EP1362090A1 - Foam regulating granulates - Google Patents

Foam regulating granulates

Info

Publication number
EP1362090A1
EP1362090A1 EP02722070A EP02722070A EP1362090A1 EP 1362090 A1 EP1362090 A1 EP 1362090A1 EP 02722070 A EP02722070 A EP 02722070A EP 02722070 A EP02722070 A EP 02722070A EP 1362090 A1 EP1362090 A1 EP 1362090A1
Authority
EP
European Patent Office
Prior art keywords
weight
paraffin wax
foam regulator
carrier material
acid
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
EP02722070A
Other languages
German (de)
French (fr)
Other versions
EP1362090B1 (en
Inventor
Volker Blank
René-Andres ARTIGA GONZALEZ
Ulrich Pegelow
Stefan Hammelstein
Adolf Wiche
Mario Sturm
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1362090A1 publication Critical patent/EP1362090A1/en
Application granted granted Critical
Publication of EP1362090B1 publication Critical patent/EP1362090B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/18—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones

Definitions

  • the invention relates to particulate foam regulating agents which can be used in washing or cleaning agents and to a process for their preparation.
  • EP 0 309 931 B1 describes particulate foam regulators which are suitable for use in detergents and cleaning agents and which consist of a water-soluble surfactant-free carrier material and a siloxane-free defoamer mixture of 5-60% by weight of soft and / or hard paraffin adsorbed thereon, 20-90% by weight of microcrystalline paraffin wax with a certain melting range and 5-20% by weight of one of C 2.7 diamines and C 12 . 22 fatty acids derived from diamids in finely divided form.
  • Such particulate foam control agents are produced by spray drying an aqueous slurry which contains the carrier material and the defoamer mixture.
  • the defoamer performance of the defoamer mixture is said to be inadequate when sprayed onto a particulate detergent.
  • foam-regulating homogeneous mixtures of nonionic surfactant and a foam regulator system which contains paraffin wax and bis fatty acid amides to improve the manufacturability and the product properties of extruded detergents and cleaning agents is known from international patent application WO 96/26258.
  • German published patent application DE 23 38 468 is a detergent containing a silicone defoamer, which is protected against interactions with the detergent components.
  • aqueous melts which contain the silicone defoamer and a carrier substance, for example polyglycol, are first spray-dried and the particles obtained are coated in a fluidized bed of a solid, water-soluble coating material Mistake. Salts which are customary in detergents, in particular tripolyphosphate or carboxymethyl cellulose, can be used as the coating material.
  • Such a multi-stage manufacturing process is comparatively technically complex.
  • German laid-open specification DE 31 28 631 describes the production of foam-damped detergents containing silicone defoamers which are microencapsulated.
  • the silicone is dispersed in an aqueous solution 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.
  • Suitable film-forming polymers are, for example, cellulose ethers, starch ethers or synthetic water-soluble polymers and mixtures thereof.
  • the microcapsules are formed spontaneously in the spray nozzle or by prior precipitation by adding electrolyte salts to the silicone dispersion.
  • the process described is inevitably linked to the production of spray-dried washing agents. This method of operation does not allow transfer to other detergents and cleaning agents produced by granulation or to other areas of application.
  • European patent application EP 097 867 describes a process for producing microencapsulated defoamer oils by mixing a silicone emulsion with an aqueous solution of carboxymethyl cellulose and precipitating the microcapsules by adding electrolytes, in particular polyvalent salts or organic solvents. There are considerable difficulties in homogeneously distributing the small amounts of silicone microcapsules required for adequate foam damping in a comparatively large amount of washing powder.
  • the German published publication DE 3436 194 describes a process for producing a pourable defoamer granulate by spray drying an aqueous defoamer dispersion containing film-forming polymers.
  • granules of the composition 1 to 10 wt .-% water-insoluble Defoamer, 0.2 to 2% by weight of a mixture of sodium carboxymethyl cellulose and methyl cellulose in a weight ratio of 80:20 to 40:60, 70 to 90% by weight of inorganic, water-soluble or dispersible carrier salts, the rest being water swell an aqueous solution containing 0.5 to 8% by weight of the cellulose ether mixture at a temperature of 15 to 60 ° C.
  • the defoaming agent is dispersed in this solution and, after addition of the carrier salts and optionally water, the homogenized dispersion is spray-dried.
  • Organopolysiloxanes, paraffins and mixtures of organopolysiloxanes and paraffins are used as defoaming agents.
  • the defoamer active ingredient content is 1 to 10% by weight, preferably 3 to 7% by weight.
  • the carrier salt preferably consists of a mixture of sodium silicate, sodium tripolyphosphate and sodium sulfate.
  • a process for producing powder detergents which contains at least 5% by weight of anionic surfactant, 20-80% by weight of aluminosilicate and paraffin wax which is essentially insoluble in water and anionic and nonionic surfactants, which comprises spraying or subsequently spraying the paraffin onto the prefabricated detergent particles as an essential process step.
  • the paraffin wax can also be used in the form of a mixture with nonionic surfactants.
  • the variant of spraying the paraffin onto a prefabricated powder detergent disclosed in the last-mentioned document can only be used with difficulty if the paraffin wax is not to be used alone but in combination with a bis-fatty acid amide which is known to enhance its foam-regulating action.
  • Such bis fatty acid amides are generally solid at room temperature and have a relatively high melting point, so that they or their combination with the paraffin can only be handled in liquid and sprayable form at an elevated temperature of, for example, about 140 ° C. If this temperature is undershot, the pipes and nozzles used may become blocked due to the solidification of the Bisfettklamids.
  • Another disadvantage is that such high temperatures of the spray material can lead to undesirable interactions with thermally sensitive components of the detergent.
  • an even distribution of the foam regulator system in the detergent is at risk if it cools down quickly as a highly heated spraying material after it hits the detergent powder.
  • the stability of the particles obtainable in this way is not always satisfactorily high. Rather, the transport and transport of the foam regulator particles can lead to their disintegration into smaller particles or powders, which still have a good foam-regulating effect, but cannot easily be incorporated evenly into particulate detergents or cleaning agents.
  • the present invention solves the problem of poor particle stability by adapting the carrier material.
  • the invention relates to a particulate foam control agent which can be used in detergents or cleaning agents and contains foam regulator active ingredient based on paraffin wax and / or silicone oil, nonionic and / or anionic emulsifier and solid carrier material, characterized in that the carrier material contains alkali carbonate and a Brßnsted acid.
  • the invention further relates to a process for the production of particulate foam regulator granules by spraying on an aqueous foam regulator emulsion, which contains 16% by weight to 70% by weight of foam regulator active substance based on paraffin wax and / or silicone oil, 2% by weight to 15% by weight of nonionic and / or anionic emulsifier and not more than 80% by weight of water, onto a solid carrier material, which is optionally followed by a drying step, which is characterized in that the carrier material contains alkali carbonate and a Bransted acid.
  • the Bransted acid is in solid form at 25 ° C. At 25 ° C it has a water solubility of preferably at least 100 g / 1. It is preferably selected from the di- and tricarboxylic acids, their acid salts, the acid salts of inorganic acids, in particular NaHSO 4 , a 2 HPO 4 and NaH 2 PO 4 , and their hybrids. In a preferred embodiment of the invention, the Bransted acid is citric acid.
  • the carrier material used in the process according to the invention contains alkali carbonate and a Bronsted acid, preferably in weight ratios of 1: 1 to 100: 1, in particular from 20: 3 to 80: 3.
  • the carrier material preferably has 40% by weight to 90% by weight, in particular 60% by weight to 80% by weight of alkali carbonate and 1-20% by weight, in particular 3% by weight to 9% by weight a Bransted acid.
  • the carrier material can consist solely of alkali carbonate and Bronsted acid or additionally contain further particulate constituents, solid and / or detergent constituents prepared in solid form being suitable.
  • These include, for example, customary powders produced by spray drying aqueous slurries of their ingredients, solid bleaching agents based on oxygen, for example alkali percarbonates or alkali perborates, which may be present as so-called monohydrates or tetrahydrates, powdered bleach activators, for example a tetraaminacetyl prepared by the process of European patent EP 0 037 026 Granules, anionic surfactant compounds not produced by conventional spray drying according to international patent application WO 93/04162 with a content of more than 80% by weight, in particular more than 90% by weight, of alkyl sulfate with alkyl chain lengths in the range from C 12 to C 18 , the Rest essentially are composed of inorganic salts and water, granular enzymes, for example an enzyme extru
  • the carrier material preferably has a combination of alkali hydrogen carbonate and alkali carbonate, the weight ratio of which is preferably 99: 1 to 10:90, in particular 95: 5 to 50:50.
  • the preferred alkali metal in the salts mentioned and also in the alkali carbonate is sodium.
  • a granulation mixer is used to carry out a build-up granulation in such a way that an amount of 40 to 110 parts by weight, in particular 60 to 90 parts by weight, of carrier material, which preferably additionally contains alkali metal sulfate and / or can contain alkali metal bicarbonate, mixes intensively and, while granulating, adds an amount of 15 to 50 parts by weight, in particular 25 to 35 parts by weight, of the foam regulator emulsion which has been heated to a temperature in the range from 70 ° C. to 180 ° C.
  • Small amounts of water, preferably not more than 10 parts by weight, in particular 1 to 5 parts by weight, of water can, if desired, also be added after or preferably before the addition of the foam regulator emulsion.
  • a paraffin wax base is understood in particular to be a combination of paraffin wax and bis fatty acid amide.
  • a foam regulator emulsion which can be used according to the invention preferably contains 15% by weight to 60% by weight, in particular 30% by weight to 50% by weight of paraffin wax or a mixture of paraffin wax and silicone oil, 1% by weight to 10% by weight , in particular 3% to 8% by weight of C 2 . 7 diamines and C 12 .
  • fatty acid-conducting bis fatty acid amide 2% by weight to 15% by weight, in particular 3% by weight to 10% by weight of nonionic and / or anionic emulsifier and not more than 80% by weight, in particular not more than 60% by weight and particularly preferably 20% by weight to 50% by weight of water.
