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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
• • 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
  • C11D3/37—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 is in the field of detergents and relates to new coated defoamer granules for special use in foaming detergents with a high anionic surfactant content.
• a typical feature of anionic surfactants is to develop foam. In many applications, such as in hand dishwashing detergents or hair shampoos, this effect is by the consumer expressly desired, since he equates him with performance, even if it does scientific point of view does not apply easily. In the field of household and industrial detergents however, foam development is essentially undesirable because it quickly causes over-foaming of the machine. After due to anionic surfactants as part of the recipes their special performance profile can usually not be waived, there is a need To provide detergent formulations with a sufficient amount of defoamers that on the one hand limit the amount of foam to an acceptable level without on the other hand the recipe reduce their performance or make them too expensive. From the state of the Technology, a variety of connections are known for this purpose, only of which at this point the soaps, the paraffins and the silicones should be mentioned.
• defoamers have been produced either by drying the corresponding ones aqueous emulsions or dispersions or by directly spraying on the defoamer component on a carrier.
• Known processes such as Fluidized bed drying or granulation, Spray mixing process and conventional countercurrent drying in the spray tower used.
• additives such as sodium sulfate or zeolite are also used here Carrier incorporated.
• Auxiliaries and defoamer components - viewed macroscopically - are in the Granules distributed homogeneously, although it turns out under the microscope that the product is also heterogeneous Has areas, for example zones in which, for example, the defoamer concentrates is present.
• the invention relates to detergent additives in solid form, which are characterized in that that they consist of a defoaming compound as the core and a layer enveloping them.
• the detergent additives according to the invention in which it is coated defoamers in contrast to non-coated comparison products of retailers are still able to develop foam detergents to regulate reliably during the entire duration of the washing process, if the detergent has a have a particularly high proportion of anionic surfactants or anionic surfactants with a particularly pronounced Foaming power included. It is not a problem if part of the coating is produced gets into the defoamer grain. The coating of the defoamer grain must also also not be complete, it is sufficient if the wrapping ensures that the hike of water and surfactants, especially non-ionic surfactants, in the grain and thus the deactivation of the defoamer is prevented.
• the detergent additives according to the invention preferably contain the defoaming compounds - based on the sum of active substance and optionally carrier - in total amounts of from 75 to 99% by weight, preferably from 80 to 95 and in particular from 85 to 90% by weight.
• the defoamers can be waxy compounds and / or silicone compounds. According to one embodiment of the present invention, only wax-like defoamer compounds are contained as defoamers.
• “Waxy” are understood to mean those compounds which have a melting point at atmospheric pressure above 25 ° C. (room temperature), preferably above 50 ° C. and in particular above 70 ° C.
• the wax-like defoamer substances which may be present according to the invention are practically insoluble in water, ie at 20 They have a solubility of less than 0.1% by weight in 100 g of water at 100 ° C.
• all wax-like defoamer substances known from the prior art can be present polyhydric alcohols and paraffin waxes or mixtures thereof, or of course the silicone compounds known for this purpose can also be used.
• Suitable paraffin waxes generally represent a complex mixture of substances without a sharp melting point. For characterization, one usually determines its melting range by differential thermal analysis (DTA), as described in "The Analyst” 87 (1962), 420 , and / or its solidification point . This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., cannot be used according to the invention. For example, the paraffin wax mixtures known from EP 0309931 A1 of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C.
• paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably absent entirely.
• Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably of 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular 40% by weight % to 55% by weight, at 80 ° C a liquid content of 80% by weight to 100% by weight, and at 90 ° C a liquid content 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 particularly preferred paraffin wax mixtures, in particular at 75 ° C. to 82 ° C.
• the paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.
• Suitable bisamides as defoamers are those which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18 C atoms and from alkylenediamines with 2 to 7 C atoms.
• Suitable fatty acids are lauric 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 bismyristoylethylene diamine, bispalmitoylethylene diamine, bisstearoylethylene diamine and mixtures thereof and the corresponding derivatives of hexamethylene diamine.
• Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms.
• these are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid.
• the alcohol part of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain.
• suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol.
