EP0566583B1 - Readily soluble dry concentrate containing washing-agent ingredients - Google Patents

Abstract

PCT No. PCT/EP91/02366 Sec. 371 Date Sep. 8, 1993 Sec. 102(e) Date Sep. 8, 1993 PCT Filed Dec. 10, 1991 PCT Pub. No. WO92/12229 PCT Pub. Date Jul. 23, 1992Free-flowing and storable granular compacts containing ingredients of detergent or cleaning compositions in concentrated form are prepared by (1) preparing an adhesively bound dry premix containing (a) fine-particle detergent ingredients substantially free of binding or adhesive properties, and (b) fine-particle detergent ingredients having binding or adhesive properties, and optionally, detergent ingredients which are liquid at room temperature, to form a substantially homogeneous premix, and (2) press-molding the premix at a temperature of from about 40 DEG C. to 80 DEG C. in the substantial absence of shear forces whereby air is microdispersed in the resultant compacts.

Description

The invention relates to a new form of offer for ingredients of detergents and / or cleaning agents, in particular textile detergents, as well as correspondingly designed detergents and / or cleaning agents and the novel method for their production. It describes in particular the production of a comparatively coarse-grained and storage-stable, free-flowing material which, on the one hand, is compressed to increased bulk densities, but on the other hand, due to its special structure, is capable of rapid interaction with, in particular, aqueous liquid phases with destruction of the grain structure.

In recent years, a large number of proposals have become known which describe the production of powdered or agglomerated solid washing and / or cleaning agents with increased bulk densities. From the recent past, reference is made to EP 340 013 and the documented prior art EP 219 328, EP 270 240 and GB 1 517 713 (all Unilever), EP 229 671 and JP 61 069 897 (Kao) and EP 220 cited therein 024 (Procter & Gamble). Described in the above-mentioned publication are detergent mixtures in granular form with a bulk density of at least 650 g / l, which are obtained by predetermined mixing ratios of selected non-soap-like surface-active agents - at least partially corresponding anionic surfactants - with predetermined amounts of crystalline or amorphous sodium aluminum silicate. The granules are to be produced in a high-speed mixer / granulator, which ensures the process elements of the mixing and comminution. The process is carried out in the presence of a liquid binder, with water being the preferred binder which, if necessary, can be added before or during the granulation step. According to the examples, the particle size of the agglomerates obtained in this way is clearly below 1 mm and generally in the range from about 400 to a maximum of 600 μm.

A more recent proposal by the same applicant can be found in EP 367 339. Here too, the production of a comparatively fine-particle detergent granulate with bulk densities of at least 650 g / l described. The production is now to be carried out in a two-stage process in such a way that in a first process stage (5 to 30 seconds) the finely divided mixture of active ingredients is treated in a high-speed mixer and simultaneously compacted, while in a subsequent second process step the granulation takes place at lower processing speeds in the period of approximately 1 to 10 minutes, but also with simultaneous compression of the material. The finished goods should be dried and / or cooled to make them flowable. The examples in this publication deal in detail with the comparison of the respective bulk densities and the associated percentage particle porosities and particle sizes. It is shown that in the two-stage process described, a significant increase in the bulk density - for example to values up to about 950 g / l - is possible and is associated with a substantial reduction in the percentage particle porosity. While the feed powders obtained by spray drying have bulk densities in the range around 400 g / l with a particle porosity in the range from 45 to 50%, the bulk densities of the two-stage compacted materials are in the range from about 700 to 900 g / l, while the particle porosity is below values 20% and in particular below 10% can be reduced. The particle size of the compacted material can reach the value of approximately 1 mm, but is generally also significantly lower here.

The applicant for the development described below describes in German patent application DE 39 26 253 a new way of producing solid and free-flowing granules of detergents and / or cleaning agents, in particular corresponding textile detergents. These granules are characterized by bulk densities of at least about 700 g / l, in particular those in the range from about 850 to 1,000 g / l. The granules are produced by extrusion using the smallest possible amounts of liquid phase, in particular water, and are preferably subsequently additionally dried by dehydration. A dry granulate of high density and high strength is obtained in this process, which has good storage stability compared to the ambient conditions in practice. A characteristic of the manufacturing process from this earlier application is an intensive mixing of the the respective mixture of substances when using high shear forces and processing pressures in screw extruders while plasticizing the mixture. The mass homogenized in this form is extruded in the form of strands through perforated molds, the emerging compacted material strands are cut to the predetermined granulate dimension and, if desired, rounded off before the granulate grains formed are loaded with other active ingredients and / or dried to the granular, free-flowing material, if necessary.

European patent application EP-A-0 273 334 describes platelets which have a large empty space between the individual particles. EP-A-0 273 334 neither discloses nor suggests that a microporous basic structure, in which the highest possible internal surface of the particles is associated with a microdisperse distribution of air in the particles, is known.

The teaching of the invention is based on the object of allowing targeted modifications in the specific design of such granular granules while maintaining the form of compacted comparatively coarse granules. In particular, the invention aims to create the possibility of controlling the grain internal structure and in particular the microporosity of the grain. The teaching of the invention is intended to make it possible to influence the inner surface of the granulate, preferably in such a way that the largest possible inner surface can be ensured in spite of a high compression of the mixture of substances in the granulate. The object of the invention is based on the objective of achieving good and rapid dissolving power in the washing or cleaning bath despite the high bulk densities of the granular concentrates. It is obvious that an increase in the inner grain surface, in particular by inclusion and protection of the proportion of the finest microdisperse air inclusions, can influence the redissolvability of the granulate.

