WO1993002176A1

WO1993002176A1 - Method of producing high-bulk-density washing agents with improved dissolving speed

Info

Publication number: WO1993002176A1
Application number: PCT/EP1992/001616
Authority: WO
Inventors: Norbert Kühne; Hubert Pawelczyk; Jochen Jacobs; Günther VOGT
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1991-07-25
Filing date: 1992-07-16
Publication date: 1993-02-04
Also published as: DE4124701A1; ATE150084T1; EP0595946B1; EP0595946A1; ES2098520T3; DE59208196D1; JPH06509369A

Abstract

The invention concerns the production of high-bulk-density solid washing and cleaning agents with improved dissolving speed, produced by mixing solid and liquid washing-agent raw materials and, at the same time or subsequently, modifying the form of the particles in the mixture and, if required, drying it. Anionic surfactants, builders and alkalisation agents are added as the solid components, and non-anionic surfactants as the liquid components. To improve the dissolution behaviour and to facilitate mixing, the liquid non-ionic surfactants are used intimately mixed with a structure breaker in the ratio by wt. of non-ionic surfactant: structure-breaker of 10:1 to 1:2. Preferred structure-breakers are poly(ethylene glycol) or poly(propylene glycol) with a relative molecular weight between 200 and 12,000, addition products produced by reacting about 20 to 80 moles of ethylene oxide with 1 mole of an aliphatic alcohol with substantially 8 to 20 carbon atoms, and mixtures thereof.

Description

METHOD FOR THE PRODUCTION OF HIGH DETERGENT DETERGENTS AND

IMPROVED LOSE SPEED

The invention relates to a process for the production of solid detergents and cleaning agents and to the detergents and cleaning agents produced by this process, which are distinguished by an improved dissolving rate, in particular at low temperatures.

Solid detergents and cleaning agents with a high bulk density, i.e. Agents with a bulk density above 500 g / 1 often have a lower dissolving rate due to their compact shape and the resulting lower surface area, especially at low temperatures around 15 to 60 ° C, than agents with a comparable composition, but have a bulk density of, for example, only 300 g / 1.

It is also known that some surfactants form a gel phase when dissolved in water or when their solutions are diluted.

It is known from European patent application EP 7049 that the viscosity of ethoxylated fatty alcohols, which form gels when diluted with water, can be reduced by adding ethoxylated alkane diols.

EP 208534 describes spray-dried granules with improved solute content. This is achieved in that the aqueous slurry which is spray dried contains polyacrylate and in particular a mixture of polyacrylate, polyethylene glycol and nonionic surfactant.

From the international patent application WO 91/02047 a process for the production of compacted granules is known which are used in detergents and cleaning agents. In this case, a homogeneous premix is extruded with the addition of a plasticizer and / or lubricant at high pressures between 25 and 200 bar. This application teaches that surfactants can be used as plasticizers and / or lubricants. there it is possible that the plasticizers and / or lubricants contain limited amounts of auxiliary liquids. These auxiliary liquids also include higher-boiling, optionally polyethoxylated alcohols, polyalkoxylates which flow at room temperature or moderately elevated temperatures and the like. However, it was not recognized that the dissolution behavior of the compressed granules can be positively influenced by the specific use of certain amounts of auxiliary liquids.

While the reduced dissolving speed is less disruptive when the agents are used mechanically, these agents are generally not accepted by the consumer when they are used manually, for example when used in a hand basin.

The object of the invention was to produce a solid washing and cleaning agent with a high bulk density, which contains conventional ingredients, including ethoxylated alcohols as nonionic surfactants, and which has an improved dissolution rate at temperatures between 15 and 60 ° C.

Surprisingly, it has now been found that the dissolving rate of solid detergents and cleaning agents with a high bulk density and conventional composition can be improved by introducing the liquid ethoxylated alcohols used as nonionic surfactants into the process in a certain form in the preparation of the agents.

