DE19855380A1 - Granulation process - Google Patents

Abstract

The invention relates to a novel neutralization and granulation method. According to said method, a neutralizing foam which is obtained by mixing an anionic surfactant in its acid form with a solid neutralizing agent and then expanding the mixture is used as a granulation adjuvant. Said neutralizing foam preferably has an average pore size of less than 10 mm, more preferably less than 5 mm and especially less than 2 mm.

Description

The present invention relates to a method for producing surfactant granules. she relates in particular to a method which allows surfactant granules or surfactant-containing Components of detergent and cleaning agent compositions or complete Detergent and cleaning agent compositions without or with reduced use of spray drying steps.

Granular detergent compositions or components therefor are largely manufactured by spray drying. When spray drying who to the ingredients such as surfactants, builders, etc. with about 35 to 50 wt .-% water an aqueous slurry, the so-called slurry, mixed and in spray towers atomized in a hot gas stream, whereby the detergent and cleaning agent particles form. Both the facilities for this process and the implementation of Ver driving are expensive because most of the slurry water is evaporated in order to obtain particles with residual water contents of around 5 to 10% by weight. In addition ha ben the granules produced by spray drying usually excellent Solubility, but have only low bulk weights, which leads to higher packaging vo lumina as well as transport and storage capacities. The flowability also sprayed Dried granules are not optimal due to their irregular surface structure, which also affects their visual appearance. Spray drying process white list a number of other drawbacks, so that there has been no lack of attempts to  Manufacture of washing and cleaning agents completely without spray drying ren or at least the smallest possible proportion of spray drying products in the finished product to have a product.

For example, W. Hermann de Groot, I. Adami, G.F. Moretti describes "The Manufacture of Modern Detergent Powders ", Hermann de Groot Academic Publisher, Wassenaar, 1995, page 102 ff. various mixing and granulating processes for the production of washing and cleaning agents agents. These processes have in common that premixed solids granulated with the addition of the liquid ingredients and optionally post-dried the.

There is also a broad state of the art in non-tower technology in patent literature. Manufacture of washing and cleaning agents. Many of these procedures start from the Acid form of the anionic surfactants, since this surfactant class is the largest in terms of quantity Share of detersive substances and the anionic surfactants in the course of their manufacture Position arise in the form of free acids, which neutralizes to the corresponding salts Need to become.

This is how the European patent application EP-A-0 678 573 (Procter & Gamble) describes it Process for the production of free-flowing surfactant granules with bulk densities above 600 g / l, in which anionic surfactant acids with an excess of neutralizing agent to a Paste are reacted with at least 40 wt .-% surfactant and this paste with or several powders, at least one of which must be spray dried and the anioni contains polymer and cationic surfactant, is mixed, the resulting Granules can optionally be dried. In this process, the paste is removed by Zu transfer of further solids into granules, with subsequent drying in many cases is necessary.

European patent application EP-A-0 438 320 (Unilever) discloses a batch Process carried out for the production of surfactant granules with bulk densities above half of 650 g / l. Here, a solution of an alkaline inorganic substance in  Water with the addition of other solids with the anionic surfactant acid and in a high speed mixer / granulator with a liquid binder granu liert. Through the use of aqueous alkali solutions, a large amount of neutralization is used introduced large amount of water into the process so that the granules obtained dried Need to become.

From the European patent application EP-A-0 402 112 (Procter & Gamble) is a cont Nuclear neutralization / granulation process for the production of FAS and / or ABS granules known from the acid, in which the ABS acid contains at least 62% NaOH neutralized and then with the addition of auxiliaries, for example ethoxylated Alcohols or alkylphenols or a polyethylene melting above 48.9 ° C Lenglykols is granulated with a molecular weight between 4000 and 50000. Here too later drying of the granules is unavoidable through the use of aqueous lye Lich.

European patent application EP-A-0 508 543 (Procter & Gamble) calls one method ren in which a surfactant acid with an excess of alkali to an at least 40 wt. % surfactant paste is neutralized, which is then conditioned and granulated, with direct cooling using dry ice or liquid nitrogen.

Dry neutralization process in which sulfonic acids are neutralized and granulated those are disclosed in EP 555 622 (Procter & Gamble). According to the teaching of this scripture finds the neutralization of the anionic surfactant acids in a high speed mixer by an excess of finely divided neutralizing agent with a medium particle size under 5 µm instead.

A similar process is also carried out in a high speed mixer and with the sodium carbonate ground to 2 to 20 µm as neutralizing agent is used, is described in WO 98/20 104 (Procter & Gamble).  

The German patent application DE-A-42 32 874 (Henkel KGaA) discloses a method ren for the production of washable and cleaning-active anionic surfactant granules by neutralis sion of anionic surfactants in their acid form. Solid, powdery substances disclosed. The granules obtained have a surfactant content of around 30 % By weight and bulk weights of less than 550 g / l. In this script too, the liquid Anionic surfactant acid added to a solid bed containing the neutralizing agent and granulated.

The present invention was based on the object of providing a method which makes it possible to produce surfactant granules for detergents and cleaning agents without or with reduced use of spray drying steps. The process to be provided should also enable direct and economically attractive processing of the acid forms of detergent raw materials, but largely avoid the disadvantage of energy-intensive water vaporization. The drying of the granules formed should preferably also be completely dispensable. Solutions that solve the described task fields to some extent are described in the prior art mentioned above. Nevertheless, the methods mentioned have a number of disadvantages:

• - In the neutralization with NaOH as described in the prior art, ent stands a significant amount of heat, whereby overheating leads to the undesirable darkening exercise of the products leads; in addition, a large amount is caused by aqueous alkalis Water entered so that the resulting granules must be dried.
• - Direct cooling with dry ice or liquid nitrogen causes high loading drive costs;
• - Cooling through indirect heat transfer requires a slow or even batch-wise reaction control with long dwell times and large container volumes, what translates into high investment costs;
• - With indirect cooling, the viscosity of the neutralization mixture often increases significantly, which requires the addition of water and subsequent drying;  
• - High concentrations of active substances usually increase the viscosity where through the homogeneous incorporation of the neutralizate in subsequent agglomeration steps on solid supports is difficult;
• - When using solid neutralizing and agglomeration agents (e.g. Natri umcarbonate) the neutralization reaction slows down and / or initially un completely, so that acid-sensitive solids such as silicates or zeolites in the solid fabric bed must not be present.

Avoiding the disadvantages mentioned above and providing a procedure rens, which enables the rapid and complete neutralization of anionic surfactant acids without the Ge overheating and particularly easy further processing includes granules which do not subsequently have to be dried, were further objects of the present invention.

