EP1167509A1 - Detergent granules with an improved dissolution rate - Google Patents

Abstract

Surfactant granulate comprises 75-97 wt.% alkysulfate, 3-25 wt.% alkenyl sulfate and water and optionally electrolyte salts to 100 wt.%.

Description

The invention is in the field of solid washing, rinsing and cleaning agents and relates to new surfactant granules, which are characterized by improved cold water solution behavior Process for their preparation and their use.

State of the art

Nowadays, surfactants are preferred for the production of solid washing, rinsing and cleaning agents used in granular, practically anhydrous form. Have to produce such supply forms the most varied of processes have proven to be suitable. Common to those in the trade However, surfactant granules that they have an inadequate dissolution rate in particular in cold water. Detergent tablets based on anionic or nonionic For this reason, surfactants can be produced despite the use of considerable amounts of explosives are not used directly in the washing-up chamber of the washing machine, but must be added directly to the wash liquor. Anionic surfactants are important ingredients for Detergents and cleaning agents. For use in powdery cleaning agents with high Bulk density or in lumpy detergents such. B. Detergent tablets are used with alkyl sulfates - Also called fatty alcohol sulfates (FAS) - preferably as a powder or granules. This FAS powder or granules are usually spray drying or drying in a continuous Fluid bed produced. In particular C16 / 18 fatty alcohol sulfate granules, which by drying and granulation in a continuous fluidized bed show at low Temperatures insufficient solubility and dispersibility. There is a risk that straight in the case of colored laundry that is to be washed in the low temperature range, traces of the detergent remain.

Because the solution to the problem for the cold washing process and for the use of detergent compactates is of great importance, the object of the present invention was long-chain alkyl sulfate granules with improved dissolving and dispersing behavior at low temperatures To make available and through the use of these granules the dissolution behavior of detergent compactates to improve.

Description of the invention

(a) 75 - 97 Gew. % eines Alkylsulfates,

(b) 3 - 25 Gew. % eines Alkenylsulfates,

mit der Maßgabe, dass sich die Mengenangaben mit Wasser und gegebenenfalls Elektrolytsalzen zu 100 Gew. % ergänzen und ein Verfahren zur Herstellung dieser Tensidgranulate.
Ein weiterer Gegenstand der Erfindung ist die Verwendung der erfindungsgemäßen Tensidgranulate in Wasch-, Spül- und Reinigungsmitteln.The invention relates to surfactant granules consisting of

(a) 75-97% by weight of an alkyl sulfate,

(b) 3 - 25% by weight of an alkenyl sulfate,

with the proviso that the quantities with water and optionally electrolyte salts add up to 100% by weight and a process for the production of these surfactant granules.
Another object of the invention is the use of the surfactant granules according to the invention in washing, rinsing and cleaning agents.

It has surprisingly been found that the preparations according to the invention dissolve spontaneously in water even at low temperatures. Detergent solids which contain the granules according to the invention have a significantly shorter disintegration time and dissolution rate. Even the addition of small amounts of alkenyl sulfate leads to a significantly better dissolution rate at low temperature (temperatures of 25 ° C ± 10 ° C).
This improved dissolution behavior can also be observed for alkyl sulfate granules which are produced in the continuous fluidized bed. Likewise, the improved dissolving behavior in detergent tablets containing explosives (based on cellulose-based explosive systems) also leads to an improved disintegration of the compact.

alkyl sulfates

Alkyl sulfates, which are also often referred to as fatty alcohol sulfates and form the surfactant component (a), are to be understood as the sulfation products of primary saturated alcohols which follow the formula (I) R ¹ O-SO ₃ X

in which R ^{1 is} a linear or branched, aliphatic alkyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates which can be used for the purposes of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, arachselyl alcohol, aridyl alcohol, elaidyl alcohol, ela-alcohol alcohol, and erucyl alcohol and their technical mixtures, which are obtained from high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The sulfation products can preferably be used in the form of their alkali metal salts, and in particular their sodium salts. Alkyl sulfate powder or needles based on C _16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable carbon chain distribution in the form of their sodium salts are particularly preferred.

alkenylsulfates

Alkenyl sulfates, which are also often referred to as ocenol sulfates, are to be understood as meaning the sulfation products of primary mono- and polyunsaturated alcohols which follow the formula (II) R ² O-SO ₃ X

in which R ^{2 is} a linear or branched, mono- or polyunsaturated aliphatic alkenyl radical having 12 to 22, preferably 16 to 18 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Alkenyl sulfates which have an iodine number between 5 and 60, preferably 10 and 20 (palmocenol) or 50-55 HD ocenol, and preferably based on C _16/18 alcohols, are particularly preferred.