The invention accordingly relates to a process for the production of solid detergents and cleaners with a high bulk density by combining solid and liquid detergent raw materials with simultaneous or subsequent shaping and, if desired, drying, anionic surfactants, builder substances and alkalizing agents being used as solid constituents, and nonionic surfactants as liquid constituents is used, and in which the liquid nonionic surfactants are used in an intimate mixture with a structure breaker in a weight ratio of liquid nonionic surfactant: structure breaker of 10: 1 to 1: 2 to improve the dissolution behavior and to facilitate incorporation. The liquid nonionic surfactants are preferably derived from ethoxylated fatty alcohols with 8 to 20 carbon atoms and an average of 1 to 15 moles of ethylene oxide per mole of alcohol and in particular from primary alcohols with preferably 9 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide per mole of alcohol, in which the alcohol residue may be linear or methyl-branched in the 2-position, or may contain linear and methyl-branched residues in the mixture, such as are usually present in oxo alcohol residues. However, linear residues of alcohols of native origin with 12 to 18 carbon atoms, such as, for example, coconut oil, tallow fat or oleyl alcohol, are particularly preferred. 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). In particular, alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups. The preferred ethoxylated alcohols include, for example, Cg-Cn-oxo alcohol with 7 E0, Ci3-Ci5-oxo alcohol with 3 E0, 5 E0 or 7 E0 and in particular Ci2-Ci4 alcohols with 3 E0 or 4 E0, Ci2-Ci8 alcohols 3 E0, 5 E0 or 7 E0 and mixtures of these, such as mixtures of Ci2-Ci4 alcohol with 3 E0 and Ci2-Ci8 alcohol with 5 E0.

A number of both solid and liquid substances which are hydrophilic, water-soluble or water-dispersible are suitable as structure breakers. Suitable are, for example, lower polyalkylene glycols which are derived from straight-chain or branched glycols having 2 to 6 carbon atoms, preferably polyethylene glycol or polypropylene glycol, and have a relative molecular weight between 200 and 12,000. In particular, polyethylene glycols with a relative molecular weight of between 200 and 4000 are preferred, the liquid polyethylene glycols with a relative molecular weight of up to 2,000 and in particular between 200 and 600 having particularly advantageous properties.

Likewise, the sulfates and in particular the disulfates of lower polyalkylene glycol ethers, in particular of polyethylene glycol and 1,2-polypropylene glycol, are suitable. The sulfates and / or disulfates which are derived from polyethylene glycols and Derive polypropylene glycols with a relative molecular mass between 600 and 6000 and in particular between 1,000 and 4,000. The disulfates generally originate from polyglycol ethers, such as those which can be caused by the slight traces of water in the alkoxylation of alcoholic components.

Another group of suitable structure breakers consists of the water-soluble salts of mono- and / or disulfosuccinates of the lower polyalkylene glycol ethers. The corresponding polyethylene glycol ether and polypropylene glycol ether compounds are of particular importance, sulfosuccinates and disulfosuccinates of polyglycol ethers having a relative molecular weight between 600 and 6,000, in particular between 1,000 and 4,000, being particularly preferred.

Any salts, but preferably the alkali metal salts, in particular the sodium and potassium salts, and ammonium salts and / or salts of organic amines, for example triethanolamine, can be used as structure breakers for the use of the anionically modified polyalkylene glycol ethers . The most important salts for practical use are the sodium and potassium salts of sulfates, disulfates, sulfosuccinates and disulfosuccinates of polyethylene glycol and polypropylene glycol.

Mixtures of the polyalkylene glycol ethers and their anionically modified derivatives are preferably also used in any mixing ratio. In particular, a mixture of polyalkylene glycol ether and the sulfosuccinates and / or disulfosuccinates of the polyalkylene glycol ether is preferred. However, a mixture of polyalkylene glycol ether and the corresponding sulfates and / or disulfates and a mixture of polyalkylene glycol ether and the corresponding sulfates and / or disulfates and the corresponding sulfosuccinates and / or sulfodisuccinates are also suitable.

