WO1999061576A1

WO1999061576A1 - Method for producing washing and cleaning agents

Info

Publication number: WO1999061576A1
Application number: PCT/EP1999/003330
Authority: WO
Inventors: Andreas Lietzmann; Dieter Jung; Rene-Andres Artiga Gonzalez; Bernd Larson; Wilfried Rähse; Markus Semrau; Hans-Friedrich Kruse
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1998-05-22
Filing date: 1999-05-14
Publication date: 1999-12-02
Also published as: DE19822941A1

Abstract

The invention relates to a method for producing washing and cleaning agents comprising the following steps: a) mixing zeolite and an aqueous sodium hydroxide solution in a mixer; b) granulating while adding anionic surfactant acid(s); c) optionally drying the granulates formed in step b); d) optionally mixing with additional constituents of washing and cleaning agents. The anionic surfactant content of the resulting washing and cleaning agents is adjusted to values ≥10 wt. %.

Description

"Process for the production of detergents and cleaning agents'

The present invention relates to a method for producing detergents and cleaning agents. In particular, it relates to a method which makes it possible to produce detergent and cleaning agent compositions without or with reduced use of spray drying steps.

Granular detergent and cleaning agent compositions are largely produced by spray drying. In spray drying, the ingredients such as surfactants, builders etc. are mixed with about 35 to 50% by weight of water to form an aqueous slurry, the so-called slurry, and atomized in spray towers in a hot gas stream, the detergents and cleaning agents being atomized - Form particles. Both the plants for this process and the implementation of the process are costly since approximately 30 to 40% by weight of the slurry water must be evaporated. In addition, the granules produced by spray drying usually have excellent solubility, but only have low bulk densities, which leads to higher packaging volumes and transport and storage capacities. The flowability of spray-dried granules is also not optimal due to their irregular surface structure, which also affects their visual appearance. Spray drying processes have a further series of disadvantages, so that there has been no lack of attempts to carry out the production of detergents and cleaning agents completely without spray drying or to have at least the smallest possible proportion of spray drying products in the finished product. For example, W. Hermann de Groot, I. Adami, GF Moretti "The Manufacture of Modern Detergent Powders", Hermann de Groot Academic Publisher, Wassenaar, 1995, page 102 ff. Describes various mixing and granulating processes for the production of detergents and cleaning agents. These processes have in common that premixed solids are granulated with the addition of the liquid ingredients and, if necessary, subsequently dried.

There is also a broad state of the art in the patent literature for the non-tower manufacture of detergents and cleaning agents. Many of these processes are based on the acid form of the anionic surfactants, since this surfactant class represents the largest proportion of wash-active substances in terms of quantity and the anionic surfactants occur in the course of their production in the form of the free acids which have to be neutralized to the corresponding salts.

There are other problems with these neutralization processes. For example, the granulation of anionic surfactants with alkali carbonates is a safe state of technical knowledge, but if detergents and cleaning agents containing zeolite and anionic surfactants are desired, problems arise when zeolite and anionic surfactant acid come into contact, since zeolites are sensitive to acid and decompose to form silicic acid if they are produced directly come into contact with the anionic surfactant acid. The anionic surfactant acids are therefore usually completely neutralized before the zeolite is incorporated.

For example, European patent application EP-A-0 678 573 (p _r0 cter & Gamble) describes a process for producing free-flowing surfactant granules with bulk densities above 600 g / 1, in which anionic surfactant acids with an excess of neutralizing agent form a paste with at least 40% by weight. % Surfactant are reacted and this paste is mixed with one or more powder (s), at least one of which must be spray-dried and which contains anionic polymer and cationic surfactant, the resulting granules optionally being able to be dried. Although this document reduces the proportion of spray-dried granules in the washing and cleaning agents, it does not completely avoid spray drying. European patent application EP-A-0 438 320 (TJnilever) discloses a batch process for the production of surfactant granules with bulk densities above 650 g / l. Anionic surfactant acid is added to a solution of an alkaline inorganic substance in water, possibly with the addition of other solids, and granulated in a high-speed mixer / granulator with a liquid binder. Neutralization and granulation take place in the same apparatus, but in separate process steps, so that the process can only be operated in batches.