  • a foam regulator emulsion based on paraffin wax which can be used according to the invention is preferably prepared by melting the paraffin wax and the bisfatty acid amide in the presence of the emulsifier, optionally cooling the melt to at most about 100 ° C. and stirring it into water. If mixtures of nonionic emulsifier and anionic emulsifier are used, it is preferred to incorporate the nonionic emulsifier into the melt of paraffin wax and bis fatty acid amide as described and to add the anionic emulsifier not to the melt but to the water before stirring in the melt. If paraffin wax and bis fatty acid amide are used in a molten, not cooled form, it is preferred to use cold water with a temperature corresponding to at most room temperature.
  • melt is cooled to a temperature of at most approx. 100 ° C. before being stirred into water, it is preferred to use water at a temperature of approx. 50 ° C. to 80 ° C.
  • Conventional stirring devices are normally sufficient to achieve the uniform distribution of all components and thus to produce the aqueous emulsion which can be used according to the invention; the use of high-speed mixers or homogenizers (e.g. Ultra Turrax®) is generally not necessary.
  • the additional incorporation of silicone oil is possible at any point in this process.
  • foam regulator emulsions which contain silicone oil as the sole foam regulator active ingredient or in a higher amount than the amount of paraffin wax
  • the silicone oil is preferably first mixed with the nonionic and / or anionic emulsifier, part of the amount of water is added with stirring so that a Emulsion of the type water in silicone is formed, continues to add water until the emulsion inverses, stirs intensely and then adds the remaining water while stirring.
  • the emulsion obtained in this way can optionally have a partially multiple character means in the outer water phase there may also be droplets of the original core emulsion of the type water in silicone.
  • the foam regulator emulsions obtainable in this way and which can be used in the process according to the invention are stable and, at 60 ° C., preferably have viscosities below 2500 mPa.s, in particular in the range from 100 mPa.s to 500 mPa.s, measured, for example, using a Brookfield rotary viscometer, spindle no 2.5 revolutions per minute.
  • paraffin waxes that come into question according to the invention are generally complex substance mixtures without a sharp melting point.
  • DTA differential thermal analysis
  • paraffins which are completely liquid at room temperature that is to say those having a solidification point below 25 ° C.
  • paraffins which are solid at room temperature can be used.
  • the paraffin wax is preferably solid at room temperature and is in completely liquid form at 100 ° C.
  • paraffin wax mixtures known from European patent application EP 0 309 931 can be used, for example from 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point from 62 ° C. to 90 ° C., 20% by weight to 49% by weight .-% hard paraffin 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.
  • the liquid fraction is as high as possible at 40 ° C. without already being 100% at this temperature.
  • Preferred paraffin wax mixtures have a liquid fraction of at least 50% by weight, in particular from 55% by weight to 80% by weight, at 40 ° C. and a liquid fraction of at least 90% by weight at 60 ° C.
  • the temperature at which reaches a liquid content of 100% by weight of the paraffin wax is still below 85 ° C., in particular at 75 ° C. to 82 ° C., in particularly preferred paraffin wax mixtures. It is also important to ensure that the paraffins do not contain any volatile components.
  • Paraffin waxes contain less than 1% by weight, in particular less than 0.5% by weight, of parts which can be evaporated at 110 ° C. and normal pressure.
  • Paraffin waxes which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Guer and Deawax® from DEA Mineralöl AG.
  • foam-regulating silicone oil or, in particular, mixtures of paraffin wax with foam-regulating silicone oil can also be used.
  • the reference to silicone oil also always means its mixing with finely divided fillers, for example hydrophilic or hydrophobic silicon dioxide, so-called highly disperse silica.
  • silicone oil for example polydimethylsiloxane
  • silicone oil is used in mixtures of paraffin wax and silicone oil, preferably in amounts such that the foam regulator emulsion used in the process according to the invention has a silicone oil content in the range from 0.1% by weight to 10% by weight. , in particular 1% by weight to 5% by weight.
  • the foam regulator emulsion to be sprayed onto the carrier material contains a mixture of silicone oil and paraffin wax in a weight ratio of 2: 1 to 1: 100, in particular 1: 1 to 1:10.
  • a particularly preferred foam regulator emulsion contains 10% by weight to 40% by weight, in particular 15% by weight to 35% by weight of silicone oil and 50% by weight to 80% by weight of water.
  • a second component of the defoamer system is preferably formed from bisfatty acid amides.
  • Bisamides are suitable which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18, carbon atoms and from alkylenediamines with 2 to 7 Derive carbon atoms.
  • Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid and mixtures thereof, as can be obtained from natural fats or hydrogenated oils, such as tallow or hydrogenated palm oil.
  • Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
  • 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.
  • Nonionic emulsifiers which can be used in emulsions which can be used according to the invention include, in particular, the alkoxylates, preferably the ethoxylates and / or propoxylates of alcohols, alkylamines, vicinal diols, carboxylic acids and / or carboxamides, the alkyl groups with 8 to 22 carbon atoms. Have atoms, preferably 12 to 18 carbon atoms, understood. The average degree of alkoxylation of these compounds is generally from 1 to 10, preferably 2 to 5. They can be prepared in a known manner by reaction with the corresponding alkylene oxides.
  • Products which can be prepared by alkoxylation of fatty acid alkyl esters with 1 to 4 carbon atoms in the ester part by the process of international patent application WO 90/13533 are also suitable.
  • the alcohol alkoxylates in question include the ethoxylates and / or propoxylates of linear or branched-chain alcohols having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
  • Derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers can also be used to prepare usable alkoxylates.
  • the ethoxylates of primary alcohols with linear dodecyl, tetra-decyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. It is also possible to use corresponding alkoxylates of mono- or polyunsaturated fatty alcohols, which include, for example, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol and erucalcohol. Esters or partial esters of carboxylic acids of corresponding carbon chain length with polyols such as glycerol or oligoglycerol can also be used.
  • Preferred anionic emulsifiers are Alkali salts of alkylbenzenesulfonic acids with 9 to 13 carbon atoms in the alkyl group, in particular sodium dodecylbenzenesulfonate.
  • Hydroxyethyl cellulose may be included.
  • a homogeneous mixture of foam regulator system and in particular nonionic emulsifier is used.
  • This can advantageously be achieved in a simple manner by melting the bisamide which is solid at room temperature in the presence of the paraffin and the emulsifier, advantageously with stirring or homogenization. If the bisamide is not used in bulk, but pre-assembled in a mixture with the paraffin, heating above the melting point of the bisamide is generally not necessary, since a solution of the bisamide in the paraffin usually forms even at lower temperatures. Subsequent to the formation of the mixture of defoamer system and emulsifier, which is preferably carried out at temperatures in the range from 60 ° C.
  • the concentration of anionic emulsifier in water is preferably 5% by weight to 15% by weight.
  • the emulsion thus obtainable is stable in storage at room temperature and preferably 3% by weight to 60% by weight, in particular 15% by weight to 45% by weight, is applied to the support material.
  • a drying step can be carried out, for example using conventional fluidized bed dryers, or the emulsion can be applied with simultaneous drying, for example likewise in a fluidized bed.
  • the foam regulator granules according to the invention or obtainable by the method according to the invention preferably contain 5% by weight to 50% by weight, in particular 8% by weight to 35% by weight foam active ingredient. Examples
  • the foam regulator granules thus obtained were added in an amount of 1% by weight each to a defoamer-free particulate detergent, which gave a defoamer performance at washing temperatures of 40 ° C., 60 ° C. and 90 ° C. which was not behind that in use conventional type of defoamer granules produced. It had a higher degree of stability and a smaller proportion of fine particles than a correspondingly produced granulate which lacked the Br ⁇ nsted acid component or in which it was replaced by polymeric alkali polycarboxylate.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

The aim of the invention is to improve the stability of particulate foam regulating granulates for using in washing and cleaning products. To this end, a solid support material containing alkali carbonate and a Brønsted acid is sprayed with an aqueous foam regulating emulsion containing between 16 wt. % and 70 wt. % of a foam regulating active ingredient based on paraffin wax and/or silicon oil, between 2 wt. % and 15 wt. % of a non-ionic and/or anionic emulsifying agent, and no more than 80 wt. % of water.

Description

Schaumregulatorgranulat Foam regulator granulate
Die Erfindung betrifft in Wasch- oder Reinigungsmitteln einsetzbare teilchenförmige Schaumregulierungsmittel sowie ein Verfahren zu deren Herstellung.The invention relates to particulate foam regulating agents which can be used in washing or cleaning agents and to a process for their preparation.
Die schaumregulierende Wirkung von Kombinationen aus Paraffinen mit Bisfettsäure- amiden in wäßrigen tensidhaltigen Systemen ist bekannt. So beschreibt zum Beispiel die europäische Patentschrift EP 0 309 931 Bl zur Nerwendung in Wasch- und Reinigungsmitteln geeignete teilchenförmige Schaumregulierungsmittel, die aus einem wasserlöslichen tensidfreien Trägermaterial und einem daran adsorbierten siloxanfreien Entschäumergemisch aus 5-60 Gew.-% Weich- und/oder Hartparaffm, 20-90 Gew.-% mikrokristallinem Paraffinwachs mit bestimmtem Schmelzbereich und 5-20 Gew.-% eines von C2.7-Diaminen und C12.22-Fettsäuren abgeleiteten Diamids in feinverteilter Form. Die Herstellung solcher teilchenförmiger Schaumregulierungsmittel erfolgt mittels Sprühtrocknung einer wäßrigen Aufschlämmung, welche das Trägermaterial und das Entschäumergemisch enthält. Die Entschäumerleistung des Entschäumergemisches wird als unzureichend angegeben, wenn man es auf ein teilchenförmiges Waschmittel aufsprüht.The foam-regulating effect of combinations of paraffins with bisfatty acid amides in aqueous surfactant-containing systems is known. For example, European Patent Specification EP 0 309 931 B1 describes particulate foam regulators which are suitable for use in detergents and cleaning agents and which consist of a water-soluble surfactant-free carrier material and a siloxane-free defoamer mixture of 5-60% by weight of soft and / or hard paraffin adsorbed thereon, 20-90% by weight of microcrystalline paraffin wax with a certain melting range and 5-20% by weight of one of C 2.7 diamines and C 12 . 22 fatty acids derived from diamids in finely divided form. Such particulate foam control agents are produced by spray drying an aqueous slurry which contains the carrier material and the defoamer mixture. The defoamer performance of the defoamer mixture is said to be inadequate when sprayed onto a particulate detergent.
