EP0566583A1

EP0566583A1 - Readily soluble dry concentrate containing washing-agent ingredients.

Info

Publication number: EP0566583A1
Application number: EP92900156A
Authority: EP
Inventors: Christiane Zeise; Wilfried Raehse; Jochen Jacobs; Juergen Hoffmeister
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1991-01-08
Filing date: 1991-12-10
Publication date: 1993-10-27
Anticipated expiration: 2011-12-10
Also published as: EP0566583B1; DE59105893D1; WO1992012229A1; ATE124448T1; DE4100306A1; US5587104A; KR100200025B1; KR930703428A; ES2073907T3; JPH06504303A

Abstract

Des produits concentrés secs présentant une faculté d'écoulement et une stabilité au stockage, sous forme de granulés comprimés à gros grains, contiennent des composants à grains fins (a) sans caractéristiques d'adhérence ou de collage marquées, ainsi que des composants de colle à grains fins (b) avec des caractéristiques d'adhérence ou de collage marquées, lesquels sont comprimés sans être soumis à des efforts de cisaillement notables. Les granulés comprimés contiennent de l'air microdispersé, ce qui garantit une grande surface interne du granulé comprimé concentré, et par conséquent une grande vitesse de dissolution du granulé comprimé.Dry concentrate products with flowability and storage stability, in the form of coarse-grained compressed granules, contain fine-grained components (a) without marked adhesion or sizing characteristics, as well as glue components. fine-grained (b) with marked adhesion or bonding characteristics, which are compressed without being subjected to appreciable shear forces. The compressed granules contain microdispersed air, which guarantees a large internal surface area of the concentrated compressed granule, and therefore a high dissolution rate of the compressed granule.

Description

EASILY SOLUBLE DRY CONCENTRATES CONTAINING INGREDIENTS OF DETERGENTS

The invention relates to a new form of offer for ingredients of detergents and / or cleaning agents, in particular textile detergents, as well as detergents and / or cleaning agents designed accordingly and the novel method for their production. It describes in particular the production of a comparatively coarse-grained and storage-stable, free-flowing product 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 detergents and / or cleaning agents with an increased bulk density or agglomerated to form a grain. From the recent past, reference is made to EP 340013 and the documented prior art EP 219328, EP 270240 and GB 1 517713 (all Unilever), EP 229671 and JP 61 069897 (Kao) and EP 220024 (Procter & Gamble) cited therein. Detergent mixtures in granular form with a bulk density of at least 650 g / l are described in the publication cited at the beginning, 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. The granules are to be manufactured in a high-speed mixer / granulator that ensures the process elements of 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. The particle size of the agglomerates obtained in this way is, according to the examples, 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 367339. Here too, the production of a comparatively fine-particle detergent granulate with bulk densities of at least 650 g / l is carried out 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 at the same time compressed, while in a subsequent second process step the granulation takes place at lower processing speeds in the period of about 1 to 10 minutes, but also with simultaneous compression of the material. The finished material should be dried and / or converted into the free-flowing state by cooling. 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 described two-stage process a significant increase in the bulk density - for example to values up to approximately 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 / 1 with a particle porosity in the range from 45 to 50%, the bulk densities of the two-stage compressed materials are in the range from about 700 to 900 g / 1, while the particle porosity is Values below 20% and in particular below 10% can be reduced. The particle size of the compacted material can reach the value of about 1 mm, but is in general also clearly below this.

The applicant for the development described below describes in German patent application DE 3926253 a new way of producing solid and free-flowing granules of detergents and / or cleaning agents, in particular corresponding textile detergents. These granules are distinguished by bulk densities of at least about 700 g / 1, in particular those in the range from about 850 to 1000 g / 1. The granules are produced by extrusion with the use of the smallest possible amounts of liquid phase, in particular water, and are 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 with simultaneous plasticization of 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 acted upon with further active ingredients and / or dried to the granular, free-flowing material, if necessary.

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 clear that an increase in the inner grain surface, in particular by inclusion and protection of the proportion of the finest microdisperse air inclusions, can have an influence on 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 mixture of substances. In particular, smearing of the individual solid particles with one another should be prevented as far as possible, as occurs, for example, when processing the corresponding solid mixtures in screw extruders due to their strong shear action. For the area of auxiliaries and ingredients of washing and / or Cleaning agents can be of particular importance for this aspect because, as a rule, heavily lubricated components such as surfactants, polymeric builder substances and other mixture components which can be deformed or even spreadable under pressure are also used here.

