ES2200240T3 - PROCEDURE FOR OBTAINING A STORAGE AND SPREADABLE GRANULATE OF WASHING AND CLEANING AGENTS CONTAINING ANIONIC TENSIANS. - Google Patents

Abstract

Storable, free-running laundry and other detergent granules with a bulk density of over 600 g/l, produced by a specified process, contain 3-12 wt.% nonionic surfactant, 10-60 wt.% alkali silicate as connecting solid and 10-35 wt.% anionic surfactant. <??>An Independent claim is also included for the production of storable, free-running laundry and other detergent granules with a bulk density of over 600 g/l, which contain anionic surfactant.

Description

Procedure for obtaining a granulate storable and dispersible cleaning and cleaning agents that They contain anionic surfactants.

The invention relates to a method for obtaining a storable and dispersible granulate agent washing and cleaning containing anionic surfactants with a  bulk weight above 600 g / l as well as agents of washing and cleaning containing anionic surfactants and not ionic, manufactured according to the procedure.

A great state of the art is known number of procedures that allow according to a form of work in continuous or in stages, the manufacture of compacted granules. In this way for example the EP-A-420 317 teaches a combination mixer / granulator, with high speed, neutralizing in first the anionic surfactants in their acidic form and they then molded into granules by adding others components. This granulate is in a plastic state, because to which other stages of the procedure are required, for example a stage of compaction and a stage for drying. East procedure has, however, the disadvantage that granules certainly have a high bulk weight, however on the other hand they have a tendency to form scabs, glued and greased, when not respected certain brand conditions. In this way the procedure has to be carried out almost anhydrously and / or in the absence of nonionic surfactants and / or in a given range of temperatures

It is known by the descriptive memory of the EP 0 642 576 B1 a two-stage procedure for the granules manufacturing. In the teachings of this document, describes the use of zeolites or phosphates as substances adjuvants However, phosphates are less preferred by way of adjuvants for ecobiological reasons. In the same way it is preferred the renunciation of zeolites as adjuvant components due to their poor solubility

It is known from the teachings of WO 93/23520 a procedure for the manufacture of washing and cleaning agents containing anionic surfactants. In this case it is prepared individually a neutralized, which contains the surfactants anionic This is then added to a solid product to a solid product mix, arranged in advance in a mixer and it is granulated in the same mixer. Through the teachings of this document prevents excessive thermal hue due to the neutralization reaction In this way of proceeding it has revealed as an inconvenience, however, the choice of solid products In this case the adjuvants are not waived from the group of zeolites or phosphates or else the crystalline alkaline silicates, usual in commerce, in case given in combination with alkali carbonates. However, due to the application of the neutralization medium on the solid product and the granulation in the same mixer only obtains a product with poor spreading capacity.

The task of the invention was to put provision of a procedure that did not present the inconveniences cited. Therefore a procedure must be made available for the manufacture of a granulate of washing agents and of cleaning, which is not sticky or greased through the stages of the method according to the invention, being able to give up the water and phosphate insoluble zeolites as components adjuvants, but at the same time they must be made available washing and cleaning agents, based on surfactants anionic, with excellent properties of washing agents and a delayed dissolution rate of components adjuvants

The object of the invention is a process for the manufacture of a storable and dispersible granulate of washing and cleaning agents containing surfactants anionics with a bulk weight above 600 g / l, characterized in that in the first place (a) a neutralized is prepared fully neutralized, containing at least one acid anionic surfactant, at least one nonionic surfactant and bleach of  sodium hydroxide, (b) this is applied on an adjuvant of type silicate, soluble in water, to obtain a precursor, (c) mixes with other usual components of the washing agents and, finally (d) it is granulated with a granulation liquid, taking to obtain the precursor and manufacture the granulate of separate in space and continuous.

According to the invention, the procedure is carried out out continuously. For this purpose they are connected in series At least two mixers. In the first mixer the precursor, that is, the neutralized one, which in turn is prepared from separately, applying thereon on the type adjuvant silicate.

In a second mixer the others are added solid and / or liquid products to the precursor and the granulation stage The subsequent sprinkling, if necessary, with creep enhancers, it is carried out well in the area of discharge of the second mixer or separately in a third mixer, connected downstream. As a third mixer is Especially preferred, for this purpose, a mixer called Schugi.