Furthermore, for the purposes of this invention, suitable and preferably used structure breakers are the addition products of about 20 to about 80 moles of ethylene oxide with 1 mole of an aliphatic alcohol with essentially 8 up to 20 carbon atoms, which have long been known ingredients of detergents and cleaning agents. The addition products of 20 to 60 mol and in particular of 25 to 45 mol of ethylene oxide with primary alcohols, such as, for example, coconut oil alcohol or tallow fatty alcohol, with oleyl alcohol, with oxo alcohols, or with secondary alcohols with 8 to 18 and preferably 12, are particularly important up to 18 carbon atoms. Examples of particularly preferred structure breakers from the group of highly ethoxylated alcohols are tallow fatty alcohol with 30 E0 and tallow alcohol with 40 E0. It is also preferred to use mixtures which contain highly ethoxylated alcohols, for example mixtures of tallow fatty alcohol with 40 E0 and water or of tallow fatty alcohol with 40 E0 and polyethylene glycol with a relative molecular weight between 200 and 2000.

Further suitable structure breakers are ethoxylated, vicinal internal alkanediols or 1,2-alkanediols with a carbon chain with 8 to 18 carbon atoms and 4 to 15 moles of ethylene oxide per mole of diol. It is possible for only one of the two OH groups or both OH groups of the alkanediol to be ethoxylated.

Modified nonionic surfactants with a terminal acid group are also suitable as structure breakers. These are nonionic surfactants, especially fatty alcohols, in which a 0H group has been converted into a group with a carboxyl group. Nonionic surfactants with a terminal acid group thus include esters or partial esters of a nonionic surfactant with a polycarboxylic acid or a polycarboxylic anhydride. Examples of acid-terminated nonionic surfactants are the known polyether carboxylic acids and esters or semi-esters of C 1 -C 6-alcohols with succinic anhydride, maleic anhydride, maleic acid or citric acid.

Another group of suitable structure breakers consists of alkylene glycol monoalkyl ethers of the general formula RO (CH2CH2θ) _n H, in which R represents a radical with 2 to 8 carbon atoms and n represents a number from 1 to 8. Examples of this group of additives are ethylene glycol monoethyl ether and diethylene glycol onobutyl ether. Water is also a suitable structural breaker in principle. However, the use of water as a structure breaker is less preferred. In most cases, the aim is to keep the free water content in the agents as low as possible in order to achieve the highest possible active ingredient concentrations in the agents. For this purpose, anhydrous ingredients, for example anhydrous soda or at least partially dewatered zeolite, are often used which are able to bind free water. It is therefore obvious that water is a less suitable structural breaker, since the agents become poorer in water during storage due to the internal drying of the agent, so that the positive effect of the improved dissolution rate after a period of use no longer applies or is no longer fully effective.

According to the invention, the liquid nonionic surfactants, in particular the ethoxylated fatty alcohols, are used in intimate mixing with the structure breaker. This intimate mixing is achieved by either producing a homogeneous solution or a dispersion from the liquid nonionic surfactants used according to the invention and the hydrophilic, water-soluble or water-dispersible structure breakers. Surprisingly, the additives even in very small amounts, for example around 8% by weight, based on the sum of liquid nonionic surfactant and structure breaker, bring about the desired improvement in the dissolving speed of the finished washing and cleaning agents, so that they are preferably in one Weight ratio of liquid nonionic surfactant: structure breaker from 8: 1 to 1: 1.5 can be used.

These solutions or dispersions of liquid nonionic surfactant and structure breaker can be used in all known processes in which detergents and cleaners have a high bulk density, ie a bulk density above 500 g / 1, preferably above 600 g / 1 and in particular between 700 and 1,000 g / l, and which contain liquid ethoxylated alcohols as nonionic surfactants according to the definition of the invention, are used. Drive Examples of such known and preferred Ver¬ are granulation, in which either the ingredient ^'e a synthetic detergent or a spray-dried detergents and Cleaning agents or a mixture of spray-dried and non-spray-dried ingredients of detergents and cleaning agents are compacted in a high-speed mixer and simultaneously in this mixer or subsequently in another device, for example in a fluidized bed, with the solution or dispersion according to the invention . A method is also preferred in which spray-dried and / or non-spray-dried ingredients of detergents and cleaning agents are granulated together with the solution or dispersion used according to the invention, which has been applied to a carrier, in particular to a zeolite-containing carrier.