In further aspects of the object according to the invention, it should nevertheless be possible to produce concentrates which are stable in free-flowing and have a high breaking strength and a low tendency for the individual grains to adhere 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 insert materials.

Accordingly, the invention relates in a first embodiment to dry concentrates, containing ingredients of detergents and / or cleaning agents, in the form of free-flowing and storage-stable, coarse-grained compacts, produced by compression molding an at least largely homogenized fine-grained premix of the ingredients, the components which are liquid even at room temperature can be added in small quantities. These compacts are characterized in the sense of the teaching according to the invention in that they consist of firmly bonded dry mixtures

(a) fine-grained ingredients with no pronounced adhesive or adhesive properties (components (a))

(b) contain fine-grained ingredients with adhesive or adhesive properties (adhesive components (b)). The compacts are to be formed by shaping the pressing with the greatest possible exclusion of shear forces on the - 73 -

Pressing mixture of substances has been produced and contained at moderately elevated temperatures

(c) Air in microdisperse distribution in the compact.

In preferred embodiments, the average inner surface of the compacts, determined by means of mercury porosity, is at least about 1 m 2 / g, with significantly higher values, for example those above 1.5 m ² / g and in particular at or above 2π) 2 / g, are 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 whose proportion of micropores with a diameter below 1 μm makes up at least about 20-25% by volume and in particular at least about 30% by volume, based on the total porosity. Particularly preferred compacts are characterized by corresponding microporous portions with pore diameters below 1 μm 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 μm.

In a further embodiment, the subject of the invention is a process for the production of these granular compacts, this process being characterized in that the components (a) and the adhesive components (b) as fine-grained material are at least largely homogeneous under conditions to loosen them Bulk mixed, under which there is still no pronounced solidifying adhesive function. If desired, liquid components to be used in this case - which are, however, only used in very limited quantities, 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 by means of 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 roller 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, a variation of the roll gap height between the pressing tool and the die surface and the operating parameters of the ring die press described in detail below make it possible to control both the desired degree of compaction and the internal porosity of the granulate.

The drying concentrates according to the invention are produced in two successive working steps:

In the first step, solid fine-grained ingredients of detergents and cleaning agents, which preferably have no particles with diameters above 100 μm, are essentially in dry form and can be assigned to two different substance classes, are mixed as homogeneously as possible. The first class of substances are ingredients without pronounced adhesive or 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 the action of pressure and temperature with subsequent cooling, form a certain adhesive and adhesive strength with respect to the adjacent solid particles. 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 which are used in practice and are solid at room temperature are suitable, as are corresponding ampholytic or zwitterionic surfactants. 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 strengthening the compacts according to the invention to strengthen 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, optionally 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 called co-builders are usually used to inactivate the 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 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 which are already liquid at room temperature. Nonionic surfactants which are liquid at room temperature are now regular active ingredient constituents in detergent and cleaning agent mixtures and, accordingly, are also important mixture constituents in the context of the teaching of 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 as part of the preparation of the mixture to be pressed. In particular, it can be used together with representatives of the substance classes (a) and / or (b) mentioned above. For example, aqueous pastes of anionic surfactants and / or of non-adhesive active ingredients according to (a), such as finely divided sodium zeolite, can 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 builder 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 hydrogen sulfate and perborate. General specialist knowledge in the particular recipe sought permits 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 the substance classes (a) and (b), which are predominantly 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 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 internal surface area 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 makes use of 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 also be used are used in such mixing ratios that among one another the conditions of the pressing in the second process stage as the primary product of the extrusion, in addition to the desired compacts, just the first traces or small amounts of powdered material which has not yet solidified are pressed out. The stickiness of the mixtures in the second The processing stage is here coordinated with one another in such a way that, under the working conditions used, the mass is precisely in the limit range 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 powdery extruded fractions can, for example, make up 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 then takes on 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 nevertheless maintenance of the microporous structure in this second work 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 implementation of this concept, working in a ring die press has proven to be sensible, as is shown, for example, in DE 38 16842. 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 jacket surfaces 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 matched to one another and adjusted to one another such that no or practically no shear forces are exerted on the mixture introduced into the interior of the ring die. The objective according to 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 is 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 m ^ / g, in particular in the range from about 3 to 5 m ^ / g. Values of this size can only be set by keeping the percentage of micropores with a diameter below 1 μm, preferably below 0.1 μm or even below 0.01 μm, comparatively high.

