EP0674703B1 - Proces for preparing a granulated washing and cleaning agent - Google Patents

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

The invention relates to a method for producing granulated detergents and cleaning agents, in particular those with high bulk density, or a component therefor, the have a special morphology, which is in a - macroscopic seen - expresses almost spherical structure.

From the international patent application WO 91/02047 extruded washing and detergent granules with an almost spherical structure are known. These granules are obtained in that a solid, free-flowing Premix with the addition of a plasticizer and lubricant at high Printing is pressed in the form of a strand and the strand is pressed out immediately after it exits the hole shape by means of a cutting device to the predetermined one Granule dimension is cut. The granules obtained in this way have a monodisperse internal structure.

On the other hand, granules produced by conventional granulation processes mechanical or pneumatic mixers with subsequent drying, Sieving and grinding of the coarse grain fraction are made, gluing of the primary granules with the liquid components. These bonds cause secondary agglomeration of primary granules (build-up granulation) and lead to a non-uniform, non-mono-disperse, raspberry-like Structure of the granules (see Figures 1 and 2). So are out the European patent application 367 339 granules known, according to a two-stage granulation process. Doing so will be porous and compressible granules, preferably spray-dried granules first in a high speed mixer and then in one slow speed mixer and granulator compressed. So that an optimal Compression can take place in the second mixer, it is necessary that the Powder can be brought into a deformable state. This can be done by Temperature control and / or by adding liquid components, especially nonionic surfactants, during the first granulation and Compression phase take place in the high-speed mixer. The entry of Liquid components in the first step with simultaneous energy input through the tools of the mixer leads however in the first mixer Bonding of the granular material and thus to the training described raspberry-like structures. In European patent application 390 251 the method according to EP 367 339 is modified by 0.1 to 40 % By weight of a powder either in the second granulation stage or between be added to the first and second pelletizing stages. Lay here thus optimal conditions for a build-up granulation. The powder agglomerates in the moist, sticky areas of the primary agglomerates and causes a further formation of raspberry-like structures. Through the However, adding large amounts of powder will make the sticky surface of the primary granules covered quickly and completely, the build-up granulation comes to a standstill and, depending on the time of adding the powder, it becomes relative receive small agglomerates. The addition of only small amounts of powder however, only partially covers the adhesive surface, so that it is combined into larger agglomerates.

The object of the invention was to provide granules with a - macroscopic seen - almost spherical surface and an almost monodisperse internal granulate structure, which so far has only been possible through an extrusion process could be produced, to be provided by a Granulation processes can be produced.

The invention accordingly relates to a process for the production a granulated detergent or cleaning agent or a component for this, the granules having a certain morphology with almost spherical and smooth surface and an almost monodisperse inner Has structure and is a roll granulate.

The washing and cleaning agent obtained or the component therefor, which one (s) is produced by a granulation process stands out in particular by a certain surface morphology. Macroscopic seen the granules are almost spherical; microscopic seen the granules are characterized by a surprisingly "smooth" Surface that shows some cracks, but without it sharp, protruding edges or protruding protrusions. The difference in the surface morphology is very clear the figures, wherein Figures 3 and 4, the invention Granules with a "smooth" surface and Figures 1 and 2 die conventional raspberry structure-like, obtained by structural granulation Show granules. The special morphology of the granules according to the invention causes them to move against each other on a rolling basis. This can be shown by a simple test, with the granules poured become. While pouring conventional granules granulate layers only slip, rolls with the granules according to the invention in each case the upper granulate layer over the granulate layer underneath from. Because of this property, the invention Granules called roll granules below.

The preferred composition of the roll granules is characterized in that 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 contain. Roll granules with 15 contain up to 35% by weight of anionic and nonionic surfactants.

Preferred anionic surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C ₁₂ -C ₁₈ monoolefins with an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ 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 C ₈ to C ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a restricted homolog distribution, are 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 tallow 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 C ₁₂ -C ₁₈ 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 also contain fractions of unsaturated alcohols, for example oleyl alcohol , can contain. Mixtures in which the proportion of the alkyl radicals is 50 to 70% by weight on C ₁₂ , 18 to 30% by weight on C ₁₄ , 5 to 15% by weight on C ₁₆ , are preferred 3% by weight on C ₁₀ and less than 10% by weight on C _{18 are} distributed.

Other suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.5 to 8% by weight. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C ₁₂ -C ₁₈ fatty acid soaps and 0 to 50% by weight of oleic acid soap.

The anionic surfactants can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases, such as mono-, di- or Triethanolamine. The anionic surfactants are preferably in Form of their sodium or potassium salts, especially in the form of the sodium salts in front.

