EP0670880A1 - Agent sans silicone pour la regulation de la mousse - Google Patents

Agent sans silicone pour la regulation de la mousse

Info

Publication number
EP0670880A1
EP0670880A1 EP94901842A EP94901842A EP0670880A1 EP 0670880 A1 EP0670880 A1 EP 0670880A1 EP 94901842 A EP94901842 A EP 94901842A EP 94901842 A EP94901842 A EP 94901842A EP 0670880 A1 EP0670880 A1 EP 0670880A1
Authority
EP
European Patent Office
Prior art keywords
weight
water
mixture
carrier material
alkali
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.)
Ceased
Application number
EP94901842A
Other languages
German (de)
English (en)
Inventor
Wolfgang Seiter
Claus-Peter KURZENDÖRFER
Hans-Josef Beaujean
Eric Sung
Karl Schwadtke
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 EP0670880A1 publication Critical patent/EP0670880A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • 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
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D3/18—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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2072—Aldehydes-ketones

Definitions

  • the invention relates to a homogeneous defoamer mixture which contains long-chain alkyl or alkenyl radicals containing ketone with at least 25 C atoms and a paraffin wax which is solid at room temperature, a pourable and free-flowing foam control agent, containing water-soluble or water-dispersible carrier material and defoamers adsorbed thereon mergemix, and a process for the production of such foam regulating agents.
  • ketones of the type concerned here and their preparation are known, for example from German Offenlegungsschrift DE 25 53990.
  • the ketones are prepared by catalytic elimination of CO2 and water from higher monocarboxylic acids, in particular higher fatty acids or their salts. Their use as a means for special foam control in the paint, paper and food industry is described in the aforementioned publication. From the European patent application EP 324339 it is known to use corresponding ketones in detergents containing active chlorine. There, however, the ketones are used as a dispersion in liquid organic carriers. Furthermore, it is known from German Offenlegungsschriften DE 1467 613 and DE 2242 541 to use ketones as foam inhibitors in detergents containing soap. In the absence of soaps and additional foam inhibitors, such as acetals and ketals, their action is insufficient in such compositions.
  • the object was accordingly to provide a defoaming mixture which is effective in detergents over a wide temperature range, that is to say in particular in the cold washing range and at medium washing temperatures, but also in the hot washing range, suppressing disruptive foaming. Furthermore, the defoamer mixture should be able to be made up into a free-flowing foam regulating agent which, when mixed with conventional detergent constituents, has a stable storage and action remains and has no adverse effects on the material to be treated and the environment.
  • the invention accordingly relates to a homogeneous defoamer mixture which is particularly suitable for adsorption onto a granular, water-soluble or water-dispersible carrier material
  • the defoamer mixture preferably contains 1% by weight to 25% by weight, in particular 5% by weight to 18% by weight of ketone (a) and 75% by weight to 99% by weight, in particular 82% to 95% by weight paraffin wax (b).
  • Another object of the invention is a granular, free-flowing foam control agent, consisting of (I) a granular, phosphate-free, water-soluble or water-dispersible carrier material and (II) a homogeneous defoamer mixture adsorbed thereon, as mentioned above, which comprises 80% by weight to 99% 5% by weight, in particular 88% by weight to 98% by weight of carrier material (I) and 0.5% by weight to 20% by weight, in particular 2% by weight to 12% by weight of defoamer mixture (II) contains.
  • the foam regulating agent according to the invention preferably contains 80% by weight to 99.5% by weight, in particular 88% by weight to 98% by weight, of carrier material (I) and 0.5% by weight to 20% by weight, in particular Contain 2 wt .-% to 12 wt .-% defoamer mixture (II).
  • ketones which can be obtained by reacting linear or branched, saturated or unsaturated carboxylic acids or carboxylic acid mixtures in which the car- bonic acids have more than 12 carbon atoms, in particular a carbon chain length of C14 to C30 and react during the ketonization with elimination of carbon dioxide and water.
  • ketones which are obtained from the ketonization of carboxylic acids or carboxylic acid salts with a carbon chain length of Ci ⁇ to C22 and mixtures thereof.
  • the ketones can usually be prepared at temperatures in the range from about 200 to 350 ° C. in the presence of metal oxides or fatty acid metal compounds.
  • Both starting materials with a uniform number of carbon atoms and fatty acid mixtures of natural origin can be used. These mixtures can also contain carboxylic acids with 12 and fewer C atoms, provided there is an excess of fatty acids with 14 and more C atoms. This results in mixtures of symmetrical and asymmetrical ketones, whereby the asymmetrical ketones can also have shorter chains than C14 or C12 depending on the material used, provided there is a longer-chain residue in the molecule, so that the total number of C atoms is at least 25 on average is.
  • Ketones or ketone mixtures of the type described are usually solid at room temperature and have melting points in the range from 60 ° C. to 105 ° C.
  • the ketones are preferably in finely divided form and in particular have an average grain size of less than 50 ⁇ m.
  • the information regarding the particle size relates to the known determination method with the "Coulter Counter".
  • the paraffin wax contained in the defoamer mixture (component b) is generally a complex mixture of substances without a sharp melting point.
  • its melting range is usually determined by differential thermal analysis (DTA), as described 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 that are completely liquid at room temperature i.e. those with a solidification point below 25 ° C, not usable according to the invention. Waxes which solidify in the range from 30 ° C. to 90 ° C. are preferably used. It should be noted that even paraffin wax mixtures which appear solid at room temperature can contain different proportions of liquid paraffin.
  • this liquid fraction is as low as possible and is preferably completely absent.
  • Preferred paraffin wax mixtures have a liquid fraction of less than 10% by weight at 30 ° C., in particular 2% to 5% by weight, and a liquid fraction of less than 30% by weight at 40 ° C. preferably from 5% by weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction from 30% by weight to 60% by weight, in particular by 40 % By weight to 55% by weight, at 80 ° C a liquid fraction of 80% by weight to 100% by weight, and at 90 ° C a liquid fraction of 100% by weight.
  • the temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C., in particular at 75 ° C. to 82 ° C., in particularly preferred paraffin wax mixtures.
  • Paraffin waxes which can be used according to the invention are, for example, Lunafle® ( R ) 902 from Guer and Deawa ⁇ ( R ) DEW 5419 from DEA Mineralöl AG.
  • the defoamer mixture can be prepared by introducing the finely divided ketone (component a) into a melt of component (b) and homogenizing it by intensive mixing.
  • the melt should have a temperature of at least 60 ° C and at most 200 ° C.
  • the temperature is preferably 80 ° C. to 160 ° C. It is essential for a good effectiveness of the defoamer that there is a stable dispersion of the ketone particles in the paraffin matrix, which can be brought about by a particle size corresponding to the definition mentioned.
  • a ketone can be used and dispersed which has the appropriate particle size from the outset, or a coarser starting material is used and the melt is subjected to grinding treatment using colloid mills, tooth mills or ball mills until the desired particle size is reached is.
  • a complete melting of the ketone in the paraffin melt and subsequent rapid cooling to temperatures below the solidification point of the ketone with simultaneous homogenization of the melt can also lead to a correspondingly fine particle size distribution of the ketone.
  • a further advantage of the defoamer mixture according to the invention is that the long-chain ketones have a significantly higher thermal capacity than conventional defoamer constituents based on carboxylic acid-bisamide.
  • a foam regulating agent according to the invention can be produced by applying the molten defoamer mixture (II) to a granular carrier material (I), for example by successive admixing, in particular as a spray, to the carrier grain.
  • the carrier grain which can be produced in the usual way by spray drying an aqueous slurry of carrier salts, is kept in motion by mixing elements or by fluidization in order to ensure a uniform loading of the carrier material.