However, the processing of the mixture homogenized in the first working step with the exclusion of significant shear forces also leads to further advantages. The individual constituents of the mixture lie next to one another individually 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 re-dissolving 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, it is not necessary to detach, for example, 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 16842. 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. In a preferred embodiment, material temperatures of approximately 80 ° C., preferably approximately 70 ° C., are not exceeded within the ring die. Lower limit values for the material temperature 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 region of 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 is also a determining factor, inter alia, for the mixing ratios of the dry components (a) to the adhesive components (b) in the multi-component 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, then in the ring matrix Press bulk densities of the extrudates extruded in the form of strands and preferably immediately thereafter cut to the grain shape of at least 500 g / l. The bulk densities of the granular compacts described according to the invention are preferably at or above about 600 g / 1, with significantly higher values being set, for example those in the range up to about 900 g / 1 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 m, the compacts being able to be of a rod-shaped or spherical shape 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 powders. As already indicated, the suitable 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 subordinate powder component, which is then used in the subsequent rounding to powder the primary granulate . The compacts thus produced 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.

General information on the list of suitable active substances and on the composition of suitable active substance mixtures follows, 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 on the basis of general specialist knowledge is possible in the light of the information on the implementation of the method according to the invention and the working conditions used here. 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.

Suitable anionic surfactants are, for example, soaps made from natural or synthetic, preferably saturated, fatty acids. Soap mixtures derived from natural fatty acids, for example coconut, palm kernel or taig fatty acids, are particularly suitable. Preferred are those which are composed of 50 to 100% of saturated Ci2-I8 "'^7e' * ^{: 'ts} ^ ^urese if ^{en un (} - ^to 0 ^D1S 50% of oleic acid soap. Further suitable synthetic anionic surfactants are those of the type of Sulfonates and sulfates.

Suitable surfactants of the sulfonate type are alkylbenzenesulfonates, preferably C9-Ci3-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from Ci2-i8-M ° no ° olefins with an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from Ci2-18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. are lent, and in particular the esters of sulfo fatty acids (ester sulfonates), for example the sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Suitable surfactants of the sulfate type are the natural Schwefelsäuremonoester from primary alcohols and synthetic origin that is, fatty alcohols from, for example, coconut oil fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, Myrjstyl-, palmityl or stearyl alcohol, or the Cιo-20 ~ O ° ^χ - alcohols, and those of 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_n alcohols with an average of 3.5 mol of ethylene oxide, are also suitable. Sulfated fatty acid onoglycerides 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 content of anionic surfactants or anionic surfactants in the detergents according to the invention 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 and 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 or tallow fatty alcohols, on oleyl alcohol, on oxo alcohols, or on secondary alcohols having 8 to 18, preferably 12 to 18, carbon atoms.

In addition to the water-soluble nonionics, non-or not completely water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble, nonionic or anionic surfactants. In addition, nonionic surfactants which can also be used are alkyl glycosides of the general formula R-0- (G) _x , in which R is a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, C-methyl-branched Atoms means G is a symbol which stands for a glycose unit with 5 or 6 C 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.

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 μm. 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 from 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 copoly 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 arbonic 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 ratio θ: Siθ2 such as 1: 1 to 1: 3.5 can be used.

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.

Graying inhibitors have the task of keeping the dirt detached from the fiber 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. Carboxy ethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone are preferably used, in particular in amounts of 0.1 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 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. As a foam-soaps are therefore such soaps of natural and synthetic origin which have a high proportion of Ci8-24-f ^re ^'tts äuren suitable. Suitable non-surfactant-like foam inhibitors are organopolysiloxanes and their mixtures with micro-fine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Bisacylamides derived from Ci2-20 ^-A l * ^c yl ^{aπl '} ' ^{nen and} * C2-6 dicarboxylic acids can also be used. Mixtures of various 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.

