite, surfactants and optionally the water-soluble organic complex-forming framework substances, and the second powder constituent from the sodium Likatpulver and optionally from the water-soluble phosphonates and other detergent additives, which are sensitive to hydrolysis and / or temperature.
  • detergents which, in addition to zeolite and water-soluble sodium silicates, as described in European patent application 10247, contain polyer polycarboxylates and their derivatives, for example polyacrylates and salts of copolymers of acrylic acid and maleic acid. These polymeric polycarboxylates are spray dried together with the zeolite during the production of the detergent.
  • the object of the invention was to further develop the field of phosphate-free builders combinations for use in textile detergents with the aim of reducing the proportion of organic synthetic compounds.
  • detergents which contain a special combination of finely divided zeolite with a relatively narrow particle size spectrum and alkali silicate as builders meet the high demands placed on modern detergents.
  • the invention relates to a detergent which contains surfactants, zeolite, alkali silicate and optionally a peroxy bleach and which is characterized in that it comprises 30 to 65% by weight of a finely divided, hydrated zeolite with an average particle size of 1 to 5 microns, 1 to 15 wt .-% of a solid alkali silicate of the molar composition M2O: Si2 ⁇ from 1: 2.0 to 1: 3.0, wherein M is sodium and / or potassium, with the proviso that the agent is free of water-soluble organic complexing agents from the group of the substituted phosphonates, free of polymeric polycarboxyates and essentially free of alkali carbonates.
  • the finely divided, hydrated zeolite generally has a water content of 17 to 25% by weight.
  • the quantities for zeolite relate to the anhydrous active substance.
  • Suitable zeolites are those of the zeolite A type. Mixtures of zeolite NaA and NaX can also be used, the proportion of zeolite NaX in such mixtures expediently being less than 30%.
  • Preferred zeolites have an average particle size between 1.8 and 4.5 ⁇ m, in particular between 2.0 and 4.0 ⁇ m (measurement method: Fraunhofer diffraction; mean value of the distribution of voltages).
  • the content of the agents in finely divided tigers, in particular crystalline, hydrated zeolite is preferably 30 to 55% by weight and in particular 32 to 54% by weight, based on the anhydrous active substance.
  • the solid alkali silicates can be amorphous or crystalline, as powder or as granules, for example as roller-compacted chip granules, or as a spray-dried compound.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na2O: SiO2 molar ratio of 1: 2 to 1: 2.8.
  • Such amorphous ATkaTisiTkate are commercially available for example under the name Portil ( R ) (Henkel).
  • Crystalline layered silicates of the formula (I) NaMSi x 02+ yH20, in which M is sodium, x is 2 or 3 and y is a number of, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates Is 0 to 20. Both ⁇ - and fr-sodium disilicate Na2Si2Ü5 are particularly preferred.
  • the content of alkali silicates in the compositions is preferably 2 to 10% by weight and in particular 3 to 10% by weight, based on the anhydrous substance.
  • the amorphous sodium silicate content of the agents is 3.5 to 8% by weight, based on the anhydrous substance.
  • the weight ratio of zeolite: amorphous silicate, in each case based on anhydrous substance is preferably 4: 1 to 10: 1.
  • the crystalline layered silicates are preferably used in amounts of 2 to 7% by weight, the weight ratio of zeolite to crystalline layered silicate, in each case based on anhydrous substance, being at least 5: 1.
  • the weight ratio of amorphous alkali silicate: crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • the agents do not contain any water-soluble organic complexing agents from the group of the phosphonates, so that the agents have a calculated phosphorus content of 0%.
  • Polymeric polycarboxylates for example polyacrylates, polyethacrylates, polymaleates or copolymers of acrylic acid with maleic acid or maleic anhydride, which are usually used in combination with zeolite, are also not present in the product according to the invention, since they do not have its primary and secondary washing power improve.
  • the agents are also essentially free of ATkaTicarbonates, which means that they contain no more than about 5% by weight, preferably no more than 4% by weight and particularly advantageously no more than 3% by weight of alkali carbonates, in particular of sodium carbonate.
  • ATkaTicarbonates which means that they contain no more than about 5% by weight, preferably no more than 4% by weight and particularly advantageously no more than 3% by weight of alkali carbonates, in particular of sodium carbonate.
  • an alkali carbonate content in the range mentioned also contributes to increased incrustation.
