EP1105453A1 - Production of defoaming granulates in a thin-layer evaporator - Google Patents

Production of defoaming granulates in a thin-layer evaporator

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Publication number
EP1105453A1
EP1105453A1 EP99941535A EP99941535A EP1105453A1 EP 1105453 A1 EP1105453 A1 EP 1105453A1 EP 99941535 A EP99941535 A EP 99941535A EP 99941535 A EP99941535 A EP 99941535A EP 1105453 A1 EP1105453 A1 EP 1105453A1
Authority
EP
European Patent Office
Prior art keywords
weight
defoamer
silicones
wax
sprayed
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.)
Granted
Application number
EP99941535A
Other languages
German (de)
French (fr)
Other versions
EP1105453B1 (en
Inventor
Karl-Heinz Schmid
Michael Neuss
Detlef Stanislowski
Karin Koren
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cognis IP Management GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
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Publication date
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Publication of EP1105453A1 publication Critical patent/EP1105453A1/en
Application granted granted Critical
Publication of EP1105453B1 publication Critical patent/EP1105453B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/162—Organic compounds containing Si
    • 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

Definitions

  • the present invention relates to a process for producing silicone-containing defoamer granules for solid detergents, the silicones being sprayed in the form of aqueous emulsions onto an admixed precursor made from carrier materials and, if appropriate, further defoamers using a thin-film evaporator. Furthermore, the present invention describes the use of such defoamer granules in solid detergents.
  • Household and industrial laundry detergents generally contain organic surfactants, builders and numerous organic and inorganic additives.
  • the surfactants used for the laundry usually tend to develop foam during the washing cycle, which has a negative effect on the washing result. Therefore, there is a practical need to control the development of foam during the washing process.
  • Silicones have proven to be particularly suitable defoamers, which are generally applied to carrier materials and, if appropriate, are used in solid detergents, coated with other organic defoaming substances.
  • DE-Al-31 28 631 discloses the production of foam-damped detergents containing silicone defoamers which are microencapsulated.
  • the silicone is dispersed in an aqueous dispersion of a film-forming polymer and the dispersion - separated from the other detergent constituents dissolved or dispersed in water - is fed to the spray drying system via a special line.
  • the two partial flows are combined in the area of the spray nozzle.
  • film-forming polymers are cellulose ethers, starch ethers or synthetic water-soluble ones Polymers in question.
  • Microcapsules form spontaneously in the spray nozzle.
  • the process described is inevitably linked to the production of spray-dried detergents. A transfer to other detergents, for example those produced by granulation, does not appear to be possible with this procedure.
  • Silicone-containing defoamers are known from European patent application EP-AI-0 496 510, a mixture of silicones and fatty alcohols, fatty acids or glycerol monoesters having special melting points being applied to starch as the carrier material.
  • EP-AI-0 496 510 a mixture of silicones and fatty alcohols, fatty acids or glycerol monoesters having special melting points being applied to starch as the carrier material.
  • the silicones and the other organic constituents are mixed with the starch in liquid form or granulated in a fluidized bed process. Spraying the silicones and the organic materials onto the carrier during the granulation proves problematic according to this method. Because of their viscosity and their sticky, oily consistency, the silicones show problems with pumpability on the one hand, and stringing and sticking in the spray nozzle on the other, which means that the desired, finely divided spraying is hardly possible.
  • a process for the production of free-flowing granules of detergent and cleaning agents is known from German published patent application DE-Al 4209339, in which dewatering in turbine dryers, i.e. in cylindrical dryers in a horizontal design with rotating internals. Anionic surfactants with sulfate-containing detergent pastes can also be dried.
  • the present invention relates to a process for the preparation of defoamer granules for solid detergents consisting of carrier materials, silicones and, if appropriate, water-insoluble wax-like defoamer substances, silicones being sprayed onto an admixed precursor of carrier materials in the form of aqueous emulsions and, if appropriate, water-insoluble wax-like defoamer substances with simultaneous drying and granulation in a thin-film evaporator.
  • a horizontally arranged thin-film evaporator is ideally suited to producing dry, free-flowing and non-tacky defoamer granules.
  • the products are also dust-free, i.e. the proportion of particles with a diameter below 200 ⁇ m is below 5% by weight.
  • suitable silicones are conventional organopolysiloxanes which have a content of finely divided silica, which in turn can also be silanated.
  • organopolysiloxanes are described, for example, in the already cited European patent application EP-A1-0 496 510.
  • Polydiorganosiloxanes which are known from the prior art are particularly preferred.
  • Suitable polydiorganosiloxanes have an almost linear chain and are identified by the following formula (I),
  • R can independently represent an alkyl or an aryl radical and n can stand for numbers in the range from 40 to 1500.
  • suitable substituents R are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl.
  • the polydiorganosiloxanes contain finely divided silica, which can also be silanized.
  • Silica-containing dimethylpolysiloxanes are particularly suitable for the purposes of the present invention.
  • the polydiorganosiloxanes advantageously have a Brookfield viscosity at 25 ° C. in the range from 5000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas.
  • An essential criterion of the present invention is that the silicones are sprayed in the form of their aqueous emulsions. As a rule, the silicone is added to the water presented with stirring. If desired, so-called thickeners, as are known from the prior art, can be added to increase the viscosity of the aqueous silicone emulsions.
  • the thickeners can be inorganic and / or organic in nature, particularly preferred are nonionic cellulose ethers such as methyl cellulose, ethyl cellulose and mixed ethers such as methylhydoxyethyl cellulose, methyl hydroxypropyl cellulose, methyl hydroxybutyl cellulose and anionic carboxy cellulose types such as the carboxymethyl cellulose sodium salt (abbreviation CMC).
  • nonionic cellulose ethers such as methyl cellulose, ethyl cellulose and mixed ethers such as methylhydoxyethyl cellulose, methyl hydroxypropyl cellulose, methyl hydroxybutyl cellulose and anionic carboxy cellulose types such as the carboxymethyl cellulose sodium salt (abbreviation CMC).
  • Particularly suitable thickeners are mixtures of CMC to nonionic cellulose ethers in a weight ratio of 80:20 to 40:60, in particular 75:25 to 60:40.
  • concentrations of approximately 0.5 to 10, in particular 2.0 to 6,% by weight, calculated as a thickener mixture and based on aqueous silicone emulsion, are recommended.
  • the content of silicones of the type described in the aqueous emulsions is advantageously in the range from 5 to 50% by weight, in particular from 20 to 40% by weight, calculated as silicones and based on the aqueous silicone emulsion.
  • the aqueous silicone solutions are given starch which is accessible from natural sources, for example from rice, potatoes, corn and wheat.
  • the starch is advantageously present in amounts of 0.1 to 50% by weight, based on the silicone emulsion, and in particular in a mixture with the already described thickener mixtures of sodium carboxymethyl cellulose and a nonionic cellulose ether in the amounts already mentioned.
  • the procedure is expediently such that the thickeners which may be present are allowed to swell in water before the silicones are added.
  • the silicones are expediently incorporated using effective stirring and mixing devices. Carrier materials
  • all known inorganic and / or organic carrier materials can be used as carrier materials.
  • typical inorganic carrier materials alkali carbonates, aluminosilicates, water-soluble sheet silicates, alkali silicates, alkali sulfates, for example sodium sulfate and alkali phosphates.
  • the alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO 2 of 1: 1.5 to 1: 3.5. The use of such silicates results in particularly good ones
  • the aluminosilicates referred to as carrier material include, in particular, the zeolites, for example zeolite NaA and NaX.
  • the compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass.
  • suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch.
  • Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof.
  • Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
  • the mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50.
  • Such cellulose ether mixtures can be used in solid form or as aqueous solutions, which can be pre-swollen in the usual way.
  • the native starch which is composed of amylose and amylopectin is particularly preferred as the carrier.
  • Starch is referred to as native starch as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat.
  • Native starch is a commercially available product and is therefore easily accessible.
  • Carrier materials which can be used are one or more of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, carboxymethyl cellulose, polyacrylate / polymethacrylate and starch.
  • alkali carbonates in particular sodium carbonate
  • alkali silicates in particular sodium silicate
  • alkali sulfates in particular sodium sulfate
  • zeolites zeolites
  • polycarboxylates in particular poly (meth) acrylate
  • cellulose ether and native starch are particularly suitable.
  • the carrier materials can be composed as follows:
  • alkali silicate 0 to 30% by weight alkali silicate
  • alkali sulfate 0 to 75% by weight alkali sulfate
  • polycarboxylates 0 to 5% by weight of polycarboxylates, the sum having to add up to 100% by weight.
  • waxy, water-insoluble defoamer compounds can also be used.
  • "Wax-like” are understood to mean those compounds which have a melting point at atmospheric pressure above 25 ° C. (room temperature), preferably above 50 ° C. and in particular above 70 ° C.
  • the wax-like defoamer substances which may be present according to the invention are practically insoluble in water, ie at 20 ° C they have a solubility of less than 0.1% by weight in 100 g of water.
  • Suitable waxy compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohols, and paraffin waxes or mixtures thereof.
  • Bisamides are suitable which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18 C atoms and from alkylenediamines with 2 to 7 C atoms.
  • Suitable fatty acids are lauric, myristic, stearic, Arachinic acid and behenic acid as well as their mixtures as they are available from natural fats or hardened oils such as tallow or hydrogenated palm oil.
  • Suitable diamines are, for example, ethylene diamine, 1,3-propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, p-phenylene diamine and toluene diamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bis-palmitoyl-ethylenediamine, bis-stearoylethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.
  • Suitable carboxylic acid esters are derived from carboxylic acids with 12 to 28 carbon atoms. In particular, these are esters of behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid.
  • the alcohol part of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain.
  • suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, methanol, ethanol, isopropanol, vinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol.
  • esters are those of methanol, ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
  • Suitable esters of polyvalent alcohols include xylitol monopalmitate, Pentarythritmonostearat, glycerol, ethylene glycol and sorbitan monostearate, sorbitan, sorbitan Sorbitandilaurat, sorbitan, sorbitan dioleate, and also mixed tallowalkyl and diesters.
  • Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred.
  • Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this.
  • esters examples include beeswax, which mainly consists of the esters CH 3 (CH2) 24COO (CH 2 ) 27CH3 and CH3 (CH 2 ) 26COO (CH 2 ) 25CH3, and carnauba wax, which is a mixture of alkyl carnauba acids, often in combination with low Free camauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.
  • Suitable carboxylic acids as a further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid and mixtures thereof, as can be obtained from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil. Saturated fatty acids with 12 to 22, in particular 14 to 18, carbon atoms are preferred.
  • Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of the fatty acids described.
  • the paraffin wax preferred as a further defoamer compound in the sense of the invention generally represents a complex mixture of substances without a sharp melting point.
  • its melting range is usually determined by differential thermal analysis (DTA), as in "The Analyst” 87 (1962), 420 , described, and / or its freezing point. This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling.
  • Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C. cannot be used according to the invention.
  • paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably absent entirely.
  • Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably of 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular 40% by weight % to 55 wt .-%, at 80 ° C a Liquid content of 80 wt .-% to 100 wt .-%, and at 90 ° C a liquid content of 100 wt .-%.