A continuous neutralization / granulation process for the production of FAS and / or ABS granules from the acid is known from the European patent application EP-A-0 402 112 (p _r0 cter & Gamble), in which the ABS acid with at least 62 % NaOH is neutralized and then granulated with the addition of auxiliaries, for example ethoxylated alcohols or alkylphenols or a polyethylene glycol melting above 48.9 ° C. with a molecular weight between 4000 and 50,000.

European patent application EP-A-0 508 543 (p _r0 cter & Gamble) mentions a process in which a surfactant acid is neutralized with an excess of alkali to form an at least 40% by weight surfactant paste, which is then conditioned and granulated.

German laid-open specification DE-A-42 32 874 (Henkel KGaA) discloses a process for producing washable and cleaning-active anionic surfactant granules by neutralizing anionic surfactants in their acid form. However, only solid, powdery substances are disclosed as neutralizing agents. The granules obtained have surfactant contents of around 30% by weight and bulk densities of less than 550 g / l.

The European patent application EP 642 576 (Henkel KGaA) describes a two-stage granulation in two consecutive mixers / granulators, with 40-100% by weight, based on the total amount of constituents used, of the solid and liquid constituents pre-granulated in a first, low-speed granulator and in one second, high-speed granulator, the pre-granulate is mixed with the remaining constituents, if necessary, and converted into a granulate.

The present invention was based on the object of providing a method which makes it possible to produce washing and cleaning agents containing zeolite and anionic surfactants without or with reduced use of spray drying steps. The problem of the decomposition of zeolite by the action of acid with the formation of insoluble residues is to be avoided. In particular, the detergents and cleaning agents obtained should not lag behind spray-dried detergents and cleaning agents with regard to their solubility and their residue behavior, even though they have high bulk densities. With regard to spray drying, the process should be able to be carried out with significantly less energy and, if possible, be able to do without energy-intensive drying steps.

The problem is solved in a multi-stage mixing and granulating process which is carried out in such a way that the residual properties of the granules enable it to be used in high-quality detergents and cleaning agents. The invention thus relates to a process for the production of detergents and cleaning agents which comprises the steps a) mixing zeolite and aqueous sodium hydroxide solution in a mixer b) granulation with the addition of anionic surfactant acid (s) c) optional drying of the granules formed in step b) , d) includes optional mixing with further ingredients of detergents and cleaning agents, the anionic surfactant content of the detergents and cleaning agents being formed being set to values> 10% by weight.

The procedure according to the invention ensures that there is sufficient alkalinity to avoid acidic decomposition of the zeolites. Compared to a changed procedure, in which the anionic surfactant acid is first neutralized and then added to the zeolite, the inventive method has the advantage of simplified equipment (only a mixer required) and the more convenient procedure, since on the one hand problems that are common with the neutralizer - tion (acidic nests) can be avoided and, on the other hand, there is no need to move or pump around highly viscous anionic surfactant pastes. At the same time it is ensured that the heat of neutralization is intercepted by the heat capacity of the powder. Local overheating and discoloration of the anionic surfactant is drastically reduced or completely prevented in this way. Furthermore, the amount of water introduced is reduced by the neutralization on the powder, as a result of which the drying can be reduced or eliminated entirely. In addition, the liquids used have lower viscosities than surfactant pastes.

All representatives of this class of substances can be used as zeolites in the process according to the invention. The fine crystalline, synthetic and bound water-containing zeolite used can be, for example, A and / or P. Zeolite ^MAP® (commercial product from Crosfield) is particularly preferred as zeolite P. Zeolite X and mixtures of A, X and / or P are also suitable and preferred in the context of the present invention. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.

The zeolites to be mixed with the sodium hydroxide solution in step a) have the general formula M _{2 / n} O 'Al ₂ O ₃ ' x SiO ₂ 'y H ₂ O, in which M is a cation of valence n, x stands for values that are greater than or equal to 2 and y can have values between 0 and 20. The zeolite structures are formed by linking AlO ₄ tetrahedra with SiO ₄ tetrahedra, this network being occupied by cations and water molecules. The cations in these structures are relatively mobile and can be exchanged for other cations in different degrees. The intercrystalline "zeolitic" water can be released continuously and reversibly, depending on the type of zeolite, while for some types of zeolite structural changes are also associated with the water release or absorption.