The problem is solved in a mixing and granulating process in which the anion is used acidic acid (s) and solid neutralizing agent combined into a neutralizate foam the one that serves as a granulating aid. The invention thus relates to a method ren for the production of surfactant granules, with an anionic surfactant in its acid form a solid neutralizing agent is neutralized and granulated and the solid neutral added to the anionic surfactant in its acid form and to a neutralizate foam is foamed, which is subsequently placed in a mixer Solid bed is given.

Furthermore, the reverse sequence of processes can also be carried out according to the invention:
Anionic surfactant acid and solid neutralizing agent are combined in a mixer to form a surfactant foam and are converted into granules by the addition of particulate components while being agitated.

Another object of the present invention is therefore a method of manufacture development of surfactant granules, an anionic surfactant in its acid form with a solid Neutralizing agent is neutralized and granulated, in which the solid neutralization  medium in a mixer with an anionic surfactant in its acid form to a neutralizate foam is foamed, which is subsequently granulated by adding solids becomes.

In the context of the present invention, the term “solid neutralization” characterizes medium "substances which are capable of neutralizing acids at room temperature The term "foam" used in the context of the present invention denotes Ge form from gas-filled, spherical or polyhedral cells (pores), which by liquid ge, semi-fluid or highly viscous cell webs are limited.

If the volume concentration of the gas forming the foam at homodisperse Distribution is less than 74%, so the gas bubbles are because of the surface-shrinking Effect of the interfacial tension spherical. Above the limit of the densest Ku gel pack, the bubbles are deformed into polyhedral lamellae, which range from approx. 4-600 nm thin cuticles. The cell webs, connected via so-called nodes dots form a coherent framework. They stretch between the cell bars Foam slats (closed-cell foam). Are the foam slats destroyed or if they flow back into the cell webs at the end of foam formation, an open cell is obtained foam. Foams are thermodynamically unstable because they are made smaller surface energy can be obtained. The stability and therefore the existence The foams according to the invention therefore depend on how far they succeed to prevent destruction.

To produce the foams, a gaseous medium can be blown into the mixtures of liquid (s) and solid (s) mentioned, or the foaming can be achieved by vigorous beating, shaking, spraying or stirring the liquid in the gas atmosphere in question. Because of the easier and more controllable and feasible foaming in the context of the present invention, foaming is clearly preferred over the other variants by blowing in the gaseous medium (“fumigation”). Depending on the desired process variant, the gassing takes place continuously or discontinuously via perforated plates, sintered discs, sieve inserts, Venturi nozzles, inline mixers, homogenizers or other conventional systems. Another - again clearly preferred - way of foaming the mixture of anionic surfactant (s) and neutralizing agent (s) consists in the choice of the neutralizing agent. If this releases gases (for example CO ₂ ) on contact with acid, the mixture is foamed per se by the neutralization reaction, which in most cases is entirely sufficient to carry out the process according to the invention. Alternatively, the "in situ foaming" of acid and neutralizing agent can be supported by additionally gassing the mixture.

Any gases or gas mixtures can be used as the gaseous medium for foaming be used. Examples of gases used in technology are nitrogen and acid substance, noble gases and noble gas mixtures, carbon dioxide etc. For cost reasons, this will be Process according to the invention preferably with air as the gaseous medium leads, if additional gases are used for foaming.

The method according to the invention includes the sub-steps of FIG Generation of a neutralized foam from an anionic surfactant in its acid form and from a solid neutralizing agent. The neutralized foam subsequently serves when added on a solid bed moved in a mixer as a granulating aid, or can itself presented in the mixer and by adding finely divided solids into a granulate leads. The ingredients of the intermediate products of the two substeps are described below.

As already mentioned above, are as solid neutralizing agents in the context of Invention all suitable substances at room temperature suitable in the Are able to neutralize the anionic surfactant in its acid form, i.e. H. into an anion to transfer acidic salt. For example, hydroxides such as NaOH or KOH come basic oxides such as alkali metal oxides or basic salts such as carbonates in Consideration. It is preferred if in the neutralization reaction gaseous in addition to water Substances are created that support the formation of the foam or alone without fumigation pass. In particularly preferred processes, Car  bonates and / or hydrogen carbonates, preferably alkali carbonates and / or alkali hydro gene carbonates and especially sodium carbonate and / or sodium hydrogen carbonate set.

Since the neutralization reaction is accelerated with a large surface, the fe Most neutralizing agents have a particle size below 500 microns, preferably below have half of 200 microns and in particular below 100 microns. Coarser qualities the solid neutralizing agent can in a manner familiar to the skilled worker on a Mill to be ground to the desired particle sizes.

The essence of the first sub-step of the method according to the invention is the generation a neutralizate foam from anionic surfactant acid and neutralizing agent. The first Process step is therefore either with stoichiometrically exact amounts or with egg an excess of neutralizing agent is carried out to complete the anionic surfactant acid dig in the washing and cleaning active salt to convert in preferred procedures the anionic surfactant in its acid form and the solid neutralizing agent in the molar Ratio from 1: 2 to 1: 1, preferably from 1: 1.5 to 1: 1 and in particular from 1: 1, that is equimolar.

One or more substances from the group are preferred as anionic surfactants in acid form the carboxylic acids, the sulfuric acid half-esters and the sulfonic acids, preferably from the Group of fatty acids, fatty alkyl sulfuric acids and alkylarylsulfonic acids puts. In order to have sufficient surface-active properties, these should be mentioned In this process, they wipe out long-chain hydrocarbon residues, i.e. in Al alkyl or alkenyl radical have at least 6 carbon atoms. Usually the C- Chain distributions of the anionic surfactants in the range from 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.

Carboxylic acids, which are used in the form of their alkali metal salts as soaps in detergents and cleaning agents, are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), today only water is used on a large technical scale to split the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. Carboxylic acids which can be used as an anionic surfactant in acid form in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. Preferred in the context of the present compound the use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), tricotanoic acid, Melissinsäu re) and the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid) (9adecadienic acid), 9cecadienoic acid , 9t, 12t-octadecadienoic acid (linolaidionic acid) and 9c, 12c, 15c-octadecatrein acid (linolenic acid). For reasons of cost, it is preferred not to use the pure species, but rather technical mixtures of the individual acids, as are accessible from fat cleavage. Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% _C14, 10 wt .-% C _16, 2 wt .-% _C18, 8 wt .-% _{C18 ',} 1 wt .-% C _18''), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt _12% C, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% _{C18 ',} 1 wt .-% C _18''), tallow ( approx. 3% by weight of C ₁₄ , 26% by weight of C _{16 '} , 2% by weight of C _16' , 2% by weight of C ₁₇ , 17% by weight of C ₁₈ , 44% by weight of C _{18 '} , 3% by weight C _18'' , 1% by weight C _18''' ), hardened tallow fatty acid (approx. 2% by weight C ₁₄ , 28% by weight C ₁₆ , 2% by weight) % C ₁₇ 63 wt .-% C _18: 1 wt .-% C _{18 '),} technical grade oleic acid (about 1 wt .-% C _12, 3 wt .-% C _14, 5 wt .-% C ₁₆ , 6 wt% C _{16 '} , 1 wt% C ₁₇ , 2 wt% C ₁₈ , 70 wt% C _18' , 10 wt% C _{18 ''} , 0.5 wt. -% C _{18 '''} ), technical palmitin / stearic acid (approx. 1% by weight C ₁₂ , 2% by weight C ₁₄ , 45% by weight C ₁₆ , 2% by weight C ₁₇ , 47 % By weight C ₁₈ , 1% by weight C _{18 '} ) and soybean oil fatty acid (approx. 2% by weight C _{1 4} , 15% by weight C ₁₆ , 5% by weight C ₁₈ , 25% by weight C _{18 '} , 45% by weight C _18'' , 7% by weight C _18''' ).