Die Nerwendung schaumregulierender homogener Gemische aus nichtionischem Tensid und einem Schaumregulatorsystem, das Paraffinwachs und Bisfettsäureamide enthält, zur Verbesserung der Herstellbarkeit und der Produkteigenschaften extrudierter Wasch- und Reinigungsmittel ist aus der internationalen Patentanmeldung WO 96/26258 bekannt.The use of foam-regulating homogeneous mixtures of nonionic surfactant and a foam regulator system which contains paraffin wax and bis fatty acid amides to improve the manufacturability and the product properties of extruded detergents and cleaning agents is known from international patent application WO 96/26258.
Gegenstand der deutschen Offenlegungsschrift DE 23 38 468 ist ein Waschmittel mit einem Gehalt an einem Silikonentschäumer, der gegen Wechselwirkungen mit den Waschmittelbestandteilen geschützt ist. Zu seiner Herstellung werden wäßrige Schmelzen, die den Silikonentschäumer sowie eine Trägersubstanz, zum Beispiel Polyglykol, enthalten, zunächst sprühgetrocknet und die erhaltenen Partikel in einem fluidisierten Bett eines festen, wasserlöslichen Hüllmaterials mit einem Überzug versehen. Als Überzugsmaterial können übliche in Waschmitteln verwendete Salze, insbesondere Tripolyphosphat oder Carboxymethylcellulose verwendet werden. Ein solches mehrstufiges Herstellungsverfahren ist vergleichsweise technisch aufwendig.The subject of German published patent application DE 23 38 468 is a detergent containing a silicone defoamer, which is protected against interactions with the detergent components. To prepare it, aqueous melts which contain the silicone defoamer and a carrier substance, for example polyglycol, are first spray-dried and the particles obtained are coated in a fluidized bed of a solid, water-soluble coating material Mistake. Salts which are customary in detergents, in particular tripolyphosphate or carboxymethyl cellulose, can be used as the coating material. Such a multi-stage manufacturing process is comparatively technically complex.
Die deutsche Offenlegungsschrift DE 31 28 631 beschreibt die Herstellung von schaumgedämpften Waschmitteln mit einem Gehalt an Silikonentschäumern, die mikroverkapselt sind. Dabei wird das Silikon in einer wäßrigen Lösung eines fϊlmbildenden Polymeren dispergiert und die Dispersion - getrennt von den übrigen in Wasser gelösten beziehungsweise dispergierten Waschmittelbestandteilen - über eine besondere Leitung der Sprühtrocknungsanlage zugeführt. Die Vereinigung der beiden Teilströme erfolgt im Bereich der Sprühdüse. Als fümbildende Polymere kommen zum Beispiel Celluloseether, Stärkeether oder synthetische wasserlösliche Polymere sowie deren Gemische in Frage. Die Bildung der Mikrokapseln erfolgt spontan in der Sprühdüse oder durch vorheriges Ausfällen durch Zugabe von Elektrolytsalzen zur Silikondispersion. Das beschriebene Verfahren ist zwangsläufig an die Herstellung sprühgetrockneter Wasclimittel gebunden. Eine Übertragung auf anderweitig, zum Beispiel durch Granulierung hergestellte Wasch- und Reinigungsmittel oder auch auf andere Einsatzgebiete, ist bei dieser Arbeitsweise nicht möglich.German laid-open specification DE 31 28 631 describes the production of foam-damped detergents containing silicone defoamers which are microencapsulated. The silicone is dispersed in an aqueous solution 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. Suitable film-forming polymers are, for example, cellulose ethers, starch ethers or synthetic water-soluble polymers and mixtures thereof. The microcapsules are formed spontaneously in the spray nozzle or by prior precipitation by adding electrolyte salts to the silicone dispersion. The process described is inevitably linked to the production of spray-dried washing agents. This method of operation does not allow transfer to other detergents and cleaning agents produced by granulation or to other areas of application.
Die europäische Patentanmeldung EP 097 867 beschreibt ein Verfahren zur Herstellung mikroverkapselter Entschäumeröle durch Mischen einer Silikonemulsion mit einer wäßrigen Lösung von Carboxymethylcellulose und Ausfällen der Mikrokapseln durch Zusatz von Elektrolyten, insbesondere mehrwertiger Salze oder organischer Lösungsmittel. Es bereitet erhebliche Schwierigkeiten, die für eine ausreichende Schaumdämpfung erforderlichen geringen Mengen an Silikon-Mikrokapseln in einer vergleichsweise großen Waschpulvermenge homogen zu verteilen.European patent application EP 097 867 describes a process for producing microencapsulated defoamer oils by mixing a silicone emulsion with an aqueous solution of carboxymethyl cellulose and precipitating the microcapsules by adding electrolytes, in particular polyvalent salts or organic solvents. There are considerable difficulties in homogeneously distributing the small amounts of silicone microcapsules required for adequate foam damping in a comparatively large amount of washing powder.
Die deutsche Offenlegungssclirift DE 3436 194 beschreibt ein Verfahren zur Herstellung eines schüttfähigen Entschäumergranulats durch Sprühtrocknen einer wäßrigen, fümbildende Polymere enthaltenden Entschäumerdispersion. Zwecks Herstellung eines Granulates der Zusammensetzung 1 bis 10 Gew.-% wasserunlöslicher Entschäumerwirkstoff, 0,2 bis 2 Gew.-% eines Gemisches aus Natriumcarboxymethylcel- lulose und Methylcellulose im Gewichtsverhältnis 80 : 20 bis 40 : 60, 70 bis 90 Gew.-% an anorganischen, in Wasser löslichen oder dispergierbaren Trägersalzen, Rest Wasser, läßt man eine 0,5 bis 8 Gew.-% des Celluloseethergemisches enthaltende wäßrige Lösung bei einer Temperatur von 15 bis 60 °C so lange quellen, bis die Viskosität der Lösung mindestens 75 % der Viskosität beträgt, die bei vollständiger Quellung der Cellu- loseether-Lösung gemessen wird, worauf man in dieser Lösung den Entschäumerwirkstoff dispergiert und nach Zusatz der Trägersalze und gegebenenfalls Wasser die homogenisierte Dispersion sprühtrocknet. Als Entschäumerwirkstoffe werden Organopolysiloxane, Paraffine sowie Gemische aus Organopolysiloxanen und Paraffinen eingesetzt. Der Entschäumerwirkstoffgehalt beträgt 1 bis 10 Gew.-%, vorzugsweise 3 bis 7 Gew.-%. Das Trägersalz besteht vorzugsweise aus einem Gemisch von Natriumsilikat, Natriumtripolyphosphat und Natriumsulfat.The German published publication DE 3436 194 describes a process for producing a pourable defoamer granulate by spray drying an aqueous defoamer dispersion containing film-forming polymers. For the production of granules of the composition 1 to 10 wt .-% water-insoluble Defoamer, 0.2 to 2% by weight of a mixture of sodium carboxymethyl cellulose and methyl cellulose in a weight ratio of 80:20 to 40:60, 70 to 90% by weight of inorganic, water-soluble or dispersible carrier salts, the rest being water swell an aqueous solution containing 0.5 to 8% by weight of the cellulose ether mixture at a temperature of 15 to 60 ° C. until the viscosity of the solution is at least 75% of the viscosity which occurs when the cellulose ether swells completely. Solution is measured, whereupon the defoaming agent is dispersed in this solution and, after addition of the carrier salts and optionally water, the homogenized dispersion is spray-dried. Organopolysiloxanes, paraffins and mixtures of organopolysiloxanes and paraffins are used as defoaming agents. The defoamer active ingredient content is 1 to 10% by weight, preferably 3 to 7% by weight. The carrier salt preferably consists of a mixture of sodium silicate, sodium tripolyphosphate and sodium sulfate.
Aus der europäischen Patentschrift EP 0 337 523 Bl ist ein Verfahren zur Herstellung pulverförmiger Waschmittel bekannt, die mindestens 5 Gew.-% anionisches Tensid, 20- 80 Gew.-% Alumosilikat und in Wasser sowie anionischen und nichtionischen Tensiden im wesentlichen unlösliches Paraffinwachs enthalten, welches das Mitversprühen oder nachträgliche Aufsprühen des Paraffins auf das vorgefertigte Waschmittelteilchen als wesentlichen Verfahrensschritt umfaßt. Das Paraffinwachs kann dabei auch in Form einer Mischung mit nichtionischen Tensiden eingesetzt werden.From European Patent EP 0 337 523 B1 a process for producing powder detergents is known which contains at least 5% by weight of anionic surfactant, 20-80% by weight of aluminosilicate and paraffin wax which is essentially insoluble in water and anionic and nonionic surfactants, which comprises spraying or subsequently spraying the paraffin onto the prefabricated detergent particles as an essential process step. The paraffin wax can also be used in the form of a mixture with nonionic surfactants.