In a preferred embodiment, claims a procedure that provides for the coating of the silicate-type adjuvant, treated with neutralized (the precursor) first with other substances. Substances Suitable coating are water soluble components of the washing agents, which are applied in the form of their aqueous solution on the silicate-type adjuvant, treated with the neutralized (fluidized bed coating). During this process of Superficial application evaporates excess water. Preferably this is achieved with disilicate and / or solutions. of polycarboxylate, for example in a sliding bed dryer from Glatt, Aeromatic or Escher-Wyss. Finally it is granulated, as described above, this "coated" precursor after addition of other components usual for washing agents, in a granulation stage or It is mixed in a mixing (drying) stage. Through this procedure called "coating" the precursor in a scalable, scalable compound, which now also It can be stored provisionally.

In an embodiment very especially of the present invention, the precursor is sprinkled with creep enhancers instead of "lining" or in addition to the coating of the precursor for example with glass soluble and / or with polycarboxylate solution. They are suitable for this.  especially Wessalith and / or precipitation silicic acids.

Both in the case of the "lining" of the precursor as well, alternatively, in the case of sprinkling the precursor without "coating" or in the case of the combination of "coating" and sprinkled is desirable until necessary - according to the water content - at least one partial evaporation of the proportion of water incorporated through of the neutralized.

Obtaining the neutralized can take carried out in vats with stirring or in all the usual mixers, traditional and is carried out separately. For the neutralization of the anionic surfactants or acids is employs concentrated sodium hydroxide bleach. Bleach concentrated sodium hydroxide contains between 30 and 60% in weight of sodium hydroxide, preferably between 45 and 55% in weight. Usually the acid (s) will be available in advance anionic surfactants and sodium hydroxide bleach will be added as a means of neutralization. A form of proceed in reverse. In another embodiment for the Obtaining the neutralized are available in advance nonionic surfactant components, surfactants are added anionic in its acidic form and finally the neutralization with concentrated bleach of sodium hydroxide. In other embodiment are fed continuously and so synchronized to the process of mixing the three components of the neutralized

The neutralized contains one or several anionic surfactants between 10 and 99% by weight, one or more nonionic surfactants between 1 and 90% by weight (referred respectively to neutralized) and a proportion of water so Small as possible. The water content that can be used depends on this case of the type and quantity of the nonionic surfactant employee. The water content must be established in any case in such a way that, after neutralization of acids anionic surfactants, a liquid phase is maintained.

The mixtures, which contain surfactants anionics, prepared according to this preferred embodiment, they are scalable and pumpable preferably at temperatures between 5 and 20 ° C, especially between 8 and 15 ° C.

How anionic surfactants enter consideration of known sulphonates and sulfates as well as soaps  preferably consisting of fatty acids or mixtures of natural fatty acids They will preferably be transformed, in the embodiment of complete neutralization, acids sulfograses and fatty acids in their anionic surfactants. It is Especially preferred is the use of saturated fatty acids and unsaturated with chain lengths with 8 to 18 atoms of carbon in the form of mixtures and / or acids α-sulfograms of fatty acids saturated with 8 to 18 carbon atoms. In an especially advantageous way they can mixtures of fatty acids and acids are also used α-sulfograses cited with other acids sulfonic and alkylsulfuric acids, for example acids alkylbenzenesulfonic and fatty alkyl sulfuric acids.

As anionic surfactants in their acid form of the sulfonic acid type come into consideration, in addition to alkylbenzenesulfonic acids, olefin sulfonic acids, is say mixtures constituted by alkene-e acids hydroxyalkanesulfonic acids, as well as sulfonic acids, such as which are obtained, for example, from monoolefins, with 12 to 18 carbon atoms with the double bond located at the end or in the inside of the chain, by trioxide sulfonation of gaseous sulfur. Alkanesulfonic acids are also suitable, which can be obtained from alkanes with 12 to 18 atoms of carbon by sulfocloration and sulfooxidation and by a subsequent hydrolysis or by adding bisulfite on olefins, as well as especially acid esters α-sulfograms, for example esters of methyl? -sulfonated fatty acids of coconut, hydrogenated palm or tallow seeds. Acids suitable alkylsulfuric are the monoesters of sulfuric acid constituted by primary alcohols of natural and synthetic origin, especially for fatty alcohols, for example fatty alcohols coconut, tallow fatty alcohols, oleyl alcohol, lauryl-, myristyl-, palmityl-, or stearylalcohol, or oxoalcohols with 10 to 20 carbon atoms, and those secondary alcohols with this chain length Monoesters of the sulfuric acid of ethoxylated alcohols with 1 to 6 moles of ethylene oxide, such as alcohols with 9 to 11 atoms of 2-methyl-branched carbon with a average of 3.5 moles of ethylene oxide. Especially is preferably, the use of at least two of the anionic surfactants cited in its acid form, for example fatty acids and acids alkylbenzenesulfonic or fatty acids or sulfo fatty acids of saturated and / or unsaturated fatty acids or alkyl esters of sulfo fatty acids of saturated fatty acids and / or unsaturated In this case it is especially advantageous if they are added first of all fatty acids to nonionic surfactants ethoxylates, arranged in advance and then the other sulphited anionic surfactants in their acid form.