  • alkali carbonate may only be added in the amounts in which it does not contribute to increased incrustation.
  • Preferred detergents contain peroxy bleach and in particular peroxy bleach in combination with bleach activators.
  • the sodium perborate tetrahydrate and the sodium perborate monohydrate are of particular importance.
  • Other bleaches that can be used are, for example, peroxycarbonate or peracidic salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid.
  • Suitable bleach activators for these peroxy bleaching agents are, for example, the N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines such as N, N, N'N'-tetraacety-methylenediamine.
  • the content of peroxygen pond middleT in the middle T is preferably 12 to 30% by weight, in particular in combination with 1 to 10% by weight, preferably 2 to 8% by weight, of a bleach activator.
  • the detergents according to the invention are not only characterized by a reduced formation of fiber incrustations compared to agents of the prior art, which usually contain polymeric polycarboxylates and / or ATkaTicarbonate in larger quantities. Surprisingly, they also have an improved pond effect or an improved stabilization of the peroxy bleaching agent, although they contain no conventional stabilizers such as phosphonate, magnesium silicate or other complexing agents such as the salts of nitrilotriacetic acid and ethylenediaminetetraacetic acid.
  • the detergents and cleaners contain known compounds from the group of anionic, nonionic and zwitterionic surfactants as further constituents.
  • sulfonates come as anionic surfactants and sulfates and soaps from preferably natural fatty acids or fatty acid mixtures.
  • Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates, esters of oc-sulfofatty acids or ⁇ -sulfofatty acid disalts are used as surfactants of the sulfonate type.
  • Suitable surfactants of the sulfate type are the Schwefelklamonoester of primary alcohols naf ⁇ or synthetic origin, ie of C - ⁇ -.
  • CISS fatty alcohols or 'length from Ci0 "-20-0 ⁇ oa koho1en ⁇ f and those of secondary alcohols also Ketten ⁇ the sulfuric acid monoesters of the alcohols reacted with 1 to 6 moles of ethylene oxide (EO) are suitable as addition products, preferably addition products of preferably 2 to 20 moles of EO to 1 mole of an aliphatic compound having essentially 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides and alkanesulfonamides are of interest, but in addition to the water-soluble nonionic surfactants, it is also important to have water-insoluble or not completely water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule, especially if
  • the total content of surfactants in the compositions is generally between 5 and 40% by weight. It is preferably 5 to 30% by weight and in particular 8 to 25% by weight.
  • the other detergent and cleaning agent components include foam inhibitors, optical brighteners, enzymes and textile-softening agents Substances, dyes and fragrances as well as neutral salts, solvents and water.
  • foam inhibitors include foam inhibitors, optical brighteners, enzymes and textile-softening agents Substances, dyes and fragrances as well as neutral salts, solvents and water.
  • graying inhibitors which are usually used in modern textile detergents, is not necessary and, in particular, is not preferred.
  • Suitable enzymes are those from the K-cup of proteases, lipases, CeTTuTases and Ayytases or their mixtures.
  • Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable.
  • Proteases of the sub-lisin type and in particular proteases obtained from Bacillus lentus are preferably used.
  • the enzymes can be adsorbed on carriers and / or embedded in protective substances in order to protect them against premature decomposition.
  • Suitable non-surfactant-like and preferably used foam inhibitors are OrganopoTysiToxane and their mixtures with microfine, optionally siliconized silica. Mixtures of different foam inhibitors are also advantageously used, e.g. B. from silicone and paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • powdery or granular detergents contain 10 to 30% by weight of surfactants, 30 to 45% by weight of a finely divided, hydrated zeolite with an average particle size of 2.0 to 3.8 ⁇ m, 2 to 10 wt .-% of amorphous Natriumsil cat with a molar ratio Na 2 O: SiO 2 from 2.0 to 2.8 or a mixture of the ge called amorphous sodium silicate having a crystalline layered silicate, preferred wise ß-NatriumdisiTikat or ⁇ '-NatriumdisiTikat and 18 to 30% by weight of peroxygen pond, preferably perborate, and 2 to 8% by weight of a Pond activator, preferably TAED.
  • a Pond activator preferably TAED.
  • the detergents according to the invention can be prepared in a conventional manner, for example by mixing, granulating and / or by spray drying. It is possible to incorporate the builders zeolite and solid alkali metal acetate into the middle in a conventional manner and with a large number of rows.
