WO1994013779A1

WO1994013779A1 - Granulated washing and cleaning agent

Info

Publication number: WO1994013779A1
Application number: PCT/EP1993/003427
Authority: WO
Inventors: Wolfgang Seiter; René-Andres ARTIGA GONZALEZ; Adolf Wiche; Sönke TAMS
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1992-12-15
Filing date: 1993-12-06
Publication date: 1994-06-23
Also published as: EP0674703A1; ES2139064T3; ATE185839T1; EP0674703B1

Abstract

The invention concerns a granulated washing and cleaning agent, or a component thereof, the granulated material being roller-produced and its particles having a particular shape with an almost spherical macroscopic surface and a smooth microscopic surface as well as an almost monodisperse internal structure. The agent can be produced by a method in which, in a first stage, the powder-form starting materials are fed in and optionally mixed with liquid ingredients, the mixture then compressed in a second stage with the input of energy, and the resulting granulated materials compression-rolled against each other. The roller-granulation procedure is stopped by the addition of a finely particulate powder as soon as the particle-size distribution has reached the required maximum.

Description

"Granular detergent and cleaning agent"

The invention relates to granulated detergents and cleaning agents, in particular those with a high bulk density, or a component therefor, which have a special morphology which is expressed in a - macroscopically - almost spherical structure, and a process for their preparation.

Extruded detergent and cleaning agent granules with an almost spherical structure are known from international patent application WO 91/02047. These granules are obtained in that a solid, free-flowing premix is extruded at high pressures with the addition of a plasticizer and lubricant, and the strand is cut to the predetermined granulate dimension directly after it emerges from the hole shape by means of a cutting device. The granules obtained in this way have a monodisperse internal structure.

On the other hand, granules which are produced by conventional granulation processes in mechanical or pneumatic mixers with subsequent drying, sieving and grinding of the coarse-grained fraction have bonds between the primary granules and the liquid components. These bonds cause secondary agglomeration of primary granules (build-up granulation) and lead to a non-uniform, non-ono-disperse, raspberry-like structure of the granules (see Figures 1 and 2). For example, European patent application 367339 discloses granules which are produced by a two-stage granulation process. Porous and compressible granules, preferably spray-dried granules, are first compressed in a high-speed mixer and then in a slow-running mixer and granulator. So that an optimal compression can take place in the second mixer, it is necessary that the powders are brought into a deformable state. This can be done by regulating the temperature and / or by adding liquid constituents, in particular nonionic surfactants, during the first granulation and compression phase in a high-speed mixer. However, the introduction of liquid components in the first step with the simultaneous input of energy by the tools of the mixer leads to the first mixer Bonding of the granular material and thus to the raspberry-like structures described. In European patent application 390 251 the method according to EP 367 339 is modified by adding 0.1 to 40% by weight of a powder either in the second granulation stage or between the first and the second granulation stage. There are therefore optimal conditions for a build-up granulation. The powder agglomerates in the moist, sticky areas of the primary agglomerates, thus further developing raspberry-like structures. However, the addition of large amounts of powder quickly and completely covers the adhesive surface of the primary granules, the build-up granulation comes to a standstill and, depending on the time at which the powder is added, relatively small agglomerates are obtained. The addition of only small amounts of powder, however, only partially covers the adhesive surface, so that they are combined to form larger agglomerates.

The object of the invention was to provide granules with a - from a macroscopic view - almost spherical surface and an almost mono-disperse internal granulate structure, which until now could only be produced in this way by an extrusion process, which can be produced by a granulation process.

_^ Object of the invention is accordingly In a first embodiment form a granulated washing and cleaning agent, or a component therefor, whereby the granules having a certain morphology with almost kugel¬ shaped and "smooth" surface, as well as a nearly monodisperse inner structure and a rolling granules .

The claimed washing and cleaning agent or the component therefor, which is (are) produced by a granulation process, is characterized in particular by a certain surface morphology. Seen macroscopically, the granules are almost spherical; From a microscopic point of view, the granules are characterized by a surprisingly "smooth" surface, which has some cracks, but without sharp, protruding edges or protruding protrusions. The difference in the morphology of the surface is very clear from the figures, with figures 3 and 4 showing the inventive moderate granules with a "smooth" surface and Figures 1 and 2 show the conventional raspberry structure-like granules obtained by build-up granulation. The special morphology of the granules according to the invention means that they can move against one another in a rolling manner. This can be shown by means of a simple test, in which the granules are poured. While granulate layers only slip when conventional granules are poured, in the granules according to the invention the upper granulate layer rolls off over the granule layer underneath. Because of this property, the granules according to the invention are called roll granules in the following.