Sulfuric acid semiesters of longer-chain alcohols are also anionic surfactants in their acid form and can be used in the process according to the invention. Your alkali metal, especially sodium salts, the fatty alcohol sulfates are commercially available from fatty alcohols which are converted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to the relevant alkyl sulfuric acids and subsequently neutralized. The fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters. The most significant industrial process for the production of fatty alkyl sulfuric acids is the sulfonation of the alcohols with SO ₃ / air mixtures in special cascade, falling film or tube bundle reactors.

Another class of anionic surfactant acids used in the process of the invention can be used are the alkyl ether sulfuric acids, their salts, the alkyl ether sulfates, compared to the alkyl sulfates by a higher water solubility and lower Characterize sensitivity to water hardness (solubility of Ca salts). Alkyl ether Like the alkyl sulfuric acids, sulfuric acids are synthesized from fatty alcohols che be reacted with ethylene oxide to the fatty alcohol ethoxylates concerned. On Instead of ethylene oxide, propylene oxide can also be used. The subsequent sul Formation with gaseous sulfur trioxide in short-term sulfonation reactors gives yields over 98% of the relevant alkyl ether sulfuric acids.

Alkanesulfonic acids and olefin sulfonic acids are also within the scope of the present invention can be used as anionic surfactants in acid form. Alkanesulfonic acids can the sulfonic acid regruppe terminally bound (primary alkanesulfonic acids) or along the C chain ten (secondary alkanesulfonic acids), only the secondary alkanesulfonic acids have commercial importance. These are by sulfochlorination or sulfoxidati made on linear hydrocarbons. Reed sulfochlorination uses n- Correspond to paraffins with sulfur dioxide and chlorine under irradiation with UV light The sulfochlorides reacted, which, in the case of hydrolysis with alkalis, directly the alkanesulfo nate, when reacted with water, the alkanesulfonic acids. Because of sulfochloria tion di- and polysulfochlorides as well as chlorinated hydrocarbons as by-products of  radical reaction can occur, the reaction is usually only up to Um Settlements of 30% carried out and then canceled.

Another process for producing alkanesulfonic acids is sulfoxidation, in which n- Paraffins reacted with sulfur dioxide and oxygen under irradiation with UV light become. In this radical reaction, successive alkylsulfonyl radicals are formed, which also Oxygen react further to the alkyl persulfonyl radicals. The reaction with unumge Set paraffin provides an alkyl radical and the alkyl persulfonic acid, which are converted into an alkyl peroxysulfonyl radical and a hydroxyl radical decays. The reaction of the two radicals with unreacted paraffin provides the alkyl sulfonic acids or water, which with Al kylpersulfonic acid and sulfur dioxide to sulfuric acid. To the yield on the to keep the two end products alkyl sulfonic acid and sulfuric acid as high as possible and Suppressing side reactions, this reaction is usually only up to implementation degrees of 1% and then terminated.

Olefin sulfonates are produced industrially by the reaction of α-olefins with sulfur trioxide posed. Intermediate hermaphrodites form here, which become so-called sulto cyclize. React under suitable conditions (alkaline or acid hydrolysis) these sultones to hydroxylalkanesulfonic acids or alkenesulfonic acids, both of which are just if can be used as anionic surfactant acids.

Alkylbenzenesulfonates as powerful anionic surfactants have been around since the 1930s of our century. At that time, monochlorination of kogasin Fractions and subsequent Friedel-Crafts alkylation prepared using alkylbenzenes Oleum sulfonated and neutralized with sodium hydroxide solution. Early 1950s was used to produce alkylbenzenesulfonates propylene to branched α-dodecylene tetramerized and the product via a Friedel-Crafts reaction using Aluminum trichloride or hydrogen fluoride converted to tetrapropylene benzene, which after subsequently sulfonated and neutralized. This economical way of manufacturing of tetrapropylene benzene sulfonates (TPS) led to the breakthrough of this class of surfactants, the subsequently displaced the soaps as the main surfactant in washing and cleaning agents.  

Due to the lack of biodegradability of TPS, there was a need to to represent new alkylbenzenesulfonates, which are characterized by an improved ecological ver keep honoring. These requirements are met by linear alkylbenzenesulfonates fills, which are the almost exclusively manufactured alkylbenzenesulfonates and with the abbreviation ABS.

Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which like which are accessible from linear olefins. For this purpose, petroleum is used on an industrial scale Fractions with molecular sieves separated into the n-paraffins of the desired purity and dehydrogenated to the n-olefins, resulting in both α- and i-olefins. The ent standing olefins are then in the presence of acidic catalysts with benzene to the Al implemented kylbenzenes, the choice of Friedel-Crafts catalyst having an influence the distribution of isomers of the linear alkylbenzenes formed has: When using Aluminum trichloride is the content of the 2-phenyl isomers in the mixture with the 3-, 4-, 5- and other isomers at about 30 wt .-%, however, hydrogen fluoride as Kataly used sator, the content of 2-phenyl isomer can be reduced to about 20 wt .-%. The Finally, sulfonation of linear alkylbenzenes is now possible on an industrial scale using oleum, Sulfuric acid or gaseous sulfur trioxide, the latter being by far the largest has interpretation. Special film or tube bundle reactors are used for sulfonation sets that deliver as a product a 97 wt .-% alkylbenzenesulfonic acid (ABSS), which in Within the scope of the present invention it can be used as anionic surfactant acid.