Die in dem letztgenannten Dokument offenbarte Variante des Aufsprühens des Paraffins auf ein vorgefertigtes pulverförmiges Waschmittel läßt sich nur unter Schwierigkeiten anwenden, wenn man das Paraffinwachs nicht alleine, sondern in Kombination mit einem bekanntlich seine Schaumregulatorwirkung verstärkenden Bisfettsäureamid einsetzen will. Derartige Bisfettsäureamide sind in der Regel bei Raumtemperatur fest und weisen einen relativ hohen Schmelzpunkt auf, so daß man sie beziehungsweise ihre Kombination mit dem Paraffin nur bei erhöhter Temperatur von beispielsweise etwa 140 °C in flüssiger und versprühbarer Form handhaben kann. Bei Unterschreitung dieser Temperatur droht die Verstopfung der verwendeten Rohrleitungen und Düsen durch die Verfestigung des Bisfettsäureamids. Weiterl in nachteilig ist, daß es durch derartig hohe Temperaturen des Aufsprühmaterials zu unerwünschten Wechselwirkungen mit thermisch empfindlichen Bestandteilen des Waschmittels kommen kann. Zudem ist eine gleichmäßige Verteilung des Schaumregulatorsystems im Waschmittel gefährdet, wenn es als hocherhitztes Aufsprühmaterial nach dem Auftreffen auf das Waschmittelpulver rasch abkühlt.The variant of spraying the paraffin onto a prefabricated powder detergent disclosed in the last-mentioned document can only be used with difficulty if the paraffin wax is not to be used alone but in combination with a bis-fatty acid amide which is known to enhance its foam-regulating action. Such bis fatty acid amides are generally solid at room temperature and have a relatively high melting point, so that they or their combination with the paraffin can only be handled in liquid and sprayable form at an elevated temperature of, for example, about 140 ° C. If this temperature is undershot, the pipes and nozzles used may become blocked due to the solidification of the Bisfettsäureamids. Another disadvantage is that such high temperatures of the spray material can lead to undesirable interactions with thermally sensitive components of the detergent. In addition, an even distribution of the foam regulator system in the detergent is at risk if it cools down quickly as a highly heated spraying material after it hits the detergent powder.
In der internationalen Patentanmeldung WO 00/36063 wurde vorgeschlagen, dieses Problem durch die Verwendung einer wäßrigen Schaumregulatoremulsion, die 16 Gew.- % bis 70 Gew.-% Schaumregulatorwirkstoff auf Paraffinwachs- und/oder Silikonolbasis, 2 Gew.-% bis 15 Gew.-% nichtionischen und/oder anionischen Emulgator sowie nicht mehr als 80 Gew.-% Wasser enthält, zu lösen. Durch Aufsprühen derartiger Emulsionen auf feste Trägermaterialien erhält man sehr gut wirksame Schaumregulatoren in Teilchenform.In international patent application WO 00/36063 it was proposed to solve this problem by using an aqueous foam regulator emulsion which contains 16% by weight to 70% by weight of foam regulator active substance based on paraffin wax and / or silicone oil, 2% by weight to 15% by weight. -% non-ionic and / or anionic emulsifier and not more than 80 wt .-% water to solve. Spraying emulsions of this type onto solid support materials gives very effective foam regulators in particle form.
Allerdings ist die Stabilität der so erhältlichen Teilchen nicht immer zufriedenstellend hoch. Vielmehr kann es bei der Förderung und dem Transport der Schaumregulatorteilchen zu deren Zerfall in kleinere Teilchen oder Pulver kommen, die zwar immer noch eine gute schaumregulierender Wirkung haben, aber sich nicht ohne weiteres gleichmäßig in teilchenförmige Wasch- oder Reinigungsmittel einarbeiten lassen.However, the stability of the particles obtainable in this way is not always satisfactorily high. Rather, the transport and transport of the foam regulator particles can lead to their disintegration into smaller particles or powders, which still have a good foam-regulating effect, but cannot easily be incorporated evenly into particulate detergents or cleaning agents.
Das Problem mangelhafter Teilchenstabilität wird mit der vorliegenden Erfindung durch die Anpassung des Trägermaterials gelöst.The present invention solves the problem of poor particle stability by adapting the carrier material.
Gegenstand der Erfindung ist ein in Wasch- oder Reinigungsmitteln einsetzbares teilchenförmiges Schaumregulierungsmittel, enthaltend Schaumregulatorwirkstoff auf Paraffinwachs- und/oder Silikonolbasis, nichtionischen und/oder anionischen Emulgator und festes Trägermaterial, dadurch gekennzeichnet, daß das Trägermaterial Alkalicarbonat und eine Brβnsted-Säure enthält.The invention relates to a particulate foam control agent which can be used in detergents or cleaning agents and contains foam regulator active ingredient based on paraffin wax and / or silicone oil, nonionic and / or anionic emulsifier and solid carrier material, characterized in that the carrier material contains alkali carbonate and a Brßnsted acid.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung teilchenformiger Schaumregulatorgranulate durch Aufsprühen einer wäßrigen Schaumregulatoremulsion, die 16 Gew.-% bis 70 Gew.-% Schaumregulatorwirkstoff auf Paraffinwachs- und/oder Silikonolbasis, 2 Gew.-% bis 15 Gew.-% nichtionischen und/oder anionischen Emulgator sowie nicht mehr als 80 Gew.-% Wasser enthält, auf ein festes Trägermaterial, woran sich gegebenenfalls ein Trocknungsschritt anschließt, welches dadurch gekennzeichnet ist, daß das Trägermaterial Alkalicarbonat und eine Bransted-Säure enthält.The invention further relates to a process for the production of particulate foam regulator granules by spraying on an aqueous foam regulator emulsion, which contains 16% by weight to 70% by weight of foam regulator active substance based on paraffin wax and / or silicone oil, 2% by weight to 15% by weight of nonionic and / or anionic emulsifier and not more than 80% by weight of water, onto a solid carrier material, which is optionally followed by a drying step, which is characterized in that the carrier material contains alkali carbonate and a Bransted acid.
Es ist bevorzugt, daß die Bransted-Säure bei 25 °C in fester Form vorliegt. Sie weist bei 25 °C eine Wasserlöslichkeit von vorzugsweise mindestens 100 g/1 auf. Vorzugsweise wird sie aus den Di- und Tricarbonsäuren, deren sauren Salzen, den sauren Salzen von anorganischen Säuren, insbesondere NaHSO4, a2HPO4 und NaH2PO4, und deren Mischlingen ausgewählt. In einer bevorzugten Ausführungsform der Erfindung handelt es sich bei der Bransted-Säure um Citronensäure.It is preferred that the Bransted acid is in solid form at 25 ° C. At 25 ° C it has a water solubility of preferably at least 100 g / 1. It is preferably selected from the di- and tricarboxylic acids, their acid salts, the acid salts of inorganic acids, in particular NaHSO 4 , a 2 HPO 4 and NaH 2 PO 4 , and their hybrids. In a preferred embodiment of the invention, the Bransted acid is citric acid.
Das in dem erfindungsgemäßen Verfahren verwendete Trägermaterial enthält Alkalicarbonat und eine Bronsted-Säure vorzugsweise in Gewichtsverhältnissen von 1 : 1 bis 100:1, insbesondere von 20:3 bis 80:3. Das Trägermaterial weist vorzugsweise 40 Gew.-% bis 90 Gew.-%, insbesondere 60 Gew.-% bis 80 Gew.-% Alkalicarbonat und 1-20 Gew.-%, insbesondere 3 Gew.-% bis 9 Gew.-% einer Bransted-Säure auf.The carrier material used in the process according to the invention contains alkali carbonate and a Bronsted acid, preferably in weight ratios of 1: 1 to 100: 1, in particular from 20: 3 to 80: 3. The carrier material preferably has 40% by weight to 90% by weight, in particular 60% by weight to 80% by weight of alkali carbonate and 1-20% by weight, in particular 3% by weight to 9% by weight a Bransted acid.
Das Trägermaterial kann dabei allein aus Alkalicarbonat und der Bronsted-Säure bestehen oder zusätzlich weitere teilchenförmige Bestandteile enthalten, wobei feste und/oder in fester Form konfektionierte Wasch- oder Reinigungsmittelbestandteile in Frage kommen. Dazu gehören beispielsweise übliche durch Sprühtrocknung wäßriger Aufschlämmungen ihrer Inhaltsstoffe hergestellte Pulver, feste Bleichmittel auf Sauerstoffbasis, beispielsweise Alkalipercarbonate oder Alkaliperborate, die als sogenannte Monohydrate oder Tetrahydrate vorliegen können, pulverförmig konfektionierte Bleichaktivatoren, beispielsweise ein nach dem Verfahren des europäischen Patentes EP 0 037 026 hergestelltes Tetraacetylethylendiamin-Granulat, nicht durch konventionelles Sprühtrocknen hergestellte Aniontensidcompounds gemäß der internationalen Patentanmeldung WO 93/04162 mit einem Gehalt von über 80 Gew.-%, insbesondere über 90 Gew.-% an Alkylsulfat mit Alkylkettenlängen im Bereich von C12 bis C18, wobei der Rest im wesent- liehen aus anorganischen Salzen und Wasser besteht, in granulärer Form vorliegende Enzyme, beispielsweise ein nach dem Verfahren der internationalen Patentanmeldung WO 92/11347 hergestelltes Enzymextrudat oder ein nach dem Verfahren der deutschen Patentanmeldung DE 43 29 463 hergestelltes Mehrenzymgranulat, pulverförmig, beispielsweise nach dem Verfahren der deutschen Patentanmeldung DE 44 08 360, konfektionierter Soil release- Wirkstoff, pulverförmige Polycarboxylat-Cobuilder, beispielsweise Alkalicitrat, feste anorganische Buildermaterialien, wie Zeolith-A, Zeolith- P, Zeolith-X und kristalline Schichtsilikate, und sonstige anorganische Salze wie Alkalisulfat, Alkalihydrogencarbonat und Alkalisilikat sowie deren Mischungen. Vorzugsweise weist das Trägermaterial eine Kombination aus Alkalihydrogencarbonat und Alkalicarbonat auf, wobei deren Gewichtsverhältnis vorzugsweise 99:1 bis 10:90, insbesondere 95:5 bis 50:50, beträgt. Bevorzugtes Alkalimetall in den genannten Salzen wie auch im Alkalicarbonat ist dabei Natrium.The carrier material can consist solely of alkali carbonate and Bronsted acid or additionally contain further particulate constituents, solid and / or detergent constituents prepared in solid form being suitable. These include, for example, customary powders produced by spray drying aqueous slurries of their ingredients, solid bleaching agents based on oxygen, for example alkali percarbonates or alkali perborates, which may be present as so-called monohydrates or tetrahydrates, powdered bleach activators, for example a tetraaminacetyl prepared by the process of European patent EP 0 037 026 Granules, anionic surfactant compounds not produced by conventional spray drying according to international patent application WO 93/04162 with a content of more than 80% by weight, in particular more than 90% by weight, of alkyl sulfate with alkyl chain lengths in the range from C 12 to C 18 , the Rest essentially are composed of inorganic salts and water, granular enzymes, for example an enzyme extrudate produced according to the method of international patent application WO 92/11347 or a multi-enzyme granulate produced according to the method of German patent application DE 43 29 463, in powder form, for example according to the method of German patent application DE 44 08 360, ready-made soil release active ingredient, powdered polycarboxylate cobuilders, for example alkali citrate, solid inorganic builder materials such as zeolite A, zeolite P, zeolite X and crystalline phyllosilicates, and other inorganic salts such as alkali sulfate, alkali hydrogen carbonate and Alkali silicate and mixtures thereof. The carrier material preferably has a combination of alkali hydrogen carbonate and alkali carbonate, the weight ratio of which is preferably 99: 1 to 10:90, in particular 95: 5 to 50:50. The preferred alkali metal in the salts mentioned and also in the alkali carbonate is sodium.