Another important determining element for the manufacturing process of the concentrates with the new structure is aimed in the same direction: the compacting and pressing of the material should be possible with the greatest possible restriction of shear forces to the respective substance mixture. In particular, smearing of the individual solid particles with one another should be prevented as far as possible, as is the case, for example when processing the corresponding solid mixtures in screw extruders due to their strong shear effect. For the area of auxiliaries and ingredients of detergents and / or cleaning agents mentioned here, this aspect can be of particular importance because, as a rule, highly lubricious components such as surfactants, polymeric builder substances and other mixture components which can be deformed or even spreadable under pressure are also used.

In further aspects of the object according to the invention, it should nevertheless be possible to produce storage-stable, free-flowing concentrates of high breaking strength and a low tendency for the individual grains to stick to one another during storage. In an important embodiment, the invention aims to enable compacts of the type described to be obtained as immediate process products without the need for an intermediate drying step.

For the technical solution of this task bundle, the invention provides a plurality of structural elements for the grain or compact structure on the one hand and for the process parameters in the production of such compressed concentrates from the at least predominantly powdery feedstocks.

• (a) feinkörnigen Inhaltsstoffen ohne ausgeprägte Haft- beziehungsweise Klebereigenschaften (Komponenten (a)) mit
• (b) feinkörnigen Inhaltsstoffen mit Haft- beziehungsweise Klebereigenschaften (Kleberkomponenten (b)) enthalten. Die Preßlinge sind dabei durch formgestaltendes Verpressen bei mäßig erhöhten Temperaturen, wobei Guttemperaturen von 80 °C nicht überstiegen werden, ohne Einwirkung wesentlicher Scherkräfte, die zu einer substantiellen Verschmierung im Prinzip schmierfähiger Mischungsbestandteile führen könnten, auf das feinkörnige Gut hergestellt worden und enthalten
• (c) Luft in mikrodisperser Verteilung im Preßling.

Die durchschnittliche innere Oberfläche der Preßlinge - bestimmt mittels Hg-Porosimetrie - beträgt dabei wenigstens etwa 1 m²/g, wobei deutlich höhere Werte, beispielsweise solche oberhalb 1,5 m²/g und insbesondere bei oder oberhalb 2m²/g, bevorzugt sind. In wichtigen Fällen können die Preßlinge eine innere Oberfläche im Bereich von etwa 3 - 5 m²/g aufweisen. In an sich bekannter Weise nimmt die innere Oberfläche eines mikroporösen Festkörpers mit dem Anstieg des Anteils der Mikroporen zu. Erfindungsgemäß können dementsprechend Preßlinge der geschilderten Art bevorzugt sein, deren Anteil an Mikroporen eines Durchmesser unterhalb 1 »m wenigstens etwa 20 - 25 Vol.% und insbesondere wenigstens etwa 30 Vol.% - bezogen auf die Gesamtporosität - ausmacht. Besonders bevorzugte Preßlinge kennzeichnen sich durch entsprechende mikroporöse Anteile mit Porendurchmessern unterhalb 1»m von wenigstens etwa 50 Vol.%. Im allgemeinen sind die erfindungsgemäßen Preßlinge durch eine breit gestreute Mikroporosität über den Gesamtbereich der individuellen Porendurchmesser von etwa 0,001 - 10 »m gekennzeichnet.Accordingly, the invention relates in a first embodiment to free-flowing and storage-stable coarse-grained compacts, containing ingredients of detergents and / or cleaning agents in concentrated form, produced by compression molding an at least largely homogenized fine-grained premix of the ingredients, the components which are liquid even at room temperature in small amounts can be added. These compacts are characterized in the sense of the teaching according to the invention in that they consist of firmly bonded dry mixtures with bulk densities of at least 500 g / l

• (a) fine-grained ingredients with no pronounced adhesive or adhesive properties (components (a)) with
• (b) contain fine-grained ingredients with adhesive or adhesive properties (adhesive components (b)). The compacts are formed by shaping pressing at moderately elevated temperatures, with product temperatures not exceeding 80 ° C are produced and contain the fine-grained material without the action of significant shear forces, which could lead to substantial smearing, in principle of lubricatable mixture components
• (c) Air in microdisperse distribution in the compact.

The average inner surface of the compacts - determined by mercury porosimetry - is at least about 1 m² / g, with significantly higher values, for example those above 1.5 m² / g and in particular at or above 2 m² / g, being preferred. In important cases, the compacts can have an inner surface in the range of about 3-5 m 2 / g. In a manner known per se, the inner surface of a microporous solid increases with the increase in the proportion of micropores. Accordingly, according to the invention, compacts of the type described can be preferred, the proportion of which is at least about 20-25% by volume and in particular at least about 30% by volume, based on the total porosity, of micropores with a diameter below 1 μm. Particularly preferred compacts are characterized by corresponding microporous portions with pore diameters below 1 »m of at least about 50% by volume. In general, the compacts according to the invention are characterized by a broadly dispersed microporosity over the entire range of the individual pore diameters of approximately 0.001-10 »m.

In a further embodiment, the subject of the invention is a process for producing these granular compacts, this process being characterized in that components (a) and adhesive component (b) are mixed as fine-grained material under conditions, at least largely homogeneously, to form a loose bulk material , under which there is no distinctly solidifying adhesive function. If desired, liquid components to be used in the process, which are only used in a very limited amount, as will be described in detail below, are mixed in here. The bulk material prepared in this way is then pressed to form compacts with the exclusion of shear forces as much as possible - at least to its main mass - with the inclusion of microdispersed air. In the preferred embodiment of the invention, these processing conditions are achieved by pressing using a die press, the bulk material being pressed onto a surface of a rotating, Bore-containing die applied and rolled into a compacted shape by means of a pressing tool rotating on or slightly above the die surface and pressed through it to form the granules.