In a preferred embodiment, prepare the neutralized, used, from acids alkylbenzenesulfonic, sodium hydroxide bleach and at least a nonionic surfactant. In this case they are especially preferred are alkylbenzenesulfonic acids with an alkyl group with 9 to 15 carbon atoms.

In another preferred embodiment, will prepare the neutralized from acids alkylbenzenesulfonic, sodium hydroxide bleach and nonionic surfactants from the group of nonionic surfactants ethoxylated.

Ethoxylated nonionic surfactants are derived from primary alcohols with preferably 9 to 18 carbon atoms and an average of 1 to 12 moles of oxide ethylene per mole of alcohol, in which the alcoholic remainder it can be linear or it can be methyl branched in position 2, or It may well contain linear and methylbranched remains in mixture, like those that usually occur in the remains of oxoalcohols. Especially, however, linear residues of naturally occurring alcohols with 12 to 18 carbon atoms, such as for example coconut alcohol, tallow fatty alcohol or oleyl alcohol The degrees of ethoxylation indicated represent statistical mean values, which can be an integer or Fractional for a special product. Alcoholetoxylates Preferred have a narrow distribution of homologues (Narrow range ethoxylate, NRE) are especially preferred alcoholetoxylates having an average of 2 to 8 groups of ethylene oxide. To the preferred ethoxylated alcohols belong, for example, oxoalcohol with 9 to 11 carbon atoms with 7 EO, oxoalcohol with 13 to 15 carbon atoms with 3 EO, 5 EO, 7 EO or 8 EO and, especially, alcohols with 12 to 14 carbon atoms with 3 EO or with 4 EO, alcohols with 12 to 18 carbon atoms with 3 EO, 5 EO or 7 EO and mixtures constituted by them such as mixtures formed by alcohol with 12 to 14 carbon atoms with 3 EO and alcohol with 12 to 18 carbon atoms with 5 EO.

This mixture consisting of surfactants anionic acid form and ethoxylated nonionic surfactants it can be prepared in a large proportion by weight, preferably in a proportion by weight between anionic surfactant in form acid and ethoxylated nonionic surfactant from 1: 0.5 to 1: 30,  especially up to 1: 20. In this case they will be used advantageously mixtures, in the case of complete neutralization, in  which the proportion by weight between the anionic surfactant in acidic form and ethoxylated nonionic surfactant is less than 1, preferably from 1: 2 to 1: 20 and, especially, less than 1 : 5.

In a preferred embodiment, apply the neutralized, manufactured separately, on the silicate-type adjuvant in a mixer at a temperature of at minus 50 ° C. In this case they are especially preferred temperatures between 70ºC and 90ºC. The dosed takes out with the mixer and the crown of blades running. How suitable mixers can be cited, for example, the Eirich mixer of the R and RV series, manufactured by the firm Maschinenfabrik Gustav Eirich, Hardheim, Germany, the mixer Fukae FS-G, manufactured by Fukae Powtech Kogyo Co., Japan, the Lödige FM, KM and CB mixers, manufactured by Lödige Maschinebau GmbH, Paderborn, Germany, or Drais series T or K-T, manufactured by Drais  Werke GmbH, Mannheim, Germany. In this case it will be entered in the The neutralized mixer preferably through nozzles. The addition can be carried out however also - even when this it is less preferred - manually, for example by removed.