  • the temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C. in particularly preferred paraffin wax mixtures, in particular at 75 ° C. to 82 ° C.
  • paraffin waxes of the type described are used in particular.
  • a preliminary product is first produced from the carrier materials and the wax-like defoamer substances which may be present. If the preliminary product also contains wax-like defoamer substances, the weight fraction of carrier materials is preferably 20 to 98% by weight, in particular 35 to 95% by weight, and that of the wax-like defoamer substances is preferably 2 to 80% by weight, in particular 5 to 65% by weight .-% - calculated on preliminary product.
  • the intermediate product can be used as a solid or as an aqueous solution or as an aqueous slurry. It is preferred to use the preliminary product as an aqueous solution or as an aqueous slurry (slurries). If the preliminary product additionally contains wax-like defoamer substances, these can be dispersed in an aqueous solution or slurry of the carrier material. A water-soluble, non-surfactant dispersion stabilizer in the form of a water-swellable polymer can be added to the dispersion.
  • the cellulose ethers mentioned homo- and copolymers of unsaturated carboxylic acids, such as acrylic acid, maleic acid and copolymerizable vinyl compounds, such as vinyl ether, acrylamide and ethylene.
  • the addition of such compounds which act as dispersion stabilizers in the aqueous slurry is preferably not more than 5% by weight, in particular 1% by weight to 3% by weight, based on the resulting precursor.
  • the water content of the slurry can be 30% by weight to 60% by weight.
  • the preliminary product can also be used as a solid.
  • the previously described slurry of carrier materials and possibly further wax-like defoamer substances can be dried in the spray tower or else simultaneous drying and granulation in the fluidized bed using the SKET process, for example in accordance with European Patent EP-B-603 207 or by the fluidized bed process.
  • the simultaneous drying and granulation of the defoamer granules is preferably carried out in a horizontally arranged thin-film evaporator with rotating internals, as it is sold, for example, by the company VRV under the name "Flashdryer".
  • this is a tube that spans several zones
  • the preliminary product is metered in via one or more shafts, which are provided with blades or shares of flies as rotating internals, sprayed with the aqueous silicone emulsion sprayed in via one or more nozzles and flung against the heated wall on the the drying takes place in a thin layer of typically 1 to 10 mm thickness. If the preliminary products are used as a slurry, the metering is carried out by means of a pump.
  • the first two zones of the evaporator can be heated to 160 ° C and the last can be cooled to 20 ° C.
  • the thin film evaporator is operated at atmospheric pressure and gassed in countercurrent with air (throughput 50 to 150 m 3 / h).
  • the gas inlet temperature is usually 20 to 30 ° C, the outlet temperature 90 to 110 ° C.
  • the throughput is of course dependent on the size of the dryer, but is typically 5 to 15 kg / h. It is advisable to temper the aqueous slurry of the preliminary product (slurry) to 40 to 60 ° C.
  • aqueous silicone emulsions it is particularly advantageous to increase the aqueous silicone emulsions to 45 to 65 ° C temper.
  • the product streams of aqueous silicone emulsion and metered preliminary product are controlled so that defoamer granules are obtained, which are preferably 2.0 to 25% by weight, in particular 5.0 to 20% by weight, of silicone - calculated as silicone and based on Defoamer granules - included. The remaining 100% by weight of the defoamer granulate results from the preliminary product.
  • the granules After drying, it has also proven to be very advantageous to place the granules, which are still around 50 to 70 ° C, on a conveyor belt, preferably an oscillating shaft, and to place them there quickly, i.e. cool within a dwell time of 20 to 60 s with ambient air to temperatures of around 30 to 40 ° C.
  • the granules can also subsequently be powdered by adding 0.5 to 2% by weight of silica.
  • the defoamer granules are regarded as dried if the free water content is below 10% by weight, preferably from 0.1 to 2% by weight, based in each case on the finished granules.
  • the defoamer granules produced by the process according to the invention are easy-flowing products which do not dust. They have a good defoaming effect and can be used in both spray-dried and granulated detergents.
  • Another object of the present invention relates to the use of the defoamer granules produced according to the invention for the production of solid detergents.
  • the defoamer granules can be present in amounts of 0.2 to 7.0% by weight, preferably in amounts of 0.5 to 4.0% by weight, based on the detergent.
  • the detergents can contain customary anionic, nonionic or cationic surfactants, as well as other customary constituents in customary amounts.
  • the detergents can contain softening agents such as tripolyphosphate or zeolite, as well as bleaching agents such as perborate or percarbonate in customary amounts as usual components.
  • the defoamer granules can easily be mixed in. Examples
  • aqueous slurry consisting of 0.5% by weight of cellulose ether, 5.0% by weight of sodium silicate, 20.7% by weight of sodium sulfate, 15.8% by weight of sodium carbonate, 2.0% of polyacrylic was obtained / methacrylate, 50% by weight water and 6% by weight of a paraffin wax mixture consisting of 40% by weight paraffin with a solidification point from 62 ° C. to 90 ° C., 30% by weight hard paraffin with a solidification point from 42 ° C. to 56 ° C and 30 wt .-% soft paraffin with a solidification point of 35 ° C to 40 ° C was produced with constant homogenization.
  • Example 2 preliminary product as a slurry
  • An aqueous slurry consisting of 0.5 wt.% Cellulose ether, 2.0 wt.% Sodium silicate, 13 wt.% Sodium sulfate, 23.5 wt.% Zeolite, 2.0 wt. lyacryl / methacrylate, 50% by weight of water, 7% by weight of paraffin with a solidification point of 62 ° C. to 90 ° C. and 2% by weight of bis-stearylethylenediamide was prepared with constant homogenization.
  • the granules were produced in a flash dryer from VRV SpA, Milan / IT. It was a horizontally arranged thin film evaporator (length 1100 mm, inside diameter: 155 mm) with 4 shafts and 22 blades, the distance to the wall of which was 2 mm. The dryer had three separate heating or cooling zones and a total heat exchanger area of 0.44 m 2 . The operation was carried out at normal pressure. A total of 10,000 kg of a slurry of the preliminary product according to Example 1, heated to 50.degree. C. and with a throughput of 11.5 kg / h, were introduced into the Pumped thin film evaporator, the heating zones 1 and 2 had been set to 160 ° C and the cooling zone 3 to 20 ° C.
  • the slurry was sprayed with a total of 2000 kg of the aqueous silicone emulsion according to Example 4.
  • the speed of the rotors was 24 ms.
  • the flash dryer was gassed with air (approx. 110 m 3 / h); the gas outlet temperature was approx. 65 ° C.
  • the pre-dried, still about 60 ° C hot granules were placed on a vibrating trough (length 1 m), gassed with room air and cooled to about 40 ° C within 30 s.
  • Granules having the following composition were obtained: 7% by weight of silicone, 2.2% by weight of cellulose ether, 9.2% by weight of sodium silicate, 38.0% by weight of sodium sulfate, 29.1% by weight of sodium carbonate , 3.7 wt .-% polyacrylic / methacrylate and 11.0 wt .-% of a paraffin wax mixture consisting of 40% paraffin with a setting point of 62 ° C to 90 ° C, 30 wt .-% hard paraffin with a setting point of 42 ° C to 56 ° C and 30% by weight soft paraffin with a solidification point of 35 ° C to 40 ° C.
  • the product showed very good flow properties and had no dust content.
  • Example 7 the aqueous slurry of the preliminary product according to Example 2 was sprayed with the aqueous silicone emulsion according to Example 5 and processed further.
  • Granules having the following composition were obtained: 7% by weight of silicone, 10.3% by weight of starch, 2.1% by weight of cellulose ether, 3.2% by weight of sodium silicate, 21.2% by weight of sodium sulfate , 38.1% by weight of zeolite, 3.3% by weight of polyacrylic / methacrylate, 11.5% by weight of paraffin and 3.3% by weight of bisstearylethylenediamide.
  • the product showed very good flow properties and had no dust content.
  • Example 7 the preliminary product was sprayed as tower powder according to Example 3 with the aqueous silicone emulsion according to Example 6 and processed further. A total of 10,000 kg of a preliminary product heated to 50 ° C. were conveyed via a screw into the thin-film evaporator at a throughput of 11.5 kg / h.
  • Granules having the following composition were obtained: 10.2% by weight of silicone, 2.8% by weight of cellulose ether, 5.6% by weight of sodium silicate, 33.3% by weight of sodium sulfate, 35.1% by weight % Sodium carbonate, 3.7% by weight polyacrylic / methacrylate and 9.3% by weight of a paraffin wax mixture consisting of 50% paraffin with a solidification point from 62 ° C to 90 ° C, 25% by weight hard paraffin with a solidification point of 42 ° C to 56 ° C and 25% by weight soft paraffin with a solidification point of 35 ° C to 40 ° C with a bulk density of 760 g / 1 and a grain size distribution of 0.1 to 1.6 mm.
  • the product showed good flow properties and had ⁇ 1% dust content.
  • the defoamer granules produced were mixed in an amount of 1.5% by weight by simply mixing them into a powdered universal detergent formulation with 8% by weight sodium alkylbenzenesulfonate, 10% by weight alkyl ethoxylate, 1.5% by weight soap, 10% by weight % Sodium carbonate, 20% by weight zeolite, 3% by weight sodium silicate, 20% by weight sodium perborate, 2% by weight tetraacetylethylene diamine (TAED), 0.5% by weight protease, balance to 100% by weight. -% sodium sulfate and water incorporated.
  • the detergents obtained had perfect foaming behavior both at 30 ° C. and at 40 ° C., 60 ° C. and 95 ° C.

Abstract

The present invention relates to a method for producing defoaming granulates containing silicon for solid detergents by simultaneous granulation and drying, whereby silicon is sprayed in the form of aqueous emulsions onto a mixed intermediate product consisting of supporting materials and, optionally, other defoamers and granulation and drying occur simultaneously, especially according to the SKET method.

Description

„ Herstellung von Entschäumergranulaten im Dünnschichtverdampfer" "Production of defoamer granules in a thin film evaporator"
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Silikon enthaltenden Entschäumergranulaten für feste Waschmittel, wobei die Silikone in Form von wäßrigen Emulsionen aufgesprüht werden auf ein zugemischtes Vorprodukt aus Trägermaterialien und ggf. weiteren Entschäumern unter Verwendung eines Dünnschichtverdampfers. Des weiteren beschreibt die vorliegende Erfindung die Verwendung derartiger Entschäumergranulate in festen Waschmitteln.The present invention relates to a process for producing silicone-containing defoamer granules for solid detergents, the silicones being sprayed in the form of aqueous emulsions onto an admixed precursor made from carrier materials and, if appropriate, further defoamers using a thin-film evaporator. Furthermore, the present invention describes the use of such defoamer granules in solid detergents.
