EP0013028B1 - Detergent with a polydimethyl-siloxane content possessing an anti-foaming activity, and process for its production - Google Patents

Detergent with a polydimethyl-siloxane content possessing an anti-foaming activity, and process for its production Download PDF

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Publication number
EP0013028B1
EP0013028B1 EP19790105371 EP79105371A EP0013028B1 EP 0013028 B1 EP0013028 B1 EP 0013028B1 EP 19790105371 EP19790105371 EP 19790105371 EP 79105371 A EP79105371 A EP 79105371A EP 0013028 B1 EP0013028 B1 EP 0013028B1
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Prior art keywords
weight
detergent
component
water
soluble
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EP19790105371
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German (de)
French (fr)
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EP0013028A1 (en
Inventor
Klaus Dr. Hachmann
Dieter Dr. Jung
Alexander Dr. Boeck
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/0026—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
    • C11D3/02—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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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 undesired strong foaming of detergents can be suppressed by adding foam-suppressing polydimethylsiloxanes. 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 before the atomization drying, this results in a homogeneous distribution state in which there is no impairment of the washing power, but at the same time the foam-suppressing effect in some cases drops considerably.
  • DE-B 2 338 468 describes a detergent in which the siloxane is incorporated into a carrier substance which is free from surface-active substances and is impenetrable to detergents.
  • the purpose of this measure is to prevent an interaction between the detergents contained in the detergent and the siloxane and thus to prevent a drop in activity during mixing and storage.
  • the powder component (A) which consists of particles with an average grain size of 0.1 to 1 mm, contains 1 to 10, preferably 2 to 8% by weight of a polydimethylsiloxane, for example one of the general formula, as a foam-suppressing component where n is a number from 20 to 2000, preferably 40 to 1000.
  • the siloxane is present in a mixture with finely divided silica with a large active surface, specifically in a weight ratio of siloxane to silica of 100: 1 to 5: 1, preferably 50: 1 to 10: 1.
  • Particularly suitable for this purpose is precipitated silica or by thermal decomposition of silicon tetrachloride produced silicon dioxide (Aerosil).
  • This silicon dioxide which has an active surface area of 100 to 180 m 2 / g, can also be silanized.
  • Silanized silica is e.g. B. obtained by reacting part of the OH groups, the proportion of which is usually about 70 to 90 meq per 100 g of silica, with dimethyldichlorosilane or trimethylchlorosilane.
  • component (A) contains 2 to 15% by weight, preferably 3 to 8% by weight, of at least one nonionic surfactant.
  • Suitable surfactants are especially ethoxylated aliphatic alcohols with 12 to 20 C atoms and 4 to 20, preferably 5 to 15 ethylene glycol ether groups (EO groups).
  • Suitable alcohol components are lauryl, myristyl, cetyl, stearyl, arichidyl, oleyl, elaidyl, linolyl and ricinolyl alcohol and mixtures thereof, such as coconut or tallow alcohols, and also synthetic alcohols, for example those prepared by oxosynthesis or ethylene polymerization .
  • Ethoxylation products of alkylphenols, fatty acids, fatty acid amides, thioalcohols and vicinal diols, each having 12 to 20 carbon atoms in the hydrophobic radical and 4 to 20, preferably 5 to 15, EO groups can also be used.
  • Mixtures of higher ethoxylated compounds containing 7 to 15 EO groups and lower ethoxylated compounds having 3 to 6 EO groups can also be used, for example in a ratio of 4: 1 to 1: 2.
  • the powder component (A) further contains 1 to 10, preferably 3 to 8% by weight of at least one water-soluble cellulose ether.
  • Carboxymethyl cellulose is preferably used in the form of the Na or K salt.
  • methyl and hydroxyethyl cellulose and mixed cellulose ethers such as methyl carboxymethyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl hydroxybutyl cellulose. Mixtures of the cellulose ethers mentioned above can also be present.
  • Another component of powder component (A) is a water-soluble or dispersible inorganic salt in an amount of 70 to 95, preferably 75 to 90% by weight.
  • B sodium sulfate, sodium carbonate, sodium hydrogen carbonate, sodium diphosphate, sodium tripolyphosphate, sodium silicates with a Na 2 0: Si0 2 ratio of 1: 1 to 1: 3.5, sodium aluminosilicates of the formula as described for example in DE-B 2 412 837, as well as magnesium silicate.
  • the potassium salts can also be used. Mixtures of the aforementioned inorganic salts, in particular those of sodium sulfate and magnesium silicate in a ratio of 10: 1 to 5: 1, can also be used.
  • the powder component (B), in which the particles have a particle size of 0.1 to 2.5 mm, preferably 0.2 to 1.5 mm, 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 which are not stable under the conditions of hot spray drying.
  • Anionic surfactants suitable for the preparation of component (B) are those of the sulfonate or sulfate type, in particular alkylbenzenesulfonates, olefin sulfonates, alkylsulfonates and oc-sulfofatty acid esters, primary alkyl sulfates and the sulfates of ethoxylated, 2 to 3 glycol ether groups having higher molecular weight alcohols.
  • the anionic surfactants are preferably in the form of the sodium salts. If the 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. In the compounds having an araliphatic hydrocarbon radical, 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 and vicinal diols each having 12 to 18 carbon atoms and of alkylphenols with 6 to 12 carbon atoms in the alkyl radical, the number of glycol ether groups likewise being 3 to 20, preferably 4 to 15.
  • the abovementioned ethoxylated 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 amount of ethylene oxide envisaged 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 with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1 to 10 carbon atoms in can also be used the alkyl chain.
  • 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.
  • pentasodium triphosphate is particularly suitable, which, in a mixture with its hydrolysis products, the mono- and diphosphates, as well as higher-condensed phosphates, e.g. B. the tetraphosphates may be present.
  • aluminosilicates generally have a grain size of 0.1 to 20 u. and are preferably crystalline.
  • the skeletal salts also include salts of complexing aminopolycarboxylic acids, in particular alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid. Also suitable are higher homologues of the aminopolycarboxylic acids mentioned. 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 acarboxylic 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 also suitable in the form of the water-soluble sodium or potassium salts, such as polyacrylic acid, polymethacrylic acid, poly- ⁇ -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- ⁇ -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 salts can be present, for. B. the alkali metal salts of aminopolyphosphonic acids, especially 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. Mixtures of the aforementioned complexing agents can also be used.
  • component (B) The other ingredients that may be contained in component (B) include washing alkalis, neutral salts, graying inhibitors, optical brighteners, stabilizers such as magnesium silicate, substances which act as aerating agents and dyes, and also additives which improve the sprayability, e.g. B. 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 groups, furthermore water-soluble polyesters and polyamides from polyvalent carboxylic acids and glycols or diamines which have free carboxyl groups, betaine groups or sulfobetaine groups which are capable of salt formation and colloidally water-soluble polymers or copolymers of vinyl alcohol, vinyl pyrrolidone, acrylamide and 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.
  • Also suitable as brighteners for polyamide fibers are those of the diarylpyrazoline type, for example 1- (p-sulfonamidophenyl) -3- (p-chlorophenyl) -J 2 -..
  • the wear Usable instead of the sulfonamido group, a carboxymethyl or acetylamino group are also substituted aminocoumarins, e.g., the 4-methyl-7-dimethylamino or 4-methyl-7-diethylaminocoumarin.
  • the compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyryl are also useful as polyamide brighteners.
  • the compounds are 2,5-di- (2-benzoxazolyl) thiophene, 2- (2-benzoxazolyl) naphto [2,3-b] thiophene and 1,2- Di- (5-methyl-2-benzoxazolyl) ethylene suitable.
  • Brighteners of the substituted diphenylstyryl type may also be present. Mixtures of the aforementioned brighteners can also be used.
  • Component (C) which is optionally present preferably contains a per compound, for example sodium percarbonate, but in particular sodium perborate tetrahydrate.
  • Additional powder components for example enzymes, may also be present or may contain bleach activators.
  • the enzymes and bleach activators can be coated with water-soluble or dispersible coating substances.
  • Another object of the invention is the preparation of the agents described.
  • a suitable production process for the powder component (A) is spray drying an aqueous slurry containing the individual components in a homogeneous mixture, the water content of which - depending on the viscosity - can be 30 to 60% by weight.
  • Spray drying can be carried out in a manner known per se by spraying the slurry through nozzles into a drying tower into which gas or air heated to 110 to 300 ° C. is introduced in cocurrent or countercurrent.
  • the spray drying is carried out in such a way that the dried powder component (A) preferably has a liter weight of 300 to 700 g and is therefore of the order of magnitude of a spray-dried detergent, which largely excludes segregation when the detergents are later transported.
  • component (A) can also be prepared by spraying an aqueous sodium sulfate solution heated to temperatures above 32.4 ° C., in which the rest Components are dispersed or dissolved and their water content is such that in the subsequent spraying, with simultaneous cooling to temperatures below 32.4 ° C., the water is completely bound to sodium sulfate decahydrate (Glauber's salt) with simultaneous solidification of the spray material.
  • the liter weight of such spray products is in the range from 430 to 800 g. It is particularly suitable for the production of detergents in which component (B) also has an increased liter weight.
  • component (A) can also be prepared by granulating an aqueous dispersion, which contains the siloxane, silica, surfactant component and cellulose ether, onto the inorganic salt, followed by drying. This procedure is less advantageous because of the increased effort involved in mixing and drying.
  • 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 250 to 500 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.
  • other components e.g. B. fragrances are introduced or sprayed onto one of the powder components or the powder mixture.
  • one of the powder components (B) or (C), but in particular the sodium perborate (component C) - as described in patent applications DE-A 2 748 970 and 2 753 680 - can be acted upon with nonionic surfactants in order to improve the washing-in behavior of the washing powder to improve.
  • the mixing ratio between component (A) and the other powder components should be such that the polydimethylsiloxane content of the detergent is 0.01 to 0.8% by weight, preferably 0.05 to 0.5% by weight .
  • the powder detergents produced in the manner indicated are characterized by favorable foaming behavior. It is advantageous that the foam-suppressing effect of the siloxanes does not suffer any noteworthy losses in the production process according to the invention or during storage, but that, on the other hand, when the agents are used, there is no graying of the tissues or no exposure of the washing machine parts to a siloxane film which is very difficult to remove .
  • the spraying took place in a spray tower which was equipped with 3 spray nozzles and in which the dry air heated to 220 ° C. was passed in countercurrent.
  • the liter weight and the average grain size of the spray products was:
  • composition of the spray-dried detergent (component B) was (in% by weight):
  • siloxane / silica mixture was added directly to the wash liquor.
  • composition A 2 containing 50% by weight of water was added to a detergent slurry containing 35% by weight of water, the solids composition of which corresponded to that of component (B) in the examples above. After homogenization, the slurry was spray-dried in the customary manner and the spray product was mixed with 20% by weight sodium perborate.
  • the respective proportions of siloxane are shown in Table 4.
  • 5 wt .-% polydimethylsiloxane were mixed according to the procedure according to DE-B 2 338 468, Example 1 with 5 wt .-% silica and 40 wt .-% of an ethoxylated tallow alcohol (25 EO) at 50 ° C and on a fluidized bed sprayed of 50 wt .-% sodium sulfate.
  • the granules obtained were mixed with the spray-dried detergent component (B) and 20% sodium perborate according to the examples above. After a standing time of 10 days, the mixtures were examined for foam behavior and graying properties in accordance with the composition given in Table 4.
  • the foaming behavior of the test samples and the formulation according to Example 3 was carried out in a drum washing machine charged with 3.5 kg of clean filling laundry at 95 ° C., a detergent concentration of 7.5 g / l using water at 3 ° dH (that is, under difficult conditions) checked. It was not the foam height (which is less suitable for an exact comparison), but the volume of the over-foamed washing liquor (so-called liquor loss) that was measured.