• Preferred esters are those of ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
• Eligible esters of polyhydric alcohols are, for example, xylitol monopalmitate, pentarythritol monostearate, glycerol monostearate, ethylene glycol monostearate and sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan dilaurate, sorbitan dististearate, sorbitan dandghenoate and mixed sorbitan dibehenate, and sorbitan dandebehenate, and sorbitan dandebehenate, and sorbitan dandebehenate, as well as sorbitan dandebehenate and mixed sorbitan dibehenate.
• Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred. Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this.
• esters as defoamers are beeswax, which mainly consists of the esters CH 3 (CH 2 ) 24 COO (CH 2 ) 27 CH 3 and CH 3 (CH 2 ) 26 COO (CH 2 ) 25 CH 3 , and carnauba wax , which is a mixture of carnauba acid alkyl esters, often in combination with small amounts of free carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.
• beeswax which mainly consists of the esters CH 3 (CH 2 ) 24 COO (CH 2 ) 27 CH 3 and CH 3 (CH 2 ) 26 COO (CH 2 ) 25 CH 3
• carnauba wax which is a mixture of carnauba acid alkyl esters, often in combination with small amounts of free carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.
• Suitable carboxylic acids as a further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid and mixtures thereof, as can be obtained from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil. Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred.
• Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of the fatty acids described.
• Dialkyl ethers may also be present as defoamers.
• the ethers can be constructed asymmetrically or symmetrically, ie contain two identical or different alkyl chains, preferably with 8 to 18 carbon atoms.
• Typical examples are di-n-octyl ether, di-i-octyl ether and di-n-stearyl ether; dialkyl ethers which have a melting point above 25 ° C., in particular above 40 ° C., are particularly suitable.
• Suitable defoamer compounds are fatty ketones of the formula (I) , in which R 1 and R 2 independently represent linear or branched hydrocarbon radicals having 11 to 25 carbon atoms and 0 or 1 double bond.
• ketones are known substances that can be obtained by the relevant methods of preparative organic chemistry. For their preparation, one starts, for example, from carboxylic acid magnesium salts which are pyrolyzed at temperatures above 300 ° C. with the elimination of carbon dioxide and water, for example according to the German laid-open specification DE 2553900 OS.
• Suitable fat ketones are those which are prepared by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, arachic acid, gadoleic acid, behenic acid or erucic acid.
• Hentriacontanon-16 (R 1 and R 2 stands for an alkyl radical with 15 carbon atoms), tritriacontanone-17 (R 1 and R 2 stands for an alkyl radical with 16 carbon atoms), stearone (pentatriacontanone-18; R 1 and R 2 stands for an alkyl radical with 17 Carbon atoms), heptatriacontanone-19 (R 1 and R 2 is an alkyl radical with 18 carbon atoms), arachinone (nonatriacontanone-20; R 1 and R 2 is an alkyl radical with 19 carbon atoms), hentetracontanone-21 (R 1 and R 2 stands for an alkyl radical with 20 carbon atoms) and / or Behenon (triatetracontanone-22; R 1 and R 2 stands for an alkyl radical with 21 carbon atoms).
• Suitable defoamers are fatty acid polyethylene glycol esters of the formula (II) , in which R 3 CO is a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms and n is a number from 0.5 to 1.5.
• Fatty acid polyethylene glycol esters of this type are preferably obtained by base-homogeneously catalyzed addition of ethylene oxide to fatty acids, in particular the addition of ethylene oxide to the fatty acids takes place in the presence of alkanolamines as catalysts.
• alkanolamines especially triethanolamine, leads to an extremely selective ethoxylation of the fatty acids, especially when it comes to producing low-ethoxylated compounds.
• fatty acid polyethylene glycol esters of the formula (II) preference is given to fatty acid polyethylene glycol esters of the formula (II) in which R 3 CO is a linear acyl radical having 12 to 18 carbon atoms and n is the number 1. Lauric acid ethoxylated with 1 mol of ethylene oxide is particularly suitable. Within the group of fatty acid polyethylene glycol esters, preference is given to those which have a melting point above 25 ° C., in particular above 40 ° C.
• the paraffin waxes described are particularly preferably used alone as wax-like defoamers or in a mixture with one of the other wax-like defoamers, the proportion of paraffin waxes in the mixture preferably making up more than 50% by weight, based on the wax-like defoamer mixture.