A ring die press which essentially consists of a rotating hollow roll into which radial bores are made is particularly suitable for carrying out the method according to the invention. In this ring die, a press roll is arranged eccentrically and rotatably mounted. The mixture is introduced into the inside of the ring die, drawn into the nip between the press roll and the ring die and extruded. In the preferred embodiment of the method according to the invention, a targeted control or adjustment of the temperature of the mixture within the ring die press, in particular by means of temperature regulation via the coolable and / or heatable pressing tool, can take place. Such a temperature control, by varying the nip height between the pressing tool and the die surface and by the operating parameters of the ring die press, which are described in detail below, make it possible to control both the desired degree of compaction and the internal porosity of the granulate.

The dry concentrates according to the invention are produced in two successive steps:
In the first step, solid fine-grained ingredients of detergents and cleaning agents, which preferably have no particles with diameters above 100 »m, are essentially in dry form and can be assigned to two different classes of material, are mixed as homogeneously as possible. The first class of substances are ingredients without pronounced adhesive properties, which are referred to here as "components (a)". In contrast, the second class of substances are fine-grained ingredients with adhesive or adhesive properties, which are referred to in the description of the invention as "adhesive components (b)".

Detergent and / or cleaning agent concentrates in dry form generally contain a large number of representatives of the two classes of substances mentioned here. Fine-particle powders of this type which are solid at room temperature are either available as commercial products or can be prepared in a manner known per se, for example by spray drying.

Adhesive components (b) in the sense of the invention are, in particular, those representatives of the ingredients of detergents and cleaning agents which are present as a solid at room temperature, but at least superficially soften by increasing the temperature and / or by adding very limited amounts of liquid additives and / or under pressure - And the effect of temperature with subsequent cooling towards the neighboring solid particles form a certain adhesive and adhesive strength. Typical examples of compounds of this type are finely divided surfactant compounds which are solid at room temperature and are generally used in detergents and cleaners. The particular type of surfactant is largely insignificant for the achievement of the object according to the invention as long as the selected surfactant compound can correspond to its function as adhesive and adhesive component (b). Both the numerous anionic surfactant compounds that are solid at room temperature and suitable ampholytic or zwitterionic surfactants are therefore suitable. Nonionic surfactant compounds can also be assigned to substance class (b), provided that they form a solid phase at room temperature. The fact that liquid auxiliary components, in particular nonionic surfactants which are liquid at room temperature, can also play an important auxiliary role in the development of the compacts according to the invention for strengthening the adhesive components (b) is described below.

Another important class of substances, which belongs to these adhesive components (b), from detergents and cleaning agents, in particular textile detergents, are selected builder or framework substances, possibly with the use of limited amounts of moisture. Typical representatives for such adhesive components are polymer compounds of synthetic and / or natural origin, examples being the polymers or copolymers of acrylic acid, which are known today as so-called Co-builders are usually used to inactivate water hardness in the washing process. It is obvious that other organic components, in particular organic polymer compounds, can also have the appropriate adhesive and adhesive function. Starch and starch derivatives, cellulose or cellulose derivatives and the like, which are used, for example, to improve the dirt-carrying capacity of the wash liquor, may be mentioned here merely by way of example.

To support the activation of the adhesive and adhesive components in the pressing process step, the use of limited amounts of components that are liquid at room temperature can be considered. The most important representatives - which can be used either alone or in a mixture with one another - are the nonionic surfactants, water and / or selected oil phases that are already liquid at room temperature. Nonionic surfactants that are liquid at room temperature are now regular active ingredient constituents in detergent and cleaning agent mixtures and, accordingly, are also important mixture constituents within the framework of the teaching according to the invention. They take on an important additional function as an activating agent for the adhesive components (b) in the context of the teaching according to the invention.

If necessary, small amounts of water can be added during the preparation of the mixture to be pressed. In particular, it can be used together with representatives of the aforementioned substance classes (a) and / or (b). For example, aqueous pastes of anionic surfactants and / or of non-adhesive active ingredients according to (a), such as finely divided sodium zeolite, can also be used in the preparation of the mixture to be pressed.

Possible oil phases for use in the mixtures according to the invention are, for example, limited amounts of paraffin oils, of ester oils, but also low-volatile mono- and / or polyfunctional alcohols, corresponding ethers and the like.

Fine-grained ingredients of washing and / or cleaning agents without pronounced adhesive or adhesive properties, ie the components (a) are a regular component of active ingredient mixtures of the type concerned here. As a rule, these are water-soluble or moderately soluble to insoluble components of inorganic origin or else organic mixture components with a comparatively high softening or melting point. The representatives can be assigned to the most diverse classes of active ingredients, for example the builders or builder substances, for example of the zeolite NaA type, bleaching agents, bleach activators, textile-softening auxiliaries such as the swellable fine-particle sheet silicates and inorganic alkaline or neutral to slightly acidic salts, for example sodium silicate, sodium carbonate, sodium hydrogen carbonate, sodium sulfate Sodium bisulfate and perborate. General specialist knowledge in the particular formulation aimed at allows the assignment of the specific components either to the group of components (a) or to the adhesive components (b) in the sense of the teaching according to the invention.

The granulation or pressing process according to the invention proceeds in two stages. In the first process stage, the fine-grained components from (a) and (b), which are mostly solid at room temperature, are intimately mixed with one another. All the slow to fast mixer types that are common in practice are suitable here, ploughshare mixers, segment screw mixers, paddle mixers, pin mixers, Eirich mixers, vortex mixers, horizontal high-speed mixers, multi-flow fluid mixers and the like being mentioned only as examples.