As silicate type adjuvant components are they will use granular sodium and / or potassium silicates, obtained by spray drying, compacting and grinding, with a molar ratio SiO 2 M 2 O preferably from 2.0 to 3.0, especially sodium silicates with some water content. The water content is preferably between 15 and 22% by weight. Within the scope of the invention, they will be used only granular silicates, especially the use will be excluded of alkali carbonates. Especially preferred are granular silicates, chosen from granular disilicates, commercially available Britesil® (commercial products of the AKZO-PQ silica signature) of type H20 (module 2.0), H20 Plus (module 2.0) and H24 (module 2.4), which are suitable as Zeolite and / or stratified disilicate substitutes crystalline Washing and cleaning agents, manufactured according to the procedure, contain at least 15% by weight, especially from 30 to 60% by weight, based on the recipe as a whole of the washing or cleaning agents of these silicates granular These water soluble, amorphous, granular silicates, they are especially preferred also against soluble glass ground. These present, in comparison with soluble glass, a Clearly delayed dissolution behavior. In this way the alkaline silicates mentioned also exert their function of adjuvant without, however, leaving insoluble washing residues or cleaning.

In another preferred embodiment, add the adjuvant, treated with the neutralized, at least one other anionic surfactant component and / or a soap component in addition of other typical components of washing agents.

In this case they come into consideration by way of surfactants preferably sulphonate surfactants, of Especially preferred alkylbenzenesulfonates with 9 to 13 carbon atoms, sulphonate olefins, that is mixtures constituted by alkene- and hydroxyalkanesulfonates as well as disulfonates, such as those obtained for example from monoolefins with 12 to 18 carbon atoms with the double bond located at the end or inside the chain by sulfonation with gaseous and subsequent sulfur trioxide alkaline or acid hydrolysis of sulfonation products. Without However, alkanesulfonates, which are obtained at from alkanes with 12 to 18 carbon atoms for example by sulfocloration or sulfooxidation with its following hydrolysis or neutralization.

Preferred anionic surfactants are also the salts of alkylbenzenesulfonic acids, which also referred to as sulfosuccinates or as acid esters sulfosuccinic and representing monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and, especially, with ethoxylated fatty alcohols. The Preferred sulfosuccinates contain traces of fatty alcohols with 8 to 18 carbon atoms or mixtures thereof. The Especially preferred sulfosuccinates contain a remainder of fatty alcohol that is derived from ethoxylated fatty alcohols, which they represent, considered in themselves, nonionic surfactants. In this case, the sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow distribution of counterparts

Acid esters are also suitable α-sulfograms (estersulfonates), for example the α-sulphonated methyl esters of the coconut, palm kernel or tallow fatty acids hydrogenated

How alq (en) ilsulfates will be preferred are alkaline salts and, especially, salts of Sodium Sulfuric Acid Sodium from Fatty Alcohols with 12 to 18 carbon atoms, for example fatty alcohols of coconut, tallow fatty alcohols, lauryl-, myristyl-, cetyl- or stearylalcohol or oxoalcohols with 10 to 20 atoms of carbon and those semi esters of secondary alcohols with these chain lengths. In addition, the alq (en) ilsulfates with chain lengths cited, containing a synthetic, chain alkyl moiety linear, manufactured in petrochemical base, having a degradation behavior similar to that of compounds Suitable based on fat chemistry raw materials. They are especially preferred for reasons of interest of the technology wash the alkyl sulfates with 12 to 16 carbon atoms and alkyl sulfates with 12 to 15 carbon atoms as well as alkyl sulfates with 14 to 15 carbon atoms. They are also suitable anionic surfactants the 2,3-alkyl sulfates, which are manufactured according to descriptive reports of US patents 3,234,258 or 5,075,041 and which can be purchased as commercial products of Shell Oil Company under the name DAN®.

Acid monoesters are also suitable sulfuric acid ethoxylated alcohols with 1 to 6 moles of oxide ethylene, such as alcohols with 9 to 11 carbon atoms 2-methyl-branched with a intermediate 3.5 moles of ethylene oxide.

Anionic surfactants can be presented in form of its sodium, potassium or ammonium salts as well as to mode of soluble salts of organic bases, such as mono-, di- or triethanolamine Preferably the anionic surfactants are present in the form of their sodium or potassium salts, especially in the form of sodium salt.

Anionic surfactants will be used preferably in amounts from 3 to 25% by weight, especially in amounts from 10 to 20% by weight, referred respectively to the sum of the components used. However its content can go beyond 15% by weight. The Preferred anionic surfactants are fatty alkyl sulfates, alkylbenzenesulfonates, sulphosuccinates, as well as mixtures of themselves, such as mixtures consisting of fatty alkyl sulfates and fatty sulphosuccinates or alkyl sulfates and alkylbenzenesulfonates fatty, especially in combination with soaps. In this case it is especially preferred that at least a part of the Sulphonate and / or sulfate surfactants should not be used as solid components but in liquid form as a component in the granulation liquid.

