DE19953797A1 - Defoamer granules - Google Patents

Abstract

Anti-foaming granules for solid detergents, rinsing agents and cleaners are disclosed, which comprise (a) at least one soft wax with a melting point in the range from 35 to 50 DEG C, (b) at least one hard wax with a melting point above 50 DEG C, (c) silicone and (d) support materials.

Description

Field of the Invention

The present invention is in the field of solid washing, rinsing and cleaning agents and relates to new defoamer granules for solid washing, rinsing and cleaning agents, processes for their production and the use of the granules for the production of solid surface-active Preparations.

State of the art

Detergent for household and industrial laundry, but also dishwashing and cleaning agents, generally contain organic surfactants, builders and numerous organic and anorga niche additives. The surfactants used for the laundry tend to tend during use for foam development, which has a negative effect on the cleaning result. Therefore there is a practical need to control the development of foam during use. As special Suitable defoamers have proven to be silicones, which are usually based on carrier materials applied and optionally be with other organic defoaming substances layers can be used in solid washing, rinsing and cleaning agents.

DE 31 28 631 A1 describes the production of foam-damped detergents with a content on silicone defoamers that are microencapsulated. The silicone is in an aqueous Dispersion of a film-forming polymer dispersed and the dispersion - separated from the rest in Detergent components dissolved or dispersed in water - via a special line of Spray drying system fed. The two sub-streams are combined in the area of Spray nozzle. Examples of film-forming polymers are cellulose ethers, starch ethers or synthetics water-soluble polymers in question. Microcapsules are formed spontaneously in the spray nozzle se. The process described is inevitable for the production of spray-dried detergents bound. A transfer to washing produced in another way, for example by granulation medium does not seem possible with this method of working.  

In this context, reference is made, for example, to European patent EP 0094250 B2 (Unile ver), from which a method for producing defoamer granules is known, in which is a mixture of silicones and paraffin waxes in an organic solvent and then sprayed this onto an absorbent. Subject of the German published application DE 37 32 947 A1 are defoamers which contain paraffins, microcrystalline paraffins and diamides. Out The European patent application EP 0496510 A1 defoamers are known, with strength as Carrier material with a mixture of silicones and fatty alcohols, fatty acids or glycerol monoesters special melting points is applied.

All these defoamers have in common that their production is fraught with problems and that Products in particular fail when regulating the foam of detergent tablets.

The object of the present invention was therefore to provide new defoamer granules for solid washing, rinsing and to provide cleaning agents which are distinguished, inter alia, by the fact that they are easy to pour and are not dusty. In particular, however, you should also use detergents especially in the form of tablets, reliable, d. H. ent over the entire course of the washing process foam, the particularly high-foaming anionic surfactants and / or particularly difficult to remove contain foaming nonionic surfactants.

Description of the invention

The invention relates to defoamer granules for solid washing, rinsing and cleaning agents, containing

(a) at least one soft wax with a melting point in the range from 35 to 50 ° C,

(b) at least one hard wax with a melting point above 50 ° C,

(c) silicones and

(d) substrates.

Surprisingly, it was found that using the defoamer gra nulate in particular those detergents can be reliably defoamed, which larger Amounts of particularly foaming anionic and particularly difficult to defoam contain nonionic surfactants. A particular advantage is that the defoaming Mereffekt remains even if the preparations, for example, by roller compact tion or tabletting can be compressed.  

Soft waxes

Soft waxes that form component (a) and a melting point in the range from 35 to 50 ° C. have, preferably belong to the group of petrolates and their hydrogenation products. you put microcrystalline paraffins and up to 70% by weight of oil are ointment-like plastically firm consistency and represent bitumen-free residues from petroleum processing distillation residues (petrolatum stock) of certain paraffin-based and ge are preferred mixed-base crude oils that are processed into petroleum jelly.

Hard waxes

Such wax-like substances are too hard waxes, which are the defoamer component (b) understand the melting point at atmospheric pressure above 50 ° C (room temperature), preferably se above 56 ° C and in particular above 70 ° C. The hard waxes are practically not in water soluble, d. H. at 20 ° C they have a solubility of less than 0.1% by weight in 100 g of water.

Suitable waxy compounds are, for example, bisamides, fatty alcohols, fatty acids, carbon acid esters of mono- and polyhydric alcohols as well as paraffin waxes or mixtures thereof. Bisamides are suitable which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18 C- Derive atoms and from alkylenediamines with 2 to 7 carbon atoms. Suitable fatty acids are lauric, Myristic, stearic, arachic and behenic acid and mixtures thereof, such as those obtained from natural fats or hardened oils, such as tallow or hydrogenated palm oil, are available. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, Hexamethylenediamine, p-phenylenediamine and toluenediamine. Preferred diamines are ethylenediamine and hexamethylenediamine. Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bis palmitoyl-ethylenediamine, bis-stearoylethylenediamine and their mixtures and the corresponding Derivatives of hexamethylene diamine. Suitable carboxylic acid esters are derived from carboxylic acids with 12 up to 28 carbon atoms. In particular, these are esters of behenic acid, stearic acid, Oleic acid, palmitic acid, myristic acid and / or lauric acid. The alcohol part of the carboxylic acid ester contains a mono- or polyhydric alcohols with 1 to 28 carbon atoms in the hydrocarbon fabric chain. Examples of suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, methanol, Ethanol, isopropanol, vinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol. Be preferred esters are those of methanol, ethylene glycol, glycerol and sorbitan, the acid part of the Esters in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid is chosen. Suitable 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 distearate, sorbitan dibehenate, sorbitan dioleate and mixed tallow alkyl sorbitan mono- and diesters. Usable glycerol esters are the mono-, Di- or triesters of glycerol and the carboxylic acids mentioned, the monoesters or diesters being preferred are. Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and Gly Cerindistearate are examples of this. Examples of suitable natural esters are bee and carnau bawax, the latter being a mixture of carnauba acid alkyl esters, often in combination with minor Proportions of free carnauba acid, other long-chain acids, high-molecular alcohols and carbons represents hydrogen. Suitable carboxylic acids as a further defoamer compound are in particular beenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid and their Mixtures such as those made from natural fats or optionally hardened oils, such as tallow or hydrogenated tem palm oil are available. Saturated fatty acids with 12 to 22, in particular 14 to 18, are preferred C atoms. Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of the fatty acids described.