In the structural subunits, the "primary binding units" (AlO ₄ tetrahedra and SiO ₄ tetrahedra) form so-called "secondary binding units", which form have one or more rings. For example, 4-, 6- and 8-membered rings appear in various zeolites (referred to as S4R, S6R and S8R), other types are connected via four- and six-membered double ring prisms (most common types: D4R as a square prism or D6R as a hexagonal prism ). These "secondary subunits" connect different polyhedra, which are denoted by Greek letters. The most common is a polyhedron, which is made up of six squares and eight equilateral hexagons and which is referred to as "ß". A variety of different zeolites can be realized with these units. To date, 34 natural zeolite minerals and around 100 synthetic zeolites are known.

The best known zeolite, zeolite 4 A, is a cubic combination of ß-cages that are linked by D4R subunits. It belongs to the zeolite structure group 3 and its three-dimensional network has pores of 2.2 Ä and 4.2 Ä size, the formula unit in the unit cell can be with Naι ₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] ^' 27 H ₂ O describe.

Zeolites of the faujasite type are particularly preferably used according to the invention in the process according to the invention. Together with the zeolites X and Y, the mineral faujasite belongs to the faujasite types within the zeolite structure group 4, which is characterized by the double six-ring subunit D6R (compare Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92). In addition to the faujasite types mentioned, the zeolite structure group 4 also includes the minerals chabazite and gmelinite as well as the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5. The latter two synthetic zeolites have no mineral analogues.

Faujasite-type zeolites are made up of ß-cages which are tetrahedral linked by D6R subunits, the ß-cages being arranged similar to the carbon atoms in the diamond. The three-dimensional network of the zeolites of the faujasite type used in the process according to the invention has pores of 2.2 and 7.4 Å, the unit cell also contains 8 cavities with a diameter of approximately 13 Å and can be by the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] ^' 264 H ₂ O describe. The network of zeolite X contains a void volume of approximately 50%, based on the dehydrated crystal, which represents the largest empty space of all known zeolites (zeolite Y: approx. 48% void volume, faujasite: approx. 47% void volume). (All data from: Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, pages 145, 176, 177).

In the context of the present invention, the term “zeolite of the faujasite type” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4. In addition to zeolite X, zeolite Y and faujasite and mixtures of these compounds can also be used according to the invention, pure zeolite X being preferred.

Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites which do not necessarily have to belong to the zeolite structure group 4 can also be used according to the invention, it being advantageous if at least 50% by weight of the zeolite consists of a zeolite of the faujasite type consist.

The aluminum silicates used in the process according to the invention are commercially available and the methods for their preparation are described in standard monographs.

Examples of commercially available X-type zeolites can be described by the following formulas:

Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] - χ H ₂ O,

K ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] - χ H ₂ O,

Ca ₄₀ Na ₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) _I06 ] ^• x H ₂ O, Sr ₂₁ Ba ₂₂ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] 'x H ₂ O,

in which x can have values between 0 and 276 and the pore sizes range from 8.0 to 8.4 Å.

Preferably commercially available and within the scope of the inventive method is used, for example, a co-crystallizate of zeolite X and zeolite A (ca. 80 wt .-% zeolite X) which is marketed by CONDEA Augusta SpA under the trade name VEGOBOND AX ^® and through the formula

nNa ^• (ln) K ₂ O ^• Al ₂ O ₃ '(2 - 2.5) SiO ₂ ^■ (3.5 - 5.5) H ₂ O

can be described.

Y-type zeolites are also commercially available and can be expressed, for example, by the formulas

Na ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] ^• x H ₂ O,

₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] - χ H ₂ O,

in which x stands for numbers between 0 and 276 and have a pore size of 8.0 Å.

The particle sizes of the faujasite-type zeolites used in the process according to the invention are in the range from 0.1 to 100 μm, preferably between 0.5 and 50 μm and in particular between 1 and 30 μm, in each case measured using standard particle size determination methods. The amount of zeolite which is introduced into the process according to the invention is usually 5 to 60% by weight, preferably 10 to 55% by weight and in particular 15 to 50% by weight, based on the finished washing and cleaning agent. In step a), in addition to the zeolite and the sodium hydroxide solution, further ingredients of detergents and cleaning agents can be introduced. Solids can be added directly to the zeolite, but it is also possible to dissolve small components that are soluble in the sodium hydroxide solution before it is added to the zeolite. So-called small components such as optical brighteners, foam inhibitors, polymers etc. are particularly suitable as additives which are introduced into the process according to the invention via the sodium hydroxide solution. If liquid ingredients are to be added in process step a), which is not preferred, it is advantageous to add this together with the sodium hydroxide solution to the zeolite or the zeolite-containing solid mixture. However, liquid ingredients are preferably introduced into the process with the anionic surfactant acid in step b).