• the paraffin waxes can be applied to carriers if necessary. All known inorganic and / or organic carrier materials are suitable as carrier materials. Examples of typical inorganic carrier materials are alkali carbonates, aluminosilicates, water-soluble sheet silicates, alkali silicates, alkali sulfates, for example sodium sulfate, and alkali phosphates.
• the alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO 2 of 1: 1.5 to 1: 3.5.
• the use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water.
• the aluminosilicates referred to as carrier material include, in particular, the zeolites, for example zeolite NaA and NaX.
• the compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass. Silicates which are commercially available under the name Aerosil® or Sipernat® can also be used.
• suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch.
• Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof.
• Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
• the mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50.
• native starch which is composed of amylose and amylopectin. Starch is referred to as native starch, as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat.
• Carrier materials which can be used individually or more than one of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch.
• alkali carbonates in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate and zeolites are particularly suitable.
• a mixture of at least one wax-like defoamer, preferably a paraffin wax, and a defoaming silicone compound is used as the defoamer.
• suitable silicones are conventional organopolysiloxanes which can have a content of finely divided silica, which in turn can also be silanated. Such organopolysiloxanes are described, for example, in European patent application EP 0496510 A1 . Polydiorganosiloxanes which are known from the prior art are particularly preferred.
• Suitable polydiorganosiloxanes can have an almost linear chain and are identified by the following formula (III) , where R 4 can independently represent an alkyl or an aryl radical and z can stand for numbers in the range from 40 to 1500.
• R 4 can independently represent an alkyl or an aryl radical and z can stand for numbers in the range from 40 to 1500.
• suitable substituents R 4 are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl.
• compounds crosslinked via siloxane can also be used, as are known to the person skilled in the art under the name silicone resins.
• the polydiorganosiloxanes contain finely divided silica, which can also be silanized. Silica-containing dimethylpolysiloxanes are particularly suitable.
• the polydiorganosiloxanes advantageously have a Brookfield viscosity at 25 ° C. in the range from 5,000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas.
• the silicones are preferably applied to carrier materials. Suitable carrier materials have already been described in connection with the paraffins.
• the carrier materials are generally present in amounts of 40 to 90% by weight, preferably in amounts of 45 to 75% by weight, based on defoamers.
• the detergent additives according to the invention contain those that envelop the defoamer Substances - based on solids - preferably in total amounts of 1 to 25% by weight, preferably from 5 to 20 and in particular from 10 to 15% by weight.
• These coating substances are preferably involved water-soluble compounds, which more preferably have a water solubility at 20 ° C of at least 10 g / l, preferably at least 50 g / l and in particular 100 g / l and advantageously have further properties useful for the overall formulation, such as, for example the complexation of hardness and heavy metal ions.
• the coating also take place from the melt, i.e. instead of water-soluble come basically also fusible connections in question.
• these substances can be the salts of inorganic mineral acids .
• these substances are the alkali and / or alkaline earth metal salts, aluminum or zinc salts of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid and silicic acid, in particular the alkali metal sulfate, alkali borates and perborates, the various alkali metal silicates ( Water glasses ”) and alkali phosphates should be mentioned.
• Typical examples are magnesium sulfate heptahydrate or borax.
• the salts of organic carboxylic acids are also suitable. Typical examples are the alkali and / or alkaline earth metal salts, aluminum or zinc salts of monocarboxylic acids with 1 to 22 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid.
• the use of sodium acetate is particularly preferred.
• corresponding C 2 -C 6 dicarboxylic acids can also be used, so that the appropriate salts in the same manner as above are the corresponding salts of succinic acid, maleic acid, fumaric acid, glutaric acid and adipic acid.
• salts of hydroxy-functionalized polyvalent carboxylic acids can also be used, such as the above-mentioned salts of malic acid, tartaric acid and in particular citric acid.
• alkali metal citrates is particularly preferred here.
• the third group of suitable coating substances are the water-soluble polymers , which can be, for example, protein hydrolyzates, polyamides, polyacrylates and polyurethanes. Urea and polyurea are also suitable. Saccharides and polysaccharides, such as sucrose, maltose or starch hydrolysates, are also suitable.