By choosing the neutralizing agent, a wide variety of salts, ie alkylbenzenesulfonates, can be obtained from the ABSS. For reasons of economy, it is preferred to prepare and use the alkali metal salts and, among them, the sodium salts of the ABSS. These can be described by the general formula I:

in which the sum of x and y is usually between 5 and 13. Processes according to the invention in which C _8-16 -, preferably C _9-13 - alkylbenzenesulfonic acids are used as the anionic surfactant in acid form are preferred. In the context of the present invention, it is further preferred to use C _8-16 -, preferably C _9-13- alkylbenzenesulfonic acids which are derived from alkylbenzenes which have a tetralin content below 5% by weight, based on the alkylbenzene. It is further preferred to use alkylbenzenesulfonic acids whose alkylbenzenes have been prepared by the HF process, so that the C _8-16 -, preferably C _9-13- alkylbenzenesulfonic acids used contain a 2-phenyl isomer below 22% by weight. %, based on the alkylbenzenesulfonic acid. The anionic surfactant in acid form can of course also be used in dilute form. Thus, according to the invention it is not only possible to use the pure anionic acid acids with almost 100% active substance, but also aqueous solutions of anionic surfactant acids, the water content of such dilute acid solutions preferably being below 20% by weight, particularly preferably below 10% by weight and in particular is below 5% by weight. The use of dilute anionic surfactant acids can on the one hand have advantages in the handling (viscosity) of the acids, on the other hand the neutralization reaction is often accelerated by the slight dilution and excessive heating is avoided. It is also possible to moisten the solid neutralizing agent which has been introduced or added to the anionic surfactant acid in order to accelerate the neutralization reaction. In all cases, the water content of the mixture should be chosen so that a stable foam is created and not a liquid phase. The addition of water is therefore expressly not intended to mean the reaction with aqueous solutions, the addition of water serves practically only as a kind of starting quantity, since water is also formed during the reaction.

The above-mentioned anionic surfactants in their acid form can be used alone or in Mi who used and foamed together in the process according to the invention the. But it is also possible and preferred that the anionic surfactant in acid form before Foaming up other, preferably acidic, ingredients of washing and cleaning agents in amounts of 0.1 to 40% by weight, preferably 1 to 15% by weight and in particular dere from 2 to 10 wt .-%, each based on the weight of the foamed Mi be added.

Suitable acidic reactants in the context of the present invention are, in addition to the "Surfactic acids" also the fatty acids, phosphonic acids, polymer acids or some neutralized polymer acids as well as "builder acids" and "complex builder acids" (single later in the text) alone as well as in any mixtures. As ingredients of Washing and cleaning agents; which the anionic surfactant acid before foaming can be mixed, especially acidic detergents and cleaning agents Ingredients, for example phosphonic acids, which in neutralized form (Phosphonates) as incrustation inhibitors, part of many detergents and cleaning agents are. The use of (partially neutralized) polymer acids such as Po lyacrylic acids, is possible according to the invention. But it is also possible to have acid-stable content Mix substances with the anionic surfactant acid before foaming. Here offer themselves For example, so-called small components, which are otherwise in complex other Steps would have to be added, for example optical brighteners, dyes etc., whereby the acid stability must be checked in individual cases.

Optionally, the anionic surfactant can be nonionic in acid form before foaming Surfactants in amounts of 0.1 to 50 wt .-%, preferably from 1 to 40 wt .-% and in particular Special from 5 to 30 wt .-%, each based on the weight of the foam Mixture to be mixed. This addition can affect the physical properties of the Improve anionic surfactant foam and a later incorporation of nonionic surfactants into the surfactant granules or all detergents and cleaning agents. The different representatives from the group of nonionic surfactants will continue to exist described below. If in the process according to the invention mixtures of anions  acidic and nonionic surfactants are used, so methods are preferred which the anionic surfactant (s) in acid form and the nonionic (s) sid (e) in a weight ratio of 5: 1 to 1: 5, preferably 3: 1 to 1: 3 and in particular from 2: 1 to 1: 2.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol residue is linear or preferably in the 2-position May be methyl branched or may contain linear and methyl branched radicals in the mixture, as are usually present in oxoalko radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferred nonionic surfactants, which are used either as allei some nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and pro poxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described, for example, in Japanese Pa tentanmeldung JP 58/217598 are described or which preferably according to the in ternational patent application WO-A-90/13 533 method described the.  

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides that can be used satisfy the general formula RO (G) _z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which stands for a glycosyl unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.

Linear alkyl polyglucosides, ie alkyl polyglycosides, are preferably used in de the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

The surfactant granules produced according to the invention can preferably alkyl polyglycosides contain, with contents of the granules of APG over 0.2 wt .-%, based on the total Granules are preferred. Particularly preferred surfactant granules contain APG in men gen from 0.2 to 10 wt .-%, preferably 0.2 to 5 wt .-% and in particular from 0.5 to 3% by weight.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alka nolamides may be suitable. The amount of these nonionic surfactants is before preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (II),

in the RCO stands for an aliphatic acyl radical having 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups . The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (III)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R2 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example, according to the teaching of the international application WO-A-95/07 331 by reaction with fatty acid remethyl esters in the presence of an alkoxide as a catalyst in the desired polyhy droxy fatty acid amides are transferred.  

To adjust the viscosity of the foam, in addition to the non-ionic ten or in their place also other non-aqueous substances to the anionic surfactant in acid be given before the foaming by adding the solid neutralization medium done. Out of the multitude of usable non-aqueous substances special substances from the group of polyethylene glycols and polypropylene glycols, Glyce rin, glycerol carbonate, ethylene glycol, propylene glycol and propylene carbonate as well as par for oils, paraffins and silicone oils have proven to be particularly suitable.

Polyethylene glycols (abbreviation PEG) which can be used according to the invention are polymers of ethylene glycol which have the general formula IV

H- (O-CH ₂ -CH ₂ ) _n -OH (IV)

are sufficient, with n assuming values between 1 (ethylene glycol, see below) and approx. 100 can. Low molecular weight PEG are within the scope of the present invention because of their lower viscosity preferred for admixing, at higher temperatures too higher PEG can be used. Various nouns exist for polyethylene glycols. clatures that can lead to confusion. The specification of the average relative molecular weight following the indication "PEG", so that "PEG 200" Polyethylene glycol with a relative molecular weight of approx. 190 to approx. 210 is characterized. According to this nomenclature within the scope of the present invention, the technically ge customary polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 can be used.

A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and a number follows the hyphen directly, which corresponds to the number n in the above formula I. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) according to the invention, for example, PEG-4, PEG-6, PEG-8, PEG 9, PEG-10, PEG-12, PEG-14 and PEG-16 can be used according to the invention.

Polyethylene glycols are commercially available, for example, under the trade names Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HÜLS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone- Poulenc), Lutrol® E300 (BASF) and the corresponding trade names with higher Numbers.

Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula V

are sufficient, with n assuming values between 1 (propylene glycol, see below) and approx. 12 can. Technically important here are in particular di-, tri- and tetrapropylene glycol, i.e. H. the representatives with n = 2, 3 and 4 in formula II.

Glycerin is a colorless, clear, difficult to move, odorless, sweet-tasting hygroscopic liquid with a density of 1.261 that solidifies at 18.2 ° C. Glycerin was originally only a by-product of fat saponification, but is now technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediate stages of allyl chloride and epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO ₃ contact via the glycide stage.

Glycerol carbonate can be obtained by transesterification of ethylene carbonate or dimethyl carbonate with glycerin, ethylene glycol or methanol being obtained as by-products. Another synthetic route starts from glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO ₂ to form glycerol carbonate. Glycerin car bonat is a clear, easily movable liquid with a density of 1.398 gcm ^-3 that boils at 125-130 ° C (0.15 mbar).

Ethylene glycol (1,2-ethanediol, "glycol") is a colorless, viscous, sweet-tasting, strong hygroscopic liquid which is miscible with water, alcohols and acetone and a Density of 1.113. The freezing point of ethylene glycol is -11.5 ° C, the Liquid boils at 198 ° C. Technically, ethylene glycol is made from ethylene oxide by heating zen obtained with water under pressure. Promising manufacturing processes can be also on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis Build gas reactions.

There are two isomers of propylene glycol, 1,3-propanediol and 1,2-propanediol. 1,3-propanediol (trimethylene glycol) is a neutral, colorless and odorless, sweet schmec kenden liquid of density 1.0597, which solidifies at -32 ° C and boils at 214 ° C. The Her Provision of 1,3-propanediol is possible from acrolein and water with subsequent catalytic shear hydrogenation.

Technically much more important is 1,2-propanediol (propylene glycol), which is an oily, colorless se, almost odorless liquid, the density 1.0381, which solidifies at -60 ° C and at Boiling at 188 ° C. 1,2-propanediol is made from propylene oxide by adding water.

Propylene carbonate is a water-bright, easily movable liquid, with a density of 1.2057 gcm ^-3 the melting point is -49 ° C, the boiling point is 242 ° C. Propylene carbonate is also available on an industrial scale through the reaction of propylene oxide and CO ₂ at 200 ° C and 80 bar.

As mentioned above, in addition to the pure anionic surfactant acids or mixtures dilute anionic surfactant solutions from pure anionic surfactant acids and nonionic surfactants be used according to the invention, which can lead to an acceleration of the reaction. Furthermore, the non-ionic surfactant or other liquids (glycerin, PEG, etc.)  be diluted with water. The reaction can also be accelerated in this way the.

The mixture of anionic surfactant acid and solid neutralizing agent to be foamed can be at room temperature before foaming, but foaming can can also be carried out at elevated temperature, both the solid neutralization Onsmittel as well as the anionic surfactant acid can be preheated (the latter is preferred). In preferred variants of the method according to the invention, the neutralized foam has Temperatures below 115 ° C, preferably between 50 and 95 ° C and in particular between 70 and 90 ° C.

The resulting neutralized foam, which is used as a granulation aid in the next process step, can be characterized by further physical parameters. For example, it is preferred that the neutralized foam has a density of maximum 0.80 gcm ^-3 , preferably from 0.10 to 0.50 gcm ^-3 and in particular from 0.20 to 0.40 gcm ^-3 . It is further preferred that the neutralized foam has average pore sizes below 10 mm, preferably below 5 mm and in particular below 2 mm. The average pore size is calculated from the sum of all pore sizes (pore diameter) divided by the number of pores and can be determined, for example, by photographic methods.

The mentioned physical parameters of temperature, density and mean Po size characterize the neutralized foam at the time of its creation. Before preferably the procedure is chosen so that the neutralized foam the criteria mentioned are also met when added to the mixer.

Procedures are possible in which the foam only one or two of the mentioned criteria when added to the mixer met, but preferably both the temperature, as well as the density and pore size in the ranges mentioned, if the foam gets into the mixer.  

After it has formed, the neutralized foam is placed in a mixer Given solid bed and serves as a granulation aid. This stage of the process can be carried out in a wide variety of mixing and granulating devices. In a suitable mixing and granulating device, for example in a corresponding one Plants of the type of an Eirich mixer, a Lödige mixer, for example one Ploughshare mixer from Lödige, or a mixer from Schugi, is sold at Um traverse speeds of the mixing elements preferably between 2 and 7 m / s (plow Scharmischer) or 3 to 50 m / s (Eirich, Schugi), in particular between 5 and 20 m / s submitted a solid bed and then with the addition of the neutralized foam granulated. At the same time, a predetermined grain can be obtained in a manner known per se size of the granulate can be set. The granulation and mixing process only needs a very short period of time, for example about 0.5 to 10 minutes, in particular about 0.5 to 5 minutes (Eirich mixer, Lödige mixer) for homogenizing the mixture with formation of the free-flowing granules. In the Schugi mixer, on the other hand, nor is sufficient usually a dwell time of 0.5 to 10 seconds to form a free-flowing granulate receive. Mixers suitable for carrying out this process step are available from for example Eirich® mixers of the R or RV series (trademark of the machine factory Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixer (product no Chen of Fukae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB mixers (Trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais® series T or K-T (trademark of Drais-Werke GmbH, Mannheim).

It is also possible according to the invention to connect several of the mixers mentioned above in series. The following combinations of consecutive mixers are particularly useful here:

• - Lödige CB / Lödige KM
• - Lödige KM / Schugi Flexomix
• - Schugi Flexomix / Lödige KM / Schugi Flexomix
• - Schugi Flexomix / Lödige CB
• - Lödige CB / Lödige KM / Schugi Flexomix

If the neutralized foam is produced in the mixer and granulated by adding fine-particle solids, the mixers from Eirich and Fukae are particularly suitable. When combining several mixers, the neutralized foam can in principle be added to each mixer. In addition to the foam, other liquid components can also be added for the granulation. In particular, tenside pastes, polymer solutions, surfactants and water glass solutions are suitable here. It has proven to be particularly advantageous if the granules are powdered at the end of the granulation with a finely divided component which has an oil adsorption capacity of at least 20 g per 100 g. The oil absorption capacity is a physical property of a substance that can be determined using standardized methods. For example, the British standard methods BS1795 and BS3483: Part B7: 1982 exist, both of which refer to the ISO 787/5 standard. In the test methods, a balanced sample of the substance in question is placed on a plate and refined flaxseed oil (density: 0.93 gcm ^-3 ) from a burette is added dropwise. After each addition, the powder is mixed vigorously with the oil using a spatula, the addition of oil being continued until a paste of smooth consistency is obtained. This paste should flow or run without crumbling. The oil absorption capacity is now the amount of the added oil, based on 100 g of absorbent and is given in ml / 100 g or g / 100g, conversions about the density of the linseed oil being possible without any problems. Examples of suitable substances are silicates, aluminum silicates and silica.