Waschmittel für die Haushaltswäsche und die industrielle Wäsche enthalten im allgemeinen organische Tenside, Builder sowie zahlreiche organische und anorganische Additive. Die für die Wäsche eingesetzten Tenside neigen gewöhnlich während des Waschzyklus zur Schaumentwicklung, was sich negativ auf das Waschergebnis auswirkt. Daher besteht ein praktisches Bedürfnis, die Schaumentwicklung während des Waschvorgangs zu kontrollieren. Als besonders geeignete Entschäumer haben sich dabei Silikone erwiesen, die in der Regel auf Trägermaterialien aufgebracht und ggf. mit weiteren organischen entschäumend wirkenden Substanzen gecoatet in festen Waschmitteln eingesetzt werden.Household and industrial laundry detergents generally contain organic surfactants, builders and numerous organic and inorganic additives. The surfactants used for the laundry usually tend to develop foam during the washing cycle, which has a negative effect on the washing result. Therefore, there is a practical need to control the development of foam during the washing process. Silicones have proven to be particularly suitable defoamers, which are generally applied to carrier materials and, if appropriate, are used in solid detergents, coated with other organic defoaming substances.
So ist aus der DE-Al-31 28 631 die Herstellung von schaumgedämpften Waschmitteln mit einem Gehalt an Silikonentschäumern, die mikroverkapselt sind, bekannt. Dabei wird das Silikon in einer wäßrigen Dispersion eines filmbildenden Polymeren dispergiert und die Dispersion - getrennt von den übrigen in Wasser gelösten bzw. dispergierten Waschmittelbestandteilen - über eine besondere Leitung der Sprühtrocknungsanlage zugeführt. Die Vereinigung der beiden Teilströme erfolgt im Bereich der Sprühdüse. Als filmbildende Polymere kommen zum Beispiel Celluloseether, Stärkeether oder synthetische wasserlösliche Polymere in Frage. Die Bildung von Mikrokapseln erfolgt spontan in der Sprühdüse. Das beschriebene Verfahren ist zwangsläufig an die Herstellung sprühgetrockneter Waschmittel gebunden. Eine Übertragung auf anderweitig, zum Beispiel durch Granulierung hergestellte Waschmittel scheint bei dieser Arbeitsweise nicht möglich.For example, DE-Al-31 28 631 discloses the production of foam-damped detergents containing silicone defoamers which are microencapsulated. The silicone is dispersed in an aqueous dispersion of a film-forming polymer and the dispersion - separated from the other detergent constituents dissolved or dispersed in water - is fed to the spray drying system via a special line. The two partial flows are combined in the area of the spray nozzle. Examples of film-forming polymers are cellulose ethers, starch ethers or synthetic water-soluble ones Polymers in question. Microcapsules form spontaneously in the spray nozzle. The process described is inevitably linked to the production of spray-dried detergents. A transfer to other detergents, for example those produced by granulation, does not appear to be possible with this procedure.
Aus der europäischen Patentanmeldung EP-AI- 0 496 510 sind Silikon enthaltende Entschäumer bekannt, wobei auf Stärke als Trägermaterial eine Mischung aus Silikonen und Fettalkoholen, Fettsäuren oder Glycerinmonoester mit speziellen Schmelzpunkten aufgebracht wird. Zur Herstellung dieser Entschäumergranulate werden die Silikone und die weiteren organischen Bestandteile in flüssiger Form mit der Stärke gemischt oder im Fließbettverfahren granuliert. Problematisch nach diesem Verfahren erweist sich das Einsprühen der Silikone und der organischen Materialien auf den Träger bei der Granulation. So zeigen die Silikone aufgrund ihrer Viskosität und ihrer klebrigen, öligen Konsistenz zum einen Probleme bei der Pumpbarkeit und zum anderen Fadenzüge und Verklebungen in der Sprühdüse, wodurch das gewünschte feinverteilte Versprühen kaum möglich ist.Silicone-containing defoamers are known from European patent application EP-AI-0 496 510, a mixture of silicones and fatty alcohols, fatty acids or glycerol monoesters having special melting points being applied to starch as the carrier material. To produce these defoamer granules, the silicones and the other organic constituents are mixed with the starch in liquid form or granulated in a fluidized bed process. Spraying the silicones and the organic materials onto the carrier during the granulation proves problematic according to this method. Because of their viscosity and their sticky, oily consistency, the silicones show problems with pumpability on the one hand, and stringing and sticking in the spray nozzle on the other, which means that the desired, finely divided spraying is hardly possible.
Aus der deutschen Offenlegungsschrift DE-Al 4209339 ist ein Verfahren zur Herstellung rieselfahiger Wasch- und Reinigungsmittelgranulate bekannt, bei dem die Entwässerung in Turbinentrocknern, d.h. in zylindrischen Trockenapparaturen in horizontaler Bauweise mit rotierenden Einbauten erfolgt. Dabei können auch anionische Tenside mit Sulfatstruktur enthaltende Reinigungsmittelpasten getrocknet werden.A process for the production of free-flowing granules of detergent and cleaning agents is known from German published patent application DE-Al 4209339, in which dewatering in turbine dryers, i.e. in cylindrical dryers in a horizontal design with rotating internals. Anionic surfactants with sulfate-containing detergent pastes can also be dried.
Aufgabe der vorliegenden Erfindung war es, ein Verfahren zur Herstellung von gut wirkenden Entschäumergranulaten für feste Waschmittel zur Verfügung zu stellen. Des weiteren sollten durch das Verfahren Entschäumergranulate zugänglich sein, die gut rieselfähig und nicht-staubend sind. Schließlich sollte das Verfahren so ausgerichtet sein, daß die Silikone gut pumpfähig sind und feinverteilt aufgesprüht werden können.It was an object of the present invention to provide a process for the preparation of good-acting defoamer granules for solid detergents. Furthermore, defoamer granules which are free-flowing and non-dusting should be accessible through the process. Finally, the process should be designed so that the silicones are pumpable and can be sprayed on in a finely divided form.
Ein Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von Entschäumergranulaten für feste Waschmittel bestehend aus Trägermaterialien, Silikonen und ggf. in Wasser unlöslichen wachsartigen Entschäumersubstanzen, wobei man Silikone in Form wäßriger Emulsionen aufsprüht auf ein zugemischtes Vorprodukt aus Trägermaterialien und ggf. in Wasser unlöslichen wachsartigen Entschäumersubstanzen unter gleichzeitigem Trocknen und Granulieren in einem Dünnschichtverdampfer.The present invention relates to a process for the preparation of defoamer granules for solid detergents consisting of carrier materials, silicones and, if appropriate, water-insoluble wax-like defoamer substances, silicones being sprayed onto an admixed precursor of carrier materials in the form of aqueous emulsions and, if appropriate, water-insoluble wax-like defoamer substances with simultaneous drying and granulation in a thin-film evaporator.
Überraschenderweise wurde gefunden, daß insbesondere ein horizontal angeordneter Dünnschichtverdampfer in idealer Weise geeignet ist, trockene, rieselfahige und nichtklebrige Entschäumergranulate herzustellen. Die Produkte sind gleichzeitig staubfrei, d.h. der Anteil an Teilchen mit einem Durchmesser unterhalb von 200 μm liegt unterhalb von 5 Gew.- %.Surprisingly, it was found that, in particular, a horizontally arranged thin-film evaporator is ideally suited to producing dry, free-flowing and non-tacky defoamer granules. The products are also dust-free, i.e. the proportion of particles with a diameter below 200 μm is below 5% by weight.
SilikoneSilicones
Im Sinne der vorliegenden Erfindung sind geeignete Silikone übliche Organopolysiloxane, die einen Gehalt an feinteiliger Kieselsäure, die wiederum auch silaniert sein kann, aufweisen. Derartige Organopolysiloxane sind beispielsweise in der schon zitierten Europäischen Patentanmeldung EP-A1-0 496 510 beschrieben. Besonders bevorzugt sind Polydiorgano- siloxane, die aus dem Stand der Technik bekannt sind. Geeignete Polydiorganosiloxane weisen eine nahezu lineare Kette auf und sind gemäß folgender Formel (I) gekennzeichnet,For the purposes of the present invention, suitable silicones are conventional organopolysiloxanes which have a content of finely divided silica, which in turn can also be silanated. Such organopolysiloxanes are described, for example, in the already cited European patent application EP-A1-0 496 510. Polydiorganosiloxanes which are known from the prior art are particularly preferred. Suitable polydiorganosiloxanes have an almost linear chain and are identified by the following formula (I),
n n
wobei R unabhängig voneinander für einen Alkyl- oder einen Arylrest und n für Zahlen im Bereich von 40 bis 1500 stehen kann. Beispiele für geeignete Substituenten R sind Methyl, Ethyl, Propyl, Isobutyl, tert. Butyl und Phenyl.where R can independently represent an alkyl or an aryl radical and n can stand for numbers in the range from 40 to 1500. Examples of suitable substituents R are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl.
In der Regel enthalten die Polydiorganosiloxane feinteilige Kieselsäure, die auch silaniert sein kann. Insbesondere geeignet sind im Sinne der vorliegenden Erfindung kieselsäurehaltige Dimethylpolysiloxane.As a rule, the polydiorganosiloxanes contain finely divided silica, which can also be silanized. Silica-containing dimethylpolysiloxanes are particularly suitable for the purposes of the present invention.
Vorteilhafterweise haben die Polydiorganosiloxane eine Viskosität nach Brookfield bei 25 °C im Bereich von 5000 mPas bis 30 000 mPas, insbesondere von 15 000 bis 25 000 mPas. Ein erfindungswesentliches Kriterium der vorliegenden Erfindung ist, daß die Silikone in Form ihrer wäßrigen Emulsionen eingesprüht werden. In der Regel gibt man das Silikon zu vorgelegtem Wasser unter Rühren. Falls gewünscht kann man zur Erhöhung der Viskosität der wäßrigen Silikon-Emulsionen sogenannte Verdickungsmittel, wie sie aus dem Stand der Technik bekannt sind, zugeben. Die Verdickungsmittel können anorganischer und/oder organischer Natur sein, besonders bevorzugt werden nichtionische Celluloseether wie Methylcellulose, Ethylcellulose und Mischether wie Methylhydoxyethylcellulose, Methylhydroxypropylcellulose, Methylhydroxybutylcellulose sowie anionische Carboxy- cellulose-Typen wie das Carboxymethylcellulose-Natriumsalz (Abkürzung CMC). Insbsonders geeignete Verdicker sind Mischungen von CMC zu nichtionischen Cellulo- seethern im Gewichtsverhältnis 80 : 20 bis 40 : 60, insbesondere 75 : 25 bis 60 : 40.The polydiorganosiloxanes advantageously have a Brookfield viscosity at 25 ° C. in the range from 5000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas. An essential criterion of the present invention is that the silicones are sprayed in the form of their aqueous emulsions. As a rule, the silicone is added to the water presented with stirring. If desired, so-called thickeners, as are known from the prior art, can be added to increase the viscosity of the aqueous silicone emulsions. The thickeners can be inorganic and / or organic in nature, particularly preferred are nonionic cellulose ethers such as methyl cellulose, ethyl cellulose and mixed ethers such as methylhydoxyethyl cellulose, methyl hydroxypropyl cellulose, methyl hydroxybutyl cellulose and anionic carboxy cellulose types such as the carboxymethyl cellulose sodium salt (abbreviation CMC). Particularly suitable thickeners are mixtures of CMC to nonionic cellulose ethers in a weight ratio of 80:20 to 40:60, in particular 75:25 to 60:40.