• the detergent additives according to the invention can be prepared by processes that are already for the production of detergents are known. Basically, the defoamer grain first by drying and optionally granulating an appropriate emulsion or dispersion prepared, which is then brought into contact with an aqueous solution of the coating substance. This is preferably done at higher temperatures, with the coating substance on the grain precipitates and essentially includes it.
• the production of the new detergent additives so that first an aqueous emulsion or dispersion a defoamer dries and on the resulting grain from an aqueous solution or melt precipitates a coating substance, possibly while the water evaporates. It is it is immediately clear, of course, that the process can be carried out in one or two stages.
• an appropriate defoamer emulsion or dispersion will first be dried and the dried powder, which in turn is a conventional market product can act, then coat.
• the aqueous defoamer emulsions or dispersions or the dried Defoamer powder used together with the coating agents In a one-step, preferably continuous process either the aqueous defoamer emulsions or dispersions or the dried Defoamer powder used together with the coating agents.
• the drying device into which the defoamer emulsions or dispersions are introduced, preferably sprayed can be any drying apparatus.
• the drying is carried out as spray drying in a drying tower.
• the preferably aqueous emulsions or dispersions are exposed in a known manner to a drying gas stream in finely divided form.
• Defoamer powders are obtained which are then intimately mixed with the required amount of coating substances in the form of an aqueous solution in a second step.
• Components such as paddle mixers from Lödige or in particular spray mixers from Schugi, in which the defoamer powder is placed in the mixing chamber and the aqueous solutions of the coating materials are sprayed on, are advantageous for this process. It is also possible to carry out the drying of the defoamer emulsions or dispersions and the mixing simultaneously in a fluidized bed dryer.
• a particularly preferred possibility consists in the optionally aqueous defoamer precursors of a fluidized bed granulation ( SKET "granulation).
• SKET "granulation” granulation with simultaneous drying, which is preferably carried out batchwise or continuously.
• the defoamers can be used both in the dried state and as an aqueous preparation.
• the aqueous solutions or melts of the coating materials become simultaneous or one after the other through one or more nozzles into the fluidized bed. It is preferable to continuously blow in defoamer powder via a nozzle into a fluidized bed approximately filled with seed material and to meter in the coating materials via a second nozzle.
• Fluidized bed apparatuses which are preferably used have base plates with dimensions of 0.4 to 5 m.
• the granulation is preferably carried out at fluidizing air speeds in the range from 1 to 8 m / s.
• the granules are preferably discharged from the fluidized bed via a size classification of the granules.
• the classification can take place, for example, by means of a sieve device or by means of an opposed air flow (classifier air) which is regulated in such a way that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed.
• the inflowing air is usually composed of the heated or unheated classifier air and the heated bottom air.
• the soil air temperature is between 80 and 400, preferably 90 and 350 ° C.
• a starting compound for example defoamer granules from an earlier test batch, is initially introduced at the start of the granulation.
• the water evaporates from the emulsions or dispersions, producing dried to dried germs, which are coated with further amounts of defoamer, granulated and, in turn, dried at the same time.
• the aqueous solutions of the coating substances can also be used together with the defoamer precursors, but this can lead to some of the coating materials ending up in the grain and the coating of the grain being incomplete.
• Another object of the present invention relates to the use of the invention
• Detergent additives as defoamers for the production of detergents, preferably those which have a high anionic surfactant content (e.g. 5 to 25% by weight) and in the form of powders, Granules, extrudates or tablets are present.
• Other preferred ingredients of the detergent, the obtained using the additives according to the invention are inorganic and organic Builder substances, whereby as inorganic builder substances mainly zeolites, crystalline Layered silicates and amorphous silicates with builder properties and - where permitted - also phosphates how tripolyphosphates are used.
• the builder substances are preferably those according to the invention Detergents in amounts of 10 to 60 wt .-% - based on detergent - included. If the substances are water-soluble, they also come as enveloping substances for the inclusion of the Defoamer grain in question. This applies, for example, to the silicates, dextrins, Polyacrylates and the like.
• the fine crystalline, synthetic and bound water-containing zeolite which is frequently used as a detergent builder is preferably zeolite A and / or P.