  • the spray mixers used for this can be operated continuously or discontinuously.
  • One embodiment for the production consists in hurling the granular carrier material in a continuous stream through the likewise continuously generated spray zone of the at least partially melted defoamer mixture, whereby retention times of the carrier material in the hot spray zone of mostly less than 1 second can be achieved . Furthermore, it is possible immediately afterwards to cool the particles of the foam regulating agent with the aid of a gas stream, so that the thermal loads on the material can be kept extremely low.
  • a wheel-shaped mixing device is described as a device for carrying out the method, in which two individually designed and driven wheel-shaped disks are superimposed.
  • the solid powder is fed to one disk, the liquid component below is charged with the liquid component.
  • Both discs run at high rotational speeds, which can range from a few 100 to a few 1000 revolutions per minute.
  • the respective pressurized writing surfaces and in particular the edge of the disk carrying the liquid are designed in such a way that on the one hand the spray zone is thrown off and continuously replicated from the edge of the wheel running at high speed of rotation, on the other hand the granular element continuously supplied to the other wheel-shaped element Material thrown through this spray zone of the liquid phase. Because of the high working speed, the two material phases come into very short contact with one another and thus only a very short time contact of the solid particles with the warm or hot spray phase.
  • the method can be carried out particularly well with the device described in EP 48 312, but it is not restricted to devices of this type. It is essential to set a relatively short contact time, which is achieved by the solid material being thrown through a continuously generated spray zone, the solid material optionally being able to be cooled in front of and / or behind the spray zone.
  • the foam regulating agent is prepared by dissolving or slurrying the carrier material (I) in water, dispersing the defoamer mixture (II) therein and then spray-drying this slurry.
  • a water-soluble, non-surfactant dispersion stabilizer in the form of a water-swellable polymer is preferably added to the dispersion, since the components of the defoamer mixture are generally not sufficiently soluble in the aqueous slurry. 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 acting 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 composition.
  • the water content of the slurry can be 30% by weight to 60% by weight.
  • the spray drying of the dispersion can be carried out in a known manner in systems provided for this purpose, so-called spray towers, using hot, co-current or counter-current drying gases. In this case, drying by drying gases carried in cocurrent with the spray material is preferred, since the loss of activity due to the potential hot air volatility of some components of the defoamer mixture can be reduced to a minimum.
  • the phosphate-free carrier material (I) has a granular structure and consists of water-soluble or water-dispersible, surfactant-free compounds, primarily of inorganic and / or organic salts which are suitable for use in detergents and cleaning agents. It preferably contains both alkali carbonate and alkali silicate, the latter in particular being responsible for the good storage properties of the agents according to the invention.
  • the carrier material preferably contains 1% by weight to 50% by weight of alkali carbonate, up to 70% by weight of alkali sulfate, up to 50% by weight of alkali alumosilicate and 10% by weight to 50% by weight of alkali silicate, but can additionally contain other water-soluble or water-insoluble, water-dispersible substances.
  • the materials which can additionally be used include, in particular, alkali metal chloride and layered silicate, for example bentonite.
  • the alkali silicate is 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 grain properties, in particular high abrasion stability and nevertheless a high rate of dissolution in water.
  • the aluminosilicates which can be used in the carrier material for the foam regulating agents according to the invention include, in particular, the zeolites, for example zeolite NaA and NaX.
  • suitable organic carrier materials are acetates, tartrates, citrates, succinates, carboxymethyl succinates and the alkali salts of amino polycarboxylic acids, such as NTA or EDTA, hydroxyalkane phosphonates and aminoalkane polyphosphonates, such as l-hydroxyethane-l, l diphosphonate, ethylene diaminotetramethylene phosphonate and diethylene triamine pentamethylene phosphonate. It is also possible to use water-soluble salts of polymeric or copolymeric carboxylic acids, for example polyacrylates and copolymers of acrylic acid and maleic acid. Mixtures of inorganic and organic salts can often be used with advantage.
  • Such additional organic carrier materials are preferably not more than 20% by weight, in particular in amounts of 2% by weight to 15% by weight, in each case pulled on entire carrier material, contained in the carrier salt mixture.
  • the preferred alkali metal in the alkali salts mentioned is sodium in all cases.
  • the carrier material can moreover contain film-forming polymers, for example polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, polyacrylates and cellulose derivatives.
  • Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose ether, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof.
  • 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.
  • film-forming polymers are preferably not contained in the carrier material in excess of 5% by weight, in particular from 0.5% by weight to 2% by weight, based on the total carrier material.
  • the foam regulating agent according to the invention contains 2% by weight to 5% by weight of alkali carbonate, in particular sodium carbonate, up to 30% by weight of alkali silicate, in particular sodium silicate, 10% by weight to 75% by weight of alkali metal sulfate , in particular sodium sulfate, up to 35% by weight, in particular 10% by weight to 30% by weight of zeolite, up to 5% by weight, in particular 1% by weight to 3% by weight of water-soluble or in what ⁇ this swellable polymer, in particular cellulose ether, and up to 17 wt .-%, in particular 5 wt .-% to 15 wt .-% water.
  • a further preferred embodiment of the foam regulating agent according to the invention contains 25% by weight to 45% by weight of alkali carbonate, 5% by weight to 20% by weight of alkali silicate, up to 50% by weight, in particular 15% by weight to 45% by weight, zeolite and / or alkali sulfate, up to 3% by weight, in particular 0.5% by weight to 2% by weight, water-soluble or water-swellable polymer and up to 20% by weight %, in particular 3% by weight to 18% by weight, water.
  • the foam regulating agents according to the invention are preferably free of surfactants in the mixture of substances.
  • Surfactants are to be understood as surface-active compounds with a hydrophobic part of the molecule and hydrophilic anionic, ampholytic, zwitterionic, cationic and nonionic groups which have a cleaning or emulsifying effect in aqueous solution or dispersion.
  • the hydrophobic part of the molecule generally consists of a hydrocarbon residue or a substituted hydrocarbon residue or a polyglycol ether residue which is poorly soluble in water, for example a polypropylene glycol or polybutylene glycol ether residue.
  • a foam regulating agent according to the invention preferably consists of particles with particle sizes not more than 2 mm, in particular from 0.1 mm to 1.6 mm. It preferably has a bulk density in the range from 300 grams per liter to 900 grams per liter, in particular from 450 grams per liter to 800 grams per liter. It is preferably used for the production of powdered detergents or cleaning agents, a further advantage of the foam regulating agents according to the invention being their low use with good defoamer performance. It is thus possible to achieve the defoamer performance of conventional silicone defoamers with equal amounts, based on active substance, of the paraffin-based foam regulating agents according to the invention. Examples
  • zeolite By mixing together pre-swollen cellulose ether in water with a paraffin-ketone melt obtained at 130 ° C., mixing with the separately prepared aqueous slurry of sodium carbonate, sodium sulfate and optionally zeolite and / or layered silicate and subsequent mixing with the optionally used sodium silicate, the zeolite in the form of an approx. 50% by weight aqueous
  • the free-flowing powder products S1 to S6 characterized by their composition, which were free of particles larger than 2 mm in diameter, parts of particles larger than 0.8 mm of 1% by weight and particles smaller than 0.2, were obtained mm of 21 wt .-% and had a bulk density of 650 grams per liter.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