Description

Bekanntlich kann das unerwünschte starke Schäumen von Waschmitteln durch einen Zusatz von schaumdämpfend wirkenden Polydimethylsiloxanen unterdrückt werden. Bekannt ist ferner, daß der Verteilungszustand der Siloxane im Waschmittel für die Wirksamkeit eine wesentliche Rolle spielt. Werden die Siloxane vor der Zerstäubungstrocknung dem Slurry zugesetzt, so resultiert zwar ein homogener Verteilungszustand, bei dem auch keine Beeinträchtigung des Waschvermögens auftritt, gleichzeitig geht aber die schaumdämpfende Wirkung teilweise erheblich zurück.As is known, the undesired strong foaming of detergents can be suppressed by adding foam-suppressing polydimethylsiloxanes. 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 before the atomization drying, this results in a homogeneous distribution state in which there is no impairment of the washing power, but at the same time the foam-suppressing effect in some cases drops considerably.

In der DE-B 2 338 468 wird ein Waschmittel beschrieben, in dem das Siloxan in eine Trägersubstanz einverleibt ist, die frei von oberflächenaktiven Stoffen und für Detergentien undurchdringbar ist. Zweck dieser Maßnahme ist es, eine Wechselwirkung zwischen den im Waschmittel enthaltenen Detergentien und dem Siloxan und damit einen Wirkungsabfall während des Mischens und Lagerns zu verhindern. Es hat sich jedoch gezeigt, daß ein solcher Verteilungszustand des Siloxans bei der Anwendung der Waschmittel zu mangelhaften Waschergebnissen führt. Dies äußert sich insbesondere in einer sehr starken Vergrauung insbesondere von Wäschestücken aus polyesterhaltigen Fasern.DE-B 2 338 468 describes a detergent in which the siloxane is incorporated into a carrier substance which is free from surface-active substances and is impenetrable to detergents. The purpose of this measure is to prevent an interaction between the detergents contained in the detergent and the siloxane and thus to prevent a drop in activity during mixing and storage. However, it has been shown that such a state of distribution of the siloxane leads to poor washing results when the detergents are used. This manifests itself in particular in a very strong graying, in particular of laundry items made of polyester-containing fibers.

Die vorliegende Erfindung ist geeignet, die geschilderten Nachteile zu beseitigen. Gegenstand der Erfindung ist ein Waschmittel mit einem Gehalt an schaumdämpfend wirkenden Polydimethylsiloxanen, dadurch gekennzeichnet, daß es aus einem Gemisch folgender Pulverkomponenten besteht

  • A) 1 Gewichtsteil einer körnigen Pulverkomponente,
    enthaltend
    • 1 bis 15 Gew.-% eines Gemisches aus Polydimethylsiloxan und feinteiliger Kieselsäure im Verhältnis 100 : 1 bis 5 : 1,
    • 2 bis 15 Gew.-% eines nichtionischen Tensids,
    • 2 bis 15 Gew.-% eines wasserlöslichen Celluloseethers und
    • 60 bis 95 Gew.-% mindestens eines in Wasser löslichen oder dispergierbaren anorganischen Salzes aus der Klasse der Sulfate, Carbonate, Polyphosphate, Silikate und Alumosilikate des Natriums, Kaliums oder Magnesiums,
  • B) 5 bis 80 Gewichtsteilen einer körnigen Pulverkomponente,
    enthaltend
    • 10 bis 40 Gew.-% mindestens eines anionischen, nichtionischen oder zwitterionischen Tensids,
    • 40 bis 80 Gew.-% mindestens eines Gerüstsalzes und
    • 10 bis 50 Gew.-% an sonstigen, nichtbleichenden Waschmittelbestandteilen,
  • C) 0 bis 30 Gewichtsteilen einer körnigen Pulverkomponente, enthaltend ein oxidativ wirkendes Bleichmittel,