In particular, however, a method is preferred, which is described in detail in international patent application WO 91/02047. In this case, a solid, homogeneous premix is extruded in the form of a strand, with the addition of a plasticizer and / or lubricant, through hole shapes with opening widths of the predetermined granule dimension at high pressures between 25 and 200 bar. The strand is cut to the predetermined granule dimension directly after it emerges from the hole shape by means of a cutting device. The application of the high working pressure causes the premix to be plasticized during the formation of the granulate and ensures the cutting ability of the freshly extruded strands. The premix consists, at least in part, of solid, preferably finely divided, conventional ingredients of detergents and cleaning agents, to which liquid constituents are optionally added. The solid ingredients can be tower powders obtained by spray drying, but also agglomerates, the mixture components selected in each case as pure substances which are mixed with one another in the finely divided state, and mixtures of these. Subsequently, the liquid ingredients are optionally added and then the plasticizer and / or lubricant selected according to the invention is mixed in. Preferred plasticizers and / or lubricants are aqueous solutions of polymeric polycarboxylates, as well as highly concentrated anionic surfactant pastes and nonionic surfactants. For a detailed description of the suitable ingredients of the premix and the suitable plasticizers and / or lubricants, reference is made to the disclosure of the international patent application WO 91/02047. According to the invention, the solutions or dispersions of liquid nonionic surfactants and hydrophilic, water-soluble or water-dispersible structure breakers can either be added to the solid premix as a liquid constituent or as a plasticizer and / or lubricant, or they are part of a solid mixture component of the premix, this solid mixture component consisting of a carrier bead which has been charged with the solution or the dispersion. However, the addition of the solution according to the invention or the dispersion in liquid form, that is to say not bound to a carrier bead, can be carried out at any point in the process, for example when preparing the premix, but also when processing the plasticized premix before passing through the perforated shape (perforated nozzle plate).

The solutions or dispersions according to the invention are preferably used in the production of washing and cleaning agents by extrusion under high pressure, the weight ratio of liquid nonionic surfactant: structure breaker in the solutions or dispersions being 10: 2 to 1: 1 and in particular 10: 3 to 10 : 8 is.

Kneaders of any configuration, for example 2-screw kneaders, can preferably be selected as the homogenizing device. The intensive mixing process can itself lead to a desired temperature increase. Moderately elevated temperatures of, for example, 60 to 70 ° C. are generally not exceeded. In a preferred embodiment, the premix is preferably fed continuously to a 2-screw kneader (extruder), the housing and the extruder granulation head of which are heated to the predetermined extrusion temperature, for example heated to 40 to 60 ° C. Under the shear action of the extruder screws, the premix is compressed at pressures from 25 to 200 bar, preferably above 30 bar and in particular at pressures from 50 to 180 bar, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally by means of the extrudate of a rotating knives preferably reduced to spherical to cylindrical granules. The hole diameter in the perforated nozzle plate and the strand cut length are reduced to selected granule dimension. In this embodiment, it is possible to produce granules of an essentially uniformly predeterminable particle size, it being possible for the absolute particle sizes to be adapted to the intended use. In general, particle diameters of up to at most 0.8 cm are preferred. Important embodiments provide for the production of uniform granules with diameters in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm. In an important embodiment, the length / diameter ratio of the chopped-off primary granules is in the range from about 1: 1 to about 3: 1. It is further preferred that the still plastic, moist primary granules undergo a further shaping processing step feed; edges present on the raw granulate are rounded off so that ultimately spherical or at least approximately spherical granules can be obtained. If desired or required, small amounts of dry powder, for example zeolite powder such as zeolite NaA powder, can also be used in this step. This shaping can take place in standard rounding devices, for example in rounding devices with a rotating base plate. The granules are then preferably fed to a drying step, for example a fluidized bed dryer. Surprisingly, it has now been found that extruded granules which contain peroxy compounds as bleaching agents, for example perborate monohydrate, can be dried at supply air temperatures between 80 and 150 ° C. without loss of active oxygen. The free water content of the dried granules is preferably up to about 3% by weight, in particular between 0.1 to 1% by weight. Alternatively, it is also possible to carry out the drying step in a rounding device directly after the extrusion of the primary granulate and thus before a final shaping, if desired.