Due to the structure of the premix and the working conditions in this preliminary stage, no significant shear forces act on the individual grain during the treatment, which could lead to substantial smearing, in principle of lubricating mixture components. In this preliminary stage, any liquid components that are used are homogeneously incorporated into the mixture of substances. This is possible, for example, by spraying on corresponding liquid constituents before or during this premixing stage or by adding aqueous pastes of active ingredients to this mixing stage.

The choice and coordination of the mixture components with one another in the subsequent second stage of the process according to the invention enables the desired microporous grain structure to be built up, which combines high bulk densities with a comparatively large inner surface of the granulate. Taking into account the explanations given below for the second process stage, the respective mixing ratios of the components to one another can be optimized within the framework of general specialist knowledge. The following working rules generally serve as guidelines:
The solid dry powder components (a) and (b) together make up at least about 90% by weight, preferably at least about 94% by weight, of the mixture to be produced in the first working step. Accordingly, liquid components are preferably present in a maximum of about 10% by weight, preferably in amounts of about 1-8% by weight and in particular in amounts of about 2-6% by weight. If water is used directly or indirectly via an aqueous paste as a constituent of the mixture, then even with the small amounts mentioned here, it is advisable to use constituents on the solid powder side which have a large water-binding capacity. In this way, the desired structure of the granulate can also be achieved without additional drying step by internal drying - for example via the process of completely or partially binding the water as crystal water.

The premix is generally present as a dry-appearing powder at the beginning of the second stage of the process. A particularly advantageous embodiment of the invention uses the following control element for the correct coordination of the active ingredient components in the mixture to be pressed: The finely divided solids with and without adhesive or adhesive properties and the liquid constituents which may be used are used in such mixing ratios that under the conditions of the pressing in the second process stage as the primary product of extrusion, in addition to the desired compacts, just the first traces or small amounts of powdery material that has not yet solidified are pressed out. The stickiness of the mixtures in the second Processing level is so coordinated here that the mass is under the working conditions used just in the border area of the compressibility to firm strands or granules to be obtained therefrom. This border area can easily be left on both sides. In a preferred embodiment, this boundary region is extended in the direction of the insufficient adhesion, ie in the direction of the coextrusion of small powdery residual fractions. The powder-co-extruded proportions can make up, for example, up to 10% by weight, preferably up to about 5% by weight, based on the total extrudate. In the processing of this extrudate into granules, which will be described in the following, the portion which has penetrated in powder form takes over the function of an auxiliary for powdering the primary extrudates, the stickiness of which is due in particular to their slightly elevated processing temperature.

The homogenized premix from the first stage of the process is compressed in the subsequent second stage of work to give a strand shape, which strands are expediently cut to the grain shape immediately after leaving the die.

An important prerequisite for the compression and maintenance of the microporous structure in this second stage is the compression of the premix with the greatest possible exclusion of shear forces on the main mass of this mixture. This results in the inclusion of micro-dispersed air, which leads to the desired microporosity.

For the technical realization of this concept, working in a ring die press has proven to be useful, as is shown for example in DE 38 16 842. Described here is a ring die press with a rotating ring die interspersed with press channels and at least one press roller connected to its inner surface, which presses the material supplied to the die press space through the press channels into a material discharge. Both the ring die and the press roller (s) are related to the outer surfaces that come into operation can be driven in the same direction. In the preferred embodiment when used in the method according to the invention, the rotational speeds of the ring die and press roll can be coordinated and adjusted to one another in such a way that no or practically no shear forces are exerted on the mixture introduced into the interior of the ring die. The objective of the invention is thereby favored in several ways. The mixture containing microdisperse air is only subjected to pressure in the direction of the extrusion pressure and thus compressed, without destroying the primarily predetermined structure of high microporosity. The desired result is the comparatively high values of the inner surface of the compacts, which can be, for example, in the range from 2 to 5 m² / g, in particular in the range from about 3 to 5 m² / g. Values of this size can only be set by keeping the percentage of micropores with a diameter below 1 »m, preferably below 0.1» m or even below 0.01 »m, comparatively high.

However, the processing of the mixture homogenized in the first step with the exclusion of significant shear forces also leads to further advantages. The individual constituents of the mixture lie next to one another in an individualized manner as in a bed, there is no smearing of plastic and / or thermoplastic good fractions over larger areas of adjacent surfaces of solid particles. This can mean substantial help for the rapid redissolvability of the compact. Easily water-soluble mixture components, for example corresponding proportions of neutral salts and / or washing alkalis, are accessible to direct interaction with the water when water enters; there is no need for detachment, for example, of a surfactant layer smeared on the fine crystalline material.

Finally, the exclusion of shear forces on the bulk material when compacting it also has an effect on restricting the temperature increase, which is always associated with the introduction of considerable mechanical forces into the bulk material to be compressed. In the sense of the invention, for further improved temperature control, it is preferred to work with ring die presses, the one Enable temperature control inside the ring die. A suitable embodiment is described in the aforementioned DE 38 16 842. It is provided here that the pressure roller is designed to be temperature-controllable by means of a heating or cooling medium. The method according to the invention makes use of it in the second working stage. Material temperatures of approximately 80 ° C., preferably approximately 70 ° C., are not exceeded within the ring matrix. Lower limit values for the temperature of the material in the processing step are usually in the temperature range from approximately 30 to 40 ° C., whereby working temperatures for compressing the bulk material in the range from approximately 45 to 60 ° C. can be particularly suitable.