wobei das Mischungsverhältnis der einzelnen Pulverkomponenten so bemessen ist, daß das Mittel insgesamt 0,01 bis 0,8 Gew.-% an Polydimethylsiloxan enthält.The present invention is suitable for eliminating the disadvantages described. The invention relates to a detergent containing foam-suppressing polydimethylsiloxanes, characterized in that it consists of a mixture of the following powder components
  • A) 1 part by weight of a granular powder component,
    containing
    • 1 to 15% by weight of a mixture of polydimethylsiloxane and finely divided silica in a ratio of 100: 1 to 5: 1,
    • 2 to 15% by weight of a nonionic surfactant,
    • 2 to 15% by weight of a water-soluble cellulose ether and
    • 60 to 95% by weight of at least one water-soluble or dispersible inorganic salt from the class of the sulfates, carbonates, polyphosphates, silicates and aluminosilicates of sodium, potassium or magnesium,
  • B) 5 to 80 parts by weight of a granular powder component,
    containing
    • 10 to 40% by weight of at least one anionic, nonionic or zwitterionic surfactant,
    • 40 to 80% by weight of at least one skeleton salt and
    • 10 to 50% by weight of other, non-bleaching detergent components,
  • C) 0 to 30 parts by weight of a granular powder component containing an oxidizing bleach,

wherein the mixing ratio of the individual powder components is such that the agent contains a total of 0.01 to 0.8 wt .-% of polydimethylsiloxane.

Die Pulverkomponente (A), die aus Partikeln mit einer mittleren Korngröße von 0,1 bis 1 mm besteht, enthält als schaumdämpfenden Bestandteil 1 bis 10, vorzugsweise 2 bis 8 Gew.-% eines Polydimethylsiloxans, beispielsweise ein solches der allgemeinen Formel

Figure imgb0001
worin n für eine Zahl von 20 bis 2000, vorzugsweise 40 bis 1000 steht.The powder component (A), which consists of particles with an average grain size of 0.1 to 1 mm, contains 1 to 10, preferably 2 to 8% by weight of a polydimethylsiloxane, for example one of the general formula, as a foam-suppressing component
Figure imgb0001
 where n is a number from 20 to 2000, preferably 40 to 1000.

Das Siloxan liegt im Gemisch mit feinteiliger Kieselsäure mit großer aktiver Oberfläche vor, und zwar im Gewichtsverhältnis Siloxan zu Kieselsäure von 100 : 1 bis 5 : 1, vorzugsweise 50: 1 bis 10 : 1. Geeignet für diesen Zweck ist insbesondere gefällte Kieselsäure bzw. durch thermische Zersetzung von Siliciumtetrachlorid hergestelltes Siliciumdioxid (Aerosil). Dieses Siliciumdioxid, das eine aktive Oberfläche von 100 bis 180 qm/g aufweist, kann auch silaniert sein. Silanierte Kieselsäure wird z. B. erhalten, indem man einen Teil der OH-Gruppen, deren Anteil meist etwa 70 bis 90 mVal pro 100 g Kieselsäure beträgt, mit Dimethyldichlorsilan bzw. Trimethylchlorsilan umsetzt. In einem silanierten »Aerosil« sind beispielsweise 35 bis 50 mVal OH-Gruppen pro 100 g durch Siloxangruppen substituiert.The siloxane is present in a mixture with finely divided silica with a large active surface, specifically in a weight ratio of siloxane to silica of 100: 1 to 5: 1, preferably 50: 1 to 10: 1. Particularly suitable for this purpose is precipitated silica or by thermal decomposition of silicon tetrachloride produced silicon dioxide (Aerosil). This silicon dioxide, which has an active surface area of 100 to 180 m 2 / g, can also be silanized. Silanized silica is e.g. B. obtained by reacting part of the OH groups, the proportion of which is usually about 70 to 90 meq per 100 g of silica, with dimethyldichlorosilane or trimethylchlorosilane. In a silanized »Aerosil«, for example, 35 to 50 mVal OH groups per 100 g are substituted by siloxane groups.

Als weiteren Bestandteil enthält die Komponente (A) 2 bis 15 Gew.-%, vorzugsweise 3 bis 8 Gew.-% mindestens eines nichtionischen Tensids. Geeignete Tenside sind insbesondere ethoxylierte aliphatische Alkohole mit 12 bis 20 C-Atomen und 4 bis 20, vorzugsweise 5 bis 15 Ethylenglykolethergruppen (EO-Gruppen). Als Alkoholkomponente kommen Lauryl-, Myristyl-, Cetyl-, Stearyl-, Arichidyl-, Oleyl-, Elaidyl-, Linolyl- und Ricinolylalkohol sowie deren Gemische, wie Cocos-oder Talgalkohole in Frage, ferner synthetische, beispielsweise durch Oxosynthese oder Ethylenpolymerisation hergestellte Alkohole. Brauchbar sind ferner Ethoxylierungsprodukte von Alkylphenolen, Fettsäuren, Fettsäureamiden, Thioalkoholen und vicinalen Diolen mit jeweils 12 bis 20 C-Atomen im hydrophoben Rest und 4 bis 20, vorzugsweise 5 bis 15 EO-Gruppen. Es können auch Gemische aus höher ethoxylierten 7 bis 15 EO-Gruppen enthaltenden Verbindungen und niedriger ethoxylierten Verbindungen mit 3 bis 6 EO-Gruppen verwendet werden, beispielsweise im Verhältnis 4 : 1 bis 1 : 2..As a further component, component (A) contains 2 to 15% by weight, preferably 3 to 8% by weight, of at least one nonionic surfactant. Suitable surfactants are especially ethoxylated aliphatic alcohols with 12 to 20 C atoms and 4 to 20, preferably 5 to 15 ethylene glycol ether groups (EO groups). Suitable alcohol components are lauryl, myristyl, cetyl, stearyl, arichidyl, oleyl, elaidyl, linolyl and ricinolyl alcohol and mixtures thereof, such as coconut or tallow alcohols, and also synthetic alcohols, for example those prepared by oxosynthesis or ethylene polymerization . Ethoxylation products of alkylphenols, fatty acids, fatty acid amides, thioalcohols and vicinal diols, each having 12 to 20 carbon atoms in the hydrophobic radical and 4 to 20, preferably 5 to 15, EO groups can also be used. Mixtures of higher ethoxylated compounds containing 7 to 15 EO groups and lower ethoxylated compounds having 3 to 6 EO groups can also be used, for example in a ratio of 4: 1 to 1: 2.

Die Pulverkomponente (A) enthält weiterhin 1 bis 10, vorzugsweise 3 bis 8 Gew.-% mindestens eines wasserlöslichen Celluloseethers. Bevorzugt wird Carboxymethylcellulose in Form des Na- oder K-Salzes eingesetzt. Brauchbar sind ferner Methyl- und Hydroxyethylcellulose sowie Cellulosemischether, wie Methyl-carboxymethylcellulose, Methylhydroxyethylcellulose, Methyl-hydroxypropylcellulose und Methyl-hydroxybutylcellulose. Auch Gemische der vorstehend genannten Celluloseether können vorliegen.The powder component (A) further contains 1 to 10, preferably 3 to 8% by weight of at least one water-soluble cellulose ether. Carboxymethyl cellulose is preferably used in the form of the Na or K salt. Also useful are methyl and hydroxyethyl cellulose and mixed cellulose ethers such as methyl carboxymethyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl hydroxybutyl cellulose. Mixtures of the cellulose ethers mentioned above can also be present.