The preferred paraffin wax in the sense of the invention as a further defoamer compound is in generally represents a complex mixture of substances without a sharp melting point. For characterization be one usually adjusts its melting range by differential thermal analysis (DTA), as in "The Analyst" 87 (1962), 420, and / or its freezing point. It is understood as the temperature at which the paraffin cools slowly from the liquid to the solid stood passes. Paraffins that are completely liquid at room temperature, i.e. those with a solidification point below 25 ° C, not usable according to the invention. It is preferably for example, from distillation residues of paraffin and mixed base crude oils and Zylin Oil-distillates, bitumen-free, oily to solid hydrocarbons separated by solvents. They are of semi-solid, quick, sticky to plastic-solid consistency and have melting points between 50 and 70 ° C. These petrolates are the most important basis for the production of Micro waxes are also suitable are those made of highly viscous, paraffin-containing lubricating oil distillates solid hydrocarbons with melting points between 63 and 79 ° C. These petrolates are mixtures of microcrystalline waxes and high-melting n-paraffins. For example, those from EP 0309931 A1 can also be used known paraffin wax mixtures from, for example, 26% by weight to 49% by weight of microcrystalline Paraffin wax with a solidification point of 62 ° C to 90 ° C, 20% by weight to 49% by weight hard paraffin with a solidification point of 42 ° C to 56 ° C and 2 wt .-% to 25 wt .-% soft paraffin with a Freezing point from 35 ° C to 40 ° C. Paraffins or paraffin mixtures are preferably used turns that solidify in the range from 50 ° C to 90 ° C. It should be noted that even with room temperature-appearing paraffin wax mixtures ent different proportions of liquid paraffin ent can hold. In the case of paraffin waxes of component (b), this liquid fraction is as low as possible Lich and preferably completely missing. For example, particularly preferred paraffin wax mixtures at 30 ° C a liquid content of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C.  Liquid content of less than 30% by weight, 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 of 30% by weight to 60% by weight, in particular from 40% by weight to 55% by weight, at 80 ° C. a liquid fraction from 80% by weight to 100% by weight, and at 90 ° C a liquid content of 100 wt .-%. The temperature at which a liquid content of 100% by weight of the paraffin wax is reached, is still particularly preferred paraffin wax mixtures below 85 ° C, especially at 75 ° C to 82 ° C. For the purposes of the invention, the Paraffin waxes of the type described are used.

Silicones

For the purposes of the present invention, suitable silicones which form component (c) are customary Organopolysiloxanes, which contain finely divided silica, which in turn can also be silanized may have. Such organopolysiloxanes are for example in the European Pa tent application EP 0496510 A1. Polydiorganosiloxanes and in particular polydimethylsiloxanes, which are known from the prior art. Suitable polydior Ganosiloxanes have an almost linear chain and a degree of oligomerization of 40 to 1500 on. Examples of suitable substituents are methyl, ethyl, propyl, isobutyl, tert. Butyl and Phenyl. Also suitable are amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-modified silicone compounds that are both liquid and resin at room temperature can be in the form. Simethicones, which are mixtures of, are also suitable Dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates. As a rule, the silicones contain in general and the polydiorgano siloxanes in particular fine-particle silica, which can also be silanized. Particularly suitable are siliceous dimethylpolysiloxanes for the purposes of the present invention. Advantageously the polydiorganosiloxanes have a Brookfield viscosity at 25 ° C (spindle 1, 10 rpm) in the loading range from 5000 mPa.s to 30,000 mPa.s, in particular from 15,000 to 25,000 mPa.s. Preferably the silicones are used in the form of their aqueous emulsions. As a rule, the silicone is added submitted water with stirring. If desired you can increase the viscosity of the aq against silicone emulsions, add thickeners as are known from the prior art. These can be of an inorganic and / or organic nature; nonionics are particularly preferred cal cellulose ethers such as methyl cellulose, ethyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl hydroxybutyl cellulose and anionic carboxy cellulose types like the carboxymethyl cellulose sodium salt (abbreviation CMC). Suitable thickeners are in particular Mixtures of CMC to nonionic cellulose ethers in a weight ratio of 80:20 to 40:60, in particular 75: 25 to 60: 40. As a rule and especially when adding the Verdik described Kermischungen recommended concentrations of about 0.5 to 10, in particular from 2.0 to 6% by weight - calculated as a thickener mixture and based on aqueous silicone emulsion. The content of  Silicones of the type described in the aqueous emulsions are advantageously in the range of 5 up to 50 wt .-%, in particular from 20 to 40 wt .-% - calculated as silicones and based on aqueous Silicone emulsion. According to a further advantageous embodiment, the aqueous sllicone emulsion is obtained Starch as a thickener, which is accessible from natural sources, for example from rice, potato feln, corn and wheat. The starch is advantageously present in quantities of 0.1 to 50% by weight on silicone emulsion - contained and in particular in a mixture with the Verdic already described Mixtures of sodium carboxymethyl cellulose and a nonionic cellulose ether in the quantities already mentioned. It is more expedient to prepare the aqueous silicone emulsions demonstrate that the thickeners, if present, are allowed to swell in water, before the silicones are added. The silicones are expediently incorporated with the aid effective stirring and mixing devices.