The preferred composition of the roll granules is characterized in that they contain at least 10% by weight of anionic and / or nonionic surfactants, in particular 10 to 45% by weight of anionic and nonionic surfactants. Roll granules containing 15 to 35% by weight of anionic and nonionic surfactants have particular advantages.

Preferred anionic surfactants of the sulfonate type are Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from Ci2-Cl8 ~ ^mono ~ olefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are obtained from C 1 -C 12 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.

Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cg to Cig ett alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, are nonionic surfactants (for a description, see below). Here again are sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with restricted homolog distribution, particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), e.g. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or Taig¬ fatty acids.

Suitable sulfate-type anionic surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin. Suitable fatty alkyl sulfates are the sulfuric acid monoesters of the Ci2-Ci8 fatty alcohols, such as lauryl, myristyl, cetyl alcohol or stearyl alcohol, and the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil, which additionally contain proportions of unsaturated alcohols, for example of oleyl alcohol. Find this mixture a preferred use, in which the proportion of the alkyl groups to 50 to 70 wt .-% to _(. 2 to 18 wt .-% to 30 bis (44 to 5 to 15 wt .-% to (45, under 3% by weight to (40 and less than 10% by weight to (48 are distributed.

Other suitable anionic surfactants are, in particular, soaps, preferably in amounts from 0.5 to 8% by weight. Saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Kosmic, palm kernel or tallow fatty acids, derived soap mixtures. In particular, preference is given to those soap mixtures which are composed of 50 to 100% by weight of saturated Ci2-Ci8 fatty acid soaps and 0 to 50% by weight of oleic acid soap.

The anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanola in. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts. The anionic surfactant content of the roll granules is preferably 5 to 20% by weight. However, their content can also exceed 20% by weight and for example up to 25% by weight. Preferred anionic surfactants are fatty alkyl sulfates, alkylbenzenesulfonates, sulfosuccinates and mixtures thereof, such as mixtures of fatty alk (en) yl sulfates and sulfosuccinates or fatty alkyl sulfates and fatty alk (en) ylbenzenesulfonates, especially in combination with soap.

Addition products of 1 to 12 moles of ethylene oxide with primary are preferred as nonionic surfactants

and their mixtures such as coconut, tallow or oleyl alcohol, or methyl-branched, in particular methyl-branched in the 2-position, primary alcohols (oxo alcohols) in the granules. In particular, Ci2-Ci4-Al ohole with 3 EO or 4 EO, Cg-Cn-alcohol with 7 EO, Ci3-Ci5-alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-Ci8 ~ alcohols with 3 EO , 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2 ~ Ci4 alcohol with 3 EO and Ci2-Ci8 ^_A ^ ohol with 5 EO. The degrees of ethoxylation given represent statistical mean values, which can be an integer or a fraction for a special product. Preferred alcohol ethoxylates have a restricted homolog distribution (narrow range ethoxylates, NRE).

The content of the ethoxylated Ci2-Ci8_f ^{: etta} alcohols in the finished granules is advantageously at least 2% by weight, preferably 5 to 15% by weight, in particular 8 to 15% by weight. In a preferred embodiment, the liquid nonionic surfactants are mixed with lower polyalkylene glycols which are derived from straight-chain or branched glycols with 2 to 6 carbon atoms and / or highly ethoxylated fatty alcohols with 20 to 80 EO, in particular tallow fatty alcohol with 30 E0 or 40 E0. Preferred lower polyalkylene glycols are polyethylene glycols or polypropylene glycols which have a relative molecular mass between 200 and 12,000, in particular between 200 and 4,000, for example up to 2,000. The weight ratio of liquid nonionic surfactant to lower polyalkylene glycol and / or highly ethoxylated fatty alcohol in these mixtures is preferably 10: 1 to 1: 2, in particular 5: 1 to 1: 1.5, and is advantageously 1.5: 1 in some cases up to 1: 1.5, for example around 1: 1. The preferred nonionic surfactants also include alkyl glycosides of the general formula R0 (G) _x , in which R is a primary straight-chain or aliphatic radical which is methyl-branched in the 2-position and has 8 to 22, preferably 12 to 18, C 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 and 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, in particular together with alkoxylated fatty alcohols, 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, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO 90/13533.