Solids which can be introduced in step a) with the zeolite and the sodium hydroxide solution are all solids used in washing and cleaning agents, for example those from the group of builders, bleaching agents, bleach activators, foam inhibitors, polymers, enzymes, dyes, etc. It is preferred according to the invention if these solids have an additional neutralization potential for the anionic surfactant acid added later, alkali metal carbonates and in particular anhydrous sodium carbonate being preferred as additives in step a). By adding the preferably anhydrous alkali carbonates, in particular sodium carbonate (“calcined soda”), the required amount of sodium hydroxide solution can be reduced and at the same time free water can be bound in the formulation, since the water-free sodium carbonate is hydrated to the monohydrate. In this way it is possible to reduce the effort for the optional drying step c) or even to do without the drying step c) entirely, which further reduces the process costs. A complete substitution of the sodium hydroxide solution by alkali carbonates, which would be equivalent to dry neutralization of the anionic surfactant acid with alkali carbonate, is not the subject of the process according to the invention. A zeolite / carbonate powder mixture does not solve the problems of decomposing the acid-sensitive zeolite. If alkali metal carbonates are also to be present in step a) in addition to the aqueous sodium hydroxide solution, it is preferred that their neutralization on potential, ie its molar proportion in the neutralization of the anionic surfactant acid (s) added in step b), based on all the neutralizing agents present, is at most 50%, preferably at most 20% and in particular at most 10%.

It is preferred according to the invention that the sodium hydroxide solution carries at least 50%, preferably at least 80% and in particular at least 90% of the neutralization potential.

It is also possible according to the invention without problems to enable the “internal drying” described above by using anhydrous sodium carbonate with the aid of other solids. For this purpose, in step a) all substances can be added which are capable of absorbing free water, preferably salts capable of hydrate formation. Among these substances, phosphates, in particular sodium tripolyphosphate, and over-dried silicates have the greatest significance as “internal drying agents” in the process according to the invention. Zeolites which are not completely hydrated, that is to say over-dried, can also be used. These over-dried zeolites are commercially available. So-called over-dried tower powders can also be used, e.g. detergent base powder produced by spray drying and over-dried in the spray drying step.

It is also possible according to the invention to add surfactant-containing solids to the mixture of zeolite and sodium hydroxide solution in step a), which solids have preferably not been produced by spray drying. It is preferred here to add anion or nonionic surfactant granules whose active substance content is between 10 and 50% by weight, preferably between 15 and 40% by weight and in particular between 20 and 30% by weight, in each case based on the granules, is. However, it is also possible to use granules or compounds with a higher surfactant content, the surfactant content of which is, for example, 90% by weight, based on the compound. If anionic surfactant granules are used, neutralization products of anionic surfactant acids with alkali metal carbonates, preferably anhydrous sodium carbonate, which are derived from other processes, can also be used. Such dry neutralization products usually have anionic surfactant contents of between 10 and 30% by weight, the rest of the granules consisting of alkali carbonate, which is used as the carrier material. rial acts. This procedure has the advantage that, on the one hand, there is further neutralization potential via the excess alkali carbonate, on the other hand, when using dry neutralization products based on calcined soda, the proportion of anhydrous sodium carbonate can be regarded as an "internal drying agent", which - as in the direct addition described above of anhydrous sodium carbonate - simplifies the drying step c) or makes it superfluous.

The sodium hydroxide solution used to neutralize the AB SS can be of any concentration, higher concentrations being preferred because of the correspondingly lower water content and lower water evaporation. It is particularly preferred in the process according to the invention if the sodium hydroxide solution used contains at least 30% by weight, preferably at least 40% by weight and in particular at least 50% by weight of NaOH.