The temperature conditions described here can in turn determine the selection of the adhesive components (b) and / or the use of liquid components in the first mixing stage. For example, adhesive components (b) in a finely particulate and essentially homogeneously distributed form in the substance mixture may be preferred which - if appropriate with the participation of the mixture components which are liquid at room temperature - soften to such an extent in the temperature range above 40 ° C. and in particular in the temperature range from approximately 45 to 70 ° C. that they form an adhesive effect under the working conditions according to the invention and subsequently in the cooled, granular extrudate.

The possibility of temperature control in the second processing step also determines, among other things, the mixing ratios of the dry components (a) to the adhesive components (b) in the multicomponent mixtures used. In general, it is preferred to use the adhesive component (s) (b) at most approximately at the same quantity as the components (a), although usually smaller mixture fractions (b), based on mixture fractions (a), can be preferred. Suitable mixtures of substances for the purposes of the invention contain the adhesive components (b) in amounts in the range from about 15 to 40% by weight, based on the compacts.

In compliance with the microporous basic structure aimed at according to the invention with a high inner surface, the ring die press can then be used Bulk weights of the extrudates extruded in the form of strands and preferably immediately thereafter cut to the grain shape of at least 500 g / l are set. The bulk densities of the granular compacts described according to the invention are preferably at or above about 600 g / l, with significantly higher values being set, for example those in the range up to about 900 g / l, or even more, depending on the working conditions and the choice and coordination of the mixture components can be. Particularly suitable bulk weights can be, for example, in the range from about 550 to 850 g / l.

Suitable grain sizes for the compacts described according to the invention are, for example, in the range from about 1 to 3 mm, it being possible for the compacts to be of rod-shaped or spherical design in a manner known per se. For this purpose, it may be expedient that the material is pressed into bores with a diameter of approximately 0.8 to 1.5 mm and is preferably cut to lengths in the range of approximately 1 to 2 mm. If desired, the freshly extruded compacts can be rounded off in a subsequent process step, the rounding expediently taking place before the material to be solidified by lowering the temperature.

Further known auxiliary measures for stabilizing the primarily occurring compacts, which can also be used in the context of the invention, are, for example, shock cooling the primarily emerging product strands and the granules obtained therefrom, for example by means of a doctor blade, if desired drying these granules, for example in a fluidized bed dryer , and / or powdering the primary granulate with finely divided powder. As already indicated, the appropriate choice of the mixture components used according to the invention in terms of type and / or quantity also makes it possible to dispense with such auxiliary measures, or to squeeze out a numerically subordinate proportion of powder which then serves to powder off the primary granules in the subsequent rounding. The compacts produced in this way can be processed further in a further process step, as a result of which the desired form of supply is obtained. For example, it is possible to mix the compacts with other detergent ingredients Granulation, spray drying, pelleting or extrusion were mixed. However, the compacts are preferably packaged separately, it being particularly preferred to pack the compacts, which are either complete detergents or detergent additives, in portions, one portion usually being sufficient for one washing operation.

The following is general information on the list of suitable active substances and the composition of suitable active substance mixtures, the assignment of the components mentioned in detail to the substance classes of the dry components (a), the adhesive components (b) or the liquid components, which may be used in small amounts, based on general knowledge in the light the information on the implementation of the method according to the invention and the working conditions used here is possible. In this context, reference should also be made to the extensive specialist literature as it results from the relevant patent literature and specialist books on detergents and cleaning agents.

As anionic surfactants e.g. Soaps from natural or synthetic, preferably saturated fatty acids can be used. Natural fatty acids, e.g. Soap mixtures derived from coconut, palm kernel or tallow fatty acids. Preferred are those which are composed of 50 to 100% of saturated C₁₂₋₁₈ fatty acid soaps and 0 to 50% of oleic acid soap. Further suitable synthetic anionic surfactants are those of the sulfonate and sulfate type.

The surfactants of the sulfonate type are alkylbenzenesulfonates, preferably C₉-C₁₃-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C₁₂₋₁₈ monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent sulfonates or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which can be obtained from C₁₂₋₁₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins are, and in particular the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Suitable sulfate-type surfactants are the sulfuric acid monoesters of primary alcohols of natural and synthetic origin, i.e. from fatty alcohols, e.g. Coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C₁₀₋₂₀ oxo alcohols, and those of secondary alcohols of this chain length. The sulfuric acid monoesters of alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C₉₋₁₁ alcohols with an average of 3.5 moles of ethylene oxide, are suitable. Sulfated fatty acid monoglycerides are also suitable.

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 30,% by weight.

Addition products of 1 to 40, preferably 2 to 20 moles of ethylene oxide with 1 mole of an aliphatic compound having essentially 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides or alkanesulfonamides can be used as nonionic surfactants. The addition products of 3 to 20 moles of ethylene oxide with primary alcohols, such as e.g. on coconut oil or tallow fatty alcohols, on oleyl alcohol, on oxo alcohols, or on secondary alcohols with 8 to 18, preferably 12 to 18, carbon atoms.

In addition to the water-soluble nonionics, polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule, which are not or not completely water-soluble, are also of interest, in particular if they are used together with water-soluble, nonionic or anionic surfactants.

In addition, alkyl glycosides of the general formula RO- (G) _x can also be used as nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18 C atoms, methyl-branched in the 2-position, G is a symbol which stands for a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x between 1 and 10, preferably between 1 and 2 and in particular significantly less than 1.5, for example between 1.1 and 1.4, lies.

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 harmless 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, are preferably used. Their particle size is usually in the range from 1 to 10 »m. Their content in the compositions is generally 0 to 60, preferably 10 to 45,% by weight, based on the anhydrous substance.

Other co-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 composed of 50% to 10% maleic acid. The molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 200 and 200,000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a 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 of acid is at least 50%. Also useful are polyacetal carboxylic acids, as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, and polymeric acid, 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.