In der Regel und besonders bei Zugabe der beschriebenen Verdickermischungen empfehlen sich Einsatzkonzentrationen von cirka 0,5 bis 10, insbesondere von 2,0 bis 6 Gew.-% - berechnet als Verdickermischung und bezogen auf wäßrige Silikonemulsion.In general, and especially when adding the thickener mixtures described, use concentrations of approximately 0.5 to 10, in particular 2.0 to 6,% by weight, calculated as a thickener mixture and based on aqueous silicone emulsion, are recommended.
Der Gehalt an Silikonen der beschriebenen Art in den wäßrigen Emulsionen liegt vorteilhafterweise im Bereich von 5 bis 50 Gew.-%, insbesondere von 20 bis 40 Gew.-% - berechnet als Silikone und bezogen auf wäßrige Silikonemulsion.The content of silicones of the type described in the aqueous emulsions is advantageously in the range from 5 to 50% by weight, in particular from 20 to 40% by weight, calculated as silicones and based on the aqueous silicone emulsion.
Nach einer weiteren vorteilhaften Ausgestaltung erhalten die wäßrigen Silikon-Lösungen als Verdicker Stärke, die aus natürlichen Quellen zugänglich ist, beispielsweise aus Reis, Kartoffeln, Mais und Weizen. Die Stärke ist vorteilhafterweise in Mengen von 0,1 bis zu 50 Gew.-% - bezogen auf Silikon-Emulsion - enthalten und insbesondere in Mischung mit den schon beschriebenen Verdickermischungen aus Natrium-Carboxymethylcellulose und einem nichtionischen Celluloseether in den schon genannten Mengen.According to a further advantageous embodiment, the aqueous silicone solutions, as thickeners, are given starch which is accessible from natural sources, for example from rice, potatoes, corn and wheat. The starch is advantageously present in amounts of 0.1 to 50% by weight, based on the silicone emulsion, and in particular in a mixture with the already described thickener mixtures of sodium carboxymethyl cellulose and a nonionic cellulose ether in the amounts already mentioned.
Zur Herstellung der wäßrigen Silikon-Emulsionen geht man zweckmäßigerweise so vor, daß man die ggf. vorhandenen Verdickungsmittel in Wasser vorquellen läßt, bevor die Zugabe der Silikone erfolgt. Das Einarbeiten der Silikone erfolgt zweckmäßigerweise mit Hilfe wirksamer Rühr- und Mischungsvorrichtungen. TrägermaterialienTo prepare the aqueous silicone emulsions, the procedure is expediently such that the thickeners which may be present are allowed to swell in water before the silicones are added. The silicones are expediently incorporated using effective stirring and mixing devices. Carrier materials
Als Trägermaterial können im Sinne der Erfindung alle bekannten anorganischen und/oder organischen Trägermaterialien eingesetzt werden. Beispiele für typische anorganische Trägermaterialien Alkalicarbonate, Alumosilikate, wasserlösliche Schichtsilikate, Alkalisilikate, Alkalisulfate, beispielsweise Natriumsulfat und Alkaliphosphate. Bei den Alkalisilikaten handelt es sich vorzugsweise um eine Verbindung mit einem Molverhältnis Alkalioxid zu Siθ2 von 1 :1,5 bis 1 :3,5. Die Verwendung derartiger Silikate resultiert in besonders gutenAccording to the invention, all known inorganic and / or organic carrier materials can be used as carrier materials. Examples of typical inorganic carrier materials alkali carbonates, aluminosilicates, water-soluble sheet silicates, alkali silicates, alkali sulfates, for example sodium sulfate and alkali phosphates. The alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO 2 of 1: 1.5 to 1: 3.5. The use of such silicates results in particularly good ones
Korneigenschaften, insbesondere hoher Abriebsstabilität und dennoch hoher Auflösungsgeschwindigkeit in Wasser. Zu den als Trägermaterial bezeichneten Alumosilikaten gehören insbesondere die Zeolithe, beispielsweise Zeolith NaA und NaX. Zu den als wasserlöslichen Schichtsilikaten bezeichneten Verbindungen gehören beispielsweise amorphes oder kristallines Wasserglas.Grain properties, especially high abrasion stability and still high dissolution rate in water. The aluminosilicates referred to as carrier material include, in particular, the zeolites, for example zeolite NaA and NaX. The compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass.
Als organische Trägermaterialien kommen zum Beispiel filmbildende Polymere, beispielsweise Polyvinylalkohole, Polyvinylpyrrolidone, Poly(meth)acrylate, Polycarboxylate, Cellulosederivate und Stärke in Frage. Brauchbare Celluloseether sind insbesondere Alkalicarboxymethylcellulose, Methylcellulose, Ethylcellulose, Hydroxyethylcellulose und sogenannte Cellulosemischether, wie zum Beispiel Methylhydroxyethylcellulose und Methyl- hydroxypropylcellulose, sowie deren Mischungen. Besonders geeignete Mischungen sind aus Natrium-Carboxymethylcellulose und Methylcellulose zusammengesetzt, wobei die Carboxy- methylcellulose üblicherweise einen Substitutionsgrad von 0,5 bis 0,8 Carboxymethylgruppen pro Anhydroglukoseeinheit und die Methylcellulose einen Substitutionsgrad von 1,2 bis 2 Methylgruppen pro Anhydroglukoseeinheit aufweist. Die Gemische enthalten vorzugsweise Alkalicarboxymethylcellulose und nichtionischen Celluloseether in Gewichtsverhältnissen von 80:20 bis 40:60, insbesondere von 75:25 bis 50:50. Derartige Celluloseethergemische können in fester Form oder als wäßrige Lösungen verwendet werden, die in üblicher Weise vorgequollen sein können. Im Sinne der Erfindung werden als Träger besonders bevorzugt die native Stärke, die aus Amylose und Amylopectin aufgebaut ist. Als native Stärke wird Stärke bezeichnet, wie sie als Extrakt aus natürlichen Quellen zugänglich ist, beispielsweise aus Reis, Kartoffeln, Mais und Weizen. Native Stärke ist ein handelsübliches Produkt und damit leicht zugänglich. Als Trägermaterialien können einzelne oder mehrere der vorstehend genannten Verbindungen eingesetzt werden, insbesondere ausgewählt aus der Gruppe der Alkalicarbonate, Alkalisulfate, Alkaliphosphate, Zeolithe, wasserlösliche Schichtsilikate, Alkalisilikate, Polycarboxylate, Carboxymethylcellulose, Polyacrylat/Polymethacrylat und Stärke. Besonders geeignet sind Mischungen von Alkalicarbonaten, insbesondere Natriumcarbonat, Alkalisilikaten, insbesondere Natriumsilikat, Alkalisulfaten, insbesondere Natriumsulfat, Zeolithen, Polycarboxylate, insbesondere Poly(meth)acrylat, und Celluloseether und nativer Stärke. Die Trägermaterialien können folgendermaßen zusammengesetzt sein:Examples of suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch. Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof. Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit. The mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50. Such cellulose ether mixtures can be used in solid form or as aqueous solutions, which can be pre-swollen in the usual way. For the purposes of the invention, the native starch which is composed of amylose and amylopectin is particularly preferred as the carrier. Starch is referred to as native starch as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat. Native starch is a commercially available product and is therefore easily accessible. Carrier materials which can be used are one or more of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, carboxymethyl cellulose, polyacrylate / polymethacrylate and starch. Mixtures of alkali carbonates, in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate, zeolites, polycarboxylates, in particular poly (meth) acrylate, and cellulose ether and native starch are particularly suitable. The carrier materials can be composed as follows:
0 bis 2 Gew.-% Celluloseether0 to 2% by weight cellulose ether
0 bis 75 Gew.-% native Stärke0 to 75% by weight native starch
0 bis 30 Gew.-% Alkalisilikat0 to 30% by weight alkali silicate
0 bis 75 Gew.-% Alkalisulfat0 to 75% by weight alkali sulfate
0 bis 95 Gew.-% Alkalicarbonat0 to 95 wt% alkali carbonate
0 bis 95 Gew.-% Zeolithe0 to 95% by weight zeolites
0 bis 5 Gew.-% Polycarboxylate, wobei sich die Summe zu 100 Gew.-% addieren muß.0 to 5% by weight of polycarboxylates, the sum having to add up to 100% by weight.
Wachsartige EntschäumerWaxy defoamers
Im Sinne der vorliegenden Erfindung können zusätzlich neben den Silikonen wachsartige , in Wasser unlösliche Entschäumerverbindungen eingesetzt werden. Als „wachsartig" werden solche Verbindungen verstanden, die einen Schmelzpunkt bei Atmospärendruck über 25 °C (Raumtemperatur), vorzugsweise über 50 °C und insbesondere über 70 °C aufweisen. Die ggf. erfindungsgemäß enthaltenen wachsartigen Entschäumersubstanzen sind in Wasser praktisch nicht löslich, d.h. bei 20 °C weisen sie in 100 g Wasser eine Löslichkeit unter 0,1 Gew.-% auf.For the purposes of the present invention, in addition to the silicones, waxy, water-insoluble defoamer compounds can also be used. "Wax-like" are understood to mean those compounds which have a melting point at atmospheric pressure above 25 ° C. (room temperature), preferably above 50 ° C. and in particular above 70 ° C. The wax-like defoamer substances which may be present according to the invention are practically insoluble in water, ie at 20 ° C they have a solubility of less than 0.1% by weight in 100 g of water.
Prinzipiell können alle aus dem Stand der Technik bekannten wachsartigen Entschäumersubstanzen zusätzlich enthalten sein. Geeignete wachsartige Verbindungen sind beispielsweise Bisamide, Fettalkohole, Fettsäuren, Carbonsäureester von ein- und mehrwertigen Alkoholen sowie Paraffinwachse oder Mischungen derselben. Geeignet sind Bisamide, die sich von gesättigten Fettsäuren mit 12 bis 22, vorzugsweise 14 bis 18 C- Atomen sowie von Alkylendia- minen mit 2 bis 7 C-Atomen ableiten. Geeignete Fettsäuren sind Laurin-, Myristin-, Stearin-, Arachin- und Behensäure sowie deren Gemische, wie sie aus natürlichen Fetten beziehungsweise gehärteten Ölen, wie Talg oder hydriertem Palmöl, erhältlich sind. Geeignete Diamine sind beispielsweise Ethylendiamin, 1,3-Propylendiamin, Tetramethylendiamin, Pentamethy- lendiamin, Hexamethylendiamin, p-Phenylendiamin und Toluylendiamin. Bevorzugte Diamine sind Ethylendiamin und Hexamethylendiamin. Besonders bevorzugte Bisamide sind Bis-myristoyl-ethylendiamin, Bis-palmitoyl-ethylendiamin, Bis-stearoylethylendiamin und deren Gemische sowie die entsprechenden Derivate des Hexamethylendiamins.In principle, all wax-like defoamer substances known from the prior art can additionally be contained. Suitable waxy compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohols, and paraffin waxes or mixtures thereof. Bisamides are suitable which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18 C atoms and from alkylenediamines with 2 to 7 C atoms. Suitable fatty acids are lauric, myristic, stearic, Arachinic acid and behenic acid as well as their mixtures as they are available from natural fats or hardened oils such as tallow or hydrogenated palm oil. Suitable diamines are, for example, ethylene diamine, 1,3-propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, p-phenylene diamine and toluene diamine. Preferred diamines are ethylenediamine and hexamethylenediamine. Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bis-palmitoyl-ethylenediamine, bis-stearoylethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.