The foam can be produced batchwise in conventional stirred kettles. In the The solid neutralizing agent is recommended for batch production of the foam do not give up on the liquids in the end, because of the onset of foaming the solid is difficult to mix. It is therefore preferred to use the solid dose before or during the addition of liquid. Of course, the above mentioned liquids are dosed as a mixture or as an individual component, wherein it has proven advantageous to dose the acidic components at the end.  

Foam production can also be done in static mixers, dynamic flow mix or flow high pressure mixers. Statics can be used as examples mixer from Sulzer, Switzerland, the continuous mixer MHD 2000 from the company IKA-Werke, Staufen, or the high-pressure mixer EHM from Dosier- und Prozess technik Salzwedel GmbH, Salzwedel.

The solid bed placed in the mixer can all be used in washing and cleaning contain substances used. In this way, with the invention Process finished detergents and cleaning agents are produced. Usually but certain ingredients of washing and cleaning agents are not granulated with undesirable reactions of these components with each other under the mechanical one to avoid the effect of the pelletizing tools. Ingredients that the resulting Ten Sidgranulate usually only afterwards, d. H. following a granulation are mixed, for example, bleaches, bleach activators, foam inhibitors and enzymes.

It is preferred that the surfactant granules produced according to the invention in addition to the Ten sid contain substances which are later used as active substances in washing and cleaning agents act. In preferred processes, the solid bed placed in the mixer therefore contains one or more substances from the builder group, in particular the alkali metal car bonates, sulfates and silicates, zeolites and polymers.

In addition to the washing-active substances, builders are the most important ingredients of Detergents and cleaning agents. In the process according to the invention, all the usual Builders usually used in detergents and cleaning agents in a solid bed be contained, in particular thus zeolites, silicates, carbonates, organic cobuilders and - if there are no ecological concerns about their use - including the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ OS ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in the international patent application WO-A-91/08 171 is.

Amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of 1: 2 to 1: 3, 3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are delayed and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction / 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 degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted in such a way that the products have microcrystalline ranges 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 the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula

nNa ₂ O. (1-n) K ₂ O.Al ₂ O _3. (2-2.5) SiO _2. (3.5-5, 5) H ₂ O

can be described. Suitable zeolites have an average particle size of we less than 10 µm (volume distribution; measurement method: Coulter Counter) on and included preferably 18 to 22% by weight, in particular 20 to 22% by weight of bound water.

It goes without saying that the generally known phosphates are also used as buildersub punching possible, provided that such use is not avoided for ecological reasons should be. The sodium salts of orthophosphates, the py rophosphates and especially the tripolyphosphates.

Usable organic builders are, for example, those in the form of their sodium salt ze usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutar acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, as well as mixing from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of this.

By adding the neutralized foam and under the influence of the mixer tools A surfactant granulate is formed. Methods according to the invention are preferred where the neutralized foam in the weight ratio foam: solid from 1: 100 to 9: 1, preferably from 1:20 to 10: 1 and in particular from 1:10 to 1: 1, to that in the mixer submitted solid bed is given. With the preferred amounts of granulating aid optimal granulation results are achieved.  

The method according to the invention is with regard to the selection of the content to be used substances and their concentration can be varied over a wide range. With the fiction According to the method, different particle sizes, bulk sizes can be used as desired weights and surfactant levels are set, with almost no restrictions ren.

Nevertheless, it is preferred if surfactant granules are produced according to the invention are, the surfactant contents above 10 wt .-%, preferably above 15 wt .-% and in particular above 20% by weight, based in each case on the granules, and bulk weights above 500 g / l, preferably above 600 g / l and in particular above 700 g / l point.

The granulation process according to the invention can be carried out in such a way that particles predetermined size distribution result. Here are methods according to the invention preferred in which the surfactant granules have a particle size distribution in which at least 50% by weight, preferably at least 60% by weight and in particular at least at least 70% by weight of the particles have sizes in the range from 400 to 1600 μm.

It is possible according to the inventive method, components for washing and To produce cleaning agents, which only after mixing with other ingredients the finished detergent and cleaning agent. Of course, fiction but also surfactant granules can be produced, which in themselves already a finished detergent and cleaning agent (for example a textile color detergent) are.

The surfactant granules produced by the process according to the invention can subsequently be mixed with further ingredients of detergents and cleaning agents to give the finished product. However, these ingredients can also be incorporated directly into the surfactant granules via the solid bed or the neutralized foam and are described below:
In addition to the constituents mentioned, surfactant and builders are, in particular in washing and cleaning agents, the usual ingredients from the group of bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors , Color transfer inhibitors and corrosion inhibitors are important.

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. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyro. phosphates, citrate perhydrates and H ₂ O ₂ -supplying acidic salts or peracids, such as per benzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Typical organic bleaches are the diacyl peroxides, such as. B. Dibenzoylpero xid. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkyl peroxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimoxyhexanoic acid PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacinic acid, diperoxydiacyldiperoxyacid, diperoxydiacyldiperoxyacid, diperoxydiacyldiperoxyacid, 1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Can also be used as bleach in machine dishwashing compositions Chlorine or bromine releasing substances are used. Among the appropriate chlorine or bromine-releasing materials come, for example, heterocyclic N-bromine and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with Cations such as potassium and sodium are considered. Hydantoin compounds such as 1,3-dichloro- 5,5-dimethylhydanthoin are also suitable.  

To be a better choice when washing or cleaning at temperatures of 60 ° C and below To achieve the greatest bleaching effect, bleach activators can be incorporated. As Bleach activators can be compounds that are aliphatic under perhydrolysis conditions Peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms Atoms, and / or optionally substituted perbenzoic acid can be used. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Multiple are preferred acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated tria Zinderivate, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acy gelled Glycolurile, in particular tetraacetylglycoluril (TAGU), N-acylimide, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol koldiacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, too so-called bleaching catalysts can be incorporated. These substances are to bleach-enhancing transition metal salts or transition metal complexes as in for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question. Bacterial strains or are particularly well suited Mushrooms such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents. Proteases of the subtilisin type and esp special proteases obtained from Bacillus lentus. Here are En enzyme mixtures, for example of protease and amylase or protease and lipase or Protease and gellulase or from cellulase and lipase or from protease, amylase and Li pase or protease, lipase and cellulase, but especially cellulase-containing Mi  of particular interest. Peroxidases or oxidases are also in one proven cases. The enzymes can be adsorbed on carriers and / or be embedded in coating substances to protect them against premature decomposition.