Carrier materials

For the purposes of the invention, all known inorganic and / or organic carrier materials can be used as carrier material (component d). Examples of typical inorganic carrier materials alkali carbonates, aluminosilicates, water-soluble sheet silicates, alkali silicates, alkali sulfates, for example sodium sulfate and alkali phosphates. The alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO ₂ of 1: 1.5 to 1: 3.5. The use of such silicates results in particularly good 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. Examples of suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch. Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof. Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit. The mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50. Such cellulose ether mixtures can be used in solid form or as aqueous solutions which are pre-swollen in the customary manner could be. For the purposes of the invention, the native starch which is composed of amylose and amylopectin is particularly preferred as the carrier. Starch is referred to as native starch as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat. Native starch is a commercially available product and is therefore easily accessible. As carrier materials, one or more of the compounds mentioned above can be used, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, carboxymethyl cellulose, polyacrylate / polymethacrylate and starch. Mixtures of alkali carbonates, in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate, zeolites, polycarboxylates, in particular poly (meth) acrylate, and cellulose ether and native starch are particularly suitable. The carrier materials can be composed as follows:
0 to 2% by weight cellulose ether
0 to 75% by weight native starch
0 to 30% by weight alkali silicate
0 to 75% by weight alkali sulfate
0 to 95 wt% alkali carbonate
0 to 95% by weight zeolites
0 to 5% by weight of polycarboxylates, the sum having to add up to 100% by weight.

Defoamer granules

In a particularly preferred embodiment of the invention, the defoamer granules

• a) 5 to 25, preferably 10 to 20 and in particular 12 to 15% by weight of at least one soft wax with a melting point in the range of 35 to 50 ° C,
• b) 1 to 10, preferably 2 to 8 wt .-% at least one hard wax with a melting point above half of 50 ° C.
• c) 1 to 10, preferably 2 to 5 wt .-% silicones and
• d) ad 100 wt .-% carrier materials

contain.

Manufacturing process

Another object of the present invention is a method for producing Defoamer granules for solid detergents, dishwashing detergents and cleaning agents, in which silicone is in the form aqueous emulsions on a mixed intermediate of soft waxes, hard waxes and carriers  applies materials and the products dry and granulate in the fluidized bed at the same time. Alterna tiv also aqueous preparations from the four components in a conventional manner Spray drying or fluid bed drying.

In the sense of a preferred embodiment of the present invention, a preliminary product is first made from the carrier materials and the defoamer waxes. The percentage by weight of carrier materials is preferably 20 to 98 wt .-%, in particular 35 to 95 wt .-%, and that of Soft and hard waxes in total preferably 2 to 80% by weight, in particular 5 to 65% by weight. calculated on preliminary product. The carrier material can be spray-dried in a conventional manner slurry. The waxes can, for example, by applying the ge melted wax-like defoamer substances onto the spray-dried, granular carrier material, for example by successive mixing, in particular in the form of a spray. The carrier material is preferably moved by mixing elements or by fluidization held to ensure a uniform loading of the carrier material. Use that for that Spray mixers can be operated continuously or discontinuously.

In a further embodiment, the production of the preliminary products can take place in such a way that the Dissolves or slurries carrier material in water, disperses the waxes therein and this Then spray dried slurry. The dispersion can be a water-soluble, non-surfactant dispersion tion stabilizer in the form of a water-swellable polymer. Examples of this 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 aq slurry is preferably not more than 5% by weight, in particular 1% by weight to 3% by weight, based on the resulting preliminary product. The water content of the slurries can depend on the species the solubility of the carrier materials is 30% by weight to 60% by weight. Spray drying the dispersion can, in a known manner, in systems provided for this purpose, so-called Spray towers, using hot, co-current or counter-current drying gases. There in the case of drying by drying gases carried in cocurrent with the spray material is preferred because so especially in the case of paraffin-containing precursors, the potential hot volatility of some Loss of activity due to components of the paraffin can be reduced to a minimum.

The aqueous silicone emulsions are sprayed onto the preliminary product within the scope of the present the invention preferably continuously on the solid intermediate with simultaneous drying and Granulate in a fluidized bed, especially in a continuously working fluidized bed the so-called SKET process. The aqueous silicone emulsions over one or several nozzles introduced into the fluidized bed. In the sense of the method according to the invention at the same time as the aqueous silicone emulsions, but separately from them the intermediate product from the carrier  mixed material and wax-like defoamer substances, preferably via an automatic regulated solids dosing. The product streams of aqueous silicone emulsion and pre-mixed product are controlled so that defoamer granules result, preferably 1 to 10% by weight, in particular 2 to 8% by weight, of silicone - calculated as silicone and based on defoaming Mergranulate - included. The remaining 100% by weight of the defoamer granules is that described preliminary product. In the fluidized bed, the aqueous silicone emulsion meets the admixed ones Preproducts with simultaneous evaporation of the water, whereby dried up to dried Germs are formed which are introduced with further aqueous silicone emulsions or with the mixed precursors are encased, granulated and again dried at the same time. The same time drying and granulation takes place in the fluidized bed above one with through openings for the circular air flow floor provided with drying air, the product to be dried being selected rend this drying phase remains stationary above the inflow floor, so that a build-up granules tion takes place. Further information on the so-called SKET process can be found in the European patent to find document EP 0603207 B1. A particular advantage of the method is that the ent foamer granules in terms of their grain size and thus also in terms of their weight from inflowing drying air are sighted or classified, so that such granules that the ge have reached the desired grain size or weight, fall out of the fluidized bed onto the vortex layered floor in a discharge lock.