The anionic surfactant content of the roll granules is preferably 5 to 20% by weight. However, their content can also exceed 20% by weight, 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 C ₁₂ -C ₁₈ fatty alcohols and their mixtures such as coconut oil, tallow oil or oleyl alcohol, or with methyl-branched, in particular methyl-branched primary alcohols (oxo alcohols) are preferred as nonionic surfactants in the Contain granules. In particular, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohol with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ - C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C 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 restricted homolog distribution (narrow range ethoxylates, NRE).

The content of the ethoxylated C ₁₂ -C ₁₈ fatty 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 having 2 to 6 carbon atoms and / or highly ethoxylated fatty alcohols with 20 to 80 EO, in particular tallow fatty alcohol with 30 EO or 40 EO , used. 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 in some cases 1.5: 1 to 1 : 1.5, for example by 1: 1.

The preferred nonionic surfactants also include alkyl glycosides of the general formula RO (G) _x , in which R is a primary straight-chain or aliphatic radical having 8 to 22, preferably 12 to 18, C-atoms and methyl-branched 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 preferred non-ionic surfactants that either as the sole nonionic surfactant or in combination with others nonionic surfactants, especially together with alkoxylated Fatty alcohols used 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 ester, as for example in the Japanese patent application JP 58/217598 are described or which are preferably according to the in the international patent application WO 90/13533 become.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may be suitable. The amount of this nonionic Surfactants are preferably no more than that of the ethoxylated ones Fatty alcohols, especially not more than half of them.

in der R²CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R³ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können. Hinsichtlich der Verfahren zu ihrer Herstellung sei auf die US-Patentschriften US 1 985 424, US 2 016 962 und US 2 703 798 sowie die Internationale Patentanmeldung WO 92/06984 verwiesen. Vorzugsweise leiten sich die Polyhydroxyfettsäureamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab. Die bevorzugten Polyhydroxyfettsäureamide stellen daher Fettsäure-N-alkylglucamide dar, wie sie durch die Formel (II) wiedergegeben werden:

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

in the R ² CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ³ 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 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 polyhydroxy fatty acid amides 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):

The polyhydroxy fatty acid amides used are preferably fatty acid N-alkylglucamides of the formula (II) in which R ^{3 is} hydrogen or an alkyl group and R ² CO is 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 C _12/14 coconut fatty acid or a corresponding derivative are particularly preferred.

In principle, the roll granules obtained according to the invention can be any known Contain ingredients of washing and / or cleaning agents. Preferred further constituents are builder substances, alkaline substances and neutral salts, bleaches, graying inhibitors, foam inhibitors and optical brighteners.

Suitable inorganic builders are, for example, phosphates, preferably tripolyphosphates, but also orthophosphates and pyrophosphates, as well as zeolite and crystalline layered silicates.

The finely 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 that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups . 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 silicates of the general formula (III) NaHSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number 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 β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Useful organic builder substances are preferred, for example polycarboxylic acids 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 such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Suitable polymeric polycarboxylates are, for example, the sodium salts 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 acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain. Their relative molecular mass, 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) polymers in the compositions Polycarboxylates is preferably 1 to 8% by weight, in particular 2 to 6 % By weight. In particular, the use of biodegradable polymers prefers.

Other suitable builder substances are polyacetals, which by reaction of dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and have at least 3 hydroxyl groups, for example as in European Patent application 280 223 can be obtained. Preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde and terephthalaldehyde as well as 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 Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably of 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 H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing 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, with perborate monohydrate being advantageously used.

Graying inhibitors have the task of removing the fiber Keep dirt suspended in the fleet and prevent 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 Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Furthermore, soluble ones Use starch preparations and other starch products than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, cellulose ethers such as carboxymethyl cellulose are preferred. Methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures used. Carboxymethyl cellulose (sodium salt), Methyl cellulose, methyl hydroxyethyl cellulose and their mixtures and polyvinyl pyrrolidone are preferred, 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 C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also advantageously used, for example those made of silicone, paraffins or waxes. The foam inhibitors, in particular silicone or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance.

As the salts of polyphosphonic acids, the neutral reacting agents can preferably be used Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and Diethylenetriaminepentamethylenephosphonate in amounts of 0.1 to 1.5% by weight be included.

As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino Group carry a diethanolamino group, a methylamino group, 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 5% by weight, preferably between 0.1 and 0.3% by weight, also in small amounts, for example 10 ^-6 to 10 ^-3 % by weight, preferably around 10 ^-5 % by weight, of a blue dye A particularly preferred dye is Tinolux ^(R) (commercial product from Ciba-Geigy).

The free, ie unbound, content of the roll granules obtained according to the invention Water is in the framework known for granules, it can for example up to 20% by weight. However, preferred granules contain not more than 10% by weight of free, unbound water.