To achieve an increased bulk density, it is advantageous to powder the dried granules again, if necessary, with finely divided dry powders. ¹ Examples of such dry powders are again zeolite-NaA powder, but also precipitated or pyrogenic silica, as are commercially available, for example, as Aerosil ( ^R ) or Sipernat ( ^R ) (products from ^' Degussa'). Highly preferred Concentrated, at least 90% by weight fatty alcohol sulfate powder, which essentially, ie at least 90%, consist of particles with a particle size smaller than 100 μm. Mixtures of zeolite and fatty alcohol sulfate powder are particularly preferred.

In a further embodiment, solid washing and cleaning agents are claimed which are produced by the process according to the invention. These washing and cleaning agents show an improved dissolving speed at temperatures between 15 and 60 ° C. and in particular between 20 and 45 ° C. In particular, detergents produced by the process according to the invention which contain 20 to 45% by weight of surfactants are preferred.

Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are alkylbenzenesulfonates (Cg-Ci5-alkyl), olefin sulfonates, ie. H. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from Ci2 ~ Ci8 monoolefins with terminal and internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are dialcan sulfonates which are obtainable from Ci2-Ci8-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and in particular the esters of α-sulfofatty acids (ester sulfonates), for example those Oc-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example coconut oil alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the Cl0 ~ C20 ~ 0 ^χoaoils and those secondary alcohols of this chain length. The sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of ethylene oxide, are also suitable. Sulfated fatty acid monoglycerides are also suitable. Soaps from natural or synthetic, preferably saturated, fatty acids can also be used. Soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids, are particularly suitable. Preferred are those which are composed of 50 to 100% of saturated Ci2-Ci8 fatty acid soaps and 0 to 50% of oleic acid soaps.

The anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The detergent content according to the invention of anionic surfactants or of anionic surfactant mixtures is preferably 5 to 40, in particular 8 to 35,% by weight. It is particularly advantageous if the content of sulfonates and / or sulfates in the compositions is 10 to 35% by weight, in particular 15 to 30% by weight, and the soap content is up to 8% by weight. , in particular 0.5 to 5 wt .-%.

The anionic surfactants can be used in solid form, for example in spray-dried or granulated form, or in liquid to pasty form. Thus, it is preferred to incorporate the anionic surfactants used as plasticizers and / or lubricants in the form of an aqueous surfactant paste.

The content of the agents in ethoxylated alcohols used according to the invention as nonionic surfactants is preferably 1 to 15% by weight and in particular 2 to 10% by weight. The content of the structure breakers used according to the invention inevitably results from this. The compositions preferably contain up to 5% by weight, in particular 1 to 3% by weight, of polyethylene glycol with a relative molecular weight between 200 and 1,500.

The weight ratio of anionic surfactant: nonionic surfactant is preferably at least 1: 1 and in particular 1: 1 to 6: 1, for example 2: 1 to 6: 1.

In addition, alkyl glycosides of the general formula R-0- (G) _x , in which R is a primary straight-chain or in 2-position methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18 carbon atoms, G is a symbol which represents a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10 , is preferably between 1 and 2 and in particular is significantly smaller than 1.4, for example in amounts of 1 to 10% by weight.

Weakly acidic, neutral or alkaline-reacting soluble and / or insoluble components which are able to precipitate or bind complex ions are suitable as organic and inorganic builders. Suitable and, in particular, ecologically safe builder substances, such as finely crystalline, synthetic water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 24 12 837), are used with preference. Their average particle size is usually in the range from 1 to 10 μm (measurement method: Coulter Counter, volume distribution). The zeolite content of the compositions is generally up to 50% by weight, preferably at least 10% by weight and in particular 20 to 40% by weight, based on the anhydrous substance. Zeolite NaA is obtained in its production as a water-containing slurry (masterbatch), which is subjected to drying, in particular spray drying, using the processes customary today for the production of textile detergents. It is possible to use the zeolite or at least zeolite fractions in the form of the undried masterbatch or an only partially dried masterbatch.