Geeignete Carbonsäureester leiten sich von Carbonsäuren mit 12 bis 28 Kohlenstoffatomen ab. Insbesondere handelt es sich um Ester von Behensäure, Stearinsäure, Ölsäure, Palmitin- säure, Myristinsäure und/oder Laurinsäure.Suitable carboxylic acid esters are derived from carboxylic acids with 12 to 28 carbon atoms. In particular, these are esters of behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid.
Der Alkoholteil des Carbonsäureesters enthält einen ein- oder mehrwertigen Alkohole mit 1 bis 28 Kohlenstoffatomen in der Kohlenwasserstoffkette. Beispiele von geeigneten Alkoholen sind Behenylalkohol, Arachidylalkohol, Kokosalkohol, 12-Hydroxystearylalkohol, Oleylalkohol und Laurylalkohol sowie Ethylenglykol, Glycerin, Methanol, Ethanol, Isopropanol, Vinylalkohol, Saccharose, Erythrit, Pentaerythrit, Sorbitan und/oder Sorbit. Bevorzugte Ester sind solche von Methanol, Ethylenglykol, Glycerin und Sorbitan, wobei der Säureteil des Esters insbesondere aus Behensäure, Stearinsäure, Ölsäure, Palmitinsäure oder Myristinsäure ausgewählt wird.The alcohol part of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain. Examples of suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, methanol, ethanol, isopropanol, vinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol. Preferred esters are those of methanol, ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
In Frage kommende Ester mehrwertiger Alkohole sind beispielsweise Xylitmonopalmitat, Pentarythritmonostearat, Glycerinmonostearat, Ethylenglykolmonostearat und Sorbitan- monostearat, Sorbitanpalmitat, Sorbitanmonolaurat, Sorbitandilaurat, Sorbitandistearat, Sorbitandibehenat, Sorbitandioleat sowie gemischte Talgalkylsorbitanmono- und -diester. Brauchbare Glycerinester sind die Mono-, Di- oder Triester von Glycerin und genannten Carbonsäuren, wobei die Mono- oder Dieester bevorzugt sind. Glycerinmonostearat, Glycerinmonooleat, Glycerinmonopalmitat, Glycerinmonobehenat und Glycerindistearat sind Beispiele hierfür.Suitable esters of polyvalent alcohols include xylitol monopalmitate, Pentarythritmonostearat, glycerol, ethylene glycol and sorbitan monostearate, sorbitan, sorbitan Sorbitandilaurat, sorbitan, sorbitan dioleate, and also mixed tallowalkyl and diesters. Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred. Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this.
Beispiele für geeignete natürliche Ester sind Bienenwachs, das hauptsächlich aus den Estern CH3(CH2)24COO(CH2)27CH3 und CH3(CH2)26COO(CH2)25CH3 besteht, und Carnauba- wachs, das ein Gemisch von Carnaubasäurealkylestern, oft in Kombination mit geringen Anteilen freier Camaubasäure, weiteren langkettigen Säuren, hochmolekularen Alkoholen und Kohlenwasserstoffen, ist.Examples of suitable natural esters are beeswax, which mainly consists of the esters CH 3 (CH2) 24COO (CH 2 ) 27CH3 and CH3 (CH 2 ) 26COO (CH 2 ) 25CH3, and carnauba wax, which is a mixture of alkyl carnauba acids, often in combination with low Free camauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.
Geeignete Carbonsäuren als weitere Entschäumerverbindung sind insbesondere Behensäure, Stearinsäure, Ölsäure, Palmitinsäure, Myristinsäure und Laurinsäure sowie deren Gemische, wie sie aus natürlichen Fetten bzw. gegebenenfalls gehärteten Ölen, wie Talg oder hydriertem Palmöl, erhältlich sind. Bevorzugt sind gesättigte Fettsäuren mit 12 bis 22, insbesondere 14 bis 18 C-Atomen.Suitable carboxylic acids as a further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid and mixtures thereof, as can be obtained from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil. Saturated fatty acids with 12 to 22, in particular 14 to 18, carbon atoms are preferred.
Geeignete Fettalkohole als weitere Entschäumerverbindung sind die hydrierten Produkte der beschriebenen Fettsäuren.Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of the fatty acids described.
Das im Sinne der Erfindung bevorzugte Paraffinwachs als weitere Entschäumerverbindung stellt im allgemeinen ein komplexes Stoffgemisch ohne scharfen Schmelzpunkt dar. Zur Charakterisierung bestimmt man üblicherweise seinen Schmelzbereich durch Differential- Thermo-Analyse (DTA), wie in "The Analyst" 87 (1962), 420, beschrieben, und/oder seinen Erstarrungspunkt. Darunter versteht man die Temperatur, bei der das Paraffin durch langsames Abkühlen aus dem flüssigen in den festen Zustand übergeht. Dabei sind bei Raumtemperatur vollständig flüssige Paraffine, das heißt solche mit einem Erstarrungspunkt unter 25 °C, erfindungsgemäß nicht brauchbar. Eingesetzt werden können beispielsweise die aus EP 309 931 bekannten Paraffinwachsgemische aus beispielsweise 26 Gew.-% bis 49 Gew.-% mikrokristallinem Paraffinwachs mit einem Erstarrungspunkt von 62 °C bis 90 °C, 20 Gew.-% bis 49 Gew.-% Hartparaffin mit einem Erstarrungspunkt von 42 °C bis 56 °C und 2 Gew.-% bis 25 Gew.-% Weichparaffin mit einem Erstarrungspunkt von 35 °C bis 40 °C. Vorzugsweise werden Paraffine bzw. Paraffingemische verwendet, die im Bereich von 30 °C bis 90 °C erstarren. Dabei ist zu beachten, daß auch bei Raumtemperatur fest erscheinende Paraffinwachsgemische unterschiedliche Anteile an flüssigem Paraffin enthalten können. Bei den erfindungsgemäß brauchbaren Paraffinwachsen liegt dieser Flüssiganteil so niedrig wie möglich und fehlt vorzugsweise ganz. So weisen besonders bevorzugte Paraffinwachsgemische bei 30 °C einen Flüssiganteil von unter 10 Gew.-%, insbesondere von 2 Gew.-% bis 5 Gew.-%, bei 40 °C einen Flüssiganteil von unter 30 Gew.-%, vorzugsweise von 5 Gew.-% bis 25 Gew.-% und insbesondere von 5 Gew.-% bis 15 Gew.-%, bei 60 °C einen Flüssiganteil von 30 Gew.-% bis 60 Gew.-%, insbesondere von 40 Gew.-% bis 55 Gew.-%, bei 80 °C einen Flüssiganteil von 80 Gew.-% bis 100 Gew.-%, und bei 90 °C einen Flüssiganteil von 100 Gew.-% auf. Die Temperatur, bei der ein Flüssiganteil von 100 Gew.-% des Paraffinwachses erreicht wird, liegt bei besonders bevorzugten Paraffinwachsgemischen noch unter 85 °C, insbesondere bei 75 °C bis 82 °C.The paraffin wax preferred as a further defoamer compound in the sense of the invention generally represents a complex mixture of substances without a sharp melting point. For characterization, its melting range is usually determined by differential thermal analysis (DTA), as in "The Analyst" 87 (1962), 420 , described, and / or its freezing point. This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., cannot be used according to the invention. For example, the paraffin wax mixtures known from EP 309 931 of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C. to 90 ° C., 20% by weight to 49% by weight hard paraffin can be used with a solidification point of 42 ° C to 56 ° C and 2 wt .-% to 25 wt .-% soft paraffin with a solidification point of 35 ° C to 40 ° C. Paraffins or paraffin mixtures which solidify in the range from 30 ° C. to 90 ° C. are preferably used. It should be noted that even paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin. In the paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably absent entirely. Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably of 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular 40% by weight % to 55 wt .-%, at 80 ° C a Liquid content of 80 wt .-% to 100 wt .-%, and at 90 ° C a liquid content of 100 wt .-%. The temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C. in particularly preferred paraffin wax mixtures, in particular at 75 ° C. to 82 ° C.
Im Sinne der Erfindung werden insbesondere die Paraffinwachse der geschilderten Art eingesetzt.For the purposes of the invention, paraffin waxes of the type described are used in particular.
Verfahrenmethod
Im Sinne der vorliegenden Erfindung wird zunächst ein Vorprodukt aus den Trägermaterialien und den ggf. enthaltenen wachsartigen Entschäumersubstanzen hergestellt. Sofern das Vorprodukt zusätzlich wachsartige Entschäumersubstanzen enthält, beträgt der Gewichtsanteil an Trägermaterialien vorzugsweise 20 bis 98 Gew.-%, insbesondere 35 bis 95 Gew.-%, und der der wachsartigen Entschäumersubstanzen vorzugsweise 2 bis 80 Gew.-%, insbesondere 5 bis 65 Gew.-% - berechnet auf Vorprodukt.For the purposes of the present invention, a preliminary product is first produced from the carrier materials and the wax-like defoamer substances which may be present. If the preliminary product also contains wax-like defoamer substances, the weight fraction of carrier materials is preferably 20 to 98% by weight, in particular 35 to 95% by weight, and that of the wax-like defoamer substances is preferably 2 to 80% by weight, in particular 5 to 65% by weight .-% - calculated on preliminary product.