Ein weiterer Bestandteil der Pulverkomponente (A) ist ein in Wasser lösliches oder dispergierbares anorganisches Salz in einer Menge von 70 bis 95, vorzugsweise 75 bis 90 Gew.-%. In Frage kommen z. B. Natriumsulfat, Natriumcarbonat, Natriumhydrogencarbonat, Natriumdiphosphat, Natriumtripolyphosphat, Natriumsilikate mit einem Na20 : Si02-Verhältnis von 1 : 1 bis 1 : 3,5, Natriumalumosilikate der Formel

Figure imgb0002
wie sie beispielsweise in der DE-B 2 412 837 beschrieben sind, sowie Magnesiumsilikat. Anstelle der beschriebenen Natriumsalze können auch die Kaliumsalze eingesetzt werden. Brauchbar sind auch Gemische der vorgenannten anorganischen Salze, insbesondere solche aus Natriumsulfat und Magnesiumsilikat im Verhältnis 10 : 1 bis 5 : 1.Another component of powder component (A) is a water-soluble or dispersible inorganic salt in an amount of 70 to 95, preferably 75 to 90% by weight. For example, B. sodium sulfate, sodium carbonate, sodium hydrogen carbonate, sodium diphosphate, sodium tripolyphosphate, sodium silicates with a Na 2 0: Si0 2 ratio of 1: 1 to 1: 3.5, sodium aluminosilicates of the formula
Figure imgb0002
 as described for example in DE-B 2 412 837, as well as magnesium silicate. Instead of the sodium salts described, the potassium salts can also be used. Mixtures of the aforementioned inorganic salts, in particular those of sodium sulfate and magnesium silicate in a ratio of 10: 1 to 5: 1, can also be used.

Die Pulverkomponente (B), in denen die Partikel eine Korngröße von 0,1 bis 2,5 mm, vorzugsweise von 0,2 bis 1,5 mm aufweisen, enthält mindestens ein anionisches, nichtionisches oder zwitterionisches Tensid, Gerüstsalze sowie sonstige, nichtbleichende Waschmittelbestandteile, wozu Waschalkalien, Vergrauungsinhibitoren, optische Aufheller, Stabilisatoren, Neutralsalze und Farbstoffe zählen, nicht jedoch Perverbindungen bzw. aktivchlorhaltige Bleichmittel, Bleichaktivatoren und Enzyme, die unter den Bedingungen einer Heißsprühtrocknung nicht beständig sind.The powder component (B), in which the particles have a particle size of 0.1 to 2.5 mm, preferably 0.2 to 1.5 mm, 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 which are not stable under the conditions of hot spray drying.

Zur Herstellung der Komponente (B) geeignete anionische Tenside sind solche vom Sulfonat- oder Sulfattyp, insbesondere Alkylbenzolsulfonate, Olefinsulfonate, Alkylsulfonate und oc-Sulfofettsäureester, primäre Alkylsulfate sowie die Sulfate von ethoxylierten, 2 bis 3 Glykolethergruppen aufweisenden höhermolekularen Alkoholen. In Frage kommen ferner Alkaliseifen von Fettsäuren natürlichen oder synthetischen Ursprungs, z. B. die Natriumseifen von Cocos-, Palmkern- oder Talgfettsäuren und, sofern eine noch weitergehende Schaumdämpfung erwünscht ist, auch solche von hydrierten Raps- oder Fischölfettsäuren. Die anionischen Tenside liegen vorzugsweise in Form der Natriumsalze vor. Sofern die genannten anionischen und zwitterionischen Verbindungen einen aliphatischen Kohlenwasserstoffrest besitzen, soll dieser bevorzugt geradkettig sein und 8 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatome aufweisen. In den Verbindungen mit einem araliphatischen Kohlenwasserstoffrest enthalten die vorzugsweise unverzweigten Alkylketten 6 bis 16, insbesondere 10 bis 14 Kohlenstoffatome. Geeignete nichtionische Tenside sind insbesondere Ethoxylierungsprodukte von gesättigten oder einfach ungesättigten aliphatischen primären Alkoholen mit 12 bis 24, vorzugsweise 12 bis 18 Kohlenstoffatomen und 3 bis 20, insbesondere 4 bis 15 Ethylenglykolethergruppen. Geeignete Alkohole, von denen sich die vorliegenden Ethoxylierungsprodukte ableiten, sind beispielsweise solche natürlichen Ursprungs, wie Cocos- oder Talgfettalkohole bzw. Oleylalkohol, ferner Oxoalkohole oder durch Ethylenpolymerisation gewonnene Synthesealkohole.Anionic surfactants suitable for the preparation of component (B) are those of the sulfonate or sulfate type, in particular alkylbenzenesulfonates, olefin sulfonates, alkylsulfonates and oc-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, for. B. the sodium soaps of coconut, palm kernel or tallow fatty acids and, if further foam attenuation is desired, also those of hydrogenated rapeseed or fish oil fatty acids. The anionic surfactants are preferably in the form of the sodium salts. If the 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. In the compounds having an araliphatic hydrocarbon radical, 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.

Weitere geeignete nichtionische Tenside sind Ethoxylierungsprodukte von sekundären Alkoholen und vicinalen Diolen mit jeweils 12 bis 18 Kohlenstoffatomen sowie von Alkylphenolen mit 6 bis 12 Kohlenstoffatomen im Alkylrest, wobei die Zahl der Glykolethergruppen ebenfalls 3 bis 20, vorzugsweise 4 bis 15 beträgt. Die vorstehend genannten ethoxylierten Alkohole und Alkylphenole können auch ganz oder teilweise durch solche ersetzt sein, bei deren Herstellung mit 0,5 bis 3 Mol Propylenoxid pro Mol Ausgangsverbindung und erst in 2. Stufe die in Aussicht genommene Menge an Ethylenoxid angelagert wird.Further suitable nonionic surfactants are ethoxylation products of secondary alcohols and vicinal diols each having 12 to 18 carbon atoms and of alkylphenols with 6 to 12 carbon atoms in the alkyl radical, the number of glycol ether groups likewise being 3 to 20, preferably 4 to 15. The abovementioned ethoxylated 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 amount of ethylene oxide envisaged is added.

Gegebenenfalls können auch solche nichtionischen Tenside anwesend sein, die sich von den vorgenannten Verbindungen ableiten und die Ethylenglykol- als auch Propylenglykolethergruppen in anderer Reihenfolge aufweisen, beispielsweise Alkohole mit 10 bis 30 Ethylenglykolethergruppen und 3 bis 30 Propylenglykolethergruppen; ferner Ethoxylierungsprodukte von Mercaptanen, Fettsäureamiden und Fettsäuren. Brauchbar sind auch die wasserlöslichen, 20 bis 250 Ethylenglykolethergruppen und 10 bis 100 Propylenglykolethergruppen enthaltenden Polyethylenoxidaddukte an Polypropylenglykol, Ethylendiaminopolypropylenglykol und Alkylpolypropylenglykol mit 1 bis 10 Kohlenstoffatomen in der Alkylkette. Die genannten Verbindungen enthalten üblicherweise pro Propylenglykol-Einheit 1 bis 5 Ethylenglykoleinheiten. Auch nichtionische Verbindungen vom Typ der Aminoxide und Sulfoxide, die gegebenenfalls auch ethoxyliert sein können, sind verwendbar.If appropriate, such 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 with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1 to 10 carbon atoms in can also be used the alkyl chain. 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.

Geeignete Gerüstsubstanzen sind die Polymerphosphate, Carbonate, Silikate und Sulfate des Kaliums und insbesondere des Natriums, wobei die Silikate ein Verhältnis von Si02 zu Na20 von 1 : 1 bis 3,5 : 1 aufweisen. Als Polymerphosphat kommt insbesondere das Pentanatriumtriphosphat in Frage, das im Gemisch mit seinen Hydrolyseprodukten, den Mono- und Diphosphaten, sowie höherkondensierten Phosphaten, z. B. den Tetraphosphaten, vorliegen kann. Brauchbar sind ferner zum Kationenaustausch befähigte, wasserhaltige Alumosilikate des Kaliums oder insbesondere des Natriums der allgemeinen Formel

Figure imgb0003
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. As a polymer phosphate, pentasodium triphosphate is particularly suitable, which, in a mixture with its hydrolysis products, the mono- and diphosphates, as well as higher-condensed phosphates, e.g. B. the tetraphosphates may be present. It is also possible to use water-containing aluminosilicates of potassium or, in particular, sodium of the general formula which are capable of cation exchange
Figure imgb0003

Diese Alumosilikate weisen allgemein eine Korngröße von 0,1 bis 20 u. auf und sind vorzugsweise kristallin.These aluminosilicates generally have a grain size of 0.1 to 20 u. and are preferably crystalline.