How other surfactants come into consideration soaps, either alone or in combination with surfactants cited anionics. Especially preferred are the soaps of saturated fatty acids, such as myristic acid salts, lauric, palmitic or stearic. Acids are also suitable unsaturated fatty acids, which are derived for example from oleic acid. Also suitable are mixtures of fatty acids, which can extracted from natural sources, for example fatty acids of coconut, palm seeds or tallow. Are especially preferred those mixtures of soaps that are constituted by 50 to 100% by weight for soaps of saturated fatty acids with 12 to 18 carbon atoms. Soaps are presented preferably in amounts from 0.5 to 8% by weight.

By way of other typical components of the washing and cleaning agents will be used for example organic adjuvants, blackening inhibitors such as by example anionic and / or non-ionic cellulose derivatives, especially carboxymethylcellulose (CMC) and / or methylcellulose (MC) and polyvinylpyrrolidone (PVP) or foam inhibitors, such as for example silicones or paraffin oils on supports granular and fatty alkyl phosphates.

Organic structuring substances employable are, for example, employable polycarboxylic acids  in the form of its sodium salts, such as citric acid, the adipic acid, succinic acid, glutaric acid, acid tartaric acid, saccharic acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as it is not questionable employment of this type for ecological reasons, as well as mixtures thereof. Preferred salts are the salts of the polycarboxylic acids such as citric acid, acid adipic acid, succinic acid, glutaric acid, acid tartaric acid, saccharic acids and mixtures thereof.

The acids themselves can also be used. Acids have, in addition to their adjuvant effect, typically also the property of an acidified component and therefore they also serve to adjust a low and soft pH value of washing or cleaning agents. In this case they can be cited especially citric acid, succinic acid, acid glutaric acid, adipic acid, gluconic acid and mixtures arbitrary of them.

Other suitable organic adjuvant substances they are dextrins, for example oligomers or hydrate polymers of carbon, which can be obtained by partial hydrolysis of starches Hydrolysis can be carried out according to procedures. usual, for example catalyzed by acids or by enzymes Preferably it is a hydrolysis product with average molecular weights in the range from 400 to 500,000. In this case, a polysaccharide with an equivalent of dextrose (SD) in the range of 0.5 to 40, especially from 2 to 30, the DE being a usual magnitude for the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with an ED included are employable between 3 and 20 and dried glucose syrups with a DE between a 20 and 37 as well as the so-called yellow dextrins and white dextrins with high molecular weights in the range from 2,000 to 30,000. A preferred dextrin is described in British patent application 94 19 091. The oxidized derivatives of such dextrins are constituted by reaction products with oxidizing agents, which are capable of oxidizing at least one alcohol function of the saccharide ring to give an acid function carboxylic. Such oxidized dextrins of the procedures for their obtaining are known for example by patent applications European EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as by international patent applications WO-A92 / 18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608. Can be especially advantageous an oxidized product in the carbon atom 6 of the saccharide ring.

Other organic adjuvants, employable are, by for example, acetylated hydroxycarboxylic acids or their salts, which may also occur in the form of lactone and containing at least 4 carbon atoms and at least one group hydroxy thus, at most, two acid groups. Such adjuvants are described for example in the patent application International WO-A-95/20029.

Suitable polymeric polycarboxylates are, by For example, the sodium salts of polyacrylic acids or polymethacrylic acids, for example those with molecular weights relative from 800 to 150,000 (referred to acid). The Suitable copolymer polycarboxylates are especially those Acrylic acid with methacrylic acid and acrylic acid with methacrylic acid and maleic acid. They have been credited as Especially suitable are acrylic acid copolymers with the maleic acid, containing from 50 to 90% by weight of Acrylic acid, and from 50 to 10% by weight of acid Maleic Their relative molecular weight, referred to free soaps, it is comprised, in general, between 5,000 and 200,000, preferably between 10,000 and 120,000 and, especially, between 50,000 and 100,000. Homopolymer salts of the acrylic acid with relative molecular weights included approximately between 2,000 and approximately 150,000, especially  between 4,000 and 10,000.

Polycarboxylates (co) polymers can be used either as a powder or an aqueous solution, being Preferred aqueous solutions of 20 to 55% by weight.