Im Sinne der Erfindung kann das Vorprodukt als Feststoff oder als wäßrige Lösung bzw. als wäßrige Aufschlämmung eingesetzt werden. Es ist bevorzugt, das Vorprodukt als wäßrige Lösung bzw. als wäßrige Aufschlämmung (Slurries) einzusetzen. Sofern das Vorprodukt noch zusätzlich wachsartige Entschäumersubstanzen enthält, können diese in einer wäßrigen Lösung bzw. Aufschlämmung des Trägermaterials dispergiert werden. Der Dispersion kann ein wasserlöslicher, nichttensidischer Dispersionsstabilisator in Form eines in Wasser quellfähigen Polymeren zugesetzt werden. Beispiele hierfür sind die genannten Celluloseether, Homo- und Copolymere von ungesättigten Carbonsäuren, wie Acrylsäure, Maleinsäure und copolymerisierbaren Vinylverbindungen, wie Vinylether, Acrylamid und Ethylen. Der Zusatz an derartigen als Dispersionsstabilisatoren wirkenden Verbindungen in der wäßrigen Aufschlämmung beträgt vorzugsweise nicht über 5 Gew.-%, insbesondere 1 Gew.-% bis 3 Gew.-%, bezogen auf das entstehende Vorprodukt. Der Wassergehalt des Slurries kann je nach Art beziehungsweise Löslichkeit der Trägermaterialien 30 Gew.-% bis 60 Gew.-% betragen. Gemäß einer weiteren Ausfuhrungsform der vorliegenden Erfindung kann das Vorprodukt auch als Feststoff eingesetzt werden. Für die Herstellung des Feststoffes kann zum einen der vorher beschriebene Slurry aus Trägermaterialien und ggf. weiteren wachsartigen Entschäumersubstanzen einer Trocknung im Sprühturm oder aber auch einer gleichzeitigen Trockung und Granulierung in der Wirbelschicht nach dem SKET- Verfahren beispielsweise gemäß der Europäischen Patentschrift EP-B- 603 207 oder nach dem Fließbettverfahren unterzogen werden. Es ist aber auch möglich den Feststoff durch Vermischen der festen Trägermaterialien mit den ggf. vorhandenen wachsartigen Entschäumersubstanzen beispielsweise in einem Schugi-Mischer herzustellen. Bei der letzten Variante empfiehlt es sich, die wachsartigen Entschäumersubstanzen vor dem Vermischen durch Erwärmen in die Schmelze zu überführen, damit eine möglichst homogene Vermischung mit den Trägermaterialien erreicht wird.For the purposes of the invention, the intermediate product can be used as a solid or as an aqueous solution or as an aqueous slurry. It is preferred to use the preliminary product as an aqueous solution or as an aqueous slurry (slurries). If the preliminary product additionally contains wax-like defoamer substances, these can be dispersed in an aqueous solution or slurry of the carrier material. A water-soluble, non-surfactant dispersion stabilizer in the form of a water-swellable polymer can be added to the dispersion. Examples of these are the cellulose ethers mentioned, homo- and copolymers of unsaturated carboxylic acids, such as acrylic acid, maleic acid and copolymerizable vinyl compounds, such as vinyl ether, acrylamide and ethylene. The addition of such compounds which act as dispersion stabilizers in the aqueous slurry is preferably not more than 5% by weight, in particular 1% by weight to 3% by weight, based on the resulting precursor. Depending on the type or solubility of the carrier materials, the water content of the slurry can be 30% by weight to 60% by weight. According to a further embodiment of the present invention, the preliminary product can also be used as a solid. For the production of the solid, on the one hand the previously described slurry of carrier materials and possibly further wax-like defoamer substances can be dried in the spray tower or else simultaneous drying and granulation in the fluidized bed using the SKET process, for example in accordance with European Patent EP-B-603 207 or by the fluidized bed process. However, it is also possible to produce the solid by mixing the solid carrier materials with the wax-like defoamer substances which may be present, for example in a Schugi mixer. In the last variant, it is advisable to transfer the wax-like defoamer substances into the melt by heating before mixing, so that the most homogeneous possible mixture with the carrier materials is achieved.
Die gleichzeitige Trocknung und Granulierung der Entschäumergranulate erfolgt vorzugsweise in einem horizontal angeordneten Dünnschichtverdampfer mit rotierenden Einbauten, wie er z.B. von der Firma VRV unter der Bezeichnung „Flashdryer" vertrieben wird. Hierbei handelt es sich, vereinfacht dargestellt, um ein Rohr, das über mehrere Zonen hinweg unterschiedlich temperiert werden kann. Über eine oder mehrere Wellen, die mit Blättern oder Flugscharen als rotierende Einbauten versehen sind, wird das Vorprodukt eindosiert , mit der über eine oder mehrere Düsen eingesprühte wäßrige Silikon-Emulsion besprüht und gegen die beheizte Wandung geschleudert, an der die Trocknung in einer dünnen Schicht von typischerweise 1 bis 10 mm Stärke erfolgt. Sofern die Vorprodukte als Slurry eingesetzt werden, erfolgt die Eindosierung über eine Pumpe. Im Sinne der Erfindung hat es sich als vorteilhaft erwiesen, an den Dünnschichtverdampfer einen Temperaturgradienten von 170 (Produkteinlaß) auf 20°C (Produktaustrag) anzulegen. Hierzu können beispielsweise die beiden ersten Zonen des Verdampfers auf 160°C geheizt und die letzte auf 20°C gekühlt werden. Der Dünnschichtverdampfer wird bei atmosphärischem Druck betrieben und im Gegenstrom mit Luft (Durchsatz 50 bis 150 m3/h) begast. Die Eintrittstemperatur des Gases liegt in der Regel bei 20 bis 30, die Austrittstemperatur bei 90 bis 110°C. Die Durchsatzmenge ist natürlich von der Größe des Trockners abhängig, liegt jedoch typischerweise bei 5 bis 15 kg/h. Es empfiehlt sich, die wäßrige Aufschlämmung des Vorproduktes (Slurry) bei der Einspeisung auf 40 bis 60°C zu temperieren. Des weiteren ist es von besonderem Vorteil, die wäßrigen Silikon- Emulsionen auf 45 bis 65 °C zu temperieren. Die Produktströme an wäßrigen Silikon-Emulsion und zudosiertem Vorprodukt werden dabei so gesteuert, daß sich Entschäumergranulate ergeben, die vorzugsweise 2,0 bis 25 Gew.-%, insbesondere 5,0 bis 20 Gew.-% Silikon - berechnet als Silikon und bezogen auf Entschäumergranulat - enthalten. Der zu 100 Gew.-% fehlende Rest des Entschäumergranulats ergibt sich aus dem Vorprodukt.The simultaneous drying and granulation of the defoamer granules is preferably carried out in a horizontally arranged thin-film evaporator with rotating internals, as it is sold, for example, by the company VRV under the name "Flashdryer". In simple terms, this is a tube that spans several zones The preliminary product is metered in via one or more shafts, which are provided with blades or shares of flies as rotating internals, sprayed with the aqueous silicone emulsion sprayed in via one or more nozzles and flung against the heated wall on the the drying takes place in a thin layer of typically 1 to 10 mm thickness. If the preliminary products are used as a slurry, the metering is carried out by means of a pump. In the sense of the invention, it has proven to be advantageous to apply a temperature gradient of 170 (product inlet ) a at 20 ° C (product discharge). For this purpose, for example, the first two zones of the evaporator can be heated to 160 ° C and the last can be cooled to 20 ° C. The thin film evaporator is operated at atmospheric pressure and gassed in countercurrent with air (throughput 50 to 150 m 3 / h). The gas inlet temperature is usually 20 to 30 ° C, the outlet temperature 90 to 110 ° C. The throughput is of course dependent on the size of the dryer, but is typically 5 to 15 kg / h. It is advisable to temper the aqueous slurry of the preliminary product (slurry) to 40 to 60 ° C. during the feed. Furthermore, it is particularly advantageous to increase the aqueous silicone emulsions to 45 to 65 ° C temper. The product streams of aqueous silicone emulsion and metered preliminary product are controlled so that defoamer granules are obtained, which are preferably 2.0 to 25% by weight, in particular 5.0 to 20% by weight, of silicone - calculated as silicone and based on Defoamer granules - included. The remaining 100% by weight of the defoamer granulate results from the preliminary product.
Nach der Trocknung hat es sich weiterhin als sehr vorteilhaft erwiesen, die noch etwa 50 bis 70°C heißen Granulate auf ein Förderband, vorzugsweise eine Schwingwelle zu geben und dort rasch, d.h. innerhalb einer Verweilzeit von 20 bis 60 s, mit Umgebungsluft auf Temperaturen von etwa 30 bis 40°C abzukühlen. Zur weiteren Verbesserung der Beständigkeit gegenüber unerwünschter Wasseraufnahme kann man die Granulate auch anschließend durch Zugabe von 0,5 bis 2 Gew.-% Kieselsäure abpudern.After drying, it has also proven to be very advantageous to place the granules, which are still around 50 to 70 ° C, on a conveyor belt, preferably an oscillating shaft, and to place them there quickly, i.e. cool within a dwell time of 20 to 60 s with ambient air to temperatures of around 30 to 40 ° C. To further improve the resistance to undesired water absorption, the granules can also subsequently be powdered by adding 0.5 to 2% by weight of silica.
Im Sinne der vorliegenden Erfindung werden die Entschäumergranulate als getrocknet betrachtet, sofern der Gehalt an freiem Wasser unter 10 Gew.-%, vorzugsweise von 0,1 bis 2 Gew. -%, jeweils bezogen auf die fertigen Granulate, beträgt.For the purposes of the present invention, the defoamer granules are regarded as dried if the free water content is below 10% by weight, preferably from 0.1 to 2% by weight, based in each case on the finished granules.
Die nach dem erfindungsgemäßen Verfahren hergestellten Entschäumergranulate sind leicht fließende Produkte , die nicht stauben. Sie zeigen eine gute entschäumende Wirkung und sind sowohl in sprühgetrockneten als auch in granulierten Waschmitteln einsetzbar.The defoamer granules produced by the process according to the invention are easy-flowing products which do not dust. They have a good defoaming effect and can be used in both spray-dried and granulated detergents.
Ein weiterer Gegenstand der vorliegenden Erfindung betrifft die Verwendung der erfindungsgemäß hergestellten Entschäumergranulate zur Herstellung von festen Waschmitteln.Another object of the present invention relates to the use of the defoamer granules produced according to the invention for the production of solid detergents.
Die Entschäumergranulate können in Mengen von 0,2 bis 7,0 Gew.-%, bevorzugt in Mengen von 0,5 bis 4,0 Gew.-% - bezogen auf Waschmittel - enthalten sein. Des weiteren können die Waschmittel übliche anionische, nichtionische oder kationische Tenside, sowie weitere übliche Bestandteile in üblichen Mengen enthalten. Als übliche Bestandteile können die Waschmittel Enthärter wie Tripolyphosphat oder Zeolith, sowie ggf. Bleichmittel wie Perborat oder Percarbonat in üblichen Mengen enthalten. Die Entschäumergranulate können auf einfache Weise untergemischt werden. B e i s p i e l eThe defoamer granules can be present in amounts of 0.2 to 7.0% by weight, preferably in amounts of 0.5 to 4.0% by weight, based on the detergent. Furthermore, the detergents can contain customary anionic, nonionic or cationic surfactants, as well as other customary constituents in customary amounts. The detergents can contain softening agents such as tripolyphosphate or zeolite, as well as bleaching agents such as perborate or percarbonate in customary amounts as usual components. The defoamer granules can easily be mixed in. Examples
I. Herstellung eines wachsartigen Entschäumersubstanz enthaltenden VorproduktsI. Production of a Wax-like Defoamer Containing Pre-Product
Beispiel 1 Vorprodukt als SlurryExample 1 Pre-product as a slurry
Es wurde ein wäßriger Slurry bestehend aus 0,5 Gew.-% Celluloseether, 5,0 Gew.-% Natriumsilikat, 20,7 Gew.-% Natriumsulfat, 15,8 Gew.-% Natriumcarbonat, 2,0 % Po- lyacryl/methacrylat, 50 Gew.-% Wasser und Gew. 6 % eines Paraffinwachsgemisches bestehend aus 40 Gew. % Paraffin mit einem Erstarrungspunkt von 62 °C bis 90 °C, 30 Gew.-% Hartparaffin mit einem Erstarrungspunkt von 42 °C bis 56 °C und 30 Gew-% Weichparaffm mit einem Erstarrungspunkt von 35 °C bis 40 °C wurde unter ständigem Homogenisieren hergestellt.An aqueous slurry consisting of 0.5% by weight of cellulose ether, 5.0% by weight of sodium silicate, 20.7% by weight of sodium sulfate, 15.8% by weight of sodium carbonate, 2.0% of polyacrylic was obtained / methacrylate, 50% by weight water and 6% by weight of a paraffin wax mixture consisting of 40% by weight paraffin with a solidification point from 62 ° C. to 90 ° C., 30% by weight hard paraffin with a solidification point from 42 ° C. to 56 ° C and 30 wt .-% soft paraffin with a solidification point of 35 ° C to 40 ° C was produced with constant homogenization.