In addition, components can be used, which the oil and fat positively affect washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times with a detergent according to the invention, this oil and fat-dissolving component contains, was washed. The preferred oil and fat dissolving components include for example nonionic cellulose ethers such as methyl cellulose and methyl hydroxy propyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and Hy droxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic Cellulose ether, as well as the polymers of phthalic acid known from the prior art and / or terephthalic acid or its derivatives, in particular polymers of ethyl lenterephthalates and / or polyethylene glycol terephthalates or anionic and / or not tionically modified derivatives of these. Of these, the sul are particularly preferred Formed derivatives of phthalic and terephthalic polymers.

The detergents and cleaning agents can, as optical brighteners, derivatives of the diaminostyle Contain bendisulfonic acid or its alkali metal salts. 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 the same well-structured compounds that a diethanolamino instead of the morpholino group group, a methylamino group, an anilino group or a 2-methoxyethylamino wear group. Brighteners of the substituted diphenylstyryl type can also be used be essential, 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 too the aforementioned brighteners can be used.

Dyes and fragrances are added to detergents and cleaning agents to improve the aesthetics to improve the impression of the products and the consumer in addition to the softness a visually and sensorially "typical and unmistakable" product  supply. As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are z. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate tat, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, 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 alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cy clamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones z. B. the Jono ne, ∝-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, Eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbon The terpenes such as limes and pinene belong mainly to fen. However, are preferred Mixtures of different fragrances are used, which together make an appealing Generate fragrance. Such perfume oils can also contain natural fragrance mixtures ten, as they are accessible from plant sources, e.g. B. Pine, Citrus, Jasmine, Pat chouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Ka millen 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, neroli oil, Orange peel oil and sandalwood oil.

The content of detergents and cleaning agents is usually lower than that of colorants 0.01% by weight, while fragrances make up up to 2% by weight of the total formulation can.

The fragrances can be incorporated directly into the washing and cleaning agents But it can also be advantageous to apply the fragrances to carriers that increase the adhesion of the Reinforcing perfumes on the laundry and slower fragrance release for longer maintain the fragrance of the textiles. Such carrier materials have, for example se cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally other auxiliaries can be coated.  

To improve the aesthetic impression of detergents and cleaning agents, you can they are dyed with suitable dyes. Preferred dyes, their selection the expert has no difficulty, have a high storage stability and Un sensitivity to the other ingredients of the agent and to light as well no pronounced substantivity towards textile fibers in order not to dye them.

The neutralized foam produced in the process according to the invention and its use So far, granulation aids have not been described in the prior art. A wide one The subject of the present invention is therefore a neutralisate foam available by combining an anionic surfactant in its acid form with a solid neutralizer onsmittel and foaming to a neutralized foam, characterized in that the Foam medium pore sizes below 10 mm, preferably below 5 mm and esp especially below 2 mm.

As already emphasized in the description of the method according to the invention, is preference is given to a neutralized foam in which the gaseous medium has at least 20% by volume, based on the volume of liquid and solid to be foamed. At The gaseous medium makes this a particularly preferred neutralized foam up to fifty times, preferably two to twenty times and in particular three to ten times the volume of the volume to be foamed from liquid and solid out. When calculating the amount of gas used for foaming, the vol men of the anionic surfactant acid (or the mixture of anionic surfactant acid and other content substances) and the bulk volume of the solid neutralizing agent added. The resulting one The value is then the volume of liquid and Solid. It is irrelevant for the implementation of the method according to the invention whether the amount of gas forming the foam is additionally supplied, or whether it is the Neutralisa tion reaction originates. As mentioned above, it is easily possible to anion to combine acidic acid with carbonates, with no further gas addition solely by the resulting carbon dioxide a foam is formed.  

Regarding the ingredients of the foams produced in separate sub-steps, it is just if on the description of preferred embodiments of the Ver driving. Preferred neutralized foams are made by combining an anion surfactants in its acid form, which optionally further, preferably acidic ingredients of detergents and cleaning agents and a solid neutralizing agent from the Group of carbonates and / or hydrogen carbonates, preferably the alkali carbonates and / or alkali hydrogen carbonates and in particular from the group sodium carbonate and / or sodium hydrogen carbonate. It is preferred that the neutralizate foam by combining an anionic surfactant in its acid form, the nonionic tensi de in amounts of 0.1 to 50% by weight, preferably 1 to 40% by weight and in particular re of 5 to 30 wt .-%, based in each case on the weight of the anionic surfactant acid and a solid neutralizing agent from the group of carbonates and / or hydrogen carbonates, preferably the alkali carbonates and / or alkali hydrogen carbonates and ins particular from the group sodium carbonate and / or sodium hydrogen carbonate has been.

The neutralizate foam according to the invention is preferably high in surfactant. Neutralisate foams, the surfactant contents from 20 to 99% by weight, preferably from 50 to 98% by weight and in particular from 60 to 97% by weight, in each case based on the weight of the foam, have are preferred.

The neutralizate foam described above can - as in the case of the ver drive described - as a granulation aid in a conventional granulation process be used. It is also possible according to the invention, the foam in the Vorge to incorporate a mixture of an extrusion, a pelletizing or a compacting. Like this probably the granules produced by the process according to the invention as well as the un ter use of premixes containing the neutralized foam according to the invention, produced extrudates, pellets or compactates can - if necessary according to Ab mixture with other components - to form molded articles, in particular tablets become.  

Another object of the present invention is the use of the Invention appropriate neutralizate foams as a granulation aid in the manufacture of surfactant granules. Regarding the proportions between granulation aids (neutral sat foam) and solid bed, the mixer to be used and the one in the solid bed Please refer to the above explanations for possible ingredients.

Examples 1. Production of neutralized foams

Anionic surfactant acid and, if necessary, further aggregate were added in a mixing device substances mixed into different liquid phases, the composition of which is shown in Table 1 is specified. In the case of the mixtures containing fatty acids, the fatty acid was added before melted. Calcined sodium carbonate from Solvay was grown on an Alpine Grind the pin disc mill to a particle size <100 µm. The sodium carbonate was placed in a stirred container and with the amount specified in Table 1 Liquid mixtures added. Due to the gas development in the neutralization reaction the neutralized foam was created, its volume increase compared to the original substances is also given in Table 1.