• zeolite P for example, zeolite MAP (R) (commercial product from Crosfield) is particularly preferred.
• zeolite X and mixtures of A, X and / or P and Y are also suitable.
• a cocrystallized sodium / potassium aluminum silicate made of zeolite A and zeolite X, which as VEGOBOND AX® (commercial product from Condea Augusta SpA) is commercially available.
• the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
• the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
• Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
• Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
• Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A1 .
• Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
• both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, it being possible, for example, to obtain ⁇ -sodium disilicate by the process described in international patent application WO 91/08171 .
• Further suitable layered silicates are known, for example, from patent applications DE 2334899 A1, EP 0026529 A1 and DE 3526405 A1 . Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here.
• small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas.
• the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca 2+ .
• the amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing.
• Useful layer silicates are known, for example, from US 3,966,629, US 4,062,647, EP 0026529 A1 and EP 0028432 A1 .
• Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
• the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties.
• the delay in dissolution compared to conventional amorphous sodium silicates can have been caused in various ways, for example by surface treatment, compounding, compacting / compaction or by over-drying.
• the term “amorphous” is also understood to mean “X-ray amorphous”.
• silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
• it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
• Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 4400024 A1 .
• Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
• phosphates As builders, provided that such use should not be avoided for ecological reasons.
• the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, in each case based on the finished composition. In some cases, it has been shown that tripolyphosphates in particular, even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing ability.
• Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
• Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. The acids themselves can also be used.
• the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents.
• Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
• Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
• the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
• DE dextrose equivalent
• Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2,000 to 30,000 can be used.
• a preferred dextrin is described in British patent application GB 9419091 A1 .
• the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0232202 A1 , EP 0427349 A1 , EP 0472042 A1 and EP 0542496 A1 as well as from international patent applications WO 92/18542 , WO 93/08251 , WO 93/16110 , WO 94 / 28030 , WO 95/07303 , WO 95/12619 and WO 95/20608 are known.
• An oxidized oligosaccharide according to German patent application DE 19600018 A1 is also suitable.
• a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
• Suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate .
• glycerol disuccinates and glycerol trisuccinates are particularly preferred in this context, as described, for example, in US Pat . Nos . 4,524,009 , 4,639,325 , in European patent application EP 0150930 A1 and in Japanese patent application JP 93/339896 .
• Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.
• organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
• Such cobuilders are described, for example, in international patent application WO 95/20029 .
• Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid and measured in each case against polystyrene sulfonic acid).
• Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
• the relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (measured in each case against polystyrene sulfonic acid).
• the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred.
• Granular polymers are usually subsequently mixed into one or more basic granules.
• biodegradable polymers composed of more than two different monomer units, for example those which, according to DE 4300772 A1, as salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or as DE 4221381 C2 as monomer salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives.
• Further preferred copolymers are those which are described in German patent applications DE 4303320 A1 and DE 4417734 A1 and which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
• polymeric aminodicarboxylic acids their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred.
• polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0280223 A1 .
• Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
• the agents can also contain components that make the oil and fat washable made of textiles.
• the preferred oil and fat dissolving components include, for example nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose a proportion of methoxyl groups from 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and those from the prior art Polymers of phthalic acid and / or terephthalic acid or their derivatives known in the art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
• Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses which have no outstanding builder properties, or mixtures of these; in particular, alkali carbonate and / or amorphous alkali silicate, especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
• the sodium carbonate content in the detergents according to the invention is preferably up to 40% by weight, advantageously between 2 and 35% by weight.
• the content of sodium silicate in the agents (without special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.
• the detergents can usually contain other known detergents additives used, for example salts of polyphosphonic acids, optical brighteners, enzymes, Enzyme stabilizers, small amounts of neutral filling salts as well as colors and fragrances, opacifiers or pearlescent agents.
• bleaching agents which serve as bleaching agents and supply H 2 O 2 in water
• sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
• Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
• the bleaching agent content of the agents is preferably 5 to 35% by weight and in particular up to 30% by weight, advantageously using perborate monohydrate or percarbonate.
• Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
• Multi-acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran and the enol esters known from German patent applications
• hydrophilically substituted acylacetals known from German patent application DE 19616769 A1 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used.
