EP0022998B1 - Verfahren zur Herstellung eines schaumgedämpften Waschmittels - Google Patents

Verfahren zur Herstellung eines schaumgedämpften Waschmittels Download PDF

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Publication number
EP0022998B1
EP0022998B1 EP80104033A EP80104033A EP0022998B1 EP 0022998 B1 EP0022998 B1 EP 0022998B1 EP 80104033 A EP80104033 A EP 80104033A EP 80104033 A EP80104033 A EP 80104033A EP 0022998 B1 EP0022998 B1 EP 0022998B1
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EP
European Patent Office
Prior art keywords
weight
spray
polysiloxane
sodium
anhydrous
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
Application number
EP80104033A
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German (de)
English (en)
French (fr)
Other versions
EP0022998A1 (de
Inventor
Heinz-Gerd Dr. Smolka
Herbert Dr. Reuter
Markus Dr. Berg
Günther Dr. Vogt
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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.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT80104033T priority Critical patent/ATE1911T1/de
Publication of EP0022998A1 publication Critical patent/EP0022998A1/de
Application granted granted Critical
Publication of EP0022998B1 publication Critical patent/EP0022998B1/de
Expired legal-status Critical Current

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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D3/0026—Low foaming or foam regulating 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones

Definitions

  • the undesirable strong foaming of detergents can be suppressed by adding foam-suppressing mixtures of polydimethylsiloxane and finely divided silica. It is also known that the state of distribution of the siloxanes in the detergent plays an important role in the effectiveness. If the siloxanes are added to the slurry prior to spray drying, this results in a homogeneous distribution state in which the washing capacity is not impaired, but at the same time the foam-suppressing effect partially decreases.
  • DE-B-23 38 468 describes a detergent in which the polysiloxane / silica mixture is incorporated into a carrier substance which is impenetrable to detergents.
  • the purpose of this measure is to prevent an interaction between the detergents contained in the detergent and the polysiloxane and thus to prevent a drop in activity during mixing and storage.
  • the polysiloxane-silica mixture is adsorbed on a solid carrier consisting of sodium carbonate, silicate, tripolyphosphate, clay, diatomaceous earth or fuller's earth or starch, polyglycols, highly ethoxylated fatty alcohols, gelatin or other gel-forming materials.
  • the granular adsorbates are produced by spray drying, spray cooling or fluidizing liquid or molten mixtures of polysiloxane foam damper and carrier material.
  • the prefabricated grains or prills are then coated with an upper coating material, which can consist of the compounds used as the carrier material.
  • the coating is intended to counteract the sticking of the grains and to prevent interactions with other detergent components, in particular surfactants.
  • the patent application advises against a method of production in which the polysiloxane component is sprayed onto a granular carrier, for example sodium tripolyphosphate, and incorporated into the detergent in this form, since this results in an unfavorable foam profile.
  • the present invention is suitable for eliminating the disadvantages described.
  • the invention relates to a process for producing a foam-damped detergent, consisting of several powdery to granular components, one of the powder components consisting of a polysiloxane defoamer adsorbed on a carrier substance and the other powder components consisting of spray-dried or granulated detergents of conventional composition and, if appropriate, bleaching agents , characterized in that for the preparation of the powder component containing the polysiloxane defoamer, a 40 to 75 percent by weight (calculated as an anhydrous compound) of at least one compound from the class of polymer phosphates, silicates, carbonates and sulfates of sodium-containing aqueous slurry which is free of surfactants is and does not contain more than 0.3 percent, based on anhydrous salt, of polysiloxane defoamers, spray-dried using 120 ° to 300 ° C hot gases in a manner known per se, and so