In the context of the present invention, anionic surfactant acids are mainly alkylbenzenesulfonic acids (ABSS), alkylsulfonic acids or alkylsulfuric acids. Based on the resulting detergent and cleaning agent, the amount of anionic surfactant acid used in the process according to the invention is selected so that the resulting detergent and cleaning agent contains> 10% by weight of anionic surfactant (s).

The ABSS in the process according to the invention is preferably C ₉ . ₁₃ - benzene sulphonic acids, olefin sulphonic, ie mixtures of alkene and hybrid droxyalkansulfonsäuren and disulfonic acids, as obtained, for example, from C ₁₂ _ ₁₈ - receives monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide or liquid, into consideration. Also suitable are the alkane sulfonic acids which can be obtained from C ₁₂ -C ₁₈ alkanes by sulfochlorination and sulfoxidation and by subsequent hydrolysis or by bisulfite addition to olefins. The alkyl sulfuric acids, which are obtained, for example, by reacting fatty alcohols with H ₂ SO ₄ , can also be used as anionic surfactant acid. Suitable alkyl sulfuric acids are, for example, the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, e.g. B. Coconut fatty alcohol fetch, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C ₁₀ -C ₂₀ oxo alcohols, and those secondary alcohols of this chain length. The sulfuric acid monoesters of alcohols etherified with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C ₉ -C _π alcohols with an average of 3.5 moles of ethylene oxide, are also suitable. Instead of pure ABSS, a mixture of ABSS and nonionic surfactant can also be used in the process according to the invention, the content of nonionic surfactant in the range from 1 to 15% by weight, preferably from 2 to 10% by weight and in particular from 3 to 7 wt .-%, based on the finished detergent, can be.

The use of saturated and unsaturated fatty acids with C ₈ -C ₁₈ chain lengths in the form of their mixtures and / or the sulfofatty acids of saturated C ₈ -C ₁₈ fatty acids is also possible in the process according to the invention. Mixtures of the fatty acids and .alpha.-sulfofatty acids mentioned with other sulfonic acids and alkylsulfuric acids, for example alkylbenzenesulfonic acids and fatty alkylsulfuric acids, can also be used with particular advantage.

In preferred process variants of the process according to the invention, an alkylbenzenesulfonic acid (ABSS) is used as the anionic surfactant acid.

The concentration of the anionic surfactant acids can vary due to the production process. In addition to the surfactant acids, the end products of the sulfonation, sulfation or sulfoxidation process usually contain water and minor amounts of impurities such as salts, for example sodium sulfate. It is preferred in the context of the present invention that the anionic surfactant acid has an active substance content of at least 60% by weight, preferably at least 75% by weight and in particular at least 85% by weight.

The anionic surfactant acids can also be used in a mixture with other substances. It is preferred here to add further acidic ingredients in step b). In addition to the mixtures of various anionic surfactant acids, for example ABSS and fatty acids, there are in particular phosphonic acids or organic polycarboxylic acids such as citric acid or polyacrylic acids. However, it is also possible to add further aqueous solutions together with the anionic surfactant acid as the granulating liquid, with the addition of aqueous polycarboxylate solutions being particularly preferred. According to the invention, it is also possible and preferred in process step b) to add the ABSS in a mixture with nonionic surfactants to the mixture of zeolite, optional further ingredients and sodium hydroxide solution. Mixtures are preferred which, based on the mixture, contain more than 30% by weight, preferably more than 40% by weight and in particular more than 50% by weight of anionic surfactant in its acid form and more than 10% by weight, preferably more Contain more than 20 wt .-% and in particular more than 30 wt .-% nonionic surfactants. Suitable nonionic surfactants which can be used in a mixture with the anionic surfactant are, in particular, alkoxylated, preferably ethoxylated alcohols with chain lengths from 8 to 28, preferably from 12 to 22 and in particular from 16 to 18 carbon atoms and degrees of alkoxylation from 1 to 40. preferably from 3 to 20 and in particular from 5 to 10, the molar ratio of anionic to nonionic surfactant in the range from 10: 1 to 1:10, preferably from 8: 1 to 1: 2 and in particular from 5: 1 to 1: 5 lies.