Nonionic surfactants of the amine oxide type, for example N-coco-alkyl-NN- _^ dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol can also be suitable. The amount of these non-ionic 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),

in the R ^ CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R3 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 up to 10 hydroxyl groups stands. 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. With regard to the processes for their preparation, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798, as well as international patent application WO 92/06984. The polyhydroxyfatty acid derivatives are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. The preferred polyhydroxy fatty acid amides are therefore fatty acid N-alkylglucamides as represented by the formula (II):

R ³ OH OH OH

IIII R2CO-N-CH ₂ -CH-CH-CH-CH-CH ₂ OH (II)

I.

0H

Preferably used as polyhydroxy fatty acid amides are fatty acid N-alkyl glucamides of the formula (II) in which R ^{3 represents} hydrogen or an alkyl group and R2C0 represents the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Fatty acid N-alkylglucamides of the formula (II) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C12 / 14-coconut fatty acid or a corresponding derivative are particularly preferred.

In principle, the roll granules according to the invention can also contain all known ingredients of detergents and / or cleaning agents. Preferred further constituents are builder substances, alkaline and neutral salts, bleaching agents, graying inhibitors, foam inhibitors and optical brighteners. Suitable inorganic builder substances are, for example, phosphates, preferably tripolyphosphates, but also orthophosphates and pyrophosphates, as well as zeolite and crystalline layered silicates.

The fine crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. However, zeolite NaX and mixtures of NaA and NaX are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production. In the case that the zeolite is used as a suspension, small additions 8 fatty alcohols can of nonionic surfactants as a rod ent lisa factors hold, for example 1 to 3 wt .-%, based on zeolite, of ethoxylier¬ th _{Ci2-C_,} with 2 to 5 ethylene oxide groups. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 20 to 22% by weight of bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium likates of the general formula (III) NaMSi _x θ2χ + ι * yH2θ, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number is from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application 164 514. Preferred crystalline sheet silicates of the formula (III) are those in which M represents sodium and x assumes the values 2 or 3. In particular, both beta and o ^" sodium disate Na2S1 ^ 05 ^ 20 are preferred.

Usable organic builders are, for example, the polycarboxylic acids preferably 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. 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. Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. The content of (co) polymeric polycarboxylates in the compositions is preferably 1 to 8% by weight, in particular 2 to 6% by weight. In particular, the use of biodegradable polymers is preferred.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application 280 223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, silicates or mixtures of these; In particular, alkali carbonate and alkali silicate, especially sodium silicate with a molar ratio Na2θ: SiÖ2 from 1: 1 to 1: 4.5, preferably from 1: 1.9 to 1: 3.3, are used. The sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 2 and 15% by weight, in particular up to 10% by weight. The sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.

Among the compounds which serve as bleaching agents and supply H2O2 in water, sodium perborate tetrahydrate and sodium perborate onohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and such as H2O2-providing peracidic salts or peracids such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used. Carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof and polyvinylpyrrolidone are preferably used, for example in amounts of 0.1 to 5% by weight, based on the composition.

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin which have a high proportion of Ci8-C24 " ^{fatty acids} . Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and also paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silicic acid or bistearylethylenediamide. Mixtures of different foam inhibitors are also advantageously used, for example those made of silicones, paraffins or waxes. The foam inhibitors, especially silicone- or paraffin-containing foam inhibitors, are particularly suitable for granular Water-soluble or dispersible carrier substance bound. The salts of polyphosphonic acids which preferably contain the neutral-reacting sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate and diethylenetriaminepentamethylenephosphonate in amounts of 0.1 to 1.5% by weight.

The agents can contain, as optical brighteners, derivatives of diaostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which contain an replace the morpholino group with a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl-4 '- (2-sulfostyryl) -diphenyls. Mixtures of the aforementioned brighteners can also be used. Uniformly white granules are obtained if, apart from the usual brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, also small amounts, for example 10 "6 to 10" 3% by weight, preferably around 10 "5% by weight, of one A particularly preferred dye is Tinoluχ ( ^R ) (commercial product from Ciba-Geigy).

-_.

The content of free, that is to say unbound, water in the roll granules according to the invention is in the range known for granules, for example up to 20% by weight. However, preferred granules contain no more than 10% by weight of free, unbound water.