  • Salt mixtures which contain at least two of the aforementioned salts are preferably used.
  • Such salt mixtures are sprayed from an aqueous slurry containing 50 to 70 percent by weight of anhydrous salt.
  • the spraying can take place in conventional spray drying systems, for example in so-called spray towers, in which the slurry is sprayed by means of nozzles and dried with the aid of gases heated in cocurrent or preferably countercurrent, in particular air or combustion gases mixed with air.
  • the inlet temperature of the dry air is 120 ° to 300 ° C, preferably 150 ° to 250 ° C, the outlet temperature is generally 75 ° to 95 ° C.
  • Salt mixtures have proven to be particularly suitable, the proportion of sodium silicate of which is 3 to 75 percent by weight, in particular 5 to 15 percent by weight, based on anhydrous salt. Such salt mixtures result in a particularly abrasion-resistant and at the same time readily soluble granular carrier substance.
  • sodium silicate used in the aforementioned weight ratios has a ratio of 1: 1.
  • a further improvement in the grain structure is achieved if a salt mixture is used which, in addition to the aforementioned sodium silicate, also contains sodium tripolyphosphate and sodium sulfate in a weight ratio of 10: 1 to 1:10, in particular 5: 1 to 1: 5, based on anhydrous sodium tripolyphosphate and anhydrous sodium sulfate.
  • the sodium tripolyphosphate is used - regardless of the calculated relationship - preferably as hexahydrate.
  • the carrier substance preferably has the following composition (calculated as anhydrous salt)
  • Carrier substances with a high tripolyphosphate content have a higher water content (10-20%), those with a high sodium sulfate have a lower water content (5-8%).
  • the water content is about 8-12 percent.
  • up to 0.3% by weight, preferably 0.05 to 0.2% by weight, of the mixture of polysiloxane and silica can be added to the aqueous slurry, based on anhydrous salts.
  • this portion added before spraying loses a certain part of its foam-suppressing effect, as stated at the beginning, this loss can be accepted, since it affects only a small percentage of the total polysiloxane defoamer to be used.
  • this additive significantly improves the sprayability of the concentrates, the grain structure of the carrier grains in the sense of an improved absorption capacity for polysiloxanes, and in particular the wettability of the powder component loaded with further polysiloxane defoamer when used later in the washing bath. If instead, as suggested in the previous literature, the entire amount of the polysiloxane-silica mixture is incorporated into the concentrate and sprayed with it, the wettability in the washing bath deteriorates and residue formation can result from undissolved particles. In addition, the foam-suppressing effect is reduced overall.
  • the carrier should be free of surfactants because surfactants also weaken the foam-suppressing effect. In addition, it should be free of water-insoluble or sparingly soluble compounds, such as the clays, diatomaceous earth, fuller's earth and cellulose recommended in the previous literature, since these substances also lead to a loss of activity, which may be due to a partial separation of the polysiloxane from the silica.
  • the carrier substance produced in the manner indicated is of a granular nature and has a particle size range from 0.05 to 2.5 mm, preferably from 0.1 to 1.6 mm with an average particle size of 0.2 to 0.8 mm. It is characterized by a good absorption capacity for the polysiloxane-silica component on the one hand and for a quick and complete dissolution in the wash bath even at low wash bath temperatures.
  • the granular carrier substance is mixed with conventional polysiloxane-silica mixtures, the weight ratio of carrier substance (calculated as anhydrous salt) to polysiloxane-silica mixture 50: 1 to 6: 1, preferably 25: 1 to 8: Is 1.
  • Suitable polysiloxanes are conventional compounds such as dimethyl, diethyl, dipropyl, dibutyl, methylethyl, methylphenyl, methylcyclohexyl and hydroxyalkyl polysiloxanes.
  • Crosslinked polysiloxanes are also suitable.
  • the polysiloxanes are used in a mixture with finely divided silica, for example Aerosil, it also being possible to use silanized silica which can be obtained by reacting silica containing hydroxyl groups with chlorosilanes.
  • the weight ratio of polysiloxane to silica is 50: 1 to 5: 1, preferably 25: 1 to 7: 1.