The process according to the invention can be carried out quickly and easily in a single apparatus, both continuously and batchwise ("batchwise"). In a suitable mixing and granulating device, for example in appropriate systems of the type of an Eirich mixer, a Lödige mixer, for example a ploughshare mixer from the Lödige company, or a mixer from the Schugi company, at peripheral speeds of the mixing elements, preferably between 1 and 6 m / s (ploughshare mixer) or 2 to 40 m / s (Eirich, Schugi), in particular between 3 and 20 m / s the zeolite and the sodium hydroxide solution and the optionally additionally introduced solids or the small components dissolved in the sodium hydroxide solution and subsequently with the addition of anionic surfactant acid or the mixture of anionic surfactant acid and optionally ingredients mixed with it. At the same time, a predetermined grain size of the granules can be set in a manner known per se. The neutralization and mixing process takes only 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) to homogenize the mixture to form the free-flowing granules. In school gi mixers, on the other hand, normally have a residence time of 0.5 to 10 seconds to obtain a free-flowing granulate. The mixing ratios of the components and, in particular, the proportions of the solid introduced are to be matched to the water fraction entered via the ABSS and the NaOH in such a way that free-flowing granules can be formed. Usually, the higher the proportion of water in the ABSS and NaOH, the more solid is required. In one embodiment of the process according to the invention, the granules are dried in a fluidized bed immediately after the granulation and the surface is treated with small amounts of finely divided zeolite, since the surfactant content and bulk density can be increased further in this way.

By adding certain ingredients, drying step c) can be completely dispensed with (see above).

The process according to the invention advantageously works continuously, with zeolite and NaOH being metered into the inlet area of the mixer via metering devices. The anionic surfactant acid can then be injected, and atomization can also take place via a multi-component nozzle, air being blown through the neutralizer / mixer / granulator as a further substance, which makes the heat of neutralization usable for water evaporation. The powder components can be dosed in a Schugi mixer. Subsequently, taking into account the direction of rotation, the sodium hydroxide solution is first injected and then granulated with the addition of anionic surfactant acid. A Lödige ploughshare mixer can be operated continuously by dividing the mixer into different chambers by means of adjustable weirs. In the first chamber, the zeolite-containing mixture is charged with the sodium hydroxide solution; in the second chamber, the anionic surfactant acid is granulated. The granulate can be powdered with powdery substances in an optionally separable third chamber.

However, there is still the possibility of operating the process according to the invention in batches by introducing the powder components, mixing them with the NaOH and then granulating with the addition of the anionic surfactant acid. In process step d), further ingredients can be added to the washing and cleaning agents produced in the previous steps, provided that these substances have not yet been added in steps a) or b). Subsequent admixing is recommended in the context of the method according to the invention whenever the granulation would have an adverse effect on the effect, for example destruction of the shell of coated ingredients. In the process step d), the ingredients of detergents and cleaning agents that can be added are described in more detail below, it also being possible to add the substances mentioned in steps a) or (see above). These are in particular substances from the groups of builders, nonionic surfactants, bleaching agents, bleach activators, polymers, foam inhibitors, colorants and fragrances and enzymes.

In addition to the zeolite already described in detail, builders in particular include silicates, carbonates and organic builders or cobuilders. 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 O ₅ -yH ₂ O are preferred, with β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171 .

Amorphous sodium silicates with a Na ^: 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, which delay the dissolution, can also be used are 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, compacting / compression or by overdrying. In the context of this invention is under the term "amorphous" also understood as "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 as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these this. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated, especially primary alcohols with chain lengths of 8 to 28, preferably 12 to 22 and in particular 16 to 18 carbon atoms and degrees of alkoxylation of 1 to 40, preferably 3 to 20 and in particular average 5 to 10 moles of alkylene oxide (AO) per mole of alcohol in which the alcohol radical may be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as is usually present in oxo alcohol radicals. In particular, however, AU alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 C atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred. Preferred ethoxyherten alcohols include for example C _I2. ₁₄ - alcohols with 3 EO or 4 EO, C ₉ . _π 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 of these, 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters, such as are described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared according to the international patent application WO-A-90/13533.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

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

R ¹

R-CO-N- [Z] (I)

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R * 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 (II) R ^! -OR ^2nd

R-CO-N- [Z] (II)

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 cychyl alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cychl alkyl radical or represents an aryl radical or an oxy-alkyl radical with 1 to 8 carbon atoms, C _M - alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated 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 be converted into the desired polyhydroxy fatty acid amides, for example according to the teaching of the international application WO-A-95/07331 <} _by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Sodium perborate tetrahydrate is preferably used as the bleaching agent in step ii) a).