• the combinations of conventional bleach activators known from German patent application DE 4443177 A1 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.
• the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0446982 B1 and EP 0453 003 B1 can also be present as so-called bleaching catalysts.
• the transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from German patent application DE 19529905 A1 and their N-analog compounds known from German patent application DE 19620267 A1, which are known from German Patent application DE 19536082 A1 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium described in German patent application DE 196 05 688 - and copper complexes with nitrogen-containing tripod ligands known from the German patent application DE 19620411 A1 cobalt, iron, copper and ruthenium-ammine complexes, the manganese described in the German patent application DE 4416438 A1, copper and cobalt complexes, the cobalt complexes described in European patent application EP 0272030 A1, which are known from the European patent application EP 0693550 A1 manganese Complexe
• Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.
• Particularly suitable enzymes are those from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
• hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and micro
• Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable.
• Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
• Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
• Known cutinases are examples of such lipolytically active enzymes.
• Peroxidases or oxidases have also proven to be suitable in some cases.
• Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
• Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
• the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
• the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
• the agents can contain further enzyme stabilizers .
• enzyme stabilizers 0.5 to 1% by weight sodium formate can be used.
• proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
• calcium salts magnesium salts also serve as stabilizers.
• boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
• Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
• Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
• Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
• cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the detergent, are preferred used.
• the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
• Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
• Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example Contain 10 -6 to 10 -3 wt .-%, preferably by 10 -5 wt .-%, of a blue dye.
• a particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).
• dirt-repellent polymers are those substances which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10 .
• the molecular weight of the linking polyethylene glycol units is in particular in the range of 750 to 5000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100.
• the polymers are characterized by an average molecular weight of approximately 5000 to 200,000 and can have a block, but preferably a random structure with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers which have linking polyethylene glycol units with a molecular weight of 750 to 5000, preferably of 1000 to about 3000 and a molecular weight of the polymer from about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
• fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances .
• Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexylpropylatepylatepylatepylatepionate, stally.
• the ethers include, for example, benzyl ethyl ether
• the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
• the ketones include, for example, the jonones, ⁇ -isomethylionone and methylcedryl ketone the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol
• the hydrocarbons mainly include the terpenes such as limonene and pinene.
• Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
• the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
• Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
• the detergents according to the invention can also contain inorganic salts as fillers or fillers, such as sodium sulfate, which is preferably present in amounts of 0 to 10, in particular 1 to 5% by weight, based on the composition.
• inorganic salts such as sodium sulfate, which is preferably present in amounts of 0 to 10, in particular 1 to 5% by weight, based on the composition.
• the detergents obtainable using the additives according to the invention can be in the form of Powders, extrudates, granules or tablets are manufactured or used. For the production such means, the corresponding methods known from the prior art are suitable.
• the agents are preferably prepared in that various particulate components Contain detergent ingredients, are mixed together.
• the particulate components can be spray dried, simple mixed or complex Granulation processes, for example fluidized bed granulation, are produced. Is preferred in particular that at least one surfactant-containing component by fluidized bed granulation will be produced. It can furthermore be particularly preferred if aqueous preparations of the alkali silicate and the alkali carbonate together with other detergent ingredients in a drying facility can be sprayed, and granulation can take place simultaneously with the drying.
• the drying device into which the aqueous preparation is sprayed can be any drying apparatus.
• the drying is carried out as spray drying in a drying tower.
• the aqueous preparations are exposed to a drying gas stream in finely divided form in a known manner.
• Patent publications by Henkel describe an embodiment of spray drying with superheated steam. The working principle disclosed there is hereby expressly made the subject of the present disclosure of the invention.
• the mixtures are then subjected to a compacting step, with further Ingredients are only added to the agents after the compacting step.
• the compacting of the ingredients takes place in a preferred embodiment of the invention in a press agglomeration process instead of.
• the press agglomeration process to which the solid premix (dried basic detergent) subject can be realized in various devices. Depending on A distinction is made between the type of agglomerator used and different press agglomeration processes.
• the four most common press agglomeration processes preferred in the context of the present invention are extrusion, roll pressing or compacting, hole pressing (Pelletizing) and tabletting, so that preferred press agglomeration processes within the scope of the present invention Extrusion, roll compacting, pelletizing or tableting processes are.