Fluidized bed apparatuses which are preferably used also have circular base plates (inflow base) a diameter between 0.4 and 5 m, for example 1.2 m or 2.5 m. Can as a base plate Perforated floor panels, a Contidurplatte (commercial product from Hein & Lehmann, Federal Republic Germany) or perforated base plates are used, the holes (through openings) of egg nem mesh are covered with mesh sizes smaller than 600 microns. The grid can be inside be arranged half or above the passage openings. However, the grid preferably lies immediately below the through openings of the inflow floor. This is advantageously so real siert that a metal gauze is sintered with the appropriate mesh size. Preferably be the metal gauze is made of the same material as the inflow floor, especially stainless steel. The mesh size of said grid is preferably between 200 and 400 μm.

For the purposes of the invention, the method is preferred at swirl air speeds between 1 and 8 mls and in particular between 1.5 and 5.5 m / s. The granules are discharged before partly by classifying the size of the granules. This classification is preferably carried out using an opposite flow of drying air (classifier air), which is regulated so that only particles come off a certain particle size is removed from the fluidized bed and smaller particles in the vortex layer can be withheld. In a preferred embodiment, the inflowing air settles from the heated or unheated classifier air and the heated soil air. The floor The air temperature is preferably between 80 and 400 ° C. The vortex air cools through heat  losses and by the heat of vaporization and is preferably about 5 cm above the Base plate 60 to 120 ° C, preferably 65 to 90 and in particular 70 to 85 ° C. The air outlet temperature is preferably between 60 and 120 ° C, especially below 80 ° C.

The residence time for the product to be dried, which remains stationary above the inflow floor, is preferably in the range of 5 to 60 minutes. For the purposes of the present invention, the Defoamer granules are considered to be dried, provided that the free water content is below 10% by weight, preferably from 0.1 to 2% by weight, based in each case on the finished granules. With the be preferably carried out process in the fluidized bed, it is necessary that at the beginning of the process a starting mass is present which acts as the initial carrier for the sprayed aqueous silicone emulsion serves. The admixed intermediate products or, in particular, the ent are suitable as starting mass foamer granules themselves, which have already been obtained in a previous process. In particular, defoamer granules with a grain size in the range above 0.2 and below 0.9 mm used as the starting mass and preferably fed in via a roller mill. Preferred who then the defoamer granules obtained from the fluidized bed in a separate Fluidized bed cooled and classified by means of a sieve into granules with grain sizes between 0.4 and 1.5 mm as good grain fraction, in granules over 1.5 mm as oversize fraction and in granules below 0.4 mm as undersize fraction. The granules of the undersize fraction are fed back into the fluidized bed returned. The oversize fraction is ground, preferably in grain sizes below 0.4 mm, and also returned to the fluidized bed.

Industrial applicability

Another object of the present invention relates to the use of the new defoamers granules for the production of solid detergents, dishwashing detergents and cleaning agents, in which they are in quantities from 0.1 to 15, preferably 1 to 10 and in particular 3 to 8% by weight, based on the composition can be hold.

The primary constituents of the agents produced using the defoamer granules are anioni ces, nonionic, cationic, amphoteric and / or zwitterionic surfactants, are preferred but present anionic surfactants or combinations of anionic and nonionic surfactants. Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefins sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfo succinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, Fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tar  trates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (esp special vegetable products based on wheat) and alkyl (ether) phosphates. Unless the anionic If surfactants contain polyglycol ether chains, these can be conventional, but preferably one have narrow homolog distribution. Alkylbenzenesulfonates, alkylsulfates, Soaps, alkanesulfonates, olefin sulfonates, methyl ester sulfonates and mixtures thereof are used.

Preferred alkylbenzenesulfonates preferably follow the formula (I)

R-Ph-SO ₃ X (I)

in which R is a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph for a phenyl radical and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, Alkanolammonium or Glucammonium stands. Of these, dodecylbenzene is particularly suitable sulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in Form of sodium salts.

Alkyl and / or alkenyl sulfates, which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary and / or secondary alcohols, which preferably follow the formula (II)

R ² O-SO ₃ Y (II)

in which R ^{2 represents} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and Y represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates that can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, arylselyl alcohol, elaidyl alcohol Gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The sulfation products can preferably be used in the form of their alkali salts and in particular their sodium salts. Alkyl sulfates based on C _16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred. In the case of branched primary alcohols are Oxoalko hole, as z. B. accessible by reaction of carbon monoxide and hydrogen to alpha-olefins by the shop process. Such alcohol mixtures are commercially available under the trade name Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®. Another possibility are oxo alcohols, such as those obtained after the classic Enichema or Condea oxo process by adding carbon monoxide and hydrogen to olefins. These alcohol mixtures are a mixture of highly branched alcohols. Such alcohol mixtures are commercially available under the trade name Lial®. Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.

Finally, soaps are to be understood as meaning fatty acid salts of the formula (III)

R ³ CO-OX (III)

in which R ³ CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and X represents alkali metal and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium. Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic acid, caprylic acid, 2-ethylhexanoic acid, calcium prinic acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaoleic acid, petoleic acid, linoleic acid, petoleic acid , Linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Before preferably coconut or palm kernel fatty acid are used in the form of their sodium or potassium salts.

Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polygly colether, fatty acid polyglycol ester, fatty acid amide polyglycol ether, fatty amine polyglycol ether, alkoxylated Triglycerides, mixed ethers or mixed formals, alk (en) yl oligoglycosides, fatty acid N-alkyl glucamides, Pro tein hydrolyzates (especially vegetable products based on wheat), polyol fatty acid esters, sugars esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants polyglycol ether ket ten contained, these can be a conventional, but preferably a narrowed homolog have distribution. Fatty alcohol polyglycol ethers, alkoxylated fatty acids are preferred alkyl ester or alkyl oligoglucoside used.

The preferred fatty alcohol polyglycol ethers follow the formula (IV)

R ⁴ O (CH ₂ CHR ⁵ O) _n H (IV)

in which R ^{4 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R ^{5 represents} hydrogen or methyl and n represents numbers from 1 to 20. Typical examples are the addition products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide onto capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol Elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, Elaeo stearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Addition products of 3, 5 or 7 moles of ethylene oxide onto technical coconut oil alcohols are particularly preferred.

Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V)

R ⁶ CO- (OCH ₂ CHR ⁷ ) _m OR ⁸ (V)

in which R ⁶ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{7 is} hydrogen or methyl, R ^{8 is a} linear or branched alkyl radical having 1 to 4 carbon atoms and m is a number from 1 to 20 stands. Typical examples are the formal insert products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, calcium acid , 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and behenic acid and behenic acid and behenic acid. The products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for. B. Calcined hydrotalcite. Reaction products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.

Alkyl and alkenyl oligoglycosides, which are also preferred nonionic surfactants, usually follow the formula (VI),

R ⁹ O- [G] _p (VI)

in which R ^{9 represents} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP-A1 0301298 and WO 90/03977. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (VI) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound and especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligo glycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ⁹ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, capric alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as those obtained in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C ₈ -C ₁₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C ₁₂ - Alcohol may be contaminated and alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ⁹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures described above, which can be obtained as well as their technical mixtures. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1 to 3 are preferred.

Typical examples of cationic surfactants are, in particular, tetraalkylammonium compounds, such as, for example, dimethyldistearylammonium chloride or hydroxyethyl hydroxycetyldimmonium chloride (Dehyquart E) or esterquats. These are, for example, quaternized fatty acid triethanolamine ester salts of the formula (VII),

in which R ¹⁰ CO for an acyl radical with 6 to 22 carbon atoms, R ¹¹ and R ¹² independently of one another for hydrogen or R ¹⁰ CO, R ¹³ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _x4 H- Group, x1, x2 and x3 in total for 0 or numbers from 1 to 12, x4 for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, as they occur, for example, in the pressure splitting of natural fats and oils. Preferably techni cal C _12/18 cocofatty acids and, in particular partly hydrogenated C _16/18 tallow or palm oil fatty acids and elaidic C _12/18 -fatty acid are used. The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 tallow or palm fatty acid (iodine number 0 to 40 ). From an application point of view, quaternized fatty acid triethanolamine ester salts of the formula (VII) have proven to be particularly advantageous in which R ¹⁰ CO is an acyl radical having 16 to 18 carbon atoms, R ^{10 is} R ¹⁰ CO, R ^{12 is} hydrogen, R ^{13 is} a methyl group , (x1 + x2 + x3) is 0 and X is methyl sulfate.

In addition to the quaternized fatty acid triethanolamine ester salts, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (VIII) are also suitable as esterquats,

in which R ¹⁴ CO for an acyl radical with 6 to 22 carbon atoms, R ¹⁵ for hydrogen or R ¹⁴ CO, R ¹⁶ and R ¹⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, x5 and x6 in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (IX) should be mentioned as a further group of suitable ester quats,

in which R ¹⁸ CO for an acyl radical with 6 to 22 carbon atoms, R ¹⁹ for hydrogen or R ¹⁸ CO, R ²⁰ , R ²¹ and R ²² independently of one another for alkyl radicals with 1 to 4 carbon atoms, x1 and x8 in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

Finally, suitable ester quats are substances in which the ester bond is replaced by an amide bond and which preferably follow the formula (X) based on diethylenetriamine,

in which R ²³ CO represents an acyl radical with 6 to 22 carbon atoms, R ²⁴ for hydrogen or R ²³ CO, R ²⁵ and R ²⁶ independently of one another for alkyl radicals with 1 to 4 carbon atoms and X for halide, alkyl sulfate or alkyl phosphate. Such amide ester quats are available on the market, for example, under the name Incroquat® (Croda).

Examples of suitable amphoteric or zwitterionic surfactants are alkylbetaines, alkylamido betaine, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. Examples of suitable alkylbetaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XI)

in which R ²⁷ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ²⁸ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ²⁹ for alkyl radicals with 1 to 4 carbon atoms, y1 for numbers from 1 to 6 and Y for a Alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, De cyldimethylamin, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C kyldimethylamin _12/14 -Kokosal, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, Stearylethylmethyl amine, oleyl dimethyl amine, C _16/18 tallow alkyl dimethyl amine and technical mixtures thereof .

Carboxyalkylation products of amidoamines which follow the formula (XII) are also suitable,

in which R ³⁰ CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, y2 represents numbers from 1 to 3 and R ²⁷ , R ²⁸ , y1 and Y have the meanings given above. Typical examples are fatomen reaction products of fatty acids with 6 to 22 CARBON, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, Palmitinsäu acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic and erucic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylamino propylamine, which are condensed with sodium chloroacetate. The use of a condensation product of C _8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate is preferred.