Zu den Gerüstsalzen zählen ferner Salze von komplexierend wirkenden Aminopolycarbonsäuren, insbesondere Alkalisalze der Nitrilotriessigsäure und Ethylendiaminotetraessigsäure. Geeignet sind ferner dte höheren Homologen der genannten Aminopolycarbonsäuren. Auch Salze stickstofffreier, mit Calciumionen Komplexsalze bildender Polycarbonsäuren, wozu auch Carboxylgruppen enthalteride Polymerisate zählen, sind geeignet. Beispiele sind Citronensäure, Weinsäure, Benzolh 'acarbonsäure und Tetrahydrofurantetracarbonsäure. Auch Carboxymethylethergruppen enthaltende Polycarbonsäuren sind brauchbar, wie 2,2'-Oxydibernsteinsäure sowie mit Glykolsäure teilweise oder vollständig veretherte mehrwertige Alkohole oder Hydroxycarbonsäuren, beispielsweise Triscarboxymethylglycerin, Biscarboxymethylglycerinsäure, Carboxymethyl-oxybernsteinsäure und carboxymethylierte bzw. oxydierte Polysaccharide. Weiterhin eignen sich die polymeren Carbonsäuren mit einem Molekulargewicht von mindestens 350 in Form der wasserlöslichen Natrium-oder Kaliumsalze, wie Polyacrylsäure, Polymethacrylsäure, Poly-α-hydroxyacrylsäure, Polymaleinsäure, Polyitaconsäure, Polymesaconsäure, Polybutentricarbonsäure sowie die Copolymerisate der entsprechenden monomeren Carbonsäuren untereinander oder mit ethylenisch ungesättigten Verbindungen wie Ethylen, Propylen, Isobutylen, Vinylmethylether oder Furan.The skeletal salts also include salts of complexing aminopolycarboxylic acids, in particular alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid. Also suitable are higher homologues of the aminopolycarboxylic acids mentioned. 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 acarboxylic 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 also suitable in the form of the water-soluble sodium or potassium salts, such as polyacrylic acid, polymethacrylic acid, poly-α-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.

Weiterhin können komplexierend wirkende polyphosphonsaure Salze anwesend sein, z. B. die Alkalisalze von Aminopolyphosphonsäuren, insbesondere Aminotri-(methylenphosphonsäure), 1-Hydroxyethan-1,1-diphosphonsäure, Phenylhydroxymethandiphosphonsäure, Methylendiphosphonsäure sowie Salze der höheren Homologen der genannten Polyphosphonsäuren. Auch Gemische der vorgenannten Komplexierungsmittel sind verwendbar.Furthermore, complexing polyphosphonic salts can be present, for. B. the alkali metal salts of aminopolyphosphonic acids, especially 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. Mixtures of the aforementioned complexing agents can also be used.

Zu den sonstigen Bestandteilen, die in der Komponente (B) enthalten sein können, zählen Waschalkalien, Neutralsalze, Vergrauungsinhibitoren, optische Aufheller, Stabilisatoren wie Magnesiumsilikat, avivierend wirkende Stoffe sowie Farbstoffe, ferner Zusätze, welche die Versprühbarkeit verbessern, z. B. Alkalisalze der Toluol-, Xylol- oder Cumolsulfonsäure.The other ingredients that may be contained in component (B) include washing alkalis, neutral salts, graying inhibitors, optical brighteners, stabilizers such as magnesium silicate, substances which act as aerating agents and dyes, and also additives which improve the sprayability, e.g. B. alkali salts of toluene, xylene or cumene sulfonic acid.

Geeignete Waschalkalien sind Alkalicarbonate, -bicarbonate, -borate und -silikate mit einem Na20 : Si02-Verhältnis von 1 : 1 bis 1 : 3,5. Als Neutralsalze kommen Natriumsulfat und Natriumchlorid in Betracht.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.

Als Vergrauungsinhibitoren eignen sich insbesondere Carboxymethylcellulose sowie Cellulosemischether, die wechselnde Mengen an Carboxymethyl-, Methyl- und/oder Hydroxyethylgruppen aufweisen, ferner wasserlösliche Polyester und Polyamide aus mehrwertigen Carbonsäuren und Glykolen bzw. Diaminen, die freie, zur Salzbildung befähigte Carboxylgruppen, Betaingruppen oder Sulfobetaingruppen aufweisen sowie kolloidal in Wasser lösliche Polymere bzw. Copolymere des Vinylalkohols, Vinylpyrrolidons, Acrylamids und Acrylnitrils.Suitable graying inhibitors are in particular carboxymethyl cellulose and cellulose mixed ethers which have varying amounts of carboxymethyl, methyl and / or hydroxyethyl groups, furthermore water-soluble polyesters and polyamides from polyvalent carboxylic acids and glycols or diamines which have free carboxyl groups, betaine groups or sulfobetaine groups which are capable of salt formation and colloidally water-soluble polymers or copolymers of vinyl alcohol, vinyl pyrrolidone, acrylamide and acrylonitrile.

Geeignete optische Aufheller sind die Alkalisalze der 4,4-Bis(-2"-anilino-4"-morpholino-1,3,5-triazinyl-6"-amino)-stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholinogruppe eine Diethanolaminogruppe, eine Methylaminogruppe oder eine ß-Methoxyethylaminogruppe tragen. Weiterhin kommen als Aufheller für Polyamidfasern solche vom Typ der Diarylpyrazoline in Frage, beispielsweise 1-(p-Sulfonamidophenyl)-3-(p-chlorphenyl)-J2-pyrazolin sowie gleichartig aufgebaute Verbindungen, die anstelle der Sulfonamidogruppe eine Carboxymethyl- oder Acetylaminogruppe tragen. Brauchbar sind ferner substituierte Aminocumarine, z. B. das 4-Methyl-7-dimethylamino- oder das 4-Methyl-7-diethylaminocumarin.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. Also suitable as brighteners for polyamide fibers are those of the diarylpyrazoline type, for example 1- (p-sulfonamidophenyl) -3- (p-chlorophenyl) -J 2 -.. pyrazoline and compounds of similar structure, the wear Usable instead of the sulfonamido group, a carboxymethyl or acetylamino group are also substituted aminocoumarins, e.g., the 4-methyl-7-dimethylamino or 4-methyl-7-diethylaminocoumarin.

Weiterhin sind als Polyamidaufheller die Verbindungen 1-(2-Benzimidazolyl)-2-(1-hydroxyethyl-2-benzimidazolyl)-ethylen und 1-Ethyl-3-phenyl-7-diethylamino-carbostyryl brauchbar. Als Aufheller für Polyester- und Polyamidfasern sind die Verbindungen 2,5-Di-(2-benzoxazolyl)-thiophen, 2-(2-Benzox- azolyl)-naphto-[2,3-b]-thiophen und 1,2-Di-(5-methyl-2-benzoxazolyl)-ethylen geeignet. Weiterhin können Aufheller vom Typ der substituierten Diphenylstyryle anwesend sein. Auch Gemische der vorgenannten Aufheller können verwendet werden.The compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyryl are also useful as polyamide brighteners. As brighteners for polyester and polyamide fibers, the compounds are 2,5-di- (2-benzoxazolyl) thiophene, 2- (2-benzoxazolyl) naphto [2,3-b] thiophene and 1,2- Di- (5-methyl-2-benzoxazolyl) ethylene suitable. Brighteners of the substituted diphenylstyryl type may also be present. Mixtures of the aforementioned brighteners can also be used.

Die gegebenenfalls anwesende Komponente (C) enthält vorzugsweise eine Perverbindung, beispielsweise Natriumpercarbonat, insbesondere jedoch Natriumperborat-tetrahydrat.Component (C) which is optionally present preferably contains a per compound, for example sodium percarbonate, but in particular sodium perborate tetrahydrate.