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the process according to the invention. As bleach activators, compounds which are subject to perhydrolysis aliphatic peroxocarboxylic acids containing preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular l, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetoxy and 2,5-diacetyloxy and 2,5-glycolacetyl, ethylene glycol 2,5-dihydrofuran.

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

Dyes and fragrances are used in the process according to the invention in order to improve the aesthetic impression of the products and, in addition to the washing and cleaning performance, to provide the consumer with a visually and sensorially "typical and unmistakable" product. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexylpropylate propionate. The ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetalde- hyd, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones include, for example, the jonones, oc-isomethyl ionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include Terpenes like limes and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The dye content of the process end products according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the total formulation.

Derivatives of diamino-stilbenedisulfonic acid or its alkali metal salts can be used as optical brighteners in the process according to the invention. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-mo holino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. 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) - diphenyls. Mixtures of the aforementioned brighteners can also be used.

As foam inhibitors, for example, soaps of natural or synthetic origin come into consideration which have a high proportion of C ₁₈ . ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for example se from silicone, paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the process end products according to the invention can be, for example, approximately 0.1 to 5% by weight, preferably 0.1 to approximately 2% by weight.

In addition, the process end products can also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Other polymers are organic builders such as polycarboxylates. Suitable polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 10 to 50% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on the free acids, is usually 5,000 to 200,000, preferably 10,000 to 120,000 and more preferably 50,000 to 100,000 polymers of the type mentioned are for example marketed by BASF under the name Sokalan ^®.

It is also possible to add the polycarboxylic acids which can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, amino carboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The physical properties of the detergents and cleaning agents produced can largely be predetermined by the procedure (residence time, circulation speed, etc.). It is preferred in the context of the present invention that an average particle size of 600 to 1200 μm is set, it being particularly preferred if the process end products have particle sizes in the range from 200 to 2000 μm, preferably in the range from 400 to 1800 μm and in particular in the Have a range of 600 to 1600 μm. In preferred processes, a bulk density above 600 g / 1, preferably above 650 g / 1 and in particular above 700 g / 1 is set. The following application examples, which illustrate the method according to the invention and show advantages over conventional methods, are only selected examples, which should not be understood as restrictive.

Examples:

Zeolite and anhydrous sodium carbonate were placed in a 50 liter Lödige ploughshare mixer and mixed with 50% strength by weight sodium hydroxide solution which was mixed with a solution of a polycarboxylate and with nonionic surfactant. A mixture of alkylbenzenesulfonic acid, fatty acid and phosphonic acid was sprayed onto this mixture and granulated while the mixing tools were running. The resulting granules were subsequently dried in a fluidized bed. The composition of the granulation batch, the total amount of which was 10 kg, is shown in Table 1.

Table 1: Composition of the granulation batch El [% by weight]

Sokalan ^® CP 5 is an acrylic acid-maleic acid copolymer (BASF)

Analogously to Example 1, an E2 granulate was produced in which the content of anhydrous sodium carbonate was increased in process step a), as a result of which the optional drying step c) could be omitted. In process step a), the solid mixture additionally contained surfactant granules S1 prepared by spray drying. The granules obtained were finally dusted with finely divided zeolite X (Wessalith XD ^®, Degussa). The composition of the granulation batch E2 is shown in Table 3. ben, the composition of the surfactant granules S1 produced by spray drying is shown in Table 2.

Table 2: Composition of the spray-dried granules [% by weight]

Table 3: Composition of the granulation batch E2 [% by weight]

In a mixer, alkylbenzenesulfonic acid was neutralized by spraying onto anhydrous sodium carbonate, a sticky surfactant granulate being formed. These granules were mixed with zeolite, a spray-dried polymer granulate S2 (for composition, see Table 2) and sodium hydroxide solution. This mixture was granulated by adding anionic surfactant acid mixed with fatty acid and nonionic surfactant. Finally, the granules E3 obtained were powdered and did not require drying. The composition of the granulation batch E3 is shown in Table 4.