Among the compounds which provide H2O2 in water and which serve as bleaching agents, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other 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.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the compositions. 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, furthermore carboxylic acid anhydrides and esters of polyols, such as glucose pentaacetate. The detergents can contain, as optical brighteners, derivatives of di-amino-stilbenedisulfonic acid or its alkali metal salts. Suitable are, 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 similar structure which are used instead of Morpholino group carry 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; for example 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 aylases or their mixtures are possible. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. 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-l, l-diphosphonic acid (HEDP) or diethylenetriamine-pentamethylene-phosphonic acid (DTPMP or DETPMP) are suitable 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 ingredient concentrates from the field of these agents, in particular for incorporation into textile detergents, the granules of different types Contain active ingredients in predetermined mixing ratios. The following case is described here merely by way of example: in order to achieve 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 stored in a mixture 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.

B e i s p i e l e

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 ° C. Since the temperature generally rises in the product while the method 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 roll 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-to-length granules were rounded in a Marumerizer-type rounding machine. The stickiness of the particle surface was prevented by powdering by means of the fine dust fraction arising during the process, so that a separate addition of a further solid was not necessary. Products 1-6 thus produced were sieved: fine fraction (less than 0.6 m) and oversize fraction (greater than 1.6 mm) were separated off. The fine fraction of the granules was below 5% in all cases, the oversize 1 was below 1%. The bulk density of the screened products varied between 650 g / 1 and 770 g / 1.

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

(Composition in% by weight) Examples: 1 2 3 4 * 5 *

28 22 16 16.5 6 5

2.2 2.2

1.8 1.8 3.5

10

0.8 0.8 Table 1 (continued)

(Composition in% by weight) Examples: 1 2 3 4 * 5 *

(K) anorg. Salts (K 1) NaHSO4-H ₂ 0 (K 2) Na2C03 (K 3) Na2S04 (K 4) NaHC03

Diameter die (mm) Distance Koller-die (mm)

Bulk weight (g / 1) 650 680 660 720 770 810

These are recipes which, after the pelletization, also contain 5.5% by weight of TAED pellets, 1.5% by weight of enzymes and 0.5% by weight of perfume, in each case based on the total Pellet and additives were mixed.

Examples 7-15

The compacts according to Example 4, as well as compacts according to the invention in a number of further recipe compositions were measured by means of mercury porosimetry. The following parameters were determined:

Total internal volume in rnm ^ / g

Total porosity in vol .-%

Average pore radius in micrometers

Specific surface area in π.2 / g The relative volume distribution in mπß / g within the following

Ranges of the respective pore radius (in μm):

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 Ci5_i8 tallow alcohol sulfate

6.0% by weight Ci2-i8 ~ fatty alcohol with 5 E0

2.0 wt% zeolite NaA

Example 8:

This is also a bleach activator granulate that has the following composition:

85 wt% TAED

10% by weight sodium dodecylbenzenesulfonate (96%)

5.0% by weight Ci2-i8 fatty alcohol with 7 E0

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. In 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 3926253. 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.

Table 2

Examples: 9 10 11 12 13 14 15

Zeolite NaA

Na-dodecy1benzo1su1fonat

Maleic / acrylic acid copolymer

Na2S04

NaHSθ4. H2O

Ci6_i8 fatty alcohol with 20 E0

Cu olsulfonate

NaHC03

50% oleyl cetyl alcohol + 5 EO

50% oleyl cetyl alcohol + 10 E0} J 1.0 1.4 2

80% Cχ2-i8 fatty alcohol + 5 E0

20% Cχ2-i8 fatty alcohol + 3 E0 J

Ci6-i8 fatty alcohol with 5 E0 1.3 0.8 added H2O 8.3 8.8

Fatty acid aminoamide (tallow amide B,

Commercial product of the applicant) 0.5 0.9

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

In- Inner Relative Volume (mrn ^ / g) in the range (μm) play total- 0.001-0.01 0.01-0.1 0.1-1 1-10 10-100 Vol.mm ^ / g

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 recipes 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 3926253 and are thus comparative products to the recipe 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 duration of the two extrudates is above 200 seconds. Examples 22-28. Universal detergent:

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 in individual cases take a not inconsiderable period of time.