Imidazolinium betaines are also suitable. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as aminoethylethanolamine (AEEA) or diethylene triamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C _12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.

The washing, rinsing, cleaning and finishing agents according to the invention can furthermore additionally che contain inorganic and organic builder substances, being inorganic builder sub punch mainly zeolites crystalline layered silicates, amorphous silicates and - if permitted - also Phosphates, e.g. B. tripolyphosphate are used. The amount of co-builder is based on that allowance for preferred amounts of phosphates.

The fine crystalline, synthetic and bound water-containing zeolite which is frequently used as a detergent builder is preferably zeolite A and / or P. As zeolite P, for example, zeolite MAP (R) (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P and Y are also suitable. Of particular interest is also a cocrystallized sodium / potassium aluminum silicate composed 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. In the event that the zeolite is used as a suspension, it 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 μm (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} .y H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number is 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 is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .y H ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171. Further suitable layered silicates are known, for example, from patent applications DE 23 34 899 A1, EP 0026529 A1 and DE 35 26 405 A1. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates, which belong to the group of water-swellable smectites, are e.g. B. those of the general formulas

(OH) ₄ Si _8-y Al _y (Mg _x Al _4-x ) O ₂₀ montmorrilonite

(OH) ₄ Si _8-y Al _y (Mg _6-z Li _z ) O ₂₀ hectorite

(OH) ₄ Si _8-y Al _y (Mg _6-z Al _z ) O ₂₀ saponite

with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Furthermore, due to their ion-exchanging properties, 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. Usable layered 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 of 1: 2 to 1: 3, 3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties. The release delay compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the 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 degrees units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide 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 44 00 024 A1. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray morphous silicates.

It goes without saying that the generally known phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons. Ge the sodium salts of orthophosphates, pyrophosphates and in particular are particularly suitable the tripolyphosphate. Their content is generally not more than 25% by weight, preferably not more than 20 wt .-%, each based on the finished agent. In some cases it has been shown that in particular tripolyphosphates even in small amounts up to a maximum of 10% by weight, based on the finished agents, in combination with other builder substances for a synergistic improvement of secondary washing power.

Useful organic builders are, for example, those in the form of their sodium salts settable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, wine acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use ecological reasons are not objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, wine acid, sugar acids and mixtures of these. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of acidifying component and thus also serve to set a lower and milder pH value of Detergents or cleaning agents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

Other 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. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure for the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. 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 196 00 018 A1 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably wise ethylenediamine disuccinate. Glyce are also particularly preferred in this context rindisuccinate and glycerol trisuccinate, as described, for example, in the US patent publications US 4,524,009, US 4,639,325, in European patent application EP 0150930 A1 and Japanese patent application JP 93/339896. Suitable amounts are in Zeolite-containing and / or silicate-containing formulations at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 Contain 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 wrote.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid and measured against polystyrene sulfonic acid). Suitable copolymeric poly Carboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or Methacrylic acid with maleic acid. Copolymers of acrylic acid have been found to be particularly suitable Maleic acid proven to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Their relative molecular weight, based on free acids, is generally from 5,000 to 200,000 preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (each measured against Po lystyrene sulfonic acid). The (co) polymeric polycarboxylates can either be as a powder or as an aqueous Solution are used, with 20 to 55 wt .-% aqueous solutions are preferred. Granules Polymers are usually mixed into one or more basic granules afterwards. In particular Biodegradable polymers made from more than two different mono are also particularly preferred mer units, for example those which according to DE 43 00 772 A1 as monomers salts of acrylic acid re and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE 42 21 381 C2 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives. Other preferred copolymers are those described in German patent applications DE 43 03 320 A1 and DE 44 17 734 A1 and preferably monomers acrolein and acrylic have acid / acrylic acid salts or acrolein and vinyl acetate. Are also preferred as others Builder substances include polymeric aminodicarboxylic acids, their salts or their precursors call. Polyaspartic acids or their salts and derivatives are particularly preferred.  

Other suitable builder substances are polyacetals, which are reacted with dialdehydes 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 can. Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalalde hyd and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid re received.

In addition, 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 Technology known polymers of phthalic acid and / or terephthalic acid or their deriva ten, 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.

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses which have no outstanding builder's 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 content of sodium carbonate in the final preparations 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.

In addition to the ingredients mentioned, the agents can include other known additives, for example Salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, defoamers, ge rings contain amounts of neutral filler salts as well as colors and fragrances and the like.

Among the compounds 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 from 5 to 35% by weight and in particular up to 30% by weight, advantageously using per borate monohydrate or percarbonate.