In einer bevorzugten Ausführungsform des Verfahrens führt man im wesentlichen wie in der internationalen Patentanmeldung WO 00/36063 beschrieben in einem Granulationsmischer eine Aufbaugranulation derart durch, daß man eine Menge von 40 bis 110 Gewichtsteilen, insbesondere 60 bis 90 Gewichtsteilen an Trägermaterial, das vorzugsweise zusätzlich Alkalisulfat und/oder Alkalihydrogencarbonat enthalten kann, intensiv mischt und unter Granulieren eine Menge von 15 bis 50 Gewichtsteilen, insbesondere 25 bis 35 Gewichtsteilen der gegebenenfalls auf eine Temperatur im Bereich von 70 °C bis 180 °C erwärmten Schaumregulatoremulsion zusetzt. Geringe Mengen Wasser, vorzugsweise nicht mehr als 10 Gewichtsteile, insbesondere 1 bis 5 Gewichtsteile Wasser können, nach oder vorzugsweise vor dem Zusatz der Schaumregulatoremulsion, gewünschtenfalls ebenfalls zugesetzt werden.In a preferred embodiment of the process, essentially as described in international patent application WO 00/36063, a granulation mixer is used to carry out a build-up granulation in such a way that an amount of 40 to 110 parts by weight, in particular 60 to 90 parts by weight, of carrier material, which preferably additionally contains alkali metal sulfate and / or can contain alkali metal bicarbonate, mixes intensively and, while granulating, adds an amount of 15 to 50 parts by weight, in particular 25 to 35 parts by weight, of the foam regulator emulsion which has been heated to a temperature in the range from 70 ° C. to 180 ° C. Small amounts of water, preferably not more than 10 parts by weight, in particular 1 to 5 parts by weight, of water can, if desired, also be added after or preferably before the addition of the foam regulator emulsion.
Unter einer Paraffinwachsbasis wird im Rahmen der vorliegenden Erfindung insbesondere eine Kombination aus Paraffinwachs und Bisfettsäureamid verstanden. Vorzugsweise enthält eine erfindungsgemäß brauchbare Schaumregulatoremulsion 15 Gew.-% bis 60 Gew.-%, insbesondere 30 Gew.-% bis 50 Gew.-% Paraffinwachs oder einer Mischung aus Paraffinwachs und Silikonöl, 1 Gew.-% bis 10 Gew.-%, insbesondere 3 Gew.-% bis 8 Gew.-% sich von C2.7-Diaminen und C12.22-Fettsäuren ableitendem Bisfettsäureamid, 2 Gew.-% bis 15 Gew.-%, insbesondere 3 Gew.-% bis 10 Gew.-% nichtionischen und/oder anionischen Emulgator sowie nicht mehr als 80 Gew.-%, insbesondere nicht mehr als 60 Gew.-% und besonders bevorzugt 20 Gew.-% bis 50 Gew.-% Wasser.In the context of the present invention, a paraffin wax base is understood in particular to be a combination of paraffin wax and bis fatty acid amide. A foam regulator emulsion which can be used according to the invention preferably contains 15% by weight to 60% by weight, in particular 30% by weight to 50% by weight of paraffin wax or a mixture of paraffin wax and silicone oil, 1% by weight to 10% by weight , in particular 3% to 8% by weight of C 2 . 7 diamines and C 12 . 22 fatty acid-conducting bis fatty acid amide, 2% by weight to 15% by weight, in particular 3% by weight to 10% by weight of nonionic and / or anionic emulsifier and not more than 80% by weight, in particular not more than 60% by weight and particularly preferably 20% by weight to 50% by weight of water.
Eine erfindungsgemäß brauchbare Schaumregulatoremulsion auf Paraffinwachsbasis wird vorzugsweise durch Aufschmelzen des Paraffinwachses und des Bisfettsäureamides in Gegenwart des Emulgators, gegebenenfalls Abkühlen der Schmelze auf höchstens ca. 100 °C und Einrühren in Wasser hergestellt. Falls Mischungen aus nichtionischem Emulgator und anionischem Emulgator eingesetzt werden, ist es dabei bevorzugt, den nichtionischen Emulgator wie beschrieben in die Schmelze aus Paraffinwachs und Bisfettsäureamid einzuarbeiten und den anionischen Emulgator nicht der Schmelze, sondern vor dem Einrühren der Schmelze dem Wasser zuzusetzen. Wenn man Paraffinwachs und Bisfettsäureamid in geschmolzener, nicht abgekühlter Form einsetzt, ist es bevorzugt, kaltes Wasser mit einer höchstens Raumtemperatur entsprechenden Temperartur zu verwenden. Falls die Schmelze vor dem Einrühren in Wasser auf eine Temperatur von höchstens ca. 100 °C abgekühlt wird, ist es bevorzugt, Wasser mit einer Temperatur von ca. 50 °C bis 80 °C einzusetzen. Übliche Rührvorrichtungen sind normalerweise ausreichend, um die gleichmäßige Verteilung aller Komponenten zu erzielen und somit die erfindungsgemäß brauchbare wäßrige Emulsion zu erzeugen; der Einsatz von Hochgeschwindigkeitsmischern oder Homogenisatoren (zum Beispiel Ultra Turrax®) ist in der Regel nicht erforderlich. Die zusätzliche Einarbeitung von Silikonöl ist an jeder Stelle dieses Verfahrens möglich. Falls Schaumregulatoremulsionen hergestellt werden sollen, die Silikonöl als alleinigen Schaumregulatorwirkstoff oder in im Vergleich zur Menge des Paraffinwachses höherer Menge enthalten, vermischt man vorzugsweise zuerst das Silikonöl mit dem nichtionischen und/oder anionischen Emulgator, gibt unter Rühren einen Teil der Wassermenge so zu, daß eine Emulsion vom Typ Wasser in Silikon entsteht, gibt so lange weiteres Wasser zu, bis es zu einer Inversion der Emulsion kommt, rührt intensiv und gibt anschließend unter Rühren das restliche Wasser zu. Die so erhältliche Emulsion kann gegebenenfalls teilweise multiplen Charakter aufweisen, das heißt in der äußeren Wasserphase können sich auch Tröpfchen der ursprünglichen Kernemulsion vom Typ Wasser in Silikon befinden.A foam regulator emulsion based on paraffin wax which can be used according to the invention is preferably prepared by melting the paraffin wax and the bisfatty acid amide in the presence of the emulsifier, optionally cooling the melt to at most about 100 ° C. and stirring it into water. If mixtures of nonionic emulsifier and anionic emulsifier are used, it is preferred to incorporate the nonionic emulsifier into the melt of paraffin wax and bis fatty acid amide as described and to add the anionic emulsifier not to the melt but to the water before stirring in the melt. If paraffin wax and bis fatty acid amide are used in a molten, not cooled form, it is preferred to use cold water with a temperature corresponding to at most room temperature. If the melt is cooled to a temperature of at most approx. 100 ° C. before being stirred into water, it is preferred to use water at a temperature of approx. 50 ° C. to 80 ° C. Conventional stirring devices are normally sufficient to achieve the uniform distribution of all components and thus to produce the aqueous emulsion which can be used according to the invention; the use of high-speed mixers or homogenizers (e.g. Ultra Turrax®) is generally not necessary. The additional incorporation of silicone oil is possible at any point in this process. If foam regulator emulsions are to be produced which contain silicone oil as the sole foam regulator active ingredient or in a higher amount than the amount of paraffin wax, the silicone oil is preferably first mixed with the nonionic and / or anionic emulsifier, part of the amount of water is added with stirring so that a Emulsion of the type water in silicone is formed, continues to add water until the emulsion inverses, stirs intensely and then adds the remaining water while stirring. The emulsion obtained in this way can optionally have a partially multiple character means in the outer water phase there may also be droplets of the original core emulsion of the type water in silicone.
Die so erhältlichen, im erfindungsgemäßen Verfahren einsetzbaren Schaumregulatoremulsionen sind stabil und weisen bei 60 °C vorzugsweise Viskositäten unterhalb von 2500 mPa.s, insbesondere im Bereich von 100 mPa.s bis 500 mPa.s, gemessen beispielsweise mit einem Brookfield-Rotationsviskosimeter, Spindel Nr. 2, 5 Umdrehungen pro Minute, auf.The foam regulator emulsions obtainable in this way and which can be used in the process according to the invention are stable and, at 60 ° C., preferably have viscosities below 2500 mPa.s, in particular in the range from 100 mPa.s to 500 mPa.s, measured, for example, using a Brookfield rotary viscometer, spindle no 2.5 revolutions per minute.