Pour les systèmes antimousse adaptés aux produits de lavage et de nettoyage à base de tensio-actifs et pouvant être adsorbés sur des matériaux de support granuleux, solubles ou dispersibles dans l'eau, on se propose d'améliorer les possibilités de réaliser un agent de régulation de la mousse coulant et d'améliorer également l'efficacité de ce produit dans une gamme de températures étendue en faisant en sorte que le mélange antimousse comme l'agent de régulation de la mousse contenant ce mélange, mélangés aux composants courants des produits de lavage, restent stables à l'entreposage et conservent leur action, et qu'ils n'exercent pas d'effet défavorable sur le produit à traiter ou l'environnement. Cet objectif a été atteint essentiellement par la préparation d'un mélange d'agents antimousse contenant 0,1 à 20 % en poids d'une cétone présentant des restes alkyle ou alcényle à longue chaîne avec au total au moins 25 atomes de C et 70 à 99,9 % en poids d'une cire de paraffine ou d'un mélange de cires de paraffine qui est solide à la température ambiante et qui est 100 % liquide à une température inférieure à 90 °C.
EP94901842A 1992-11-30 1993-11-22 Agent sans silicone pour la regulation de la mousse Ceased EP0670880A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4240166 1992-11-30
DE19924240166 DE4240166A1 (de) 1992-11-30 1992-11-30 Silikonfreies Schaumregulierungsmittel
PCT/EP1993/003270 WO1994012604A1 (fr) 1992-11-30 1993-11-22 Agent sans silicone pour la regulation de la mousse