Table 4: Special detergents (Special WM)

Examples: 16 17 18 19 20 21

Sodium dodecylbenzene sulfonate (96%) 13.517.635.035.035.035.0 zeolite NaA 25.437.035.030.025.020.0 50% oleyl cetyl alcohol + 5 E0 1

50% oleyl cetyl alcohol + 10 E0 J 1.0 1.4 1.0 1.0 1.0 1.0 tallow amide B 0.5 0.9 -

Maleic acid acrylic acid

Copolymer 3.0 4.0 2.0 2.0 2.0 2.0

Na ₂ Sθ4 45.629.5 17.0 17.0 17.0 17.0

Na2CO3

NaHSθ4.H2θ tallow alcohol + 20 E0 cumene sulfonate NaHC03

Tallow alcohol + 5 E0 added H2O

Water contained in raw materials was not considered separately. Table 5: Universal detergent (UWM)

Examples: 22 23 24 25 26 27 * 28 *

Sodium dodecy1benzo1 sulfonate (96%) 22.4 11.1 13.6 13.7 13.6 zeolite NaA 2.6 21.7 23.6 13.7 13.5

Tallow alcohol + '5 EO 1.2 1.8 0.8 0.9 0.9 maleic-acrylic acid-

Copoly erisat 5.0 6.4 5.6 7.1 6.4

Na ₂ CO 3 9.0 16.6 16.9 20.5 20.5

80% Ci2-i8 fatty alcohol with 5 E0

20% Ci2_i4 fatty alcohol with 3 E0 2.3 4.3 - 6.0 6.1

Sodium silicate

(Na2θ: Siθ2 1: 3.0) - 1.8 5.4 2.1 2.1 sodium perborate monohydrate 16.0 17.8 18.0 foam inhibitor concentrate 5.2 - zeolite-containing carrier bead (Wessalith ( ^R ) CD, Handels ¬ product from Degussa,

Federal Republic of Germany) 31.3 - - 22.2 22.5 Small components (dye, perfume, inorganic

Salts) 1.5 1.4 0.9 1.8 2.3

H ₂ 0 2.3 16.3 13.4 12.0 11.7

Ci2-i8 sodium fatty acid soap 1.2 0.8 1.8 - 0.4

Example 27: corresponds to Example 23 Example 28: corresponds to Example 22 Table 6

* 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 any increase in conductivity. The time until the conductivity is constant is the dissolving time of the entire detergent (100%). The dissolution time at 90% resolution was determined by calculation.

Claims

Patent claims

1. dry concentrates, containing ingredients of detergents and / or cleaning agents, in the form of free-flowing and storage-stable coarse-grained compacts, produced by compression molding an at least largely homogenized fine-grained premix of the ingredients, to which liquid components can also be added in small quantities at room temperature, characterized in that they consist of firmly bonded dry mixtures

(a) Fine-grained ingredients with no pronounced adhesive or adhesive properties

(b) contain fine-grained ingredients with adhesive or adhesive properties, which have been produced by shaping pressing at moderately elevated temperatures without the action of significant shear forces on the fine-grained material unc

(c) Air in microdisperse distribution contained in the compact.

2. compacts according to claim 1, characterized in that they have bulk densities of at least about 500 g / 1, preferably at or above about 600 g / 1, for example in the range up to about 850 g / 1.

3. compacts according to one of claims 1 or 2, characterized in that they have an inner surface - determined by means of mercury porosimetry - of at least 1 m2 / g, preferably at or above 1.5 - 2 m2 / g, which can be in particular in the range from about 3 to 5 m ² / g.

4. compacts according to one of claims 1 to 3, characterized in that their proportion of micropores of a diameter below 1 micron makes up at least about 30 vol.%, Preferably at least about 50 vol.% Of the total porosity.

5. compacts, according to one of claims 1 to 4, characterized in that they contain the components (a) to the adhesive components (b) in quantitative ratios which, under the working conditions of compression, lead to the border area of the formation of dimensionally stable compacts, Mixing ratios are preferred which, in the shaping processing step, lead to small amounts of powdery material in addition to the compacts.