Weiterhin können noch zusätzliche Pulverkomponenten anwesend sein, die beispielsweise Enzyme oder Bleichaktivatoren enthalten können. Zum Schutz gegen Zersetzung oder Wechselwirkungen mit den übrigen Pulverbestandteilen des Waschmittels können die Enzyme und Bleichaktivatoren mit in Wasser löslichen bzw. dispergierbaren Hüllsubstanzen überzogen sein.Additional powder components, for example enzymes, may also be present or may contain bleach activators. To protect against decomposition or interactions with the other powder components of the detergent, the enzymes and bleach activators can be coated with water-soluble or dispersible coating substances.

Ein weiterer Gegenstand der Erfindung ist die Herstellung der beschriebenen Mittel.Another object of the invention is the preparation of the agents described.

Ein geeignetes Herstellungsverfahren für die Pulverkomponente (A) ist die Sprühtrocknung einer wäßrigen, die Einzelbestandteile in homogener Mischung enthaltenden Aufschlämmung, deren Wassergehalt - je nach Viskosität - 30 bis 60 Gew.-% betragen kann. Die Sprühtrocknung kann in an sich bekannter Weise durch Einsprühen der Aufschlämmung über Düsen in einen Trockenturm erfolgen, in den auf 110 bis 300°C erhitztes Gas bzw. Luft im Gleichstrom oder Gegenstrom eingeführt wird. Die Sprühtrocknung wird so geführt, daß die getrocknete Pulverkomponente (A) vorzugsweise ein Litergewicht von 300 bis 700 g aufweist und damit in der Größenordnung eines sprühgetrockneten Waschmittels liegt, was Entmischungen beim späteren Transport der Waschmittel weitgehend ausschließt.A suitable production process for the powder component (A) is spray drying an aqueous slurry containing the individual components in a homogeneous mixture, the water content of which - depending on the viscosity - can be 30 to 60% by weight. Spray drying can be carried out in a manner known per se by spraying the slurry through nozzles into a drying tower into which gas or air heated to 110 to 300 ° C. is introduced in cocurrent or countercurrent. The spray drying is carried out in such a way that the dried powder component (A) preferably has a liter weight of 300 to 700 g and is therefore of the order of magnitude of a spray-dried detergent, which largely excludes segregation when the detergents are later transported.

Die Herstellung der Komponente (A) kann, sofern das anorganische Salz zu wenigstens einem Drittel, insbesondere wenigstens zur Hälfte aus kristallisiertem Natriumsulfat besteht, auch durch Versprühen einer wäßiigen auf Temperaturen oberhalb 32,4°C erwärmten Natriumsulfat-Lösung erfolgen, in denen die übrigen Bestandteile dispergiert bzw. belöst sind und deren Wassergehalt so bemessen ist, daß bei dem nachfolgenden Versprühen unter gleichzeitiger Abkühlung auf Temperaturen unterhalb 32,4° C eine vollständige Bindung des Wassers zu Natriumsulfat-Dekahydrat (Glaubersalz) bei gleichzeitiger Verfestigung des Sprühgutes erfolgt. Das Litergewicht derartiger Sprühprodukte liegt im Bereich von 430 bis 800 g. Es eignet sich insbesondere zur Herstellung solcher Waschmittel, bei denen die Komponente (B) ebenfalls ein erhöhtes Litergewicht aufweist.If at least one third, in particular at least half, of the inorganic salt consists of crystallized sodium sulfate, component (A) can also be prepared by spraying an aqueous sodium sulfate solution heated to temperatures above 32.4 ° C., in which the rest Components are dispersed or dissolved and their water content is such that in the subsequent spraying, with simultaneous cooling to temperatures below 32.4 ° C., the water is completely bound to sodium sulfate decahydrate (Glauber's salt) with simultaneous solidification of the spray material. The liter weight of such spray products is in the range from 430 to 800 g. It is particularly suitable for the production of detergents in which component (B) also has an increased liter weight.

Schließlich kann die Herstellung der Komponente (A) auch durch Aufgranulieren einer wäßrigen Dispersion, welche das Siloxan, die Kieselsäure, die Tensidkomponente und den Celluloseether enthält, auf das anorganische Salz unter anschließender Trocknung erfolgen. Diese Arbeitsweise ist wegen des erhöhten Aufwandes beim Mischen und Trocknen weniger vorteilhaft.Finally, component (A) can also be prepared by granulating an aqueous dispersion, which contains the siloxane, silica, surfactant component and cellulose ether, onto the inorganic salt, followed by drying. This procedure is less advantageous because of the increased effort involved in mixing and drying.

Die Pulverkomponente (B) wird vorteilhaft durch Sprühtrocknung in bekannter Weise aus einem wäßrigen Slurry hergestellt. Derartige Sprühpulver weisen üblicherweise ein Litergewicht von 250 bis 500 g auf und neigen nach dem Vermischen mit der durch Versprühen hergestellten Komponente (A) nicht zu Entmischungen während des Abfüllens und beim Transport. Gegebenenfalls kann die Komponente (B) auch durch bekannte Granulierverfahren hergestellt werden.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 250 to 500 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.

Die Vereinigung der verschiedenen Pulverkomponenten erfolgt durch Vermischen in üblichen Mischvorrichtungen, die vorzugsweise kontinuierlich bzw. nach dem Freifallprinzip arbeiten. Vor oder während des Mischprozesses können auch noch weitere Bestandteile, z. B. Duftstoffe eingebracht bzw. auf eine der Pulverkomponenten oder das Pulvergemisch aufgesprüht werden. Schließlich kann auch eine der Pulverkomponenten (B) oder (C), insbesondere jedoch das Natriumperborat (Komponente C) - wie in den Patentanmeldungen DE-A 2 748 970 und 2 753 680 beschrieben - mit nichtionischen Tensiden beaufschlagt sein, um das Einspülverhalten des Waschpulvers zu verbessern.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, other components, e.g. B. fragrances are introduced or sprayed onto one of the powder components or the powder mixture. Finally, one of the powder components (B) or (C), but in particular the sodium perborate (component C) - as described in patent applications DE-A 2 748 970 and 2 753 680 - can be acted upon with nonionic surfactants in order to improve the washing-in behavior of the washing powder to improve.

Das Mischungsverhältnis zwischen der Komponente (A) und den übrigen Pulverkomponenten soll so bemessen sein, daß der Gehalt des Waschmittels an Polydimethylsiloxan insgesamt 0,01 bis 0,8 Gew.-%, vorzugsweise 0,05 bis 0,5 Gew.-% beträgt.The mixing ratio between component (A) and the other powder components should be such that the polydimethylsiloxane content of the detergent is 0.01 to 0.8% by weight, preferably 0.05 to 0.5% by weight .

Die in der angegebenen Weise hergestellten pulverförmigen Waschmittel zeichnen sich durch ein günstiges Schaumverhalten aus. Von Vorteil ist, daß die schaumdämpfende Wirkung der Siloxane bei dem erfindungsgemäßen Herstellungsverfahren bzw. während der Lagerung keine nennenswerten Einbußen erleidet, daß aber andererseits bei der Anwendung der Mittel keine Vergrauung der Gewebe bzw. keine Beaufschlagung der Waschmaschinenteile mit einem nur sehr schwer entfernbaren Siloxanfilm eintritt.The powder detergents produced in the manner indicated are characterized by favorable foaming behavior. It is advantageous that the foam-suppressing effect of the siloxanes does not suffer any noteworthy losses in the production process according to the invention or during storage, but that, on the other hand, when the agents are used, there is no graying of the tissues or no exposure of the washing machine parts to a siloxane film which is very difficult to remove .