Beispiel 2 : Vorprodukt als SlurryExample 2: preliminary product as a slurry
Es wurde ein wäßriger Slurry bestehend aus 0,5 Gew.-% Celluloseether, 2,0 Gew.-% Natriumsilikat, 13 Gew.-% Natriumsulfat, 23,5 Gew.-% Zeolith, 2,0 Gew.-% Po- lyacryl/methacrylat, 50 Gew.-% Wasser, 7 Gew.-% Paraffin mit einem Erstarrungspunkt von 62 °C bis 90 °C und 2 Gew. % Bis-stearylethylendiamid wurde unter ständigem Homogenisieren hergestellt.An aqueous slurry consisting of 0.5 wt.% Cellulose ether, 2.0 wt.% Sodium silicate, 13 wt.% Sodium sulfate, 23.5 wt.% Zeolite, 2.0 wt. lyacryl / methacrylate, 50% by weight of water, 7% by weight of paraffin with a solidification point of 62 ° C. to 90 ° C. and 2% by weight of bis-stearylethylenediamide was prepared with constant homogenization.
Beispiel 3 : Vorprodukt als TurmpulverExample 3: Pre-product as tower powder
25.000 kg eines wäßrigen Slurry bestehend aus 0,5 Gew.-% Celluloseether, 3,0 Gew.-% Natriumsilikat, 18,0 Gew.-% Natriumsulfat, 19,0 Gew.-% Natriumcarbonat, 2,0 % Po- lyacryl/methacrylat, 52,5 Gew.-% Wasser und 5,0 % Gew. eines Paraffmwachsgemisches bestehend aus 45 Gew. % Paraffin mit einem Erstarrungspunkt von 62 °C bis 90 °C, 25 Gew.-% Hartparaffm mit einem Erstarrungspunkt von 42 °C bis 56 °C und 20 Gew-% Weichparaffin mit einem Erstarrungspunkt von 35 °C bis 40 °C wurde unter ständigem Homogenisieren unter einem Druck von 40 bar in einem Sprühturm zerstäubt und mittels heißer, im Gegenstrom geführter Verbrennungsgase (Temperatur im Ringkanal 250 °C, im Turmaustritt 105°C) getrocknet. II. Herstellung der wäßrigen Silikon-Emulsion25,000 kg of an aqueous slurry consisting of 0.5% by weight cellulose ether, 3.0% by weight sodium silicate, 18.0% by weight sodium sulfate, 19.0% by weight sodium carbonate, 2.0% polyacrylic / methacrylate, 52.5% by weight of water and 5.0% by weight of a paraffin wax mixture consisting of 45% by weight of paraffin with a solidification point from 62 ° C. to 90 ° C., 25% by weight of hard paraffin with a solidification point of 42 ° C to 56 ° C and 20% by weight soft paraffin with a solidification point of 35 ° C to 40 ° C was atomized with constant homogenization under a pressure of 40 bar in a spray tower and by means of hot, countercurrent combustion gases (temperature in the ring channel 250 ° C, in the tower outlet 105 ° C) dried. II. Preparation of the aqueous silicone emulsion
Beispiel 4Example 4
2000 kg einer wäßrigen Lösung, enthaltend 3,7 Gew.-% einer Verdickermischung aus Na- trium-Carboxymethylcellulose und Methylcellulose im Gewichtsverhältnis 70 : 30 wurden 4 Stunden bei 25 °C quellen gelassen. Zu dieser Lösung wurden 20 Gew.-% eines Polysiloxan- Entschäumers (Polydimethylsiloxan mit mikrofeiner silanierter Kieselsäure) zugesetzt. Man erhielt eine stabile wäßrige Emulsion.2000 kg of an aqueous solution containing 3.7% by weight of a thickener mixture of sodium carboxymethyl cellulose and methyl cellulose in a weight ratio of 70:30 were left to swell at 25 ° C. for 4 hours. 20% by weight of a polysiloxane defoamer (polydimethylsiloxane with microfine silanized silica) were added to this solution. A stable aqueous emulsion was obtained.
Beispiel 5Example 5
2000 kg einer wäßrigen Lösung, enthaltend 3,7 Gew.-% einer Verdickermischung aus Na- trium-Carboxymethylcellulose und Methylcellulose im Gewichtsverhältnis 70 : 30) wurden 4 Stunden bei 25 C quellen gelassen. Zu dieser Lösung wurden 30 Gew.-% Maisstärke und 20 Gew.-% eines Polysiloxan-Entschäumers (Polydimethylsiloxan mit mikrofeiner silanierter Kieselsäure) zugesetzt. Man erhielt eine stabile wäßrige Emulsion.2000 kg of an aqueous solution containing 3.7% by weight of a thickener mixture of sodium carboxymethyl cellulose and methyl cellulose in a weight ratio of 70:30) were allowed to swell at 25 ° C. for 4 hours. 30% by weight of corn starch and 20% by weight of a polysiloxane defoamer (polydimethylsiloxane with microfine silanized silica) were added to this solution. A stable aqueous emulsion was obtained.
Beispiel 6Example 6
5.000 kg einer wäßrigen Lösung, enthaltend 4,0 Gew.-% einer Verdickermischung aus Na- trium-Carboxymethylcellulose und Methylcellulose im Gewichtsverhältnis 70 : 30 wurden 4 Stunden bei 25 °C quellen gelassen. Zu dieser Lösung wurden 22 Gew.-% eines Polysiloxan- Entschäumers (Polydimethylsiloxan mit mikrofeiner silanierter Kieselsäure) zugesetzt. Man erhielt eine stabile wäßrige Emulsion.5,000 kg of an aqueous solution containing 4.0% by weight of a thickener mixture of sodium carboxymethyl cellulose and methyl cellulose in a weight ratio of 70:30 were left to swell at 25 ° C. for 4 hours. 22% by weight of a polysiloxane defoamer (polydimethylsiloxane with microfine silanized silica) were added to this solution. A stable aqueous emulsion was obtained.
III. Herstellung der Granulate im DünnschichtverdampferIII. Production of the granules in a thin film evaporator
Beispiel 7Example 7
Die Herstellung der Granulate erfolgte in einem Flashdryer der VRV S.p.A., Mailand/IT. Es handelte sich hierbei um einen horizontal angeordneten Dünnschichtverdampfer (Länge 1100 mm, Innendurchmesser : 155 mm) mit 4 Wellen und 22 Blättern, deren Abstand zur Wandung 2 mm betrug. Der Trockner besaß drei separate Heiz- bzw. Kühlzonen und eine Wärmeaustauscherfläche von insgesamt 0,44 m2. Der Betrieb erfolgte bei Normaldruck. Über eine Schwingpumpe wurden insgesamt 10 000 kg eines auf 50°C temperierten Slurries des Vorproduktes nach Beispiel 1 mit einem Durchsatz von 11,5 kg/h in den Dünnschichtverdampfer gepumpt, dessen Heizzonen 1 und 2 auf 160°C und dessen Kühlzone 3 auf 20°C eingestellt worden waren. Direkt bei Eintritt in das Rohr wurde der Slurry besprüht mit insgesamt 2000 kg der wäßrigen Silikon-Emulsion nach Beispiel 4. Die Geschwindigkeit der Rotoren betrug 24 m s. Der Flashdryer wurde mit Luft (ca. 110 m3/h) begast; die Gasaustrittstemperatur betrug ca. 65°C. Das vorgetrocknete, noch etwa 60°C heiße Granulat wurde auf eine Schwingrinne (Länge 1 m) gegeben, mit Raumluft begast und innerhalb von 30 s auf etwa 40°C abgekühlt.The granules were produced in a flash dryer from VRV SpA, Milan / IT. It was a horizontally arranged thin film evaporator (length 1100 mm, inside diameter: 155 mm) with 4 shafts and 22 blades, the distance to the wall of which was 2 mm. The dryer had three separate heating or cooling zones and a total heat exchanger area of 0.44 m 2 . The operation was carried out at normal pressure. A total of 10,000 kg of a slurry of the preliminary product according to Example 1, heated to 50.degree. C. and with a throughput of 11.5 kg / h, were introduced into the Pumped thin film evaporator, the heating zones 1 and 2 had been set to 160 ° C and the cooling zone 3 to 20 ° C. As soon as it entered the tube, the slurry was sprayed with a total of 2000 kg of the aqueous silicone emulsion according to Example 4. The speed of the rotors was 24 ms. The flash dryer was gassed with air (approx. 110 m 3 / h); the gas outlet temperature was approx. 65 ° C. The pre-dried, still about 60 ° C hot granules were placed on a vibrating trough (length 1 m), gassed with room air and cooled to about 40 ° C within 30 s.
Man erhielt ein Granulat mit folgender Zusammensetzung: 7 Gew.-% Silikon, 2,2 Gew.-% Celluloseether, 9,2 Gew.-% Natriumsilikat, 38,0 Gew.-% Natriumsulfat, 29,1 Gew.-% Natriumcarbonat, 3,7 Gew.-% Polyacryl/methacrylat und 11,0 Gew.-% eines Paraffinwachsgemisches bestehend aus 40 % Paraffin mit einem Erstarrungspunkt von 62 °C bis 90 °C, 30 Gew.-% Hartparaffin mit einem Erstarrungspunkt von 42 °C bis 56 °C und 30 Gew% Weichparaffin mit einem Erstarrungspunkt von 35 °C bis 40 °C. Das Produkt zeigte eine sehr gute Rieselfähigkeit und hatte keinerlei Staubanteile.Granules having the following composition were obtained: 7% by weight of silicone, 2.2% by weight of cellulose ether, 9.2% by weight of sodium silicate, 38.0% by weight of sodium sulfate, 29.1% by weight of sodium carbonate , 3.7 wt .-% polyacrylic / methacrylate and 11.0 wt .-% of a paraffin wax mixture consisting of 40% paraffin with a setting point of 62 ° C to 90 ° C, 30 wt .-% hard paraffin with a setting point of 42 ° C to 56 ° C and 30% by weight soft paraffin with a solidification point of 35 ° C to 40 ° C. The product showed very good flow properties and had no dust content.
Beispiel 8Example 8
Entsprechend Beispiel 7 wurde der wäßrige Slurry des Vorprodukts nach Beispiel 2 mit der wäßrigen Silikon - Emulsion nach Beispiel 5 besprüht und weiterverarbeitet. Man erhielt ein Granulat mit folgender Zusammensetzung: 7 Gew.-% Silikon, 10,3 Gew.-% Stärke, 2,1 Gew.- % Celluloseether, 3,2 Gew.-% Natriumsilikat, 21,2 Gew.-% Natriumsulfat, 38,1 Gew.-% Zeolith, 3,3 Gew.-% Polyacryl/methacrylat, 11,5 Gew.-% Paraffin und 3,3 Gew.-% Bis- stearylethylendiamid. Das Produkt zeigte eine sehr gute Rieselfähigkeit und hatte keinerlei Staubanteile.According to Example 7, the aqueous slurry of the preliminary product according to Example 2 was sprayed with the aqueous silicone emulsion according to Example 5 and processed further. Granules having the following composition were obtained: 7% by weight of silicone, 10.3% by weight of starch, 2.1% by weight of cellulose ether, 3.2% by weight of sodium silicate, 21.2% by weight of sodium sulfate , 38.1% by weight of zeolite, 3.3% by weight of polyacrylic / methacrylate, 11.5% by weight of paraffin and 3.3% by weight of bisstearylethylenediamide. The product showed very good flow properties and had no dust content.