Table 1

Neutralisate foams [% by weight]

2. Granulation

Various powdery components, including two tower powders, their Zu composition is given in Table 2, were in a 130 liter mixer (Lödige- Ploughshare mixer) submitted. The parts by weight of this powder given in Table 3 were by adding the parts by weight also given in Table 3 of the in Neutralisate foams described in Table 1 are granulated and the resulting granules are removed finally powdered with Zeolite X (Wessalith® XD, Degussa). It came out very well  free-flowing granules with a high degree of whiteness, their physical properties are also given in Table 3. By using the neutralis according to the invention The foams did not need to dry the granules.

Table 2

Composition of the tower powders [% by weight]

Table 3

Composition of the granulation batches [% by weight]

Claims (24)

1. A process for the preparation of surfactant granules, wherein an anionic surfactant in its acid form is neutralized and granulated with a solid neutralizing agent, characterized in that the solid neutralizing agent is added to the anionic surfactant in its acid form and foamed into a neutralized foam, which is subsequently added to a a solid bed placed in a mixer is given. 2. Process for the preparation of surfactant granules, wherein an anionic surfactant in its Acid form is neutralized with a solid neutralizing agent and granulated because characterized in that the solid neutralizing agent in a mixer with egg an anionic surfactant is foamed into a neutralizate foam in its acid form, which is subsequently granulated by adding solids. 3. The method according to any one of claims 1 or 2, characterized in that as new Tralisationsmittel carbonates and / or hydrogen carbonates, preferably alkali carbo nates and / or alkali hydrogen carbonates and in particular sodium carbonate and / or Sodium bicarbonate can be used. 4. The method according to any one of claims 1 to 3, characterized in that the anion surfactant in its acid form and the solid neutralizing agent in a molar ratio from 1: 2 to 1: 1, preferably from 1: 1.5 to 1: 1 and in particular from 1: 1, that is to say equi molar. 5. The method according to any one of claims 1 to 4, characterized in that as an anion surfactant in acid form one or more substances from the group of carboxylic acids, the Sulfuric acid half-esters and sulfonic acids, preferably from the group of fats acids, the fatty alkyl sulfuric acids and the alkylarylsulfonic acids can be used.   6. The method according to any one of claims 1 to 5, characterized in that C _8-16 -, preferably C _9-13 alkylbenzenesulfonic acids used as the anionic surfactant in acid form. 7. The method according to any one of claims 1 to 6, characterized in that the Anionic surfactant in acid form before combination with the solid neutralizing agent and foaming further, preferably acidic, ingredients of washing and Detergents in amounts from 0.1 to 40% by weight, preferably from 1 to 15 % By weight and in particular from 2 to 10% by weight, in each case based on the weight of the to be foamed mixture. 8. The method according to any one of claims 1 to 7, characterized in that the Anionic surfactant in acid form before combination with the solid neutralizing agent and the foaming of nonionic surfactants in amounts of 0.1 to 50% by weight preferably from 1 to 40% by weight and in particular from 5 to 30% by weight, in each case based on to the weight of the mixture to be foamed. 9. The method according to claim 8, characterized in that the anionic surfactant (s) in acid form and the nonionic surfactant (s) in the weight ratio of 5: 1 to 1: 5, preferably from 3: 1 to 1: 3 and in particular from 2: 1 to 1: 2 become. 10. The method according to any one of claims 1 to 9, characterized in that the neutra lisate foam temperatures below 115 ° C, preferably between 50 and 95 ° C and in particular between 65 and 90 ° C. 11. The method according to any one of claims 1 to 10, characterized in that the Neu tralisatschaum a density of at most 0.80 gcm ^-3 preferably from 0.10 to 0.50 gcm ^-3 and in particular from 0.2 to 0.40 gcm ^-3 . 12. The method according to any one of claims 1 to 11, characterized in that the new tralisate foam average pore sizes below 10 mm, preferably below 5 mm and in particular below 2 mm. 13. The method according to any one of claims 10 to 12, characterized in that the new tralisate foam meets the stated criteria when added to the mixer. 14. The method according to any one of claims 1 to 13, characterized in that the Mixer submitted solid bed one or more substances from the group builder fe, in particular the alkali metal carbonates, sulfates and silicates, the zeolites and Polymers. 15. The method according to any one of claims 1 to 14, characterized in that the new tralisate foam in the foam: solid weight ratio of 1: 100 to 9: 1, preferably two se from 1: 30 to 2: 1 and in particular from 1: 20 to 1: 1, based on that in the mixer Solid bed is given. 16. The method according to any one of claims 1 to 15, characterized in that the ten sidgranulate surfactant contents above 10% by weight, preferably above 15% by weight and in particular above 20% by weight, based in each case on the granules, and bulk weights above 500 g / l, preferably above 600 g / l and in particular above 700 g / l. 17. The method according to any one of claims 1 to 16, characterized in that the ten sidgranulates have a particle size distribution in which at least 50% by weight, preferably at least 60% by weight and in particular at least 70% by weight of the Particle sizes in the range of 400 to 1600 microns have. 18. Neutralisate foam, obtainable by combining an anionic surfactant in its acid form with a solid neutralizing agent and foam into a neutralizate  foam, characterized in that the foam has average pore sizes below 10 mm, preferably below 5 mm and in particular below 2 mm. 19. Neutralisate foam according to claim 18, characterized in that the gaseous Medium at least 20 vol .-%, based on the volume to be foamed from rivers liquid and solid. 20. Neutralisate foam according to claim 19, characterized in that the gaseous Medium one to fifty times, preferably two to twenty times, and in particular in particular three to ten times the volume of the volume to be foamed Makes up liquid and solid. 21. Neutralisate foam according to one of claims 18 to 20, characterized in that by combining an anionic surfactant in its acid form, which may be wide re, preferably contains acidic ingredients of detergents and cleaning agents and a solid neutralizing agent from the group of carbonates and / or hydrogen carbonates, preferably the alkali carbonates and / or alkali hydrogen carbonates and especially from the group sodium carbonate and / or sodium hydrogen carbonate, he was holding. 22. Neutralized foam according to one of claims 18 to 21, characterized in that by combining an anionic surfactant in its acid form, the nonionic surfactant in amounts of 0.1 to 50% by weight, preferably 1 to 40% by weight and in particular dere from 5 to 30 wt .-%, based in each case on the weight of the anionic surfactant holds and a solid neutralizing agent from the group of carbonates and / or Hydrogen carbonates, preferably the alkali carbonates and / or alkali hydrogen carbo nate and in particular from the group sodium carbonate and / or sodium hydrogen car bonat, was obtained. 23. Neutralisate foam according to one of claims 18 to 22, characterized in that he surfactant content from 20 to 99 wt .-%, preferably from 50 to 98 wt .-% and ins  in particular from 60 to 97% by weight, based in each case on the weight of the foam points. 24. Use of neutralized foams according to one of claims 17 to 22 as Gra aids in the manufacture of surfactant granules.