Further builder constituents which can be used in particular together with the zeolites are (co) polymeric polycarboxylates, such as polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those from 50% to 10% maleic acid. The relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, in which the proportion the acidity is at least 50%. Also useful are polyacetal carboxylic acids, such as those described in US Pat. Nos. 4,144,226 and 4,146,495, and polymeric acids which are obtained by polymerizing acrolein and subsequent disproportionation using alkalis and are composed of acrylic acid units and vinyl alcohol units or acrolein units. The (co) polymeric polycarboxylates are introduced into the process in solid form or in liquid form, ie in the form of an aqueous solution, preferably in the form of a 30 to 55% strength by weight aqueous solution. The content of the agents in (co) polymeric polycarboxylates is preferably up to 10% by weight and in particular 2 to 8% by weight.

Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid and nitrilotriacetate (NTA), provided that such use is not objectionable for ecological reasons.

Other suitable ingredients of the agents are water-soluble inorganic alkalizing agents such as bicarbonates, carbonates or silicates; In particular, alkali carbonate and alkali silicate, especially sodium silicate with a molar ratio Na2θ: Siθ2 of 1: 1 to 1: 4.0, are used. The alkalizing agents are preferably introduced into the process in solid form. However, it is also possible to use at least some of the alkalizing agents in the form of an aqueous solution, e.g. in the form of an aqueous alkali silicate solution or a mixture of solid alkali carbonate and an alkali silicate solution. The sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight. The sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.

The other detergent components include graying inhibitors (dirt carriers), foam inhibitors, bleaching agents and bleach activators, optical brighteners, enzymes, fabric softening agents, colorants and fragrances as well as neutral salts. Among the compounds which serve as bleaching agents and supply H2O2 in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, peroxycarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracid salts or peracids, such as perbenzoates, peroxaphthalates, 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.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetylethylenediamine, further carboxylic anhydrides and esters of polyols such as Glucose pentaacetate. The bleach activator content of the bleach-containing agents is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.

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, such as, 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, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. Carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof and polyvinylpyrrolidone are preferably used, in particular in amounts of 0.5 to 5% by weight, based on the composition. The foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like organic substances. A reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, for example sulfates and / or sulfonates with nonionic surfactants and / or with soaps. In the case of soaps, the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid ester. Soaps of natural and synthetic origin that contain a high proportion of Ci8-C24 fatty acids are therefore suitable as foam-inhibiting soaps. Suitable non-surfactant-like foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Bisacylamides derived from Ci2-C20-alkylamines and C2-Co-dicarboxylic acids can also be used. Mixtures of different foam inhibitors are also advantageously used, for example those made from silicones and paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance or are admixed with the plasticizer and / or lubricant.

The detergents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) -stilbene-2,2 ^, -disulfonic acid or compounds of the same structure are suitable which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group. Brighteners of the substituted 4,4'-distyryl-di-phenyl type may also be present; for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

According to a further preferred embodiment of the invention, uniformly white granules are obtained if, apart from the customary optical brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5, preferably around 0.1 to 0.3, by weight. -%, even small quantities, for example, 10 "^ to 10" 3 wt .-%, preferably around 10 ~ 5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux ( ^R ) (product name of Ciba-Geigy).

Enzymes from the class of proteases, lipases and amylases or mixtures thereof can be used. 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 obtained from Bacillus lentus are preferably used. The enzyme * can be adsorbed on carrier substances and / or embedded in coating substances in order to protect them against premature decomposition.

The salts of polyphosphonic acids, in particular l-hydroxyethane-l, l-diphosphonic acid (HEDP), are suitable as stabilizers, in particular for per-compounds and enzymes.

The detergents and cleaning agents can be produced uniformly from extrudates which have the above-mentioned ingredients. However, the agents can also be obtained from a mixture of several different granules, of which the extrudates according to the invention form the main component. For example, the bleach activator, the enzymes, and colorants and fragrances can be subsequently added to the extrudates. It is preferred to use the bleach activator and the enzymes in each case in compacted granular form, for example as extrudates produced separately in each case, which are obtained by means of a kneader of the configuration described above or via a pellet press.