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

In cases where a phosphate content is tolerated, phosphates can also be used, in particular pentasodium triphosphate, optionally also pyrophosphates and orthophosphates, which act primarily as precipitants for lime salts. The phosphate content, based on pentasodium triphosphate, is below 30% by weight. However, agents without a phosphate content are preferably used.

Suitable inorganic, non-complexing salts are the bicarbonates, carbonates, borates or silicates of the alkalis, which are also referred to as "washing alkalis"; Of the alkali silicates, especially the sodium silicates with a Na₂O: SiO₂ ratio of 1: 1 to 1: 3.5 can be used.

The other detergent ingredients include graying inhibitors (dirt carriers), foam inhibitors, bleaching agents and bleach activators, optical brighteners, enzymes, fabric softening agents, dyes and fragrances as well as neutral salts.

Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying. For this purpose, water-soluble colloids of mostly organic nature are suitable, 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 (Na salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone are preferably used, in particular in amounts of 0.1 to 5 wt .-%, based on the agent.

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, e.g. of sulfates and / or sulfonates with nonionics 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 residue. Soaps of natural and synthetic origin that have a high proportion of C₁₈₋₂ aufweisen 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 C₁₂₋₂₀ alkylamines and C₂₋₆ dicarboxylic acids are also useful. Mixtures of different foam inhibitors are also advantageously used, e.g. those made of silicone and paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.

Of the compounds used as bleaching agents which supply H₂O₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxycarbonate, peroxypyrophosphates, citrate perhydrates and H₂O₂-delivering peracid salts or peracids, such as perbenzoates, peroxaphthalates, diperazelaic acid or diperdodecanedioic acid.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the agents. 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, also carboxylic anhydrides and esters of polyols, such as glucose pentaacetate.

The detergents can contain derivatives of di-aminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2 'disulfonic acid or compounds of the same structure which instead of the morpholino group have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present; e.g. the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

Enzymes from the class of prostheses, lipases and amylases or their mixtures are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.

The salts of polyphosphonic acids, in particular the sodium salts of 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriamine-pentamethylenephosphonic acid (DTPMP or DETPMP) come into consideration as stabilizers, in particular for per-compounds and enzymes.

The teaching according to the invention is suitable both for the production of washing and / or cleaning agent mixtures, in particular textile detergents in the form of readily water-soluble storage-stable granules, and for the production of active substance concentrates from the field of these working materials, in particular for incorporation into textile detergents, the granules of different active substances contain predetermined mixing ratios. The following case is described here merely by way of example: in order to establish a good storage stability of a dry-type textile detergent suitable for textile washing at low washing temperatures, perborates and bleach activators are separate from one another to be provided in different granules, which are then mixed in predetermined proportions. Both grain types can be produced or formed separately from one another according to the invention and then be mixed with one another in a storage-stable manner. For example, the process according to the invention can be used advantageously for the production of bleach activator granules, as described, for example, in the older German patent application DE 4024759.

Examples

To produce the granular, easily soluble dry concentrates, the components (A) to (K), of which only the components (B) are in liquid form - all other components are solid - in the mixing ratios specified in the table in a ploughshare mixer (Fa Lödige, Germany) mixed thoroughly for one minute. The premix obtained in this way was then fed continuously to a ring die press (pellet press, embodiment DE 3816842, from Schlueter, Germany), the temperable roller (press roll) of which was cooled to 20.degree. Since the temperature generally rises in the product while the process is being carried out, cooling of the pan is necessary. In this way, a maximum product temperature of 50 ° C could be ensured. The diameter of the press channels in the ring die was 1 - 1.5 mm (see Table 1). The distance between the press roller and the ring die was 1.8 - 2 mm (see Table 1). The emerging strand was cut to a length of 1.2-1.5 mm by a knife attached to the outside of the ring die. In addition, the cut granules were rounded off in a Marumerizer-type rounding machine. The stickiness of the particle surface was prevented by powdering by means of the proportion of fine dust produced during the process, so that a separate addition of a further solid was not necessary. The products 1 - 6 thus produced were sieved: fine fraction (smaller than 0.6 mm) and oversize fraction (larger than 1.6 mm) were separated off. The fine fraction of the granules was below 5% in all cases, the oversize fraction was below 1%. The bulk density of the screened products varied between 650 g / l and 770 g / l.

The concentrates produced in Examples 1 to 6 can be mixed directly as detergents or - if desired - with non-pelleted or pelleted but separately prepared formulation components.

Examples 7-15

The compacts according to Example 4, as well as compacts of a number of other recipe combinations designed according to the invention were measured by means of mercury porosimetry. The following parameters were determined:
Total internal volume in mm³ / g
Total porosity in vol .-%
Average pore radius in micrometers
Specific surface area in m² / g
The relative volume distribution in mm³ / g within the following ranges of the respective pore radius (in »m):
0.001 to 0.01; 0.01 to 0.1; 0.1 to 1; 1 to 10 and 10 to 100
The compacts examined were produced as previously given for Examples 1 to 6 and correspond to the following overall formulations:

Example 4:

as previously stated

Example 7:

Bleach activator granules from the following components:
80 wt% TAED
8.0% by weight sodium dodecylbenzenesulfonate (96%)
4.0% by weight of C₁₆₋₁ Tal tallow alcohol sulfate
6.0% by weight of C₁₂₋₁₈ fatty alcohol with 5 EO
2.0 wt% zeolite NaA

Example 8:

Die durch Hg-Porosimetrie erfaßten Meßwerte sind in der nachfolgenden Tabelle 3 zusammengefaßt.