Die erfindungsgemäß in Frage kommenden Paraffinwachse sind im allgemeinen komplexe Stoffgemische ohne scharfen Schmelzpunkt. Zur Charakterisierung bestimmt man üblicherweise ihren Schmelzbereich durch Differential-Thermo-Analyse (DTA), wie in "The Analyst" 87 (1962), 420, beschrieben, und/oder ihren Erstarrungspunkt. Darunter versteht man die Temperatur, bei der das Wachs durch langsames Abkühlen aus dem flüssigen in den festen Zustand übergeht. Erfindungsgemäß sind sowohl bei Raumtemperatur vollständig flüssige Paraffine, das heißt solche mit einem Erstarrungspunkt unter 25 °C, als auch bei Raumtemperatur feste Paraffine brauchbar. Vorzugsweise ist das Paraffinwachs bei Raumtemperatur fest und liegt bei 100 °C in vollständig flüssiger Form vor. Eingesetzt werden können beispielsweise die aus der europäischen Patentanmeldung EP 0 309 931 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 beziehungsweise 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 der Flüssiganteil bei 40 °C möglichst hoch, ohne bei dieser Temperatur schon 100 % zu betragen. Bevorzugte Paraffinwachsgemische weisen bei 40 °C einen Flüssiganteil von mindestens 50 Gew.-%, insbesondere von 55 Gew.-% bis 80 Gew.-%, und bei 60 °C einen Flüssiganteil von mindestens 90 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. Außerdem ist darauf zu achten, daß die Paraffine möglichst keine flüchtigen Anteile enthalten. Bevorzugte Paraffinwachse enthalten weniger als 1 Gew.-%, insbesondere weniger als 0,5 Gew.-% bei 110 °C und Normaldruck verdampfbare Anteile. Erfindungsgemäß brauchbare Paraffinwachse können beispielsweise unter den Handelsbezeichnungen Lunaflex® der Firma Füller sowie Deawax® der DEA Mineralöl AG bezogen werden. Anstelle des Paraffinwachses können auch schaumregulierendes Silikonöl oder insbesondere Gemische aus Paraffinwachs mit schaumregulierendem Silikonöl eingesetzt werden. Die Bezugnahme auf Silikonöl bedeutet im Rahmen der vorliegenden Erfindung immer auch dessen Abmischung mit feinteiligen Füllstoffen, beispielsweise hydrophilem oder hydrophobem Siliciumdioxid, sogenannter hochdisperser Kieselsäure. Dabei ist pyrogenes oder gefälltes, insbesondere hydrophobiertes Siliciumdioxid mit einer Oberfläche von mindestens 50 m2/g besonders bevorzugt, wie es beispielsweise under den Bezeichnungen Aerosil® oder Sipernat® im Handel erhältlich ist. In einer Ausführungsform der Erfindung wird Silikonöl, beispielsweise Polydimethylsiloxan, in Mischungen aus Paraffinwachs und Silikonöl vorzugsweise in solchen Mengen eingesetzt, daß die im erfindungsgemäßen Verfahren verwendete Schaumregulatoremulsion einen Gehalt an Silikonöl im Bereich von 0,1 Gew.-% bis 10 Gew.-%, insbesondere 1 Gew.-% bis 5 Gew.-% aufweist. In einer weiteren bevorzugten Ausgestaltung der Erfindung enthält die auf das Trägermaterial aufzusprühende Schaumregulatoremulsion eine Mischung aus Silikonöl und Paraffinwachs im Gewichtsverhältnis 2:1 bis 1:100, insbesondere 1:1 bis 1:10. Eine besonders bevorzugt eingesetzte Schaumregulatoremulsion enthält 10 Gew.-% bis 40 Gew.-%, insbesondere 15 Gew.-% bis 35 Gew.-% Silikonöl und 50 Gew.-% bis 80 Gew.-% Wasser.The paraffin waxes that come into question according to the invention are generally complex substance mixtures without a sharp melting point. For characterization, one usually determines their melting range by differential thermal analysis (DTA), as described in "The Analyst" 87 (1962), 420, and / or their solidification point. This is the temperature at which the wax changes from the liquid to the solid state by slow cooling. According to the invention, paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., and paraffins which are solid at room temperature can be used. The paraffin wax is preferably solid at room temperature and is in completely liquid form at 100 ° C. For example, the paraffin wax mixtures known from European patent application EP 0 309 931 can be used, for example from 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point from 62 ° C. to 90 ° C., 20% by weight to 49% by weight .-% hard paraffin 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, the liquid fraction is as high as possible at 40 ° C. without already being 100% at this temperature. Preferred paraffin wax mixtures have a liquid fraction of at least 50% by weight, in particular from 55% by weight to 80% by weight, at 40 ° C. and a liquid fraction of at least 90% by weight at 60 ° C. The temperature at which reaches a liquid content of 100% by weight of the paraffin wax, is still below 85 ° C., in particular at 75 ° C. to 82 ° C., in particularly preferred paraffin wax mixtures. It is also important to ensure that the paraffins do not contain any volatile components. Preferred paraffin waxes contain less than 1% by weight, in particular less than 0.5% by weight, of parts which can be evaporated at 110 ° C. and normal pressure. Paraffin waxes which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Füller and Deawax® from DEA Mineralöl AG. Instead of paraffin wax, foam-regulating silicone oil or, in particular, mixtures of paraffin wax with foam-regulating silicone oil can also be used. In the context of the present invention, the reference to silicone oil also always means its mixing with finely divided fillers, for example hydrophilic or hydrophobic silicon dioxide, so-called highly disperse silica. Pyrogenic or precipitated, in particular hydrophobized, silicon dioxide with a surface area of at least 50 m 2 / g is particularly preferred, as is commercially available, for example, under the names Aerosil® or Sipernat®. In one embodiment of the invention, silicone oil, for example polydimethylsiloxane, is used in mixtures of paraffin wax and silicone oil, preferably in amounts such that the foam regulator emulsion used in the process according to the invention has a silicone oil content in the range from 0.1% by weight to 10% by weight. , in particular 1% by weight to 5% by weight. In a further preferred embodiment of the invention, the foam regulator emulsion to be sprayed onto the carrier material contains a mixture of silicone oil and paraffin wax in a weight ratio of 2: 1 to 1: 100, in particular 1: 1 to 1:10. A particularly preferred foam regulator emulsion contains 10% by weight to 40% by weight, in particular 15% by weight to 35% by weight of silicone oil and 50% by weight to 80% by weight of water.
Falls die erfindungsgemäß brauchbare Schaumregulatoremulsion Paraffinwachs enthält, wird eine zweite Komponente des Entschäumersystems vorzugsweise aus Bisfettsäureamiden gebildet. Geeignet sind Bisamide, die sich von gesättigten Fettsäuren mit 12 bis 22, vorzugsweise 14 bis 18 C- Atomen sowie von Alkylendiaminen 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, Penta- methylendiamin, 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 .If the foam regulator emulsion which can be used according to the invention contains paraffin wax, a second component of the defoamer system is preferably formed from bisfatty acid amides. Bisamides are suitable which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18, carbon atoms and from alkylenediamines with 2 to 7 Derive carbon atoms. Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid and mixtures thereof, as can be obtained from natural fats or hydrogenated oils, such as tallow or hydrogenated palm oil. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. 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.
Unter nichtionischen Emulgatoren, die in erfindungsgemäß brauchbaren Emulsionen zum Einsatz kommen können, werden insbesondere die Alkoxylate, vorzugsweise die Ethoxy- late und/oder Propoxylate von Alkoholen, Alkylaminen, vicinalen Diolen, Carbonsäuren und/oder Carbonsäureamiden, die Alkylgruppen mit 8 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen, besitzen, verstanden. Der mittlere Alkoxylierungsgrad dieser Verbindungen beträgt dabei in der Regel von 1 bis 10, vorzugsweise 2 bis 5. Sie können in bekannter Weise durch Umsetzung mit den entsprechenden Alkylenoxiden hergestellt werden. Auch Produkte, die durch Alkoxylierung von Fettsäurealkylestern mit 1 bis 4 C- Atomen im Esterteil nach dem Verfahren der internationalen Patentanmeldung WO 90/13533 herstellbar sind, kommen in Frage. Zu den in Frage kommenden Alkohol- alkoxylaten gehören die Ethoxylate und/oder Propoxylate von linearen oder verzweigt- kettigen Alkoholen mit 8 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen. Geeignet sind insbesondere die Derivate der Fettalkohole, obwohl auch deren verzweigtkettige Isomere zur Herstellung verwendbarer Alkoxylate eingesetzt werden können. Brauchbar sind demgemäß insbesondere die Ethoxylate primärer Alkohole mit linearen Dodecyl-, Tetra- decyl-, Hexadecyl- oder Octadecylresten sowie deren Gemische. Auch der Einsatz entsprechender Alkoxylate von ein- oder mehrfach ungesättigten Fettalkoholen, zu denen beispielsweise Oleylalkohol, Elaidylalkohol, Linoleylalkohol, Linolenylalkohol, Gadoleylalkohol und Erucaalkohol gehört, ist möglich. Auch Ester beziehungsweise Partialester von Carbonsäuren entsprechender C-Kettenlänge mit Polyolen wie Glycerin oder Oligoglycerin können eingesetzt werden. Bevorzugte anionische Emulgatoren sind Alkalisalze der Alkylbenzolsulfonsäuren mit 9 bis 13 C-Atomen in der Alkylgruppe, insbesondere Natriumdodecylbenzolsulfonat. Zusätzlich zu derartigen Emulgatoren können geringe Mengen, gegebenenfalls bis zu 4 Gew.-%, anionischer und/oder nichtionischer Celluloseether wie Carboxymethylcellulose und/oderNonionic emulsifiers which can be used in emulsions which can be used according to the invention include, in particular, the alkoxylates, preferably the ethoxylates and / or propoxylates of alcohols, alkylamines, vicinal diols, carboxylic acids and / or carboxamides, the alkyl groups with 8 to 22 carbon atoms. Have atoms, preferably 12 to 18 carbon atoms, understood. The average degree of alkoxylation of these compounds is generally from 1 to 10, preferably 2 to 5. They can be prepared in a known manner by reaction with the corresponding alkylene oxides. Products which can be prepared by alkoxylation of fatty acid alkyl esters with 1 to 4 carbon atoms in the ester part by the process of international patent application WO 90/13533 are also suitable. The alcohol alkoxylates in question include the ethoxylates and / or propoxylates of linear or branched-chain alcohols having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms. Derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers can also be used to prepare usable alkoxylates. Accordingly, the ethoxylates of primary alcohols with linear dodecyl, tetra-decyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. It is also possible to use corresponding alkoxylates of mono- or polyunsaturated fatty alcohols, which include, for example, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol and erucalcohol. Esters or partial esters of carboxylic acids of corresponding carbon chain length with polyols such as glycerol or oligoglycerol can also be used. Preferred anionic emulsifiers are Alkali salts of alkylbenzenesulfonic acids with 9 to 13 carbon atoms in the alkyl group, in particular sodium dodecylbenzenesulfonate. In addition to such emulsifiers, small amounts, optionally up to 4% by weight, of anionic and / or nonionic cellulose ethers such as carboxymethyl cellulose and / or
Hydroxyethylcellulose, enthalten sein.Hydroxyethyl cellulose may be included.