Table 4: Composition of the granulation batch E3 [% by weight]

The bulk density of the finished products E1 to E3 was determined, the test for residues was carried out with a laundry item made of 4 black leotards made of textured Polymaid with a weight of approx. 320 g. The following devices were used: Arcelik wash-wing tub washing machine without centrifuge centrifuge at a speed of 1400 rpm Polyethylene bowls 30 l of city water (16 ° dH) were let into the tub washing machine, then 80 g of powder were dissolved by stirring. The laundry item was added and the machine heated to 30 ° C. After this temperature had been reached, the laundry was washed for 10 minutes by actuating the agitator, the washing liquor was then drained off and rinsed three times. During the rinsing, 30 liters of water were admitted, beaten for 30 seconds and then the existing rinsing water was drained. After rinsing, the laundry was spun for 15 seconds, placed in a polyethylene bowl and dried overnight.

The residues on the textiles were then visually assessed by at least 5 inspectors. The following grades were awarded:

Grade 1: flawless, no disturbing residues

Grade 2: tolerable, isolated, not yet particularly noticeable residues

Grade 3: recognizable residues that are already annoying when viewed critically

Grade 4: clearly recognizable, annoying residues

Note 5: annoying residues that occur in large numbers and are noticeable to every observer

Grade 6: very large quantities of annoying, clearly visible residues

The grades of the individual examiners were combined to an average, whereby the examiners can also assign intermediate grades. The results of the tests are shown in Table 5.

Table 5: physical properties of detergents and cleaning agents

Claims

Claims:

1. Process for the preparation of detergents and cleaning agents containing zeolite and anionic surfactants, characterized by the steps

a) mixing zeolite and aqueous sodium hydroxide solution in a mixer b) granulation with the addition of anionic surfactant acid (s) c) optional drying of the granules formed in step b), d) optional mixing with further ingredients of washing and cleaning agents,

wherein the anionic surfactant content of the detergents and cleaning agents formed is adjusted to> 10% by weight.

2. The method according to claim 1, characterized in that a zeolite of a faujasite type, preferably zeolite X, is used.

3. The method according to any one of claims 1 or 2, characterized in that the sodium hydroxide used contains at least 30 wt .-%, preferably at least 40 wt .-% and in particular at least 50 wt .-% NaOH.

4. The method according to any one of claims 1 to 3, characterized in that an alkylbenzenesulfonic acid (ABSS) is used as anionic surfactant acid.

5. The method according to any one of claims 1 to 4, characterized in that the anionic surfactant has an active substance content of at least 60 wt .-%, preferably at least 75 wt .-% and in particular at least 85 wt .-%.

6. The method according to any one of claims 1 to 5, characterized in that in step a) further solids, preferably alkali carbonates and in particular anhydrous sodium umcarbonate, can be added.

7. The method according to any one of claims 1 to 6, characterized in that in step a) further surfactant-containing solids, preferably anion and / or nonionic surfactant granules, preferably with active substance contents between 10 and 50 wt .-%, preferably between 15 and 40 wt. -% and in particular between 20 and 30 wt .-%, each based on the surfactant granules, are added.

8. The method according to any one of claims 1 to 7, characterized in that the anionic surfactant before step b) with other ingredients of detergents and cleaning agents, preferably phosphonic acids, is mixed.

9. The method according to any one of claims 1 to 8, characterized in that the anionic surfactant before step b) is mixed with other surfactants, preferably nonionic surfactants.

10. The method according to claim 9, characterized in that the anionic surfactant before step b) with alkoxylated, preferably ethoxylated alcohols with chain lengths of 8 to 28, preferably from 12 to 22 and in particular from 16 to 18 carbon atoms and degrees of alkoxylation from 1 to 40 , preferably from 3 to 20 and in particular from 5 to 10, the molar ratio of anion to nonionic surfactant being in the range from 10: 1 to 1:10, preferably from 8: 1 to 1: 2 and in particular from 5: 1 to 1: 5.

11. The method according to any one of claims 1 to 10, characterized in that an average particle size is set above 600 microns.

12. The method according to any one of claims 1 to 11, characterized in that the end products of the process have particle sizes in the range from 200 to 2000 μm, preferably in the range from 400 to 1800 μm and in particular in the range from 600 to 1600 μm. sen.

13. The method according to any one of claims 1 to 12, characterized in that a

Bulk weight above 600 g / 1, preferably above 650 g / 1 and in particular above 700 g / 1 is set.