Polymers are also especially preferred. constituted by more than two different monomer units, by example those that contain, according to the DE-A-43 00 772 as a monomer salts of acrylic acid and maleic acid as well as alcohol vinyl or derivatives of vinyl alcohol or containing, according to DE-C-42 21 381 by way of monomers salts of acrylic acid and salts of acids 2-alkylsulfonic as well as derivatives saccharics

Other preferred copolymers are those that are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and presenting mode of monomers preferably acrolein and acrylic acid / salts of acrylic acid or acrolein and vinyl acetate.

Other suitable adjuvant substances are the oxidation products of polyglucosannes containing carboxyl groups and / or their water soluble salts, such as those described for example in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110. Oxidized oligosaccharides according to the previous German patent application are also suitable
P 196 00 018.1.

They must also be cited as other preferred adjuvant substances, aminodicarboxylic acids polymers, their salts or their precursor substances. They are Especially preferred are polyasaparaginic acids or their salts or derivatives, of which it is disclosed in the application for German patent P 195 40 086.0 which in addition to properties of adjuvants also have a stabilizing effect of Whitening.

Other suitable adjuvant substances are polyacetals, which can be obtained by dialdehyde reaction with polycarboxylic acid, having 5 to 7 atoms of carbon and at least 3 hydroxyl groups, for example as described in the European patent application EP-A-0 280 223. Polyacetals Preferred are obtained from dialdehydes such as glyoxal, glutaroaldehyde, terephthaloaldehyde as well as their mixtures and starting of polycarboxylic acids such as gluconic acid and / or the glucoheptonic acid

To the other granular components belong, for example, also granules of bleaching agents or of compacted bleach activators, of enzymatic granules, foam inhibitor granules, preferably granules concentrated foam inhibitors as well as granular supports for dyes and perfumes.

As bleaching activators they serve, for example, N-acyl- or O-acyl compounds that form organic peracids with H2O2, preferably diamines N, N'-tetraacylated, plus acid anhydrides carboxylic and polyol esters such as pentaacetate glucose. The content of bleach activators in the agents that They contain bleaches is in the usual range, preferably between 1 and 10% by weight and, especially between 2 and 8% by weight. The activators of especially preferred bleaching are the N, N, N ', N'-tetraacetylethylenediamine (TAED) and the 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT).

Enzymes are those of the classes of proteases, lipases, amylases, cellulases or mixtures thereof. Especially good enzymatic active products obtained from bacterial or fungal strains, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus , are suitable. Preferably, subtilisin type proteases and, especially, proteases that are obtained from Bacillus lentus will be used . Its proportion can be approximately 0.2 to approximately 2% by weight. The enzymes may be adsorbed on a support and / or may be embedded in coating substances for protection against premature decomposition.

As stabilizers especially for percomposed and enzymes come into consideration, for example, salts of polyphosphoric acids, especially acid 1-hydroxyethane-1,1-diphosphonic (HEDP).

As foam inhibitors they are suitable for example soaps of natural or synthetic origin, presenting a high proportion of fatty acids with 18 to 24 atoms of carbon. Non-surfactant type foam inhibitors suitable are, for example, organopolysiloxanes and mixtures thereof with silicic acid or microfine, if appropriate silanized as well as paraffins, waxes, microcrystalline waxes and mixtures with acid silanized silicic. Advantageously, mixtures will also be used. constituted by the various foam inhibitors, for example those constituted by silicones, paraffins or waxes.

By way of other typical components of the washing agents can be used bleaching agents or precursors

In a preferred embodiment, they will use perborates and / or bleaching agents especially percarbonates Preferably, tetrahydrate of sodium perborate and perborate perborate monohydrate sodium. Among the percarbonates, the sodium percarbonates In addition to or instead of the or perborates and percarbonates or can be used in case given also peroxypyrophosphates, citrateperhydrates, as well as peracid or peracid salts that supply H 2 O 2, by example perbenzoates and / or peroxaphthalates. The proportion of bleaching agents, referred to the finished product, assumes from a 5 to 25% by weight, especially from 10 to 20% in weight. According to the invention bleaching agents will be added together to the other usual components of the washing agents previously mentioned, to the adjuvant treated for obtaining of the precursor. If necessary, the addition of the whitening agents totally or partially also in a stage of elaboration carried out downstream of the granulation.

The precursor or the precursor additionally treated by "coating" and / or sprinkled it is mixed in the second mixer with the other usual raw materials for washing agents and granulate with the addition of one or more liquids In this case, the use of a solution of liquid polycarboxylate for granulation.