  • the carrier substance (hereinafter called powder component A) loaded with the polysiloxane / silica mixture has a bulk density of 450 to 700, preferably 500 to 650 g / l. It is of the same order of magnitude as the bulk density of spray-dried detergent powder, which is why the powder mixtures cannot separate during transport and storage.
  • the powder component A is mixed with further powdery to granular detergent components in a manner known per se, the proportions being such that - depending on the strength of the desired effect - 0.01 to 0.5, preferably 0.05 to 0.2 percent by weight Polysiloxane-silica mixture contained in the detergent.
  • the detergent component (hereinafter called powder component B) containing surfactants and skeletal salts should have a grain size of 0.05 to 2.5 mm, preferably 0.1 to 1.6 mm. It contains at least one anionic, nonionic or zwitterionic surfactant, skeletal salts and other non-bleaching detergent components, which include washing alkalis, graying inhibitors, optical brighteners, stabilizers, neutral salts and dyes, but not per compounds or bleaches containing active chlorine, bleach activators and enzymes that spray under the conditions of a hot spray are not stable.
  • Anionic surfactants suitable for the preparation of component (B) are those of the sulfonate or sulfate type, in particular alkylbenzenesulfonates, olefin sulfonates, alkylsulfonates and ⁇ -sulfofatty acid esters, primary alkyl sulfates and the sulfates of ethoxylated, 2 to 3 glycol ether groups having higher molecular weight alcohols.
  • Alkaline soaps of fatty acids of natural or synthetic origin are also suitable, for example the sodium soaps of coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants are preferably in the form of the sodium salts.
  • anionic and zwitterionic compounds mentioned have an aliphatic hydrocarbon radical, this should preferably be straight-chain and have 8 to 22, preferably 12 to 18, carbon atoms.
  • the preferably unbranched alkyl chains contain 6 to 16, in particular 10 to 14, carbon atoms.
  • Suitable nonionic surfactants are, in particular, ethoxylation products of saturated or monounsaturated aliphatic primary alcohols having 12 to 24, preferably 12 to 18 carbon atoms and 3 to 20, in particular 4 to 15, ethylene glycol ether groups.
  • Suitable alcohols from which the present ethoxylation products are derived are, for example, those of natural origin, such as coconut oil or tallow fatty alcohols or oleyl alcohol, furthermore oxo alcohols or synthetic alcohols obtained by ethylene polymerization.
  • nonionic surfactants are ethoxylation products of secondary alcohols, vicinal diols and amino alcohols each having 12 to 18 carbon atoms and alkylphenols with 6 to 12 carbon atoms in the alkyl radical, the number of glycol ether groups also being 3 to 20, preferably 4 to 15.
  • the abovementioned ethoxylated alcohols, amino alcohols and alkylphenols can also be replaced in whole or in part by those which are prepared with 0.5 to 3 moles of propylene oxide per mole of starting compound and only in the second stage the envisaged amount of ethylene oxide is added.
  • nonionic surfactants can also be present which are derived from the abovementioned compounds and which have ethylene glycol and propylene glycol ether groups in a different order, for example alcohols with 10 to 30 ethylene glycol ether groups and 3 to 30 propylene glycol ether groups; also ethoxylation products of mercaptans, fatty acid amides and fatty acids.
  • the water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1 to 10 carbon atoms in the alkyl chain can also be used.
  • the compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
  • Nonionic compounds of the amine oxide and sulfoxide type which can optionally also be ethoxylated, can also be used.
  • Suitable builder substances are the polymer phosphates, carbonates, silicates and sulfates of potassium and in particular of sodium, the silicates having a ratio of SiO 2 to Na 2 O of 1: 1 to 3.5: 1.
  • the pentasodium triphosphate is suitable as the polymer phosphate, which can be present in a mixture with its hydrolysis products, the mono- and diphosphates, and also more highly condensed phosphates, for example the tetraphosphates.
  • aluminosilicates generally have a grain size of 0.1 to 20 11 m and are preferably crystalline.