The bulk density of the roll granules is generally between about 400 and 1200 g / 1. However, preferred roll granules have a bulk density between 600 and 1100 g / 1, preferably between 700 and 950 g / 1. Despite the possibly high proportions of ethoxylated niotene surfactants, the granules are non-greasy. The diameter of the roll granules is arbitrary and preferably predeterminable, ie specifically adjustable to a desired value. In a preferred embodiment, roll granules are preferred in which the maximum of the particle size distribution (weight distribution) is less than 2 mm, preferably between 0.8 and 1.4 mm. In In a further preferred embodiment, roll granules are preferred in which the maximum particle size distribution (weight distribution) is between 0.2 and 0.6 mm, preferably between 0.3 and 0.5 mm.

The roll granules according to the invention can either be used directly as detergents and cleaning agents, and / or they are added with further amounts, preferably small amounts, for example in the range from 2 to 10% by weight, based on the total amount of the proportions used liquid nonionic surfactants or nonionic surfactant mixtures are sprayed in a manner known per se, and / or they are mixed in a preparation step with further constituents, preferably granular and in particular granular and compacted constituents of detergents and cleaning agents. The other granular constituents include, for example, compacted bleaching agent or bleach activator granules, enzyme granules and granular carriers for colorants and fragrances, but also carbonates, zeolite, layered silicates, polycarboxylates or polycarboxylic acids such as citric acid and / or polymeric polycarboxylates.

Examples of bleach activators are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose-pentaacetate. The bleach activators are added in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight, based on the finished detergent and cleaning agent. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients 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. Their proportion can be about 0.2 to about 2% by weight, based on the finished washing and cleaning agent. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The roll granules claimed according to the invention are preferably obtained by a process in which the powdery starting materials are introduced in a first process stage and optionally mixed with liquid constituents, the mixture is compressed in a second process stage by the introduction of energy and the resulting products Granules are rolled in a compacting manner against one another, whereby they obtain a "smooth" surface (microscopic) and an almost monodisperse inner structure, and the roll-up granulation is stopped by adding a fine-particle powder after the granules have been given a predetermined maximum particle size distribution has grown. The diameter of the roll granules that can be produced by this method can thus be predetermined.

In the first stage of the process, powdered starting materials are introduced and mixed with one another. Preferred powdery starting materials are anionic surfactants, zeolite, silicate, soda, and in particular also peroxy bleaching agents such as perborate. Granular precursors, for example spray-dried or granulated surfactant compounds, can also be used, although it is preferred that these precursors are first broken up or ground. Foam inhibitors, which are bound to a granular carrier substance, are preferably also mixed with the other powdered starting materials in the first process stage.

It is not essential for every composition, but it is preferred that liquid constituents are also used in this process step. Premixes rich in anionic surfactants can, for example, also be rolled against one another in a compacting manner and, if appropriate, by increasing the temperature in the second process stage. However, the powdery starting materials are preferably charged with liquid constituents in the first process stage. Suitable liquid constituents are liquid nonionic surfactants, water and any possible mixture of niotene surfactants, lower polyalkylene glycols, highly ethoxylated fatty alcohols, water, aqueous solutions, for example aqueous solutions of (co) polymeric polycarboxylates or water glass solutions, but also aqueous anionic surfactant pastes , and optionally liquid foam inhibitors, for example silicone oil. In a preferred embodiment, liquid nonionic surfactants, preferably ethoxylated ones, are used as liquid constituents in the first process stage

and / or water or aqueous solutions or mixtures of the abovementioned type are added in such amounts that rollable but non-sticky granules are obtained in the second process stage. The optimal amount of liquid constituents for each recipe can be determined by simply trying it out.

If both liquid constituents and granular foam inhibitors are to be used, then the granular foam inhibitor is preferably added only after the powdery starting materials have been applied, in order to prevent the granular foam inhibitors from becoming wet. The granular foam inhibitor is added before entering the second process stage.

The first process stage can be carried out in all mixers, mixing plates, granulators, even in high-speed mixers, as long as these apparatuses can be operated in such a way that the powder is only mixed and charged, but no granulation or agglomeration takes place. The exception to this is the binding of fine fractions, which on the contrary is even desirable. Since in a preferred embodiment the process is carried out continuously, mixer types which can be operated continuously are also preferred in the first process stage.

In the second stage of the process, the powdered starting materials are then transferred to a second mixer in which the powdered starting materials are rolled in a compacting manner by the energy input of the tools. If desired, small amounts of liquid components can also be added in this process stage, as long as the roll granulation is not impaired thereby. However, it is particularly preferred not to introduce any further components in this process stage before the roll granulation is terminated. A large number of granulators are also suitable in this stage, for example pan granulators, plate granulators, rounders such as Marumerizer (R) and Spheronizer (R), but also, for example, ploughshare mixers or ring Layer mixer. A continuously operating ploughshare mixer is preferred at this point.