The bulk density of the roll granules is generally between about 400 and 1200 g / l. However, preferred roll granules have a bulk density between 600 and 1100 g / l, preferably between 700 and 950 g / l. The Despite possibly high proportions of ethoxylated nonionic surfactants, granules are non-greasy. The diameter of the roll granules is arbitrary and preferably predeterminable, d. H. targeted to a desired value adjustable. So in a preferred embodiment, roll granules preferred, where 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 where the maximum of the particle size distribution (weight distribution) is between 0.2 and 0.6 mm, preferably between 0.3 and 0.5 mm.

The roll granules produced according to the invention can either be used directly as washing and Detergents are used, and / or they are mixed with other quantities, preferably small amounts, for example in the range from 2 to 10 % By weight, based on the total amount of the proportions used, of liquid Sprayed nonionic surfactants or nonionic surfactant mixtures in a manner known per se, and / or they are processed in a preparation step with other components, preferably granular and in particular granular and compacted Components of detergents and cleaning agents mixed. To the Other granular components include compacted ones Bleaching agent or bleach activator granules, enzyme granules and granular Carrier for colors 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 H ₂ O ₂ , preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. The addition of bleach activators is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight, based on the finished washing 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.

Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Are particularly well suited Strains of bacteria or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably become proteases of the subtilisin type and in particular proteases that are obtained from Bacillus lentus. Their share can be about 0.2 amount to about 2 wt .-%, based on the finished detergent. The enzymes can be adsorbed on carrier substances and / or in coating substances embedded to protect them against premature decomposition.

The roll granules are after obtained a process, the powdered in a first process stage Starting materials submitted and, if necessary, with liquid components are mixed, the mixture in a second process stage is compressed by the entry of energy and the resulting Granules are rolled compacting against each other, being a smooth surface (microscopic) and an almost monodisperse inner Preserve structure, and roll-up granulation by adding a fine particle Powder is stopped after placing the granules on a given Maximum of the particle size distribution has grown. Of the The diameter of the roll granules that can be produced by this method is thus predeterminable.

In the first stage of the process, powdered starting materials are presented and mixed together. Preferred powdered starting materials are anionic surfactants, zeolite, silicate, soda, and in particular also Peroxy bleaches such as perborate. Granular precursors, for example spray-dried or granulated surfactant compounds be, but it is preferred that these precursors first be crushed or ground. Foam inhibitors, which are bound to a granular carrier substance with the other powdery starting materials mixed in the first process stage.

It is not essential for every composition, but preferred that too liquid components are used in this stage of the process. High in anionic surfactants Premixes can, for example, also be used alone and if necessary compressing by increasing the temperature in the second process stage roll against each other. However, the powdery ones are preferred Starting materials in the first stage of the process with liquid components acted upon. Suitable liquid components are liquid non-ionic surfactants, water and any possible mixture of non-ionic 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 C ₁₂ -C ₁₈ fatty alcohols, and / or water or aqueous solutions or mixtures of the type mentioned above are added as liquid constituents in the first process stage in such amounts that rollable in the second process stage , but non-adhesive granules can be obtained. The optimal amount of liquid components for each recipe can be determined by simply trying them out.

If both liquid components and granular foam inhibitors should be used, then the granular foam inhibitor is added preferably only after the powder has been applied Starting materials to moisturize the granular foam inhibitors prevent. The granular foam inhibitor is added before entry in the second stage.

The first stage of the process can be used in all mixers, mixing plates, granulators, yes even be carried out in high speed mixers as long as these devices can be operated so that only a mixture and Powder applied, but no granulation or agglomeration takes place. The exception to this is the binding of fine fractions that are in the The opposite is even desirable. Since in a preferred embodiment Processes carried out continuously are also in the first process stage Mixer types that are operated continuously are preferred can.

In the second process stage, the charged powdery starting materials are then transferred to a second mixer, in which the powdery starting materials are rolled against one another by the energy input of the tools. If desired, small amounts of liquid can also be added in this process stage, as long as the roll granulation is not affected. 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 annular layer mixers. A continuously operating ploughshare mixer is preferred at this point.

The resulting granules grow in with increasing dwell time the second stage of the process during the compacting roll-up granulation on. The size of the granules is therefore determined by the residence time in the second mixer or by the duration of the compacting roll granulation certainly. Before the discharge from the mixer / granulator there is a termination the compacting roll granulation by adding a fine particle Powder causes. The resulting granules become like this powdered that the rolling process is stopped abruptly, but the plasticity the resulting granules are 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 as well as all powders that are about 90% particle size exist below 30 µm. The fine-particle powder is then broken off roll-up granulation preferably in amounts of up to 10% by weight, in particular added in amounts of 0.5 to 8 wt .-%. It is particularly advantageous the addition of finely divided powders in amounts of 1 to 5% by weight.