  • the skeletal salts also include salts of complexing aminopolycarboxylic acids, in particular alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid.
  • the higher homologues of the aminopolycarboxylic acids mentioned are also suitable.
  • Salts of nitrogen-free polycarboxylic acids which form complex salts with calcium ions, including polymers containing carboxyl groups, are also suitable. Examples are citric acid, tartaric acid, benzene hexacarboxylic acid and tetrahydrofuran tetracarboxylic acid.
  • Polycarboxylic acids containing carboxymethyl ether groups can also be used, such as 2,2'-oxydisuccinic acid and polyhydric alcohols partially or completely etherified with glycolic acid or hydroxycarboxylic acids, for example triscarboxymethylglycerol, biscarboxymethylglyceric acid, carboxymethyloxysuccinic acid and carboxymethylaccharated or oxidized polysaccharide.
  • the polymeric carboxylic acids with a molecular weight of at least 350 are suitable in the form of the water-soluble sodium or potassium salts, such as polyacrylic acid, polymethacrylic acid, poly-a-hydroxyacrylic acid, polymaleic acid, polyitaconic acid, polymesaconic acid, polybutene tricarboxylic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such as ethylene, propylene, isobutylene, vinyl methyl ether or furan.
  • the water-soluble sodium or potassium salts such as polyacrylic acid, polymethacrylic acid, poly-a-hydroxyacrylic acid, polymaleic acid, polyitaconic acid, polymesaconic acid, polybutene tricarboxylic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such as ethylene, propylene, isobutylene,
  • complexing polyphosphonic acid salts may be present, e.g. the alkali metal salts of aminopolyphosphonic acids, in particular aminotri- (methylenephosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, phenylhydroxymethane diphosphonic acid, methylene diphosphonic acid and salts of the higher homologues of the polyphosphonic acids mentioned.
  • aminopolyphosphonic acids in particular aminotri- (methylenephosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, phenylhydroxymethane diphosphonic acid, methylene diphosphonic acid and salts of the higher homologues of the polyphosphonic acids mentioned.
  • component (B) includes washing alkalis, neutral salts, graying inhibitors, optical brighteners, stabilizers such as magnesium silicate, substances which have an aerating effect and dyes, and further additives which improve the sprayability, e.g. Alkali salts of toluene, xylene or cumene sulfonic acid.
  • Suitable washing alkalis are alkali carbonates, bicarbonates, borates and silicates with a Na 2 0: Si0 2 ratio of 1: 1 to 1: 3.5.
  • Sodium sulfate and sodium chloride are suitable as neutral salts.
  • Suitable graying inhibitors are, in particular, carboxymethyl cellulose and cellulose mixed ethers which have varying amounts of carboxymethyl, methyl and / or hydroxyethyl, hydroxypropyl and hydroxybutyl groups, in particular methyl hydroxypropyl cellulose and methyl hydroxybutyl cellulose, furthermore colloidally water-soluble polymers or copolymers of vinyl alcohol and vinyl alcohol and vinyl alcohol, vinyl acrylamide, vinyl alcohol Acrylonitrile.
  • Suitable optical brighteners are the alkali salts of 4,4-bis (-2 "-anilino-4" -morpholino-1,3,5-triazinyl-6 "-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which carry a diethanolamino group, a methylamino group or a .beta.-methoxyethylamino group instead of the morpholino group.
  • Further possible brighteners for polyamide fibers are those of the diarylpyrazoline type, for example 1- (p-sulfonamidophenyl) -3- (p-chlorophenyl) -A ' -pyrazoline and compounds of the same structure which carry a carboxymethyl or acetylamino group instead of the sulfonamido group.
  • Substituted aminocoumarins for example 4-methyl-7-dimethylamino or 4-methyl-7-diethylaminocoumarin, can also be used.
  • the compounds are also polyamide brighteners 1- (2-Benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) -ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyryl can be used.
  • the compounds 2.5 are brighteners for polyester and polyamide fibers -Di- (2-benzoxaz olyl) thiophene, 2- (2-benzoxazolyl) naphto [2,3-b] thiophene and 1,2-di (5-methyl-2-benzoxyzolyl) ethylene are suitable.
  • Brighteners of the substituted diphenylstyryl type may also be present. Mixtures of the aforementioned brighteners can also be used.