Publications (1)

Publication Number Publication Date
EP0670880A1 true EP0670880A1 (fr) 1995-09-13

Family

ID=6473974

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94901842A Ceased EP0670880A1 (fr) 1992-11-30 1993-11-22 Agent sans silicone pour la regulation de la mousse

Country Status (3)

Country Link
EP (1) EP0670880A1 (fr)
DE (1) DE4240166A1 (fr)
WO (1) WO1994012604A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2109720T3 (es) * 1993-08-02 1998-01-16 Henkel Kgaa Granulado regulador de la espuma y procedimiento para su fabricacion.
US5695575A (en) * 1995-10-06 1997-12-09 Lever Brothers Company, Division Of Conopco, Inc. Anti-form system based on hydrocarbon polymers and hydrophobic particulate solids
DE19851742A1 (de) * 1998-11-10 2000-05-11 Cognis Deutschland Gmbh Entschäumergranulate mit Ketonen

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1467615C3 (de) * 1965-08-20 1975-02-13 Henkel & Cie. Gmbh, 4000 Duesseldorf Waschmittel mit geringem Schaumvermögen
DE2242541A1 (de) * 1972-08-30 1974-03-07 Henkel & Cie Gmbh Schwachschaeumende wasch-, reinigungs- und enthaertungsmittel
DE2553990A1 (de) * 1975-12-01 1977-06-08 Henkel & Cie Gmbh Mittel zur schaumbekaempfung
DE3400008A1 (de) * 1984-01-02 1985-07-11 Henkel KGaA, 4000 Düsseldorf Zur verwendung in tensidhaltigen mitteln geeignetes schaumregulierungsmittel
DE3800483A1 (de) * 1988-01-11 1989-07-20 Henkel Kgaa Chlorstabile entschaeumer fuer aktivchlor enthaltende reinigungsmittel, insbesondere geschirreinigungsmittel
DE4117032A1 (de) * 1991-05-24 1992-11-26 Henkel Kgaa Silikonhaltiges entschaeumergranulat

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9412604A1 *

Also Published As

Publication number Publication date
WO1994012604A1 (fr) 1994-06-09
DE4240166A1 (de) 1994-06-01

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