This is also a bleach activator granulate that has the following composition:
85 wt% TAED
10% by weight sodium dodecylbenzenesulfonate (96%)
5.0 wt .-% C₁₂₋₁₈ fatty alcohol with 7 EO
The recipes for the granules or compacts according to Examples 9 to 15 are summarized in Table 2 below. The materials of Examples 11 to 15 in the sense of the invention are molded articles produced by means of the pellet press. By contrast, the granules according to Examples 9 and 10 are extrudates which have been produced by extrusion in a screw extruder with a downstream perforated plate in accordance with the teaching of German patent application DE 39 26 253. These two examples are included here as comparative examples and show in particular when comparing the specific inner ones Surface (Table 3) of the granules significantly lower values than the pellets from the pellet press defined in the sense of the invention.

The measured values determined by mercury porosimetry are summarized in Table 3 below.

Examples 16-28

The formulations of Examples 16-21 summarized in Table 4 below describe special detergent compositions (Special WM) which are compressed into granules with an average particle size in the range from 1 to 1.2 mm. The following applies in detail:

The formulations of Examples 16 and 17 were in turn produced by extrusion in a screw extruder with a downstream perforated plate in accordance with the teaching of German patent application DE 39 26 253 and are therefore comparison products with the formulation mixtures according to Examples 18-21 processed by the pellet press.

Table 5 below summarizes the formulations of Examples 22-28, all of which deal with universal detergents (UWM). Here, too, two representatives are processed by means of extrusion via a screw extruder with a downstream perforated plate in the manner given above (Examples 22 and 23). The same starting recipes are then processed again into pellets via the pellet press in the sense of the invention, the recipe of example 22 corresponding to example 28 according to the invention and the recipe of example 23 corresponding to example 27 according to the invention.

The dissolving time in water (in seconds) is determined on the granulated active compound mixtures according to Examples 16-28 under identical standard conditions in each case. The results obtained are summarized in Table 6 below. The evaluation of the sample groups shows the following:

Examples 16 - 21. Special detergents:

While the pelletized mixtures according to the invention consistently show a dissolving time below 100 seconds, the solubility time of the two extrudates is above 200 seconds.

Examples 22-28. Universal detergent:

In Rohstoffen enthaltenes Wasser wurde nicht separat berücksichtigt.

Tabelle 6 Beispiel Lösezeit (90%ige Auflösung in Wasser unter Standardbedingungen* (sec) Partikelgröße (mm) 16 Spez.WM-Extrudat 252 1,2 17 Spez.WM-Extrudat 230 1,2 18 Spez.WM-Pellet 80 0,4 1,25 19 Spez.WM-Pellet 91 0,4 1,25 20 Spez.WM-Pellet 80 0,4 1,25 21 Spez.WM-Pellet 99 0,4 1,25 22 UWM-Extrudat 324 1,6 23 UWM-Extrudat 282 1,4 24 UWM-Pellet 264 1,2 25 UWM-Pellet 216 1,0 26 UWM-Pellet 378 1,2 27 UWM-Pellets (entsprechend UWM-Extrudat 23) 198 1,0 28 UWM-Pellets (entsprehend UWM-Extrudat 22) 222 1,0 * In ein 1 Liter-Glasgefäß wurden 500 g demineralisiertes Wasser (20 °C) eingefüllt, der Propellerrührer mit einer Drehzahl von 900 Umdrehungen pro Minute eingeschaltet und die Leitfähigkeitsmeßzelle eingetaucht. Danach wurden 5 g des Waschmittels zugegeben. Die Änderung der Leitfähigkeit wurde über einen Schreiber festgehalten. Die Messung erfolgte solange, bis kein Anstieg der Leitfähigkeit mehr feststellbar war. Die Zeit bis zum Erreichen der Leitfähigkeitskonstanz ist die Lösezeit des gesamten Waschmittels (100 %). Die Lösezeit bei 90%iger Auflösung wurde rechnerisch ermittelt. It is interesting to compare the extrudates (22 and 23) with the corresponding pellets (28 and 27). A comparison of the two pairs belonging to each other shows the shorter dissolving time of the pellets compared to the respective extrudate. Examples 24-26 then show, however, that - depending on the recipe - the dissolution of granules according to the invention in pellet form can require a not inconsiderable period of time in individual cases.

Water contained in raw materials was not considered separately.

Table 6 example Dissolving time (90% dissolution in water under standard conditions * (sec) Particle size (mm) 16 World Cup extrudate 252 1.2 17th World Cup extrudate 230 1.2 18th World Cup pellet 80 0.4 1.25 19th World Cup pellet 91 0.4 1.25 20th World Cup pellet 80 0.4 1.25 21 World Cup pellet 99 0.4 1.25 22 UWM extrudate 324 1.6 23 UWM extrudate 282 1.4 24th UWM pellet 264 1.2 25th UWM pellet 216 1.0 26 UWM pellet 378 1.2 27 UWM pellets (corresponding to UWM extrudate 23) 198 1.0 28 UWM pellets (corresponding to UWM extrudate 22) 222 1.0 * 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. 5 g of the detergent were then added. The change in conductivity was recorded by a recorder. The measurement was carried out until there was no longer an increase in conductivity. The time to reach constant conductivity is the dissolving time of the entire detergent (100%). The dissolution time at 90% resolution was calculated.