After the roll-up granulation has been terminated, the resulting granules can be processed be further processed. For example, it is possible to either by usual screening of unwanted coarse and / or fine grain fractions or for example by homogenizing the granules in another Mixers, for example in a Schugi mixer or a commercially available one Rounder, a more uniform grain spectrum with a smaller width too to reach. The setting of the high bulk density is made once by the rolling compression of the charged powdery raw materials to others also by powdering and by the possible density Bulking of the almost spherical granules seen macroscopically. The existence of finely divided granules usually leads to this a further increase in bulk density.

If desired, the granules can then be dried, for example be dried in a fluidized bed, or left harden by cooling. There is drying in the fluidized bed also possible when using peroxy bleach. Keep the granules even when drying in the fluidized bed its seen macroscopically almost spherical structure because of the complete powdering of the Granules no further granulation can take place.

Examples Example 1:

64.35 parts by weight of a spray-dried granulate (corresponding to 5.5 parts by weight of C ₉ -C ₁₃ alkylbenzenesulfonate, 1.85 parts by weight of tallow fatty alcohol with 5 ethylene oxide groups, 0.8 to 5 parts by weight) C ₁₂ -C ₁₈ 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 Na ₂ O: SiO ₂ ratio of 1: 3.0, 4.85 parts by weight of a polymeric polycarboxylate (Sokalan CP 5 ^(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 parts by weight. % aqueous C ₉ -C ₁₃ alkylbenzenesulfonate solution mixed in a continuously operating mixer (Schugi) and then with a high energy input in a CB mixer from Lödige with the addition of 4.8 parts by weight of a C ₁₂ -C ₁₈ fatty alcohol with 5 ethylene oxide groups. The throughput was 1 t / h. The bulk density of the granules after drying was 785 g / l. If the roll granulation was broken off 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 ₉ -C ₁₃ alkylbenzenesulfonate (ABS), 0.55 parts by weight of tallow alcohol with 5 EO, 0.7 parts by weight . Parts of C ₁₂ -C ₁₈ 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 5 ^(R) , 0.3 parts by weight of phosphonate and the rest of water and salts from solutions were introduced into 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 ingredients mentioned in Example 1, being spray-dried Granules are used with a composition according to Example 2 were in a Lödige ploughshare mixer with a Throughput of approx. 2 t / h mixed and then discontinuously in another Lödige mixer FK with an extension of the dwell time granulated.

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

After a granulation time of 10 minutes, the bulk density of the undried and not powdered granules to 837 g / l, by stopping The roll granulation by adding 2% by weight of zeolite resulted in an increase in the bulk density of the undried granules to 908 g / l and afterwards Dried to 937 g / l.

Example 4:

65 parts by weight of spray-dried granules (corresponding to 19.05 parts by weight of ABS, 0.7 parts by weight of tallow fatty alcohol with 5 EO, 0.85 parts by weight of C ₁₂ -C ₁₈ 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 CP5 ^{( R)} and the rest of the water and salts from solutions) together with 22 parts by weight of perborate monohydrate and 4.5 parts by weight of silicone defoamer granules with the addition of 3 parts by weight of a mixture of C ₁₂ -C ₁₈ fatty alcohol with 5 EO and tallow fatty alcohol with 40 EO in a weight ratio of 1: 1.2 and 6.5 parts by weight of a 30% by weight aqueous Sokalan CP5 ^(R) solution. 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 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 particles Silicic acid and / or with a powdered silicone defoamer processed.

Analogous results were obtained by replacing ABS with C ₁₂ -C ₁₈ fatty alk (en) yl sulfate.

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

Claims (4)

1. A process for the production of a detergent or a detergent component, the granules having a certain morphology with a substantially spherical (macroscopically) and smooth (microscopically) surface and a substantially monodisperse inner structure and any, i.e. predeterminable, diameter, characterized in that, in a first stage, the powder-form starting materials are introduced into a mixer and optionally mixed with liquid constituents, the mixture is compacted by the introduction of energy in a second stage of the process carried out in a mixer and the granules formed are rolled compactingly against one another so that they assume a smooth surface (microscopically) and a substantially monodisperse inner structure and the pan granulation process is stopped by the addition of a fine-particle powder after the granules have been allowed to grow to a predetermined maximum of their particle size distribution.
2. A process as claimed in claim 1, characterized in that, to stop the pan granulation process, the fine-particle powder is added in quantities of up to 10% by weight, preferably in quantities of 0.5 to 8% by weight and more preferably in quantities of 1 to 5% by weight.
3. A process as claimed in claim 1 or 2, characterized in that the granules are dried.
4. A process as claimed in any of claims 1 to 3, characterized in that, in the first stage of the process, liquid nonionic surfactants, preferably ethoxylated C_12-18 fatty alcohols, and/or water or aqueous solutions or mixtures are added as liquid constituents in such quantities that rollable but non-tacky granules are obtained in the second stage of the process.

Images