  • Any further powder component (C) which is present preferably contains a per compound, for example sodium percarbonate, but in particular sodium perborate tetrahydrate.
  • Additional powder components may also be present, which may contain enzymes or bleach activators, for example.
  • the enzymes and bleach activators can be coated with water-soluble or dispersible coating substances.
  • the powder component (B) is advantageously produced by spray drying in a known manner from an aqueous slurry.
  • Such spray powders usually have a liter weight of 300 to 600 g and, after mixing with the component (A) produced by spraying, do not tend to separate during filling and during transport. If necessary, component (B) can also be prepared by known granulation processes.
  • the various powder components are combined by mixing in conventional mixing devices, which preferably operate continuously or on the free-fall principle. Before or during the mixing process, further constituents, for example fragrances, can also be introduced or sprayed onto one of the powder components or the powder mixture. Finally, one of the powder components (B) or (C), but especially the sodium perbo rat (component C) - as described in DE-A-27 48 970 and 27 53 680 - with nonionic surfactants to improve the washing behavior of the washing powder.
  • the spray products according to Examples 4, 5 and in particular 6 show very favorable grain spectra. Grain fractions over 1.6 mm in diameter were sieved out before further processing.
  • the spray products (temperature 20 ° C.) were mixed in a drum mixer with step by step with a homogeneous mixture of 6 parts by weight of polydimethylsiloxane and 1 part by weight of silanized silica heated to 50 ° C.
  • the viscosity of the polysiloxane-silica mixture was 1300 cP at 20 ° C and 750 cP at 50 ° C.
  • examples 1, 2, 4 and 5, 5 parts by weight of polysiloxane-silica mixture per 95 parts by weight of carrier were used. In Example 3 this ratio was 10 to 90 and in Example 6 (spray product containing 0.2 percent by weight polysiloxane) 4.8 to 95.2 parts by weight.
  • the polysiloxane / silica mixture was completely absorbed by the carrier substance.
  • the impregnated granules proved to be dry, pourable, non-sticky and non-greasy.
  • the literge the weight of the granules was between 560 and 590 g / l.
  • composition of the spray-dried detergent (component B) was (in percent by weight):
  • the powder components (A) and (B) were mixed with the addition of sodium perborate tetrahydrate (component C) in the mixing ratios given in Table 2.
  • the foam behavior was tested after 10 days of storage of the mixture in a commercial washing machine with a horizontally arranged drum at temperatures of 30 °, 60 ° and 95 ° C. For this purpose, the machine was loaded with 3.5 kg of clean laundry (cotton).
  • the detergent concentration was 7.5 g and the water hardness was 16 ° dH.
  • the respective foam height was checked through the sight glass of the front door and graded as follows:
  • 5 wt .-% polydimethylsiloxane were mixed according to the procedure according to DE-A-23 38 468, Example 1 with 5 wt .-% silica and 40 wt .-% of an ethoxylated tallow alcohol (25 EO) at 50 ° C and a fluidized Sprayed bed of 50 wt .-% sodium sulfate.
  • Comparative experiment V was repeated with the modification that instead of the sodium sulfate a crystalline powdered sodium aluminum silicate of the composition 0.9 Na 2 0.Al 2 O 3 .2 Si0 2 .3 H 2 0 was used, the particle size of which was 1-15 ⁇ m.
  • the solution behavior of the siloxane-containing powder component was determined as follows.
  • a beaker volume 500 cm 3
  • 200 ml of a solution of 1 g of sodium dodecylbenzenesulfonate in 1 liter of water at a temperature of 22 ° C are mixed with a motorized stirrer equipped with 4 stirring blades that are bent downwards at an angle of 30 ° a constant number of revolutions of 700 rpm. stirred.
  • the distance between the agitator blades and the bottom of the vessel is 2.5 cm.
  • 1 g of the sample is carefully poured into the stirring cone, avoiding lumps.
  • the solution is poured through a tared sieve with a mesh size of 0.1 mm and a diameter of 7 cm and sucked off using a suction bottle. Remnants of substance remaining in the beaker are transferred onto the sieve using as little water as possible.
  • the sieve is weighed back in air after a drying time of 24 hours. The results of 10 experiments are averaged.