In another preferred embodiment, add as a liquid for granulation at the stage of granulation, a mixture consisting of optical brighteners and polycarboxylate solution. How optical brighteners come in under consideration derivatives of diaminoestylbendisulfonic acid or Well its alkali metal salts. They are suitable for example acid salts 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) stilben-2,2'-disulfonic  or similarly constituted compounds, bearing, instead from the morpholino group, a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, optical brighteners of the type of 4,4'-diethyryl-di-phenyl substituted, for example compound 4, 4'-bis (4-chloro-3-sulfoesteryl) diphenyl. Mixtures of optical brighteners can also be used previously indicated. White granules are obtained especially unitary if the agents contain, in addition to the usual optical brighteners in usual quantities, for example between 10 -6 to 10 -3% by weight, preferably between 0.1 and 0.3% by weight, also small amounts for example from 10 -6 to 10 -3% by weight, preferably in the proximities of 10-5% by weight of a blue dye. A Especially preferred dye is Tinolux® (product commercial of the firm Ciba-Geigy).

The granulation is carried out according to the invention by way of granulation in a mixture, by pressing or by rolling in the mixers, extruders or rolling presses known by a person skilled in the art. However, granulation is carried out especially preferably in a mixer / granulator. As suitable mixers there may be mentioned, for example, the Eirich mixer of the R and RV series, manufactured by Maschinenfabrik Gustav Eirich, Hardheim, Germany, the Fukae FS-G mixer, manufactured by the Fukae Powtech Kogyo Co., Japan, the mixers Lödige FM, KM and CB, manufactured by Lödige Maschinebau GmbH, Paderborn, Germany, or the Drais T or KT series, manufactured by Drais Werke GmbH, Mannheim, Germany. The firm's intensive mixers also come into consideration
IMCATEC (Germany). The usual residence times, necessary for granulation, in these mixers are in the range from 1 minute to about 10 minutes.

In a preferred embodiment, sprinkle and dry the granulate prepared according to the invention with the use of influx improvers at the end of the granulation. In this case they are especially preferred, by way of influx enhancers, amorphous aluminosilicates and / or crystalline as well as silicic acids. Among aluminosilicates are especially preferred to zeolite A and / or X and / or P, for example Wessalith P® (commercial product of Degussa, Germany), and among the silicic acids very particularly preferably the Sipernat®. Creep improvers intermingle usually with the granulate. Its proportion, referred to the product finished, it is between 0.5 and 8% by weight. It is a proportion of silicic acids especially preferred between 0.5 and 3% by weight and / or a proportion of the Zeolites comprised of 1.5 and 7.5% by weight.

The intermediate product contains, so typical, between 0 and 10% by weight of non-ionic surfactants, from 40 to 65% by weight of disilicate, from 5 to 5 15% by weight of ABS, from 2 to 10% by weight of improvers of the influx, from 0 to 20% by weight of polycarboxylate, as well as water.

The stage for drying is carried out in bed fluidized, especially at air intake temperatures by below 180 ° C. Products manufactured according to the invention of this mode have a bulk weight greater than 600 g / l. The granules, manufactured according to the invention, they are capable of being charged to bulk and spreadable, they are not sticky and are practically dust free

Then it is verified, according to the procedure, the preparation of the granulate to give the product finish, known to the person skilled in the art.

Granular washing and cleaning agents, manufactured according to the process of the invention, contain preferably between 3 and 12% by weight, especially between 3 and 6% by weight of non-ionic surfactants, from 10 to 10 60% by weight, preferably between 30 and 60% by weight of alkali silicates as solid products arranged in advance and from 10 to 35% by weight, especially between 15 and 35% in weight of anionic surfactants. The granules manufactured according to the invention have a bulk weight above 600 g / l, preferably between 700 and 1,000 g / l.

The present invention is described in greater detail. detail by means of the following embodiments:

Examples Example 1

a) They were placed in a mixer with an arm of 130 liter Lödige plow, 13.44 kg of Britesil H20® and se Dosed neutralization solution, prepared from alcohols fatty acids with 12 to 18 carbon atoms with 7 EO (1.5 kg), acids alkylbenzenesulfonic acids (ABS acids) (1.7 kg) and hydroxide bleach of 50% by weight sodium (0.46 kg), at 80 ° C with the mixer and crown of blades in operation.

b) To this precursor was added 1.8 kg of Sokalan CP5® (copolymer of the sodium salt of acrylic acid and maleic acid) in powder form, 0.3 kg of soap, 0.26 kg of phosphonate, 6.3 kg of alkyl sulfate with 12 to 18 carbon atoms (FAS) and
17 g of optical brightener and with the mixer and the crown of blades in operation, it was granulated with the second granulation liquid, which contained a 30% by weight solution of Sokalan CP5® (1.7 kg) and optical brightener (4 g ). To improve creep, 1.6 kg of zeolite A and 1 kg of silicic acid were then mixed and the granulate, thus obtained, dried in a fluidized bed dryer.