• binders can be used as an aid to compaction.
• the invention uses a binder that at temperatures up to 130 ° C, preferably up to a maximum of 100 ° C. and in particular up to 90 ° C. is already completely in the form of a melt.
• the binder must therefore be selected depending on the process and process conditions or the process conditions, especially the process temperature - if a certain one Binder is desired - to be adapted to the binder.
• the actual compression process is preferably carried out at processing temperatures that at least in the compression step at least the temperature of the softening point, if not correspond to the temperature of the melting point of the binder.
• the process temperature is significantly above the melting point or above the temperature at which the binder is in the form of a melt.
• the process temperature in the compression step is not more than 20 ° C above the melting temperature or the upper limit of the melting range of the binder. It is technical quite possible to set even higher temperatures; but it has been shown that a Temperature difference from the melting temperature or softening temperature of the binder of 20 ° C is generally sufficient and even higher temperatures no additional advantages cause.
• Such a temperature control has the other Advantage that also thermally sensitive raw materials, for example peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, increasingly processed without serious loss of active substance can be.
• thermally sensitive raw materials for example peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, increasingly processed without serious loss of active substance can be.
• the possibility of precise temperature control of the binder in particular in the decisive step of compression, i.e. between the mixing / homogenization of the Premix and the shape, allows an energetically very favorable and for the temperature sensitive Components of the premix extremely gentle process management, because the premix is only exposed to the higher temperatures for a short time.
• the working tools of the press agglomerator (the screw (s) of the extruder, the roller (s) of the roller compactor and the press roller (s) of the pellet press) have a temperature of a maximum of 150 ° C, preferably a maximum of 100 ° C and in particular a maximum of 75 ° C and the process temperature is 30 ° C and in particular a maximum of 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.
• the duration is preferably the temperature effect in the compression area of the press agglomerators a maximum of 2 minutes and is particularly in a range between 30 seconds and 1 minute.
• Preferred binders which can be used alone or in a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and also modified polyethylene glycols and polypropylene glycols.
• the modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12,000 and in particular between 1,000 and 4,000.
• Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which again have relative molecular weights between 600 and 6,000, preferably between 1,000 and 4,000.
• polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C 3 -C 5 glycols and glycerol and mixtures of these as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included.
• the polyethylene glycols which are preferably used can have a linear or branched structure, linear polyethylene glycols in particular being preferred.
• the particularly preferred polyethylene glycols include those with relative molecular weights between 2,000 and 12,000, advantageously around 4,000, polyethylene glycols with relative molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4,000, and can be used Such combinations advantageously have more than 50% by weight, based on the total amount of polyethylene glycols, of polyethylene glycols with a relative molecular weight between 3,500 and 5,000.
• polyethylene glycols can also be used as binders, which are per se in liquid state at room temperature and a pressure of 1 bar; Here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600.
• these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C.
• suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000. Relative molecular weight ranges between 3,000 and 30,000, for example around 10,000 are preferred.
• Polyvinylpyrrolidones are preferably not used as sole binders but in combination with other used in particular in combination with polyethylene glycols.
• the compressed material preferably has temperatures immediately after it leaves the production apparatus not above 90 ° C, with temperatures between 35 and 85 ° C particularly preferred are. It has been found that outlet temperatures - especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, are particularly advantageous.
• the detergent according to the invention is produced by means of an extrusion , as described, for example, in European patent EP 0486592 B1 or international patent applications WO 93/02176 and WO 94/09111 or WO 98/12299 .
• a solid premix is pressed in the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate after it has emerged from the hole shape by means of a cutting device.
• the homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work.
• Preferred plasticizers and / or lubricants are surfactants and / or polymers.
• the premix is preferably fed to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guidance, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature.
• the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally, under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knife.
• the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension. In this way, the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use.
• particle diameters up to at most 0.8 cm are preferred.
• Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.
• the length / diameter ratio of the chopped-off primary granules is preferably in the range from about 1: 1 to about 3: 1. It is also preferred to feed the still plastic primary granules to a further shaping processing step; edges present on the crude extrudate are rounded off so that ultimately spherical to approximately spherical extrudate grains can be obtained.