Beispiel 9Example 9
Entsprechend Beispiel 7 wurde das Vorprodukt als Turmpulver nach Beispiel 3 mit der wäßrigen Silikon- Emulsion nach Beispiel 6 besprüht und weiterverarbeitet. Über eine Schnecke wurden insgesamt 10 000 kg eines auf 50°C temperierten Vorproduktes mit einem Durchsatz von 11,5 kg/h in den Dünnschichtverdampfer befördert.According to Example 7, the preliminary product was sprayed as tower powder according to Example 3 with the aqueous silicone emulsion according to Example 6 and processed further. A total of 10,000 kg of a preliminary product heated to 50 ° C. were conveyed via a screw into the thin-film evaporator at a throughput of 11.5 kg / h.
Man erhielt ein Granulat mit folgender Zusammensetzung: 10,2 Gew.-% Silikon, 2,8 Gew.-% Celluloseether, 5,6 Gew.-% Natriumsilikat, 33,3 Gew.-% Natriumsulfat, 35,1 Gew.-% Natriumcarbonat, 3,7 Gew.-% Polyacryl/methacrylat und 9,3 Gew.-% eines Paraffinwachsgemisches bestehend aus 50 % Paraffin mit einem Erstarrungspunkt von 62 °C bis 90 °C, 25 Gew.-% Hartparaffin mit einem Erstarrungspunkt von 42 °C bis 56 °C und 25 Gew% Weichparaffm mit einem Erstarrungspunkt von 35 °C bis 40 °C mit einem Schüttgewicht von 760 g/1 und einer Kornverteilung von 0,1 bis 1,6 mm. Das Produkt zeigte eine gute Rieselfahigkeit und hatte < 1 % Staubanteile.Granules having the following composition were obtained: 10.2% by weight of silicone, 2.8% by weight of cellulose ether, 5.6% by weight of sodium silicate, 33.3% by weight of sodium sulfate, 35.1% by weight % Sodium carbonate, 3.7% by weight polyacrylic / methacrylate and 9.3% by weight of a paraffin wax mixture consisting of 50% paraffin with a solidification point from 62 ° C to 90 ° C, 25% by weight hard paraffin with a solidification point of 42 ° C to 56 ° C and 25% by weight soft paraffin with a solidification point of 35 ° C to 40 ° C with a bulk density of 760 g / 1 and a grain size distribution of 0.1 to 1.6 mm. The product showed good flow properties and had <1% dust content.
IV. Anwendungstechnische VersucheIV. Application tests
Die hergestellten Entschäumergranulate wurden in einer Menge von 1,5 Gew.-% durch einfaches Vermischen in eine pulverförmige Universalwaschmittelrezeptur mit 8 Gew.-% Natrium- Alkylbenzolsulfonat, 10 Gew.-% Alkylethoxylat, 1,5 Gew.-% Seife, 10 Gew.-% Natriumcarbonat, 20 Gew.-% Zeolith, 3 Gew.-% Natriumsilikat, 20 Gew.-% Natriumperborat, 2 Gew.-% Tetraacetylethylendiamin (TAED), 0,5 Gew.-% Protease, Rest auf 100 Gew.-% Natriumsulfat und Wasser eingearbeitet. Die erhaltenen Waschmittel wiesen einwandfreies Schaumverhalten sowohl bei 30 °C als auch bei 40 °C, 60 °C und 95 °C auf. The defoamer granules produced were mixed in an amount of 1.5% by weight by simply mixing them into a powdered universal detergent formulation with 8% by weight sodium alkylbenzenesulfonate, 10% by weight alkyl ethoxylate, 1.5% by weight soap, 10% by weight % Sodium carbonate, 20% by weight zeolite, 3% by weight sodium silicate, 20% by weight sodium perborate, 2% by weight tetraacetylethylene diamine (TAED), 0.5% by weight protease, balance to 100% by weight. -% sodium sulfate and water incorporated. The detergents obtained had perfect foaming behavior both at 30 ° C. and at 40 ° C., 60 ° C. and 95 ° C.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Verfahren zur Herstellung von Entschäumergranulaten für feste Waschmittel bestehend aus Trägermaterialien, Silikonen und ggf. in Wasser unlöslichen wachsartigen Entschäumersubstanzen, wobei man Silikone in Form wäßriger Emulsionen aufsprüht auf ein zugemischtes Vorprodukt aus Trägermaterialien und ggf. in Wasser unlöslichen wachsartigen Entschäumersubstanzen unter gleichzeitigem Trocknen und Granulieren in einem Dünnschichtverdampfer.1. A process for the preparation of defoamer granules for solid detergents consisting of carrier materials, silicones and, if appropriate, water-insoluble wax-like defoamer substances, silicones in the form of aqueous emulsions being sprayed onto a mixed precursor from carrier materials and, if appropriate, water-insoluble wax-like defoamer substances with simultaneous drying and Granulate in a thin film evaporator.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man Silikone in Form wäßriger Emulsionen kontinuierlich aufsprüht auf ein zugemischtes Vorprodukt aus Trägermaterialien und ggf. wachsartigen Entschäumersubstanzen unter gleichzeitigem Trocknen und Granulieren in einem horizontal angeordnetem Dünnschichtverdampfer mit rotierenden Einbauten, wobei man vorzugsweise an den Dünnschichtverdampfer vom Produkteingang bis zum Produktaustrag einen abnehmenden Temperaturgradienten anlegt, im Gegenstrom mit Luft begast und die Trocknung ausschließlich über die beheizte Wandung erfolgt.2. The method according to claim 1, characterized in that silicones in the form of aqueous emulsions are continuously sprayed onto an admixed precursor of carrier materials and optionally wax-like defoamer substances with simultaneous drying and granulation in a horizontally arranged thin-film evaporator with rotating internals, preferably on the thin-film evaporator create a decreasing temperature gradient from product receipt to product discharge, gassed with air in countercurrent and drying takes place exclusively via the heated wall.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man Polydisiloxane in Form ihrer wäßrigen Emulsionen aufsprüht.3. The method according to claim 1 or 2, characterized in that polydisiloxanes are sprayed on in the form of their aqueous emulsions.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man die Silikone in Form wäßriger Emulsionen aufsprüht, die ein anorganisches oder organisches Verdickungsmittel, vorzugsweise eine Mischung von Natrium-Carboxymethylcellulose und einem nichtionischen Celluloseether, insbesondere in Mengen von 0,5 bis 10 Gew.-% - bezogen auf wäßrige Silikon-Emulsion - enthalten.4. The method according to any one of claims 1 to 3, characterized in that the silicones are sprayed on in the form of aqueous emulsions containing an inorganic or organic thickener, preferably a mixture of sodium carboxymethyl cellulose and a nonionic cellulose ether, in particular in amounts of 0.5 up to 10 wt .-% - based on aqueous silicone emulsion - contain.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Silikone in Form wäßriger Emulsionen aufsprüht, die eine Mischung aus Natrium-Carboxymethylcellulose, einem nichtionischen Celluloseether in einem Gewichtsverhältnis von 80 : 20 bis 40 : 60 in Mengen von 0,5 bis 10 Gew.-% sowie 0,1 bis 50 Gew.-% Stärke, vorzugsweise native Stärke, - bezogen auf wäßrige Silikon-Emulsion - enthalten. 5. The method according to any one of claims 1 to 4, characterized in that the silicones are sprayed in the form of aqueous emulsions which contain a mixture of sodium carboxymethyl cellulose, a nonionic cellulose ether in a weight ratio of 80:20 to 40:60 in amounts of 0 , 5 to 10 wt .-% and 0.1 to 50 wt .-% starch, preferably native starch, based on aqueous silicone emulsion.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Silikone in Form wäßriger Emulsionen in Mengen von 5,5 bis 20,0 Gew.-% - berechnet als Silikon und bezogen auf Entschäumergranulat - aufsprüht.6. The method according to any one of claims 1 to 5, characterized in that the silicones in the form of aqueous emulsions in amounts of 5.5 to 20.0 wt .-% - calculated as silicone and based on defoamer granules - sprayed on.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man als Trägermaterial mindestens eine Verbindung ausgewählt aus der von Alkalicarbonate, Alkalisulfate, Alkaliphosphate, Zeolithe, Alkalisilikate, Cellulosether, Polycarboxylate und Stärke gebildeten Gruppe, einsetzt.7. The method according to any one of claims 1 to 6, characterized in that at least one compound selected from the group formed by alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, alkali metal silicates, cellulose ethers, polycarboxylates and starch is used as the carrier material.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man als wachsartige Entschäumersubstanzen mindestens eine Verbindung ausgewählt aus der von Bisamiden, Fettsäuren, Fettalkoholen, Carbonsäureester oder Paraffinwachse gebildeten Gruppe einsetzt.8. The method according to any one of claims 1 to 7, characterized in that at least one compound selected from the group formed by bisamides, fatty acids, fatty alcohols, carboxylic acid esters or paraffin waxes is used as wax-like defoamer substances.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man ein Vorprodukt zumischt bestehend aus 20 bis 98 Gew.-% Trägermaterialien und 2 bis 80 Gew.-% wachsartigen Entschäumersubstanzen.9. The method according to any one of claims 1 to 8, characterized in that a preliminary product is mixed consisting of 20 to 98 wt .-% carrier materials and 2 to 80 wt .-% wax-like defoamer substances.
10. Verwendung der nach Anspruch 1 hergestellten Entschäumergranulate zur Herstellung von festen Waschmitteln. 10. Use of the defoamer granules produced according to claim 1 for the production of solid detergents.
EP99941535A 1998-08-17 1999-08-07 Production of defoaming granulates in a thin-layer evaporator Expired - Lifetime EP1105453B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19837196A DE19837196A1 (en) 1998-08-17 1998-08-17 Producing defoaming granulate, for solid detergents, by spraying aqueous silicone emulsion onto pre-product mixture, while drying and granulating
DE19837196 1998-08-17
PCT/EP1999/005721 WO2000011126A1 (en) 1998-08-17 1999-08-07 Production of defoaming granulates in a thin-layer evaporator

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EP1105453A1 true EP1105453A1 (en) 2001-06-13
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ES2231122T3 (en) 1999-08-13 2005-05-16 Dow Corning S.A. SILICONE-BASED FOAM CONTROL AGENT.
DE60039559D1 (en) 1999-08-13 2008-09-04 Dow Corning Sa Silicone-containing foam control agent

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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
EP0771864A1 (en) * 1995-11-03 1997-05-07 The Procter & Gamble Company Granular suds suppressing component

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DE59903195D1 (en) 2002-11-28

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