  • the pourable powder-form or granular preparations preferably consist of a dry homogeneous mixture of at least 2 powder components, at least the first of which is in the form of spray-dried granules. It is done by a conventional way Spray drying of a slurry available which contains at least the anionic surfactants and optionally nonionic surfactants.
  • This slurry preferably additionally contains at least part of the zeolite and / or the silicate.
  • the slurry can partly, but not more than 3% by weight and in particular not more than 2% by weight, in each case based on the total, finished agents containing amorphous silicates.
  • the rest of the amorphous alkali silicates present as powder or granules, like the crystalline layered silicates which may be present, which are in granular form or adsorbed on a carrier consisting, for example, of sodium sulfate, are subsequently mixed into the spray product.
  • the zeolite-containing slurry be free of amorphous alkali silicates and that these are added to the spray-dried product altogether.
  • the slurry does not contain zeolite, it is possible to incorporate the entire proportion of the amorphous alkali silicates into the slurry and to spray-dry them.
  • the crystalline layered silicates which may be present are preferably not spray-dried, but are added subsequently in granular form or adsorbed onto a support.
  • the zeolite is then also incorporated into the compositions as a powder or, preferably, as a commercially available compound, for example as Wessalith ( R ) CS or Wessalith ( R ) CB (commercial products from Degussa, Federal Republic of Germany).
  • zeolite-containing and a silicate-containing slurry it is also possible for a zeolite-containing and a silicate-containing slurry to be spray-dried separately and then mixed. However, it is particularly advantageous if the zeolite-containing slurry and the silicate-containing slurry are introduced into a spray tower at the same time.
  • Bleaching agents such as perborate, as usual, are not spray-dried together with the constituents of the first powder component because of their thermal sensitivity, but are also only added to the spray product subsequently.
  • Granular detergents of the following composition were produced and tested.
  • the perborate, the bleach activator, the alkali silicate and enzyme granules and silicone oil granules were subsequently mixed into the spray-dried product from a slurry which contained the remaining constituents.
  • the test was carried out under practical conditions in household washing machines (Miele W 717). The washing conditions are specified in more detail in the individual examples.
  • the degree of whiteness was measured in a Zeiss reflectometer at 460 nm (suppression of the AufheT-ter effect). Remission differences of 2% and more are significant and can be traced directly by the consumer.
  • the center T E according to the invention and the comparing center T V had the following composition:
  • Zeolite NaA anhydrous AS
  • 24.0 average particle size 4.2 ⁇ m
  • ZeoTith NaA (anhydrous AS) 38.0 mean particle size 3.3 ⁇ m amorphous sodium 5.5
  • Example 1 Stabilization of the peroxy bleach using washing conditions: tap water of 17 ° d (equivalent to 170 mg Ca0 / 1),
  • Main wash 1: 4, ⁇ repeated rinsing with tap water, spinning and
  • the machines were loaded with 3.5 kg of normally soiled household linen (bed linen, table linen, underwear) and 0.5 kg of test fabric. Strips of standardized cotton fabric (laundry research institute Krefeld), of refined cotton fabric and of a mixed fabric of polyester and refined cotton were used as the test fabric.
  • Soiling grease / pigment soiling and bleachable
  • Soiling such as red wine, tea, cocoa, wild berries
  • the specified reflectance values reflect the average values across all measurements.
  • Washing conditions tap water of 23 ° d, 3.5 kg of clean laundry, dosage of detergent 146 g, 25 washes; aTTe further parameters as in example 1.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Des détergents renfermant de 30 à 65 % en poids d'une zéolite hydratée en fines particules, d'une granulométrie moyenne de 1 à 5 νm, et de 1 à 15 % en poids d'un silicate alcalin solide, de composition molaire M2O:SiO2 de 1:2,0 à 1:3,0, et qui sont exempts de complexants organiques solubles dans l'eau, du groupe des phosphonates substitués, exempts de polycarboxylates polymères et sensiblement exempts de carbonates alcalins, sont en mesure de remplacer des détergents commerciaux renfermant des phosphonates, des polycarboxylates polymères et/ou des carbonates alcalins en plus grandes quantités, sans qu'il en résulte une diminution des performances La proportion de composés synthétiques organiques peut ainsi être réduite dans les détergents.
PCT/EP1992/000390 1991-03-05 1992-02-25 Detergents WO1992015663A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE59204203T DE59204203D1 (de) 1991-03-05 1992-02-25 Waschmittel.
EP92905355A EP0574436B1 (fr) 1991-03-05 1992-02-25 Detergents
JP50465492A JPH06505045A (ja) 1991-03-05 1992-02-25 洗剤