The resulting granules grow with increasing residence time in the second process stage during the compacting roll-up granulation. The size of the granules is therefore determined by the residence time in the second mixer or by the duration of the compacting roll-up granulation. Before the discharge from the mixer / granulator, the compacting roll-up granulation is broken off by the addition of a finely divided powder. The resulting granules are powdered in such a way that the rolling process is stopped abruptly, but the plasticity of the resulting granules is not completely lost. Suitable fine-particle powders are, for example, zeolite powders such as zeolite NaA powder, but also magnesium silicate, silicas, powdered silicone defoamers and all powders which consist of approximately 90% of particles with a particle size below 30 μm. The fine-particle powder is preferably added in amounts of up to 10% by weight, in particular in amounts of 0.5 to 8% by weight, to terminate the roll-up granulation. The addition of finely divided powders in amounts of 1 to 5% by weight is particularly advantageous.

After the roll-up granulation has been terminated, the resulting granules can be further processed. For example, it is possible to achieve a more uniform grain spectrum with a smaller width either by conventional screening of undesired coarse-grain and / or fine-grain fractions or, for example, by homogenizing the granules in a further mixer, for example in a Schugi mixer or a commercially available rounder. The setting of the high bulk density is achieved on the one hand by the rolling compression of the charged powdery starting materials, on the other hand also by the powdering and by the possible dense filling of the macroscopically almost spherical granules. The existence of finely divided granules usually leads to a further increase in the bulk density.

If desired, the granules can then be dried, for example in a fluidized bed, or they are allowed to harden by cooling. There is drying in the fluidized bed also possible when using peroxy bleach. The granules retain their macroscopically almost spherical structure even when dried in the fluidized bed, since no further granulation can take place due to the complete powdering of the granules.

B e i s i e l e

Example 1 :

There were 64.35 parts by weight of spühgetrockneten granules (corresponding to 5.5 parts by weight of Cg-Cj _j alkylbenzene sulfonate, 1.85 parts by weight Taigfettal¬ alcohol with 5 ethylene oxide groups, 0.8 to 5 wt Parts of Ci2- i8 fatty acid soap, 21.75 parts by weight of zeolite, based on anhydrous active substance, 15.25 parts by weight of sodium carbonate, 1.85 parts by weight of amorphous alkali silicate with a Na2θ: SiÜ2 ratio of 1: 3.0, 4.85 parts by weight of a polymeric polycarboxylate (Sokalan CP δ ( ^R )), 0.7 parts by weight of phosphonate and the rest of water and salts from solutions) together with 17.7 parts by weight Perborate monohydrate and 6.93 parts by weight of a silicone defoamer granulate (carrier material based on sodium sulfate, sodium carbonate and sodium silicate) with the addition of 1.25 parts by weight of water and 8.0 parts by weight of a 34. 6% by weight aqueous Cg-C ^ -alkylbenzenesulfonate solution mixed in a continuous mixer (Schugi) and then combined with high energy in a CB mixer from Lödige with the addition of 4.8 parts by weight of one

^π, granulated ^{according to} 5 ethylene oxide groups. The throughput was 1 t / h. The bulk density of the granules after drying was 785 g / 1. If the roll granulation was stopped according to the invention with about 2% by weight, based on the finished granulate, of zeolite powder, the bulk density of the dried granules was 860 g / l.

Example 2:

Continuous process as in Example 1, but using spray-dried granules containing 13.4 parts by weight of C 1 -C 4 -alkylbenzenesulfonate (ABS), 0.55 parts by weight of tallow alcohol with 5% , 7 parts by weight of Ci2-Cχ8 soap, 20 parts by weight of zeolite, based on anhydrous active substance, 13.45 parts by weight of sodium carbonate, 1.85 parts by weight of amorphous sodium silicate (1: 3 , 0), 5.15 parts by weight of Sokalan CP δ ( ^R ), 0.3 parts by weight of phosphonate and the rest of water and salts from solutions in the granulation process. The bulk density of the dried granules was 745 g / l without powdering with zeolite and 760 g / l after powdering with zeolite. Example 3:

All of the constituents mentioned in Example 1, the granules having a composition according to Example 2 being used as spray-dried granules, were mixed in a ploughshare mixer from Lödige at a throughput of about 2 t / h and then batchwise in another Lödige Mixer FK granulates when the dwell time is extended.