BeispieleExamples

Zur Herstellung der Komponente (A) wurden 50 Gew.-% Wasser enthaltende Slurries angesetzt, nach deren Sprühtrocknung Sprühprodukte folgender Zusammensetzung erhalten wurden (in Gew.-0 /o):

Figure imgb0004
For the preparation of the component (A) 50 wt .-% water-containing slurries were prepared, obtained by the spray-drying spray products of the following composition (in weight 0 / o):
Figure imgb0004

Das Versprühen erfolgte in einem Sprühturm, der mit 3 Sprühdüsen ausgestattet war und in dem die auf 220°C erhitzte Trockenluft im Gegenstrom geführt wurde. Das Litergewicht und die mittlere Korngröße der Sprühprodukte betrug:

Figure imgb0005
The spraying took place in a spray tower which was equipped with 3 spray nozzles and in which the dry air heated to 220 ° C. was passed in countercurrent. The liter weight and the average grain size of the spray products was:
Figure imgb0005

Wurde zum Vergleich beim Ansetzen des Slurry ohne Zusatz von Carboxymethylcellulose und nichtionischem Tensid gearbeitet, so konnte kein homogenes Gemisch erzielt werden. Bei Abwesenheit von Carboxymethylcellulose, jedoch Anwesenheit von nichtionischem Tensid entstand zwar bei intensivem Rühren eine homogene Suspension; jedoch schied sich einige Minuten nach Abstellen des Rührers Siloxan als Tropfen an der Flüssigkeitsoberfläche ab. Die erfindungsgemäßen Slurry-Ansätze waren nach kurzem Rühren einwandfrei homogen und blieben auch während einer längeren Standzeit stabil.If a comparison was made when preparing the slurry without adding carboxymethyl cellulose and nonionic surfactant, no homogeneous mixture could be achieved. In the absence of carboxymethyl cellulose, but the presence of nonionic surfactant, a homogeneous suspension was formed with intensive stirring; however, a few minutes after the stirrer was switched off, siloxane separated out as drops on the surface of the liquid. The slurry batches according to the invention were perfectly homogeneous after brief stirring and remained stable even over a long service life.

Die Zusammensetzung des sprühgetrockneten Waschmittels (Komponente B) lautete (in Gew.-%):

Figure imgb0006
The composition of the spray-dried detergent (component B) was (in% by weight):
Figure imgb0006

Die Pulverkomponenten (A) und (B) wurden unter Zusatz von Natriumperborat-tetrahydrat (Komponente C) in den in Tabelle angegebenen Mischungsverhältnissen gemischt. Das Schaumverhalten wurde nach 10tägiger Lagerung des Gemisches in einer handelsüblichen Waschmaschine mit horizorital angeordneter Trommel bei Temperaturen von 60° und 95° C geprüft. Hierzu wurde die Maschine mit 3,5 kg sauberer Füllwäsche (Baumwolle) beschickt. Die Waschmittelkonzentration betrug 7,5 g und die Wasserhärte 16° dH. Die jeweilige Schaumhöhe wurde durch das Sichtglas der Fronttüre kontrolliert und wie folgt benotet:

  • kein Schaum = 0
  • ¼ der Sichtgtashöhe = 1
  • ½ der Sichtglashöhe = 2
  • ¾ der Sichtglashöhe = 3
  • 4/4 der Sichtglashöhe = 4
  • Überschäumen = 5
The powder components (A) and (B) were mixed with the addition of sodium perborate tetrahydrate (component C) in the mixing ratios given in the table. 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 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:
  • no foam = 0
  • ¼ of the visible gas height = 1
  • ½ of the sight glass height = 2
  • ¾ the sight glass height = 3
  • 4/4 = 4 of the sight glass
  • Exuberance = 5

Die Ergebnisse sind in Tabelle 3 zusammengestellt.

Figure imgb0007
The results are summarized in Table 3.
Figure imgb0007

Vergleichsversuch V1 Comparative experiment V 1

Das Siloxan-Kieselsäuregemisch wurde direkt der Waschflotte zugegeben.The siloxane / silica mixture was added directly to the wash liquor.

Vergleichsversuch V2 Comparative experiment V2

Ein 50 Gew.-% Wasser enthaltendes Gemisch der Zusammensetzung A2 wurde einem 35 Gew.-% Wasser enthaltenden Waschmittelslurry zugesetzt, dessen Feststoffzusammensetzung derjenigen der Komponente (B) in den obigen Beispielen entsprach. Nach dem Homogenisieren wurde der Slurry in üblicher Weise sprühgetrocknet und das Sprühprodukt mit 20 Gew.-% Natriumperborat vermischt. Die jeweiligen Anteile an Siloxan sind der Tabelle 4 zu entnehmen.A mixture of composition A 2 containing 50% by weight of water was added to a detergent slurry containing 35% by weight of water, the solids composition of which corresponded to that of component (B) in the examples above. After homogenization, the slurry was spray-dried in the customary manner and the spray product was mixed with 20% by weight sodium perborate. The respective proportions of siloxane are shown in Table 4.

Vergleichsversuch V3 Comparative experiment V 3

5 Gew.-% Polydimethylsiloxan wurden entsprechend der Arbeitsweise nach DE-B 2 338 468, Beispiel 1 mit 5 Gew.-% Kieselsäure und 40 Gew.-% eines ethoxylierten Talgalkohols (25 EO) bei 50°C vermischt und auf ein fluidisiertes Bett von 50 Gew.-% Natriumsulfat aufgesprüht. Die erhaltenen Granulate wurden der sprühgetrockneten Waschmittelkomponente (B) und 20% Natriumperborat gemäß vorstehenden Beispielen zugemischt. Nach einer Standzeit von 10 Tagen wurden die Gemische entsprechend der in der Tabelle4 angegebenen Zusammensetzung auf Schaumverhalten und Vergrauungseigenschaften untersucht.5 wt .-% polydimethylsiloxane were mixed according to the procedure according to DE-B 2 338 468, Example 1 with 5 wt .-% silica and 40 wt .-% of an ethoxylated tallow alcohol (25 EO) at 50 ° C and on a fluidized bed sprayed of 50 wt .-% sodium sulfate. The granules obtained were mixed with the spray-dried detergent component (B) and 20% sodium perborate according to the examples above. After a standing time of 10 days, the mixtures were examined for foam behavior and graying properties in accordance with the composition given in Table 4.

Das Schaumverhalten der Versuchsproben und der Rezeptur gemäß Beispiel 3 wurde in einer mit 3,5 kg sauberer Füllwäsche beschickten Trommelwaschmaschine bei 95° C, einer Waschmittelkonzentration von 7,5 g/I unter Verwendung von Wasser von 3°dH (also unter erschwerten Bedingungen) geprüft. Gemessen wurde nicht die Schaumhöhe (die für einen exakten Vergleich weniger geeignet ist), sondern das Volumen der übergeschäumten Waschflotte (sogen. Flottenverlust).The foaming behavior of the test samples and the formulation according to Example 3 was carried out in a drum washing machine charged with 3.5 kg of clean filling laundry at 95 ° C., a detergent concentration of 7.5 g / l using water at 3 ° dH (that is, under difficult conditions) checked. It was not the foam height (which is less suitable for an exact comparison), but the volume of the over-foamed washing liquor (so-called liquor loss) that was measured.

Zur Prüfung des Vergrauungsverhaltens wurden Textilproben aus Polyesterfaser in Gegenwart von Gewebestücken gewaschen, die unter standardisierten Bedingungen mit Ruß, Kaolin, Eisenoxidschwarz und Hautfett angeschmutzt worden waren. Die Versuche wurden in einer Trommelwaschmaschine bei einer Temperatur von 60°C, einer Waschmittelkonzentration von 7,5 g/I und einer Wasserhärte von 16°dH durchgeführt. Der Weißgrad der Polyestergewebe wurde nach 25 Waschbehandlungen photometrisch bestimmt (Anfangswert 79,4).To test the graying behavior, textile samples made of polyester fiber were washed in the presence of fabric pieces which had been soiled with soot, kaolin, iron oxide black and skin fat under standardized conditions. The tests were carried out in a drum washing machine at a temperature of 60 ° C, a detergent concentration of 7.5 g / l and a water hardness of 16 ° dH. The whiteness of the polyester fabrics was determined photometrically after 25 washing treatments (initial value 79.4).