• small amounts of dry powder for example zeolite powder such as zeolite NaA powder, can also be used in this step.
• extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (from Amandus Kahl) or in the Bepex extruder.
• the temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is preferably designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded.
• the duration of the temperature influence in the compression range of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.
• the detergents according to the invention can also be produced by means of roller compaction .
• the premix is metered in between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe.
• the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
• smooth rollers smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which, for example, certain shapes of the later detergent particles can be specified.
• the sliver belt is subsequently broken up into smaller pieces by a knocking-off and crushing process and can be processed into granules in this way, which can be refined by further known surface treatment processes, in particular in an approximately spherical shape.
• the temperature of the pressing tools that is to say of the rollers, is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at a maximum of 75 ° C.
• Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
• the duration of the temperature effect in the compression area of the smooth rollers or with depressions of a defined shape is a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
• the detergent according to the invention can also be produced by pelleting .
• the premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization.
• the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device.
• the most varied configurations of the pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers.
• the press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation.
• An apparatus suitable for carrying out the method is described, for example, in German laid-open specification DE 3816842 A1 .
• the ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
• the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
• the temperature of the pressing tools is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at a maximum of 75 ° C.
• Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
• Another pressing agglomeration process that can be used to produce the detergents according to the invention is tableting. Because of the size of the molded articles produced, it may be useful for tableting to add conventional disintegration aids, for example cellulose and its derivatives, in particular in coarser form, or crosslinked PVP in addition to the binder described above, which facilitate the disintegration of the compacts in the wash liquor.
• the particulate press agglomerates obtained can either be used directly as detergents or aftertreated and / or prepared beforehand by customary methods.
• the usual aftertreatments include, for example, powdering with finely divided ingredients from washing or cleaning agents, which generally further increases the bulk density.
• a preferred aftertreatment is also the procedure according to German patent applications DE 19524287 A1 and DE 19547457 A1 , in which dusty or at least finely divided ingredients (the so-called fine fractions) are adhered to the particulate end products of the process, which serve as the core, and thus give rise to agents , which have these so-called fines as an outer shell.
• this advantageously takes place by melting agglomeration.
• the solid detergents are in tablet form, these tablets preferably having rounded corners and edges, in particular for storage and transport reasons.
• the base of these tablets can be circular or rectangular, for example.
• Multi-layer tablets in particular tablets with 2 or 3 layers, which can also have different colors, are particularly preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred.
• Detergent tablets generally contain a disintegrant, which is said to bring about the rapid dissolution of the tablet or the rapid disintegration of the tablet in the aqueous liquor.
• a disintegrant which is said to bring about the rapid dissolution of the tablet or the rapid disintegration of the tablet in the aqueous liquor.
• a fluidized bed was filled with up to 70% of the fluidized bed capacity with a dried silicone / paraffin defoamer mixture from the trade (Dehydran® 760) as the seed material. Subsequently, at a soil air temperature of 160 ° C (ie a temperature of approx. 95 ° C in the fluidized bed), further defoamer powder was introduced continuously using a first nozzle. A 56% by weight aqueous urea solution was introduced through a second nozzle to coat the defoamer. The material flows were adjusted by regularly checking the discharged and classified coated granules from the fluidized bed in such a way that the urea content in the end product was 25% by weight.
• Example H2 was repeated using a commercial powdered silicone defoamer (Dow Corning Powdered Antifoam®). The coating was carried out with a 60% by weight aqueous solution of sodium citrate dihydrate. The material flows were adjusted so that the content of sodium citrate in the end product was 15% by weight.
• a commercial powdered silicone defoamer (Dow Corning Powdered Antifoam®). The coating was carried out with a 60% by weight aqueous solution of sodium citrate dihydrate. The material flows were adjusted so that the content of sodium citrate in the end product was 15% by weight.
• Test formulation for detergent tablets and washing tests (data in% by weight, water ad 100%) composition 1 2nd V1 V2 Dodecylbenzenesulfonate sodium salt 7.2 7.2 7.2 7.2 C 12/18 coconut fatty alcohol + 7EO 6.2 6.2 6.2 6.2 Palm kernel fatty acid sodium salt 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3

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