After a granulation time of 2 minutes, the bulk density of the non-powdered granules increased from 476 g / 1 to 690 g / 1; stopping the roll granulation by powdering with 2% by weight of zeolite brought about an increase in the bulk density of the undried granules to 818 g / l.

After a granulation time of 10 minutes, the bulk weight of the undried and unpowdered granules increased to 837 g / 1, stopping the roll granulation by adding 2% by weight of zeolite resulted in an increase in the bulk weight of the undried granules to 908 g / 1 and after then drying to 937 g / 1.

Example 4:

In an analogous manner, 65 parts by weight of spray-dried granules (corresponding to 19.05 parts by weight of ABS, 0.7 parts by weight of taig fatty alcohol with 5 E0, 0.85 parts by weight of Ci2-Ci8 ~ soap, 26, 5 parts by weight of zeolite, based on anhydrous active substance, 3.8 parts by weight of sodium carbonate, 1.7 parts by weight of amorphous sodium silicate (1: 3.0), 2.4 parts by weight of Sokalan CPδ ( ^R ) as well as residual water and salts from solutions) together perborate monohydrate with 22 parts by weight and 4.5 parts by weight silicone antifoam granules with the addition of 3 parts by weight of a mixture of Ci2-CI8 F ^e ttalkohol 5 E0 and tallow fatty alcohol with 40 E0 in a weight ratio of 1: 1.2 and 6.5 parts by weight of a 30% by weight aqueous Sokalan CP5. ^R ) solution granulated. The roll granulation was stopped by powdering with 2.5 parts by weight of zeolite in powder form. The granules had a bulk density of 810 g / l.

The rolled granules, which were dried in a fluidized bed, were mixed with bleach activator granules and enzyme granules, introduction of perfume and final powdering with a mixture of zeolite powder and fine Particulate silica and / or processed with a powdered silicone defoamer.

Analogous results were obtained by replacing ABS with Ci2-Ci8 ~ fatty alk (en) y1 sulfate.

The granules obtained according to Examples 1 to 4 had an almost monodisperse internal granulate structure and a surface as shown in Figures 3 and 4.

Claims

1. Granulated washing and cleaning agent or component therefor, characterized in that the granulate has a certain morphology with an almost spherical (macroscopic) and "smooth" (microscopic) surface and an almost monodisperse internal structure and is a roll granulate.

2. Composition according to claim 1, characterized in that it contains at least 10% by weight of anionic and / or nonionic surfactants, preferably 10 to 45% by weight and in particular 15 to 35% by weight of anionic and nonionic surfactants.

3. Composition according to claim 2, characterized in that it contains 2 to 15 wt .-%, preferably 5 to 15 wt .-% ethoxylated Ci2-Ci8 fatty alcohols.

4. Composition according to one of claims 1 to 3, characterized in that it has a bulk density between 600 and 1100 g / 1, preferably between 700 and 950 g / 1.

5. Composition according to one of claims 1 to 4, characterized in that it has any, preferably predeterminable diameter auf¬.

6. Composition according to claim 5, characterized in that the maximum of the particle size distribution (weight distribution) is less than 2 mm, preferably between 0.8 and 1.4 mm.

7. Composition according to claim 5, characterized in that the maximum of the particle size distribution (weight distribution) is between 0.2 and 0.6 mm, in particular between 0.3 and 0.5 mm.

8. A process for the preparation of a detergent or cleaning agent or a component therefor, the granules having a specific morphology with an almost spherical (macroscopic) and "smooth" (microscopic) surface and an almost monodisperse internal structure and one have any diameter that can be predetermined, characterized in that the powdery starting materials are introduced in a first process stage and, if appropriate, mixed with liquid constituents, the mixture is compressed in a second process stage by the introduction of energy and the resulting granules are compacted against one another are rolled, which gives them a "smooth" surface (microscopic) and an almost monodisperse internal structure, and the build-up roll granulation is stopped by adding a finely divided powder after the granules have been allowed to grow to a predetermined maximum of the particle size distribution.

9. The method according to claim 8, characterized in that the finely divided powder to abort the roll-up granulation in amounts up to 10 wt .-%, preferably in amounts of 0.5 to 8 wt .-% and in particular in amounts of 1 to 5 wt. -% is added.

10. The method according to claim 8 or 9, characterized in that the granules are dried.

11. The method according to any one of claims 8 to 10, characterized in that liquid nonionic surfactants, preferably ethoxylated, as liquid constituents in the first process step

and / or water or aqueous solutions or mixtures are added in such amounts that rollable but non-adhesive granules are obtained in the second process stage.