As bleach activators, compounds which are aliphatic under perhydrolysis conditions oxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or ge optionally substituted perbenzoic acid result, are used. Substances that are suitable O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl carry groups. Multi-acylated alkylenediamines, in particular tetraacetylethylene, are preferred diamine (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, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyl oxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5- dihydrofuran and those from German patent applications DE 196 16 693 A1 and DE 196 16 767 A1 known enol esters as well as acetylated sorbitol and mannitol or their in the European The patent application EP 0525239 A1 describes mixtures (SORMAN), acylated sugars derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octa acetyl lactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications gen WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498 are known. The hydrophilic sub. Known from German patent application DE 196 16 769 A1 substituted acylacetals and those in German patent application DE 196 16 770 and the internatio Nale patent application WO 95/14075 described acyllactams are also preferably used puts. The combinations known from German patent application DE 44 43 177 A1 conventional bleach activators can be used. Such bleach activators are common Quantity range, preferably in amounts from 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total average. In addition to the conventional ones listed above Len bleach activators or in their place can also those from the European patent specifications EP 0446982 B1 and EP 0453 003 B1 known sulfonimines and / or bleach-boosting agents transition metal salts or transition metal complexes as so-called bleaching catalysts be included. The transition metal compounds in question include in particular those Manganese, iron, cobalt, rutheni known from German patent application DE 195 29 905 A1 um or molybdenum salt complexes and those from German patent application DE 196 20 267 A1 Known N-analog connections, which is known from German patent application DE 195 36 082 A1 manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in the German Patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, Titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, derived from the German Patent application DE 196 20 411 A1 known cobalt, iron, copper and ruthenium amine complexes, the manganese, copper and cobalt described in German patent application DE 44 16 438 A1 Complexes described in the European patent application EP 0272030 A1 cobalt Complexes, the manganese complexes known from European patent application EP 0693550 A1,  the manganese, iron, cobalt and copper known from European patent EP 0392592 A1 fer complexes and / or those in the European patent EP 0443651 B1 or the European Patent applications EP 0458397 A1, EP 0458398 A1, EP 0549271 A1, EP 0549272 A1, EP 0544490 A1 and EP 0544519 A1 described manganese complexes. Combinations of bleach activators and Transition metal bleaching catalysts are, for example, from the German patent application DE 196 13 103 A1 and the international patent application WO 95/27775 are known. Bleaching enhancer Transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are in usual amounts, preferably in an amount up to 1 wt .-%, especially of 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 entire mean.

Enzymes in particular come from the class of hydrolases, such as proteases, Estera sen, lipases or lipolytic enzymes, amylases, cellulases or other glyco sylhydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases carry in the Laundry for removing stains, such as stains containing protein, fat or starch, and Graying at. Cellulases and other glycosyl hydrolases can be removed by removing pilling and microfibrils help to maintain color and increase the softness of the textile. To bleach or to inhibit color transfer, oxidoreductases can also be used. Especially from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens enzymatic active ingredients obtained. Preferably who the proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus the, used. There are enzyme mixtures, for example from protease and amylase or Pro tease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipoly enzymes or protease having a table action, lipase or enzymes and cellulase having a lipolytic action, in particular, however, protease- and / or lipase-containing mixtures or mixtures with lipolytic acting enzymes of particular interest. Examples of such lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also been found in some cases proven. Suitable amylases include in particular α-amylases, iso-amylases, pul lulanases and pectinases. Cellobiohydrolases, endoglucanases are preferably used as cellulases and β-glucosidases, which are also called cellobiases, or mixtures thereof. Because 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 around them protect against premature decomposition. The percentage of 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.  

In addition to the mono- and polyfunctional alcohols, the agents can contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. In addition to calcium salts, magnesium salts also serve as stabilizers. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H ₃ BO ₄ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous. .

Graying inhibitors have the task of removing the dirt detached from the fibers in the liquor to keep suspended and thus prevent the dirt from re-opening. Here are what Suitable water-soluble colloids mostly organic in nature, for example the water-soluble salts poly merer carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch ke 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. Next Soluble starch preparations and starch products other than those mentioned above can be used the, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. Prefers However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarb oxymethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone, for example in amounts of 0.1 up to 5 wt .-%, based on the agent used.

The agents can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Are suitable for. B. 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 morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyle type may be present, e.g. B. 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. Uniform white granules are obtained if the agents, in addition to the usual brighteners, are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, even small amounts , for example 10 ^-6 to 10 ^-3 wt .-%, preferably around 10 ^-5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).

Dirt-repellant polymers ("should repellants") are those substances which are preferred Contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio Ethylene terephthalate to polyethylene glycol terephthalate can 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, d. that is, the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 up to 100. The polymers have an average molecular weight of about 5000 to 200,000 and can have a block, but preferably a random structure. Preferred polymers are those 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. Next preferred are those polymers which link polyethylene glycol units with one mole molecular weight from 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of Have polymers from about 10,000 to about 50,000. Examples of commercially available polymers are Products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).

The solid preparations can also contain disintegrants. This includes substances stand, which are added to the moldings, in order to disintegrate them when they come into contact with water to accelerate. Overviews can be found e.g. B. in J. Pharm. Sci. 61 (1972) or Römpp Chemi lexicon, 9th edition, volume 6, p. 4440. The disintegrants can be macroscopically in the molded body tries to be homogeneously distributed, but microscopically they form Zo due to the manufacturing process increased concentration. The preferred disintegrants include polysaccharides, such as. B. na natural starch and its derivatives (carboxymethyl starch, starch glycolates in the form of their alkali salts, Agar agar, guar gum, pectins etc.), celluloses and their derivatives (carboxymethyl cellulose, micro crystalline cellulose), polyvinylpyrrolidone, collidone, alginic acid and their alkali salts, amorphous or also partially crystalline layered silicates (bentonites), polyurethanes, polyethylene glycols as well as gas systems. Other disintegrants that may be present in the sense of the invention are in for example the publications WO 98/40462 (Rettenmeyer), WO 98/55583 and WO 98/55590 (Unile ver) and WO 98/40463, DE 197 09 991 and DE 197 10 254 (Henkel). On the teaching of this Writings are expressly referred to. The moldings can contain the disintegrants in quantities of 0.1 to 25, preferably 1 to 20 and in particular 5 to 15% by weight, based on the moldings contain.