Den Vergleichsgemischen wurde eine Zusammensetzung unter Verwendung des Sprühgemisches A2 gegenübergestellt. Die Ergebnisse sind in Tabelle 4 zusammengestellt.

Figure imgb0008
The comparison mixtures were compared with a composition using the spray mixture A 2 . The results are summarized in Table 4.
Figure imgb0008

Aus den Ergebnissen geht hervor, daß bei einem direkten Zusatz des Siloxan zur Waschlauge (Versuch V1) zwar eine optimale Schaumdämpfung erzielt wird, andererseits jedoch eine sehr starke Vergrauung resultiert. Wird der Schauminhibitor in den Waschmittelslurry eingearbeitet (Versuch V2), ist zwar nur eine geringe Vergrauung zu verzeichnen, die Schaumdämpfung ist jedoch unbefriedigend. Gegenüber dem Vergleichsversuch V3 ist der Flottenverlust bei der Verwendung des erfindungsgemäßen Mittels nur sehr geringfügig erhöht, der Weißgrad aufgrund der erheblich geringeren Vergrauung jedoch wesentlich verbessert.The results show that if the siloxane is added directly to the wash liquor (test V 1 ), optimal foam damping is achieved, but on the other hand there is a very high degree of graying. If the foam inhibitor is incorporated into the detergent slurry (test V 2 ), there is only a slight graying, but the foam damping is unsatisfactory. Compared to comparative experiment V 3 , the liquor loss when using the agent according to the invention is increased only very slightly, but the degree of whiteness is significantly improved due to the considerably lower graying.

Bei 25 Waschbehandlungen in einer Haushaltswaschmaschine entsprechend der Arbeitsweise nach V1 und V3 bildete sich ein fettiger, schmierender Belag auf den Gummidichtungen der Beschickungstür, während eine solche Belagsbildung bei der erfindungsgemäßen Arbeitsweise sowie bei Versuch V2 unterblieb.With 25 washing treatments in a household washing machine according to the procedure according to V 1 and V 3 , a greasy, greasy coating formed on the rubber seals of the loading door, while such a formation did not occur in the procedure according to the invention and in test V 2 .

Claims (11)

1. A detergent containing foam-damping polydimethyl siloxanes, characterised in that it consists of a mixture of the following powder components
A) 1 part by weight of a granular powder component
containing
from 1 to 15% by weight of a mixture of polydimethyl siloxane and finely divided silica in a ratio of from 100 : 1 to 5 : 1,
from 2 to 15% by weight of a nonionic surfactant,
from 2 to 15% by weight of a water-soluble cellulose ether and
from 60 to 95% by weight of at least one water-soluble or water-dispersible inorganic salt from the class of sulfates, carbonates, polyphosphates, silicates and alumosilicates of sodium, potassium or magnesium,
B) from 5 to 80 parts by weight of a granular powder component
containing '
from 10 to 40% by weight of at least one anionic, nonionic or hybrid-ionic surfactant,
from 40 to 80% by weight of at least one builder salt and
from 10 to 50% by weight of-other, non-bleaching detergent constituents,
C) from 0 to 30 parts by weight of a granular powder component containing an oxidative bleach,

the mixing ration between the individual powder components being gauged in such a way that the detergent contains a total of from 0.01 to 0.8% by weight of polydimethyl siloxane.
2. A detergent as claimed in Claim 1, charackterised in that the ratio by weight of siloxane to silica is from 50 : 1 fo 10 : 1.
3. A detergent as claimed in Claims 1 and 2, characterised in that the silica is present is silanised form.
4. A detergent as claimed in Claim 1, characterised in that the nonionic surfactant present in component (A) consists of at least one ethoxylated aliphatic alcohol containing from 12 to 20 C-atoms and from 4to 20 ethylene glycol ether groups.
5. A detergent as claimed in Claims 1 and 4, characterised in that the ethoxylated aliphatic alcohol present in component (A) contains from 5 to 15 ethylene glycol ether groups.
6. A detergent as claimed in Claims 1, 4 and 5, characterised in that the proportion of surfactant present in component (A) amounts to between 3 and 8% by weight.
7. A detergent as claimed in Claim 1, characterised in that the cellulose ether consists of sodium carboxymethyl cellulose.
8. A detergent as claimed in Claim 1, charackterised in that the proportion of water-soluble or water-dispersible salts in component (A) amounts to between 75 and 90% by weight.
9. A detergent as claimed in Claims 1 and 8, characterised in that the water-soluble or water-dispersible salts in component (A) consist of a mixture of sodium sulfate and magnesium silicate in a ratio of from 10 : 1 to 5 : 1.
10. A detergent as claimed in Claims 1 to 9, characterised in that its polydimethyl siloxane content amounts to a total of from 0.05 to 0.5% by weight.
11. A process for producing the detergent claimed in Claims 1 to 10, characterised in that a homogeneous suspension of the substances present in component (A) containing from 35 to 60% by weight of water is spray-dried in known manner and the spray-dried product is miexed with granular powder components (B) and (C) and optionally other powder constituents.
EP19790105371 1979-01-02 1979-12-24 Detergent with a polydimethyl-siloxane content possessing an anti-foaming activity, and process for its production Expired EP0013028B1 (en)

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DE2900063 1979-01-02
DE19792900063 DE2900063A1 (en) 1979-01-02 1979-01-02 DETERGENT WITH A CONTENT OF FOAM-ABSORBING POLYDIMETHYLSILOXANE AND METHOD FOR THE PRODUCTION THEREOF

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GR75649B (en) * 1980-07-28 1984-08-02 Procter & Gamble
DE3128631A1 (en) * 1981-07-20 1983-02-03 Henkel Kgaa "METHOD FOR PRODUCING A FOAMED, SILICONE-CONTAINING DETERGENT"
DE3373918D1 (en) * 1982-04-13 1987-11-05 Procter & Gamble Foam-controlling detergent additive compositions and use thereof in detergent compositions
GB8323131D0 (en) * 1983-08-27 1983-09-28 Procter & Gamble Ltd Detergent compositions
DE3504450A1 (en) * 1985-02-09 1986-08-14 Degussa Ag, 6000 Frankfurt DETERGENT PICTURES
DE3504451A1 (en) * 1985-02-09 1986-08-14 Degussa Ag, 6000 Frankfurt DETERGENT PICTURES
DE3805624A1 (en) * 1988-02-24 1989-08-31 Degussa POWDERED DETERGENT DEFOAMER
JPH05504162A (en) * 1990-02-15 1993-07-01 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン Method for producing flowable phosphate-free antifoam formulations
DE4117032A1 (en) * 1991-05-24 1992-11-26 Henkel Kgaa SILICONE-CONTAINING DECORATIVE GRANULATE
US5691294A (en) * 1993-03-30 1997-11-25 The Procter & Gamble Company Flow aids for detergent powders comprising sodium aluminosilicate and hydrophobic silica
DE69325014T2 (en) * 1993-03-30 2000-01-20 Procter & Gamble Flow aid for detergent powder containing sodium aluminum silicate and hydrophobic silica
GB9315671D0 (en) * 1993-07-29 1993-09-15 Dow Corning Sa Foam control agents and their use
US5589449A (en) * 1993-07-29 1996-12-31 Dow Corning S.A. Particulate foam control agents
GB9426236D0 (en) * 1994-12-24 1995-02-22 Dow Corning Sa Particulate foam control agents and their use
US5846454A (en) * 1997-05-23 1998-12-08 Osi Specialties, Inc. Water dispersible antifoam concentrates
GB9823259D0 (en) * 1998-10-24 1998-12-16 Dow Corning Sa Particulate foam control agents
DE60017223T2 (en) 1999-08-13 2005-12-08 Dow Corning S.A. Foam control agent based on silicone
ATE401945T1 (en) 1999-08-13 2008-08-15 Dow Corning Sa SILICONE FOAM REGULATOR
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AT373908B (en) 1984-03-12

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