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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)
  • Bidet-Like Cleaning Device And Other Flush Toilet Accessories (AREA)
EP80104033A 1979-07-20 1980-07-12 Verfahren zur Herstellung eines schaumgedämpften Waschmittels Expired EP0022998B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80104033T ATE1911T1 (de) 1979-07-20 1980-07-12 Verfahren zur herstellung eines schaumgedaempften waschmittels.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2929359 1979-07-20
DE19792929359 DE2929359A1 (de) 1979-07-20 1979-07-20 Verfahren zur herstellung eines schaumgedaempften waschmittels

Publications (2)

Publication Number Publication Date
EP0022998A1 EP0022998A1 (de) 1981-01-28
EP0022998B1 true EP0022998B1 (de) 1982-12-01

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EP80104033A Expired EP0022998B1 (de) 1979-07-20 1980-07-12 Verfahren zur Herstellung eines schaumgedämpften Waschmittels

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EP (1) EP0022998B1 (da)
AT (1) ATE1911T1 (da)
DE (2) DE2929359A1 (da)
DK (1) DK154828C (da)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3128631A1 (de) * 1981-07-20 1983-02-03 Henkel Kgaa "verfahren zur herstellung eines schaumgedaempften, silikone enthaltenden waschmittels"
GB8619634D0 (en) * 1986-08-12 1986-09-24 Unilever Plc Antifoam ingredient
DE4113783C1 (da) * 1991-04-26 1992-11-19 Rudolf Gmbh & Co Kg Chemische Fabrik, 8192 Geretsried, De
GB9410677D0 (en) 1994-05-27 1994-07-13 Unilever Plc Detergent compositions

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1407997A (en) * 1972-08-01 1975-10-01 Procter & Gamble Controlled sudsing detergent compositions
AT388744B (de) * 1975-10-14 1989-08-25 Procter & Gamble Feste wasch- und reinigungsmittelzusammensetzung
US4136045A (en) * 1976-10-12 1979-01-23 The Procter & Gamble Company Detergent compositions containing ethoxylated nonionic surfactants and silicone containing suds suppressing agents
DE2748970C2 (de) * 1977-11-02 1979-12-20 Henkel Kgaa, 4000 Duesseldorf Verfahren zur Herstellung pulverförmiger, organische Siliciumpolymere enthaltender Waschmittel mit verbesserten Lösungseigenschaften
DE2753680C2 (de) * 1977-12-02 1986-06-26 Henkel KGaA, 4000 Düsseldorf Verfahren zur Herstellung pulverförmiger, organische Siliciumpolymere enthaltender Waschmittel mit verbesserten Lösungseigenschaften
CH636123A5 (de) * 1978-06-07 1983-05-13 Ciba Geigy Ag Verfahren zur herstellung schaumregulierter waschmittel.

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DE2929359A1 (de) 1981-02-12
DK267280A (da) 1981-01-21
ATE1911T1 (de) 1982-12-15
DE3061216D1 (en) 1983-01-05
DK154828C (da) 1989-05-16
EP0022998A1 (de) 1981-01-28
DK154828B (da) 1988-12-27

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