6. compacts according to one of claims 1 to 5, characterized in that to form the adhesive material composite in the compact together with the solid, fine-particle adhesive components (b), limited amounts of mixture constituents which are liquid at room temperature with or without their own action for washing and / or Contain cleaning agents, which are preferably largely homogeneously distributed in the compact and are present without substantial impairment of the microporosity.

7. compacts according to one of claims 1 to 6, characterized in that they contain, as adhesive components (b), mixture components with their own action in detergents and / or cleaning agents, and in particular corresponding components of an organic nature, solid surfactant compounds and / or corresponding polymer compounds of natural and / or synthetic origin are preferred, which can be activated in their adhesive function by using small amounts of liquid constituents at room temperature.

8. compacts according to any one of claims 1 to 7, characterized in that they contain adhesive components (b) in a finely particulate and substantially homogeneously distributed form in the substance mixture, which - if appropriate with the participation of the mixture components which are liquid at room temperature - in the temperature range above Soften at 40 ° C, especially at temperatures of around 45 - 80 ° C.

9. compacts according to one of claims 1 to 8, characterized in that they contain the adhesive components (b) at most approximately equal in quantity to the Contain components (a), but smaller proportions of mixture (b) are preferred, for example in the range of about 15-40% by weight, based on the compacts.

10. compacts according to any one of claims 1 to 9, characterized in that their content of mixture constituents which are liquid at room temperature does not make up more than about 10% by weight and is preferably in the range of about 2-8% by weight, the corresponding being Components, in particular nonionic surfactants, oils and / or restricted amounts of water which are liquid at room temperature, can be considered.

11. compacts according to one of claims 1 to 10, characterized in that as components (a) finely divided solid inorganic and / or organic mixture components with their own action in detergents and / or cleaning agents such as builders or builders, an¬ organic alkaline and neutral to light acidic salts, bleaching agents, bleach activators and swellable layered silicates are present.

12. compacts according to one of claims 1 to 11, characterized in that components are used as components (a) which are capable of internal water binding - for example in the form of water of crystallization.

13. A process for the production of the compacts according to one of claims 1 to 12, characterized in that the components (a) and adhesive components (b) are mixed at least largely homogeneously under such conditions to form a loose premix, under which there is still no markedly solidifying adhesive function , mixes in the liquid components that are used, if desired, and compresses the premix to form compacts, with the greatest possible exclusion of shear forces on its main mass, including micro-dispersed air.

14. The method according to claim 13, characterized in that the compression is carried out at a slightly elevated bulk material temperature, which is preferably in the range from approximately 40 to 80 ° C., in particular approximately 45-60 ° C.

15. The method according to any one of claims 13 or 14, characterized gekennzeich¬ net that the compression is carried out by means of a die press, in particular in a ring die press, the bulk material is applied to a surface of a rotating die having bores and by means of a or slightly above the die surface of the rotating pressing tool is rolled into the bores under compression and pressed through it in a strand-like manner and cut into granules, the degree of compaction and the internal porosity of the granules being adjusted in particular by checking the temperature of the material and by varying the roll gap height between the pressing tool and the die surface become.

16. The method according to any one of claims 13 to 15, characterized in that the die and the pressing tool are driven with the same direction of rotation, the setting of essentially identical jacket speeds being preferred.

17. The method according to any one of claims 13 to 16, characterized in that the pressing tool is cooled and the temperature of the bulk material to be pressed is thereby regulated.

18. The method according to any one of claims 13 to 17, characterized in that the pressed masses are cut to length immediately after emerging from the bores of the die, preferably by means of a doctor blade.

19. The method according to any one of claims 13 to 18, characterized in that the compacts, if desired after a drying, for example in a fluidized bed dryer, but preferably without additional drying, further processed, if necessary with light powdering, in particular packaged.

20. The method according to any one of claims 13 to 19, characterized in that one works with such mixing ratios of the components (a) to the adhesive components (b) that small amounts of unbound powder are obtained during the molding pressing together with the compacts, which are preferably account for no more than about 10% by weight and in particular no more than about 5% by weight of the discharge from the press.

21. The method according to any one of claims 13 to 20, characterized in that the material is pressed into bores with a diameter of about 0.8 to 1.5 mm and is preferably cut to lengths in the range of about 1 to 2 mm.