Wesentlich zur Herstellung erfindungsgemäß brauchbarer Emulsionen ist, daß man eine homogene Mischung aus Schaumregulatorsystem und insbesondere nichtionischem Emulgator einsetzt. Diese kann man vorteilhaft in einfacher Weise durch Aufschmelzen des bei Raumtemperatur festen Bisamids in Gegenwart des Paraffins und des Emulgators, zweckmäßigerweise unter Rühren beziehungsweise Homogenisieren, erreichen. Falls das Bisamid nicht in Substanz, sondern vorkonfektioniert in Abmischung mit dem Paraffin eingesetzt wird, ist ein Erhitzen über den Schmelzpunkt des Bisamids hinaus in der Regel nicht erforderlich, da sich bereits bei niedrigeren Temperaturen in der Regel eine Lösung des Bisamids im Paraffin bildet. Anschließend an die vorzugsweise bei Temperaturen im Bereich von 60 °C bis 150 °C, insbesondere 80 °C bis 150 °C vorgenommene Bildung des Gemisches aus Entschäumersystem und Emulgator wird dieses, gegebenenfalls nach Abkühlen, mit dem Wasser vermischt, wobei dem Wasser zuvor ein insbesondere anionischer Emulgator zugesetzt worden sein kann. In diesem Fall beträgt die Konzentration an anionischem Emulgator in Wasser vorzugsweise 5 Gew.-% bis 15 Gew.-%.It is essential for the production of emulsions which can be used according to the invention that a homogeneous mixture of foam regulator system and in particular nonionic emulsifier is used. This can advantageously be achieved in a simple manner by melting the bisamide which is solid at room temperature in the presence of the paraffin and the emulsifier, advantageously with stirring or homogenization. If the bisamide is not used in bulk, but pre-assembled in a mixture with the paraffin, heating above the melting point of the bisamide is generally not necessary, since a solution of the bisamide in the paraffin usually forms even at lower temperatures. Subsequent to the formation of the mixture of defoamer system and emulsifier, which is preferably carried out at temperatures in the range from 60 ° C. to 150 ° C., in particular 80 ° C. to 150 ° C., this is mixed with the water, if appropriate after cooling, the water being previously in particular anionic emulsifier may have been added. In this case, the concentration of anionic emulsifier in water is preferably 5% by weight to 15% by weight.
Die so erhältliche Emulsion ist bei Raumtemperatur lagerstabil und man bringt vorzugsweise 3 Gew.-% bis 60 Gew.-%, insbesondere 15 Gew.-% bis 45 Gew.-% an ihr auf das Trägermaterial auf. Nach dem Aufsprühen der wäßrigen Emulsion kann ein Trocknungsschritt, beispielweise unter Verwendung üblicher Wirbelschichttrockner, angeschlossen werden, oder man bringt die Emulsion unter gleichzeitiger Trocknung, zum Beispiel ebenfalls in einer Wirbelschicht, auf. Die erfindungsgemäßen beziehungsweise nach dem erfindungsgemäßen Verfahren erhältlichen Schaumregulatorgranulate enthalten vorzugsweise 5 Gew.-% bis 50 Gew.-%, insbesondere 8 Gew.-% bis 35 Gew.-% Schaumregulatorwirkstoff. BeispieleThe emulsion thus obtainable is stable in storage at room temperature and preferably 3% by weight to 60% by weight, in particular 15% by weight to 45% by weight, is applied to the support material. After the aqueous emulsion has been sprayed on, a drying step can be carried out, for example using conventional fluidized bed dryers, or the emulsion can be applied with simultaneous drying, for example likewise in a fluidized bed. The foam regulator granules according to the invention or obtainable by the method according to the invention preferably contain 5% by weight to 50% by weight, in particular 8% by weight to 35% by weight foam active ingredient. Examples
306 Gew.-Teile einer gemäß WO 00/36063 erhaltenen Schaumregulatoremulsion, enthaltend 40 Gew.-% Paraffinwachs mit einem Erstarrungspunkt nach DLN ISO 2207 von 45 °C und einem Flüssiganteil bei 40 °C von ca. 66 Gew.-% und bei 60 °C von ca. 96 % (Lunaflex®, Hersteller DEA), 6 Gew.-% Bistearylsäureethylendiamid, 4,5 Gew.-% Silikonöl, 5,5 Gew.-% anionischen (Na-Dodecylbenzolsulfonat) und 5 Gew.- % nichtionischen (3 -fach ethoxylierter C12/14-Fettalkohol, Hersteller Cognis Deutschland GmbH) Emulgator, Rest Wasser, wurden in einem Mischer auf die darin vorgelegte Kombination aus Natriumcarbonat (704 Gew.-Teile) und Citronensäure (63 Gew.-Teile), die man zuvor mit 30 Gew. -Teilen Wasser versetzt hatte, aufgebracht, wobei sich ein Granulat bildete. Dieses wurde anschließend in einem Wirbleschichttrockner bei 80 - 90 °C getrocknet. Das so erhaltene Schaumregulator-Granulat wurden in einer Menge von jeweils 1 Gew.-% zu einem entschäumerfreien teilchenförmigen Waschmittel zugesetzt, was bei Waschtemperaturen von 40 °C, 60 °C und 90 °C eine Entschäumerleistung ergab, die nicht hinter derjenigen bei Einsatz auf konventionelle Art hergestellter Entschäumergranulate zurückstand. Es wies einer höhere Konstabilität und einen geringeren Feinkornateil auf als ein entsprechend hergestelltes Granulat, dem der Br0nsted-Säure-Anteil fehlte oder bei dem dieser durch polymeres Alkalipolycarboxylat ersetzt war. 306 parts by weight of a foam regulator emulsion obtained according to WO 00/36063, containing 40% by weight paraffin wax with a solidification point according to DLN ISO 2207 of 45 ° C and a liquid fraction at 40 ° C of approx. 66% by weight and at 60 ° C of approx. 96% (Lunaflex®, manufacturer DEA), 6% by weight bisstearyl acid ethylenediamide, 4.5% by weight silicone oil, 5.5% by weight anionic (Na-dodecylbenzenesulfonate) and 5% by weight Nonionic (triple ethoxylated C 12/14 fatty alcohol, manufacturer Cognis Deutschland GmbH) emulsifier, the rest water, were mixed in a mixer with the combination of sodium carbonate (704 parts by weight) and citric acid (63 parts by weight) , which had previously been mixed with 30 parts by weight of water, whereby granules formed. This was then dried in a fluidized bed dryer at 80-90 ° C. The foam regulator granules thus obtained were added in an amount of 1% by weight each to a defoamer-free particulate detergent, which gave a defoamer performance at washing temperatures of 40 ° C., 60 ° C. and 90 ° C. which was not behind that in use conventional type of defoamer granules produced. It had a higher degree of stability and a smaller proportion of fine particles than a correspondingly produced granulate which lacked the Brønsted acid component or in which it was replaced by polymeric alkali polycarboxylate.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung teilchenformiger Schaumregulatorgranulate durch Aufsprühen einer wäßrigen Schaumregulatoremulsion, die 16 Gew.-% bis 70 Gew.-% Schaumregulatorwirkstoff auf Paraffinwachs- und/oder Silikonolbasis, 2 Gew.-% bis 15 Gew.-% nichtionischen und/oder anionischen Emulgator sowie nicht mehr als 80 Gew.-% Wasser enthält, auf ein festes Trägermaterial, woran sich gegebenenfalls ein Trocknungsschritt anschließt, dadurch gekennzeichnet, daß das Trägermaterial Alkalicarbonat und eine Bronsted-Säure enthält.1. Process for the production of particulate foam regulator granules by spraying on an aqueous foam regulator emulsion containing 16% by weight to 70% by weight of foam regulator active substance based on paraffin wax and / or silicone oil, 2% by weight to 15% by weight of nonionic and / or anionic Contains emulsifier and not more than 80 wt .-% water, on a solid carrier material, which is optionally followed by a drying step, characterized in that the carrier material contains alkali carbonate and a Bronsted acid.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Bronsted-Säure bei 25 °C in fester Form vorliegt.2. The method according to claim 1, characterized in that the Bronsted acid is present at 25 ° C in solid form.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Bronsted-Säure bei 25 °C eine Wasserlöslichkeit von mindestens 100 g/1 aufweist.3. The method according to claim 1 or 2, characterized in that the Bronsted acid at 25 ° C has a water solubility of at least 100 g / 1.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Bransted- Säure aus den Di- und Tricarbonsäuren, deren sauren Salzen, den sauren Salzen von anorganischen Säuren, insbesondere NaHSO4, Na2HPO4 und NaH2PO4, und deren Mischungen ausgewählt wird.4. The method according to any one of claims 1 to 3, characterized in that the Bransted acid from the di- and tricarboxylic acids, their acid salts, the acid salts of inorganic acids, in particular NaHSO 4 , Na 2 HPO 4 and NaH 2 PO 4 , and their mixtures is selected.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Trägermaterial Alkalicarbonat und eine Bronsted-Säure in Gewichtsverhältnissen von 1:1 bis 100:1, insbesondere von 20:3 bis 80:3 enthält.5. The method according to any one of claims 1 to 4, characterized in that the carrier material contains alkali carbonate and a Bronsted acid in weight ratios of 1: 1 to 100: 1, in particular from 20: 3 to 80: 3.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Trägermaterial 40 Gew.-% bis 90 Gew.-%, insbesondere 60 Gew.-% bis 80 Gew.-% Alkalicarbonat und 1-20 Gew.-%, insbesondere 3 Gew.-% bis 9 Gew.-% einer Br0nsted-Säure aufweist. 6. The method according to any one of claims 1 to 5, characterized in that the carrier material 40 wt .-% to 90 wt .-%, in particular 60 wt .-% to 80 wt .-% alkali carbonate and 1-20 wt .-% , in particular 3% by weight to 9% by weight of a Bronsted acid.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Trägermaterial zusätzlich weitere feste und/oder in fester Form konfektionierte Wasch- oder Reinigungsmittelbestandteile enthält.7. The method according to any one of claims 1 to 6, characterized in that the carrier material additionally contains further solid and / or solid detergent components.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man eine wäßrige Schaumregulatoremulsion, enthaltend 16 Gew.-% bis 70 Gew.-% Schaumre- gulatorwirkstoff auf Paraffinwachs- und/oder Silikonolbasis, 2 Gew.-% bis 15 Gew.- % nichtionischen und/oder anionischen Emulgator sowie nicht mehr als 80 Gew.- % Wasser, einsetzt.8. The method according to any one of claims 1 to 7, characterized in that an aqueous foam regulator emulsion containing 16 wt .-% to 70 wt .-% foam regulator active ingredient based on paraffin wax and / or silicone oil, 2 wt .-% to 15 % By weight nonionic and / or anionic emulsifier and not more than 80% by weight water.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man eine wäßrige Schaumregulatoremulsion, enthaltend 15 Gew.-% bis 60 Gew.-% Paraffinwachs oder einer Mischung aus Paraffinwachs und Silikonöl, 1 Gew.-% bis 10 Gew.- % sich von C2.7-Diaminen und Cι2.22-Fettsäuren ableitendem Bisfettsäureamid, 2 Gew.-% bis 15 Gew.-% nichtionischen und/oder anionischen Emulgator sowie nicht mehr als 80 Gew.-% Wasser, einsetzt.9. The method according to any one of claims 1 to 8, characterized in that an aqueous foam regulator emulsion containing 15 wt .-% to 60 wt .-% paraffin wax or a mixture of paraffin wax and silicone oil, 1 wt .-% to 10 wt. -% of C 2.7 diamines and Cι 2 . 22 fatty acid-conducting bis fatty acid amide, 2% by weight to 15% by weight of nonionic and / or anionic emulsifier and not more than 80% by weight of water.