As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic pro Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used the. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert.- Butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, Benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzylsa licylate. The ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear Alka nale with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitro nellal, lilial and bourgeonal, to the ketones z. B. the Jonone, α-Isomethylionon and Methylcedrylke clay, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpi neol, the hydrocarbons mainly include terpenes such as limonene and pinene. Before however, mixtures of different odoriferous substances are used, which together address one  Generate the appropriate fragrance. Such perfume oils can also contain natural fragrance mixtures, as they are accessible from plant sources, e.g. B. 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 they can also be advantageous to apply the fragrances on carriers, which the adhesion of the perfume on the Wä strengthening and slower fragrance release for long-lasting fragrance of textiles For example, cyclodextrins have proven themselves as such carrier materials, the cyclo dextrin-perfume complexes can also be coated with other auxiliaries. If desired, the final preparations can also contain inorganic salts as fillers or fillers contain, such as sodium sulfate, which is preferably in amounts of 0 to 10, in particular whose 1 to 5 wt .-% - based on agent - is included.

Examples

Manufacturing example. 10,000 kg of an aqueous slurry consisting of 0.5% by weight cellulose ether, 5.0% by weight sodium silicate, 20.7% by weight sodium sulfate, 15.8% by weight sodium carbonate, 2.0% polyacrylic / methacrylate, 50% by weight of water and 6% by weight of a mixture of 80% by weight of partially hydrogenated petrolatum wax with a solidification point of 43 ° C. and 20% by weight of ethylenediamine bisstearate was in with constant homogenization under a pressure of 40 bar atomized in a spray tower and dried using hot, countercurrent combustion gases (temperature in the ring channel 250 ° C, in the tower outlet 98 ° C). In parallel, 2000 kg of an aqueous solution containing 3.7% by weight of a thickener mixture of sodium carboxymethyl cellulose and methyl cellulose in a weight ratio of 70:30 were allowed to swell at 25 ° C. for 4 hours. 20% by weight of a polysiloxane defoamer (polydimethylsiloxane with microfine silanized silica) were added to this solution. A stable aqueous emulsion was obtained. In a fluidized bed apparatus (SKET system) with a circular fluidized bed, through which drying air with approx. 20,000 m ³ air / h flowed at a temperature of 140 ° C, 650 kg of the powdery intermediate product were continuously fed per hour via a solids metering and 350 kg per hour of the previously prepared aqueous silicone emulsion were continuously sprayed onto this powdery preliminary product. The temperature in the fluidized bed above the fluidized bed was 85 ° C, the exhaust air 79 ° C. Granules with the following composition were obtained: 13% by weight of petrolatum (soft wax), 2% by weight of ethylenediamine bisstearate (hard wax), 3% by weight of silicone and ad 100% by weight of carrier materials. The product had a bulk density of 800 g / l and a particle size distribution in which 95% by weight of the particles had an average diameter below 1.5 mm. The product showed a very good trickle and had practically no dust content.

Application tests. The defoamer granules produced were in an amount of 1.5% by weight by simply mixing it into a powdered universal detergent formulation 8% by weight sodium alkylbenzenesulfonate, 10% by weight alkyl ethoxylate, 1.5% by weight soap, 10% by weight natri umcarbonate, 20% by weight zeolite, 3% by weight sodium silicate, 20% by weight sodium perborate, 2% by weight Tetraacetylethylenediamine (TAED), 0.5% by weight of protease, balance on 100% by weight of sodium sulfate and what this incorporated. The detergent obtained had perfect foam behavior both at 30 ° C. as well as at 40 ° C, 60 ° C and 95 ° C.

Claims (10)

1. Defoamer granules for solid washing, rinsing and cleaning agents, containing

• a) at least one soft wax with a melting point in the range from 35 to 50 ° C,
• b) at least one hard wax with a melting point above 50 ° C.
• c) silicones and
• d) carrier materials.

2. defoamer granules according to claim 1, characterized in that they are as soft waxes (Component a) contain petrolates or their hydrogenation products. 3. defoamer granules according to claims 1 and / or 2, characterized in that they are as Hard waxes (component b) bisamides, fatty acids, fatty alcohols, carboxylic acid esters and / or Paraffin waxes included. 4. defoamer granules according to at least one of claims 1 to 3, characterized in that that they contain polydiorganosiloxanes as silicones (component c). 5. defoamer granules according to at least one of claims 1 to 4, characterized in that they

• a) 5 to 25% by weight of at least one soft wax with a melting point in the range from 35 to 50 ° C,
• b) 1 to 10 wt .-% at least one hard wax with a melting point above 50 ° C.
• c) 1 to 10 wt .-% silicone and
• d) contain ad 100 wt .-% carrier materials.

6. Process for the production of defoamer granules for solid washing, rinsing and cleaning medium, in which silicones in the form of aqueous emulsions are mixed onto a mixed intermediate Soft waxes, hard waxes and carrier materials and the products in the Fluid bed dries and granulates.   7. Process for the production of defoamer granules for solid washing, rinsing and cleaning medium, in which aqueous preparations of soft waxes, hard waxes, silicones and Trä spray dried. 8. Process for the production of defoamer granules for solid washing, rinsing and cleaning medium, in which aqueous preparations of soft waxes, hard waxes, silicones and Trä Germ materials in the fluid bed dry. 9. The method according to claims 6 to 8, characterized in that one has a good grain fraction with a grain diameter in the range of 0.4 to 1.5 mm. 10. Use of defoamer granules according to claim 1 for the production of solid washing, Detergents and cleaning agents.