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4106880.7 1991-03-05
DE4106880A DE4106880A1 (de) 1991-03-05 1991-03-05 Waschmittel

Publications (1)

Publication Number Publication Date
WO1992015663A1 true WO1992015663A1 (fr) 1992-09-17

Family

ID=6426447

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1992/000390 WO1992015663A1 (fr) 1991-03-05 1992-02-25 Detergents

Country Status (6)

Country Link
EP (1) EP0574436B1 (fr)
JP (1) JPH06505045A (fr)
AT (1) ATE129743T1 (fr)
DE (2) DE4106880A1 (fr)
ES (1) ES2079858T3 (fr)
WO (1) WO1992015663A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994018294A1 (fr) * 1993-02-15 1994-08-18 Henkel Kommanditgesellschaft Auf Aktien Additif pour detergent, contenant des tensioactifs et des adjuvants

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9021761D0 (en) * 1990-10-06 1990-11-21 Procter & Gamble Detergent compositions
DE4134914A1 (de) * 1991-10-23 1993-04-29 Henkel Kgaa Wasch- und reinigungsmittel mit ausgewaehlten builder-systemen
ES2373300B1 (es) 2011-12-14 2012-12-20 Soro Internacional, S.A. Detergente para lavavajillas.

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2335594A1 (fr) * 1975-12-15 1977-07-15 Colgate Palmolive Co Composition detergente
DE2742484A1 (de) * 1976-09-24 1978-03-30 Lion Fat Oil Co Ltd Verfahren zur herstellung eines koernigen wasch- oder reinigungsmittels
EP0010247A1 (fr) * 1978-10-12 1980-04-30 Henkel Kommanditgesellschaft auf Aktien Produit pour le lavage sans phosphates et procédé pour sa fabrication
EP0061296A1 (fr) * 1981-03-20 1982-09-29 Unilever Plc Procédé pour la préparation de compositions détergentes contenant de l'aluminosilicate de sodium
EP0150613A2 (fr) * 1983-12-21 1985-08-07 Unilever Plc Compositions détergentes
EP0240356A1 (fr) * 1986-04-04 1987-10-07 Unilever Plc Poudres de détergentes et procédé pour leur préparation
EP0260971A2 (fr) * 1986-09-19 1988-03-23 Unilever Plc Composition détergente et son procédé de production
EP0405122A2 (fr) * 1989-06-24 1991-01-02 Hoechst Aktiengesellschaft Agent de renforcement pour détergent de matière textile

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2335594A1 (fr) * 1975-12-15 1977-07-15 Colgate Palmolive Co Composition detergente
DE2742484A1 (de) * 1976-09-24 1978-03-30 Lion Fat Oil Co Ltd Verfahren zur herstellung eines koernigen wasch- oder reinigungsmittels
EP0010247A1 (fr) * 1978-10-12 1980-04-30 Henkel Kommanditgesellschaft auf Aktien Produit pour le lavage sans phosphates et procédé pour sa fabrication
EP0061296A1 (fr) * 1981-03-20 1982-09-29 Unilever Plc Procédé pour la préparation de compositions détergentes contenant de l'aluminosilicate de sodium
EP0150613A2 (fr) * 1983-12-21 1985-08-07 Unilever Plc Compositions détergentes
EP0240356A1 (fr) * 1986-04-04 1987-10-07 Unilever Plc Poudres de détergentes et procédé pour leur préparation
EP0260971A2 (fr) * 1986-09-19 1988-03-23 Unilever Plc Composition détergente et son procédé de production
EP0405122A2 (fr) * 1989-06-24 1991-01-02 Hoechst Aktiengesellschaft Agent de renforcement pour détergent de matière textile

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994018294A1 (fr) * 1993-02-15 1994-08-18 Henkel Kommanditgesellschaft Auf Aktien Additif pour detergent, contenant des tensioactifs et des adjuvants

Also Published As

Publication number Publication date
ATE129743T1 (de) 1995-11-15
DE59204203D1 (de) 1995-12-07
DE4106880A1 (de) 1992-09-10
ES2079858T3 (es) 1996-01-16
JPH06505045A (ja) 1994-06-09
EP0574436B1 (fr) 1995-11-02
EP0574436A1 (fr) 1993-12-22

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