B e i s p i e l e

example 1

A solid premix consisting of 2,000 g of Cg-Ci3-alkylbenzenesulfonate sodium salt powder (90% by weight of active substance), 2,250, was placed in a batch mixer (20 liters) equipped with a cutter head chopper g Ci2-Ci8 fatty alcohol sulfate powder (91% by weight of active substance), 200 g Ci2-Ci8 sodium fatty acid soap, 3700 g Wessalith p ( ^R ) (Zeolith NaA; commercial product from Degussa, Federal Republic of Germany), 650 g of anhydrous sodium carbonate, 880 g of Sokalan CPδ ( ^R ) powder (copolymer of acrylic acid and maleic acid, 95% by weight of active substance; commercial product from BASF, Federal Republic of Germany), 1,650 g of a foam inhibitor concentrate containing 8% by weight Silicone oil and 58 wt .-% sodium sulfate and 20 wt .-% water glass as an inorganic carrier, and 2 100 g sodium perborate monohydrate and with mixing tools in operation with a mixture of 330 g Ci2-Ci8 fatty alcohol with 5 E0, 200 g taig fatty alcohol with 5 E0 and 250 g polyethylene glycol a relative molecular mass of 400. Subsequently, 780 g of a 35% by weight aqueous sodium silicate solution (Na2θ: Siθ2 1: 3.0) and 165 g of a 30% by weight aqueous solution of the 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt were added . The mixture was homogenized for 2 minutes and then fed to a twin-screw extruder, the housing of which, including the extruder pelletizing head, was heated to 45 ° C. Under the shear action of the extruder screws, the premix was plasticized and then extruded at a pressure of 120 bar through the extruder head perforated die plate into fine strands with a diameter of 1.2 mm, which after the die outlet were comminuted into approximately spherical granules by means of a knock-out knife (Length / diameter ratio about 1, hot cut). The resulting warm granulate was rounded off for 1 minute in a Maru erizer-type rounding device available on the market and then dried at a supply air temperature of 120 ° C. in a fluidized bed dryer. The low-dust product was sieved through a sieve with a mesh size of 1.6 mm. The proportion above 1.6 mm was below 3%. The granules obtained had a bulk density of 820 g / l. The dissolving rate of the granules was determined using the conductivity measurement method:

500 g of demineralized water (20 ° C.) were poured into a 1 liter glass vessel, the propeller stirrer was switched on at a speed of 900 revolutions per minute and the conductivity measuring cell was immersed. Then 5 g of the detergent granules were added. The change in conductivity was recorded by a writer. The measurement was carried out until there was no longer any increase in conductivity. The time to reach constant conductivity is the dissolution time of the entire granulate (100%). The dissolution time at 90% resolution was calculated.

The dissolving time of the granules according to the invention was 2.20 minutes at 20 ° C. and 90% resolution.

Comparative Example 1

A premix of the same composition as in the example according to the invention was produced, but the ethoxylated alcohols and the polyethylene glycol were not added in a mixture, but separately in succession.

As in the example according to the invention, the premix was extruded, cut, rounded, dried and sieved. The bulk density of the granules VI was approximately 820 g / l.

The dissolving time of the granules VI at 20 ° C. and 90% resolution was 3.77 minutes.

Comparative Example 2

As in the example according to the invention, a premix was prepared which contained the same constituents in the same amounts as in the example according to the invention, with the exception that the additive polyethylene glycol was dispensed with. The premix was as in the invention Example extruded, cut, rounded, dried and sieved. The bulk density of the granules V2 was about 820 g / 1.

The dissolving time of the Granules V2 was 3.85 minutes at 20 ° C and 90% resolution.

Claims

Patent claims

1. A process for the preparation of solid detergents and cleaning agents with a high bulk density by joining solid and liquid detergent raw materials with simultaneous or subsequent shaping and drying if desired, anionic surfactants, builder substances and alkalizing agents being used as solid constituents and nonionic surfactants being used as liquid constituents, characterized in that that to improve the dissolving behavior and to facilitate incorporation, the liquid nonionic surfactants are used in an intimate mixture with a structure breaker in a weight ratio of liquid nonionic surfactant: structure breaker 10: 1 to 1: 2.