Claims (21)

1. Free-flowing and storable coarse-particle compacts containing ingredients of detergents and/or cleaning products in concentrated form, produced by the press-moulding of an at least substantially homogenized fine-particle premix of the ingredients to which components liquid at room temperature may also be added in small quantities, characterized in that they contain adhesively bound dry mixtures with apparent densities of at least 500 g/l of

   (a) fine-particle ingredients without pronounced binding or adhesive properties with

   (b) fine-particle ingredients with adhesive or binding properties (adhesive components (b)), have been produced by press-moulding at moderately elevated temperatures, material temperatures of 80°C not being exceeded, and in the substantial absence of shear forces on the fine-particle material which could lead to significant smearing of basically smearable constituents of the mixture and

   (c) contain air in microdispersion in the compact and have an inner surface, as determined by mercury porosimetry, of at least 1 m²/g.
2. Compacts as claimed in claim 1, characterized in that they have apparent densities of the order of 600 g/l or higher, for example in the range up to about 850 g/l.
3. Compacts as claimed in claim 1 or 2, characterized in that they have an inner surface of the order of 1.5 to 2 m²/g or higher and, more particularly, in the range from about 3 to 5 m²/g.
4. Compacts as claimed in any of claims 1 to 3, characterized in that their percentage content of micropores smaller than 1 »m in diameter makes up at least about 30% by volume and preferably at least about 50% by volume of the total porosity.
5. Compacts as claimed in any of claims 1 to 4, characterized in that they contain the components (a) and the adhesive components (b) in quantity ratios which, under the operating conditions prevailing during press-moulding, lead to the borderline for the formation of dimensionally stable compacts, preferred mixing ratios being those which, in addition to the compacts, lead to small quantities of powder in the pressing step.
6. Compacts as claimed in any of claims 1 to 5, characterized in that, to establish firm adhesion in the compact, they contain limited quantities of optionally washing-active mixture constituents liquid at room temperature in conjunction with the solid fine-particle adhesive components (b), these mixture constituents preferably being distributed substantially homogeneously in the compact and having no significant effect on its microporosity.
7. Compacts as claimed in any of claims 1 to 6, characterized in that they contain washing-active mixture constituents and, in particular, organic washing-active constituents as adhesive components (b), preferably surfactant compounds solid at room temperature and/or corresponding polymer compounds of natural and/or synthetic origin which may be activated in their adhesive function through the use of small quantities of constituents liquid at room temperature.
8. Compacts as claimed in any of claims 1 to 7, characterized in that they contain fine-particle adhesive components (b) distributed substantially homogeneously in the mixture which soften at temperatures above 40°C and, in particular, at temperatures in the range from about 45 to 80°C - optionally under the effect of the mixture constituents liquid at room temperature.
9. Compacts as claimed in any of claims 1 to 8, characterized in that they contain the adhesive components (b) in at most substantially the same quantities as the components (a) and preferably in smaller quantities, for example in the range from about 15 to 40% by weight, based on the compacts.
10. Compacts as claimed in any of claims 1 to 9, characterized in that their content of mixture constituents liquid at room temperature is no more than about 10% by weight and is preferably in the range from about 2 to 8% by weight, nonionic surfactants liquid at room temperature, oils and/or limited quantities of water being particularly suitable for use as these mixture constituents.
11. Compacts as claimed in any of claims 1 to 10, characterized in that solid, inorganic and/or organic washing-active mixture components, such as builders, inorganic alkaline and neutral to mildly acidic salts, bleaches, bleach activators and swellable layer silicates are present as components (a).
12. Compacts as claimed in any of claims 1 to 11, characterized in that constituents capable of binding internal water, for example in the form of water of crystallization, are used as components (a).
13. A process for the production of the granular compacts claimed in any of claims 1 to 12, characterized in that the components (a) and adhesive components (b) are mixed at least substantially homogeneously to form a loose material under conditions under which no decidedly solidifying adhesive function is performed, the liquid components used, if any, are mixed in at the same time and the premix is then press-moulded in the substantial absence of shear forces (on the main part of the material) with inclusion of microdisperse air to form compacts, an inner surface - as determined by mercury porosimetry - of at least 1 m²/g being generated and apparent densities of at least 500 g/l being established.
14. A process as claimed in claim 13, characterized in that press-moulding is carried out at a slightly elevated temperature of the loose material which is preferably in the range from about 40 to 80°C and, more preferably, in the range from about 45 to 60°C.
15. A process as claimed in claim 13 or 14, characterized in that press-moulding is carried out in a cavity press, more particularly in an annular cavity press, the loose material being applied to a surface of a rotating multiple-bore cavity, rolled into the bores and, at the same time, compacted by means of a pressing tool rotating on or slightly above the surface of the cavity and extruded in strand-form through the bores and cut into granules, the degree of compaction and the internal porosity of the granules being controllable in particular through the material temperature and by variation of the height of the roller gap between the pressing tool and the surface of the cavity.
16. A process as claimed in any of claims 13 to 15, characterized in that the cavity and the pressing tool are rotated in the same direction, preferably at substantially the same peripheral speeds.
17. A process as claimed in any of claims 13 to 16, characterized in that the pressing tool is cooled to control the temperature of the loose material to be pressed.
18. A process as claimed in any of claims 13 to 17, characterized in that, immediately after leaving the bores of the cavity, the strands are chopped up, preferably by means of stripping blades.
19. A process as claimed in any of claims 13 to 18, characterized in that the compacts are further processed and, in particular, packed in portions, if desired after drying, for example in a fluidized bed dryer, but preferably without additional drying and optionally with a light scattering of powder.
20. A process as claimed in any of claims 13 to 19, characterized in that the components (a) and the adhesive components (b) are mixed in such ratios that small quantities of loose powder, preferably no more than about 10% by weight and, in particular, no more than about 5% by weight of the material discharged from the press, accumulate together with the compacts during the pressing step.
21. A process as claimed in any of claims 13 to 20, characterized in that the material is pressed in bores approximately 0.8 to 1.5 mm in diameter and is preferably cut to lengths of about 1 to 2 mm.