10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die wäßrige Schaumregulatoremulsion 30 Gew.-% bis 50 Gew.-% Paraffmwachs oder einer Mischung aus Paraffinwachs und Silikonöl enthält.10. The method according to any one of claims 1 to 9, characterized in that the aqueous foam regulator emulsion contains 30 wt .-% to 50 wt .-% paraffin wax or a mixture of paraffin wax and silicone oil.
11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die wäßrige Schaumregulatoremulsion eine Mischung aus Silikonöl und Paraffinwachs im Gewichtsverhältnis 2:1 bis 1:100, insbesondere 1:1 bis 1:10, enthält.11. The method according to any one of claims 1 to 10, characterized in that the aqueous foam regulator emulsion contains a mixture of silicone oil and paraffin wax in a weight ratio of 2: 1 to 1: 100, in particular 1: 1 to 1:10.
12. Verfahren nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß das Paraffmwachs bei Raumtemperatur fest ist und bei 100 °C in vollständig flüssiger Form vorliegt.12. The method according to any one of claims 1 to 11, characterized in that the paraffin wax is solid at room temperature and is in completely liquid form at 100 ° C.
13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, daß das Paraffinwachs bei 40 °C einen Flüssiganteil von mindestens 50 Gew.-%, insbesondere von 55 Gew.-% bis 80 Gew.-%, und bei 60 °C einen Flüssiganteil von mindestens 90 Gew.-% aufweist.13. The method according to claim 12, characterized in that the paraffin wax at 40 ° C has a liquid content of at least 50 wt .-%, in particular 55 wt .-% up to 80 wt .-%, and at 60 ° C has a liquid content of at least 90 wt .-%.
14. Verfahren nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß die wäßrige Schaumregulatoremulsion 3 Gew.-% bis 8 Gew.-% sich von C2.7-Diaminen und C12.22-Fettsäuren ableitendem Bisfettsäureamid enthält.14. The method according to any one of claims 1 to 13, characterized in that the aqueous foam regulator emulsion 3 wt .-% to 8 wt .-% of C 2 . 7 diamines and C 12 . Contains 22 fatty acid-derived bis fatty acid amide.
15. Verfahren nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, daß die wäßrige Schaumregulatoremulsion einen Gehalt an Silikonöl im Bereich von 0,1 Gew.-% bis 10 Gew.-%, insbesondere 1 Gew.-% bis 5 Gew.-% aufweist.15. The method according to any one of claims 1 to 14, characterized in that the aqueous foam regulator emulsion has a silicone oil content in the range of 0.1 wt .-% to 10 wt .-%, in particular 1 wt .-% to 5 wt .-% % having.
16. Verfahren nach einem der Ansprüche 1 bis 15, dadurch gekemizeichnet, daß die wäßrige Schaumregulatoremulsion 3 Gew.-% bis 10 Gew.-% nichtionischen und/oder anionischen Emulgator enthält.16. The method according to any one of claims 1 to 15, characterized in that the aqueous foam regulator emulsion contains 3% by weight to 10% by weight of nonionic and / or anionic emulsifier.
17. Verfahren nach Anspruch 16, dadurch gekennzeichnet, daß der nichtionische Emulgator unter den Alkoxylaten, insbesondere den Ethoxylaten und/oder Propoxy- laten von Alkoholen, Alkylaminen, vicinalen Diolen und/oder Carbonsäureamiden, die Alkylgruppen mit 8 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen, besitzen, und deren mittlerer Alkoxylierungsgrad von 1 bis 10, insbesondere 2 bis 5 beträgt, ausgewählt wird.17. The method according to claim 16, characterized in that the nonionic emulsifier among the alkoxylates, in particular the ethoxylates and / or propoxylates of alcohols, alkylamines, vicinal diols and / or carboxamides, the alkyl groups with 8 to 22 carbon atoms, preferably Have 12 to 18 carbon atoms, and their average degree of alkoxylation is from 1 to 10, in particular 2 to 5, is selected.
18. Verfaliren nach einem der Ansprüche 1 bis 17, dadurch gekennzeichnet, daß man in einem Granulationsmischer eine Aufbaugranulation derart durchführt, daß man eine Menge von 40 bis 110 Gewichtsteilen, insbesondere 60 bis 90 Gewichtsteilen an Trägermaterial intensiv mischt und unter Granulieren eine Menge von 15 bis 50 Gewichtsteilen, insbesondere 25 bis 35 Gewichtsteilen der gegebenenfalls auf eine Temperatur im Bereich von 70 °C bis 180 °C erwärmten Schaumregulatoremulsion zusetzt.18. Verfaliren according to any one of claims 1 to 17, characterized in that one carries out a build-up granulation in a granulation mixer in such a way that an amount of 40 to 110 parts by weight, in particular 60 to 90 parts by weight of carrier material is mixed intensively and with granulation an amount of 15 up to 50 parts by weight, in particular 25 to 35 parts by weight, of the foam regulator emulsion optionally heated to a temperature in the range from 70 ° C. to 180 ° C.
19. Verfaliren nach einem der Ansprüche 1 bis 18, dadurch gekennzeichnet, daß die Bransted-Säure Citronensäure ist. 19. Verfaliren according to any one of claims 1 to 18, characterized in that the Bransted acid is citric acid.
0. In Wasch- oder Reinigungsmitteln einsetzbares teilchenförmiges Schaumregulierungsmittel, enthaltend Schaumregulatorwirkstoff auf Paraffmwachs- und/oder Silikonolbasis, nichtionischen und/oder anionischen Emulgator und festes Trägermaterial, dadurch gekennzeichnet, daß das Trägermaterial Alkalicarbonat und eine Bronsted-Säure enthält. 0. Particulate foam regulating agent which can be used in washing or cleaning agents, containing foam regulating agent based on paraffin wax and / or silicone oil, nonionic and / or anionic emulsifier and solid carrier material, characterized in that the carrier material contains alkali carbonate and a Bronsted acid.
EP02722070A 2001-02-22 2002-02-13 Foam regulating granulates Expired - Lifetime EP1362090B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10108459A DE10108459A1 (en) 2001-02-22 2001-02-22 Stability of foam-regulator granulates for use in detergents is improved by using a carrier containing alkali carbonate and a Bronsted acid
DE10108459 2001-02-22
PCT/EP2002/001458 WO2002074894A1 (en) 2001-02-22 2002-02-13 Foam regulating granulates

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EP1362090A1 true EP1362090A1 (en) 2003-11-19
EP1362090B1 EP1362090B1 (en) 2006-09-13

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EP02722070A Expired - Lifetime EP1362090B1 (en) 2001-02-22 2002-02-13 Foam regulating granulates

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US (1) US7279453B2 (en)
EP (1) EP1362090B1 (en)
DE (2) DE10108459A1 (en)
ES (1) ES2272700T3 (en)
WO (1) WO2002074894A1 (en)

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Also Published As

Publication number Publication date
EP1362090B1 (en) 2006-09-13
US20040152615A1 (en) 2004-08-05
DE50208134D1 (en) 2006-10-26
ES2272700T3 (en) 2007-05-01
WO2002074894A1 (en) 2002-09-26
US7279453B2 (en) 2007-10-09
DE10108459A1 (en) 2002-09-12

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