2. The method according to claim 1, characterized in that as a structure breaker polyethylene glycol or polypropylene glycol, sulfates and / or disulfates of polyethylene glycol or polypropylene glycol, sulfosuccinates and / or disulfosuccinates of polyethylene glycol or polypropylene glycol or mixtures of these are used.

3. The method according to claim 1, characterized in that ethoxylated Cs-Cis fatty alcohols with 20 to 45 E0, preferably Taig fat alcohols with 30 and 40 E0 are used as structure breakers.

4. The method according to any one of claims 1 to 3, characterized in that ethoxylated aliphatic alcohols having 8 to 20 carbon atoms and an average of 1 to 15 moles of ethylene oxide per mole of alcohol are used as liquid nonionic surfactants.

5. The method according to any one of claims 1 to 4, characterized in that the weight ratio of liquid nonionic surfactant: structure breaker is 8: 1 to 1: 1.5.

6. The method according to claim 5, characterized in that an intimate mixture of ethoxylated alcohol and structure breaker in one Weight ratio of ethoxylated alcohol: structure breaker from 10: 2 to 1: 1, preferably 10: 3 to 10: 8.

7. The method according to any one of claims 1 to 6, characterized in that the anionic surfactants are used in solid or liquid to pasty form.

8. The method according to any one of claims 1 to 7, characterized in that surfactants are used in amounts of 20 to 45 wt .-%, based on the Mit¬ tel.

9. The method according to claim 8, characterized in that 5 to 40 wt .-%, preferably 8 to 35 wt .-% anionic surfactants and 1 to 15 wt .-%, preferably 2 to 10 wt .-% nonionic surfactants, each based on the agent, the weight ratio of anionic surfactant: nonionic surfactant preferably being at least 1: 1 and in particular 1: 1 to 6: 1.

10. The method according to claim 8 or 9, characterized in that one uses 0.5 to 5 wt .-%, based on the agent, of soap.

11. The method according to any one of claims 1 to 10, characterized in that an optical brightener and a blue dye are used as further components.

12. The method according to any one of claims 1 to 11, characterized in that bleaching agents, preferably perborate monohydrate, in amounts of 5 to 25% by weight, based on the agent, are used as further solid constituents.

13. The method according to any one of claims 1 to 12, characterized in that one uses as further constituents (co) polymeric polycarboxylates in solid or liquid form.

14. The method according to any one of claims 1 to 13, characterized in that that the joining and shaping is carried out according to a process in which a solid, homogeneous premix with the addition of a plasticizer and / or lubricant is extruded via hole shapes with opening widths of the predetermined granule dimension at high pressures between 25 and 200 bar and the extrudate immediately after the exit from the hole shape is cut to the predetermined granule size by means of a cutting device.

15. The method according to claim 14, characterized in that the bleach activator, the enzymes and dyes and fragrances are subsequently added to the extrudates.

16. The method according to claim 15, characterized in that the bleach activator and the enzymes are used in compact form as extrudates which are produced separately and are obtained by means of a kneader or a pellet press.

17. The method according to any one of claims 1 to 13, characterized in that the assembly and shaping is carried out by a method in which either the ingredients of a washing and cleaning agent or a spray-dried washing and cleaning agent or a mixture of spray-dried and non-spray-dried ingredients of detergents and cleaning agents are compacted in a fast-running mixer and at the same time the intimate mixing of liquid nonionic surfactant and structure breaker is applied in this mixer or subsequently in another device.

18. The method according to any one of claims 1 to 13, characterized in that the assembly and shaping is carried out by a method in which spray-dried and / or non-spray-dried ingredients of detergents and cleaning agents together with the solution or dispersion liquid nonionic surfactant and structure breaker, which has been applied to a carrier, preferably to a zeolite-containing carrier, is granulated.

19. The method according to any one of claims 1 to 18, characterized in that a bulk density of the detergent and cleaning agent between 600 and 1000 g / 1 is set.