The granulate, with a FAS weight ratio: ABS of approximately 3.3: 1 was perfectly spreadable and It had a bulk weight of 810 g / l.

Example 2

The components used in example 1, in this recipe were prepared in the same manner as in example 1. Apart from the modified ratio of FAS: ABS (1,2: 1) and the resulting modification thereof in the neutralization composition or in the neutralized part the same quantities of products were arranged
-especially of anionic surfactants- than in the case of the recipe of example 1.

The granulate obtained was also perfectly spreadable and had a bulk weight of 920 g / l.

Example comparative

The manufacture of this granulate was carried out according to the "single stage procedure", meaning that this processing was carried out in the same mixer without separation of obtaining the precursor and granulation. The recipe of the mixture, used in the present comparative example, and the materials raw materials, compounds and granulation liquids correspond to the recipe and the subjects of example 1.

In this case they were arranged in advance Britesil®, Sokalan CP 5® in powder form, soaps, phosphonate, FAS  and the optical brightener in the same manner as in example 1 and the neutralized one was added first and then (b) the granulation liquid containing the copolymer. TO then it was granulated during the same period of time as in the case of examples 1 and 2. The other stages of the procedure (sprinkled with creep and drying improvers) were identical to those indicated in examples 1 and 2.

The granulate formed lumps in the dryer and in the sieving separation of subsequent coarse grains of such way they formed crusted. Therefore it was not possible to safe production from the point of view of exploitation industrial.

Claims (14)

1. Procedure for obtaining a storable and dispersible granulate of washing and cleaning agents containing anionic surfactants with a bulk weight above 600 g / l, characterized in that first (a) a completely neutralized neutralized is prepared , which contains at least one anionic surfactant, at least one nonionic surfactant and sodium hydroxide bleach, (b) this is applied on a water soluble silicate-type adjuvant to obtain a precursor, (c) it is mixed with other usual components of the washing agents and, finally (d) it is granulated with a granulation liquid, the precursor and the manufacture of the granulate being carried out separately in space and continuously. 2. Method according to claim 1, characterized in that after manufacturing the non-spreadable precursor, this is treated by a "coating" with coating substances. 3. Method according to claims 1 or 2, characterized in that the precursor is sprinkled, as a prior step to granulation, with a creep improver. Method according to one of the preceding claims, characterized in that the neutralized agent has been prepared from alkylbenzenesulfonic acids, sodium hydroxide solution and at least one non-ionic surfactant. 5. Method according to claim 4, characterized in that the neutralized agent has been prepared from alkylbenzenesulfonic acids, sodium hydroxide bleach and non-ionic surfactants from the group of ethoxylated non-ionic surfactants. Method according to one of the preceding claims, characterized in that the dosing of the neutralized is carried out at a temperature of at least 50 ° C and with the mixer running. Method according to one of the preceding claims, characterized in that at least one second anionic surfactant and / or at least one other soap component are added to the adjuvants, obtained after the neutralization treatment, among the other components of the washing agents. . Method according to one of the preceding claims, characterized in that perborates and / or percarbonates are used as bleaching agents. 9. Method according to one of the preceding claims, characterized in that a polycarboxylate solution is used as the dosed granulation liquid as a granulated liquid. 10. Method according to claim 9, characterized in that the polycarboxylate solution contains optical brighteners. Method according to one of the preceding claims, characterized in that the granulated product is dusted by superficial incorporation of creep improvers. 12. Method according to claim 11, characterized in that as amorphous and / or crystalline zeolites and / or crystalline aluminosilicates are used as creep improvers. 13. Washing and cleaning agents, manufactured according to one of the preceding claims, characterized in that they contain from 3 to 12% by weight of non-ionic surfactants, from 10 to 60% by weight of alkali metal silicates as a product solid arranged beforehand and from 10 to 35% by weight of non-ionic surfactants. 14. Washing and cleaning agents, manufactured according to one of the preceding claims, characterized in that they contain from 3 to 12% by weight of non-ionic surfactants, from 30 to 60% by weight of alkali metal silicates as a product solid arranged beforehand and from 15 to 35% by weight of anionic surfactants.