Residual moisture and electrolyte salts

Depending on the production process, drying conditions and storage conditions, residual moisture of 0.5 to 7% by weight, preferably 0.5 to 1.5% by weight, of residual moisture is present in the surfactant granules according to the invention.
Likewise, due to the production process, free sodium hydroxide solution, 0.2 to 1.2% by weight, preferably 0.4 to 0.8% by weight, free fatty alcohols 0.5 to 6% by weight, preferably 0.5 to 4% by weight .%, and different amounts of electrolyte salts, such as, for example, sodium sulfate 0.2 to 10% by weight, preferably 0.5 to 5% by weight and / or sodium chloride 0 to 2% by weight, preferably 0 to 0.5% by weight , contained in the surfactant granulate.

production method

The surfactant granules are produced by the customary known processes, which include SKET granulation, spray drying and dropletization.
The granules can also be produced by compacting, which includes press agglomeration, extrusion, roller compaction, pelleting and tableting as work processes.

fluidized bed

A particularly preferred method for producing the surfactant granules according to the invention is in subjecting the mixtures to fluidized bed granulation ("SKET" granulation). this includes is to be understood as a granulation with simultaneous drying, preferably batchwise or done continuously. The mixtures of surfactants and disintegrants can be dried Condition as well as used as an aqueous preparation. Preferred fluidized bed apparatus have floor slabs measuring 0.4 to 5 m. Preferably the Granulation was carried out at fluidizing air speeds in the range from 1 to 8 m / s. The discharge of the Granules from the fluidized bed are preferably made by size classification of the granules. The Classification can be done, for example, by means of a screening device or by an opposing one Air flow (classifier air) takes place, which is regulated so that only particles above a certain particle size removed from the fluidized bed and smaller particles retained in the fluidized bed become. The inflowing air usually settles out of the heated or unheated classifier air and the heated soil air together. The soil air temperature is between 80 and 400, preferably 90 and 350 ° C. A starting mass is advantageously added at the beginning of the granulation, for example, a surfactant granulate from an earlier test approach.

Drying and granulating in the flash dryer

The simultaneous drying and granulation can also be carried out in a horizontally arranged thin-film evaporator or dryer with rotating internals, as is sold, for example, by VRV under the name "Flashdryer" or by VOMM under the name "Turbodryer". In simple terms, this is a pipe that can be tempered at different temperatures across several zones. The paste-like feed material, which is metered in via a pump, is flung against the heated wall by means of one or more shafts, which are provided with blades or shares of flies as rotating internals, on which the drying takes place in a thin layer, typically 1 to 10 mm thick he follows. In the sense of the invention, it has proven to be advantageous to apply a temperature gradient from 130 (product inlet) to 20 ° C. (product discharge) to the thin-film evaporator. For this purpose, for example, the first two zones of the evaporator are heated to 120 to 130 ° C and the last are cooled to 20 ° C. The thin-film evaporator or dryer is operated at atmospheric pressure and gassed in countercurrent with air, but preferably with an alkaline gas stream, for example ammonia (throughput 50 to 150 m ³ / h). The inlet temperature of the gas is usually 20 to 30, the outlet temperature 90 to 110 ° C. The throughput of the surfactant pastes is of course dependent on the size of the dryer, for example 5 to 25 kg / h. It is advisable to temper the pastes at 40 to 60 ° C. during the feed and to add 0.05 to 0.5% by weight, based on the solids content, of alkali carbonate, preferably sodium carbonate, to avoid hydrolysis processes.

Another preferred embodiment of the method according to the invention is the aqueous Mix surfactant on the hot contact surface with the already dried end product. For this is a partial product stream of about 10 to 40, preferably 15 to 25 wt .-% - based on the mass flow the paste used - removed at the dryer outlet and using a solid dosing screw dosed directly into the apparatus in the immediate vicinity of the paste inlet. Through this Measure succeeds in reducing the stickiness of the aqueous surfactant and in better wall contact of the product on the entire available surface. hereby product transport is evened out and product drying intensified. At the same time by adding the end product, the grain size distribution of the granulate is targeted to coarser products postponed, i.e. the undesirable proportion of fine dust can be significantly reduced. With this Measure is an increase in throughput based on analog process conditions without solids recycling to reach.

After drying, it has also proven to be very advantageous, which is still about 50 to 70 ° C To give granules on a conveyor belt, preferably a vibrating trough or the like and there quickly, i.e. within a dwell time of 20 to 60 s, with ambient air at temperatures of cool about 30 to 40 ° C. To further improve resistance to unwanted The granules of particularly hygroscopic surfactants can also be absorbed subsequently Powder off by adding 0.5 to 2% by weight of silica.

Other procedures

In a further embodiment, the surfactant granules are produced by means of an extrusion , as are described, for example, in European patent EP 0486592 B1 or international patent applications WO 93/02176 and WO 94/09111 and WO 98/12299 . In this case, a solid premix is pressed in the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate after it has emerged from the hole shape by means of a cutting device. The homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work. Preferred plasticizers and / or lubricants are surfactants and / or polymers. To explain the actual extrusion process, reference is hereby expressly made to the patents and patent applications mentioned above. The premix is preferably fed to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guidance, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature. Under the shear action of the extruder screws, the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally, under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knife. The hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension. In this way, the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use. In general, particle diameters up to at most 0.8 cm are preferred. Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm. The length / diameter ratio of the chopped-off primary granules is preferably in the range from about 1: 1 to about 3: 1. It is also preferred to feed the still plastic primary granules to a further shaping processing step; edges present on the crude extrudate are rounded off, so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired, small amounts of dry powder, for example zeolite powder such as zeolite NaA powder, can also be used in this step. This shape can be done in standard rounding machines. It is important to ensure that only small amounts of fine grain are produced in this stage. Drying, which is described as a preferred embodiment in the abovementioned prior art documents, is subsequently possible, but not absolutely necessary. It may just be preferred not to carry out any drying after the compacting step. Alternatively, extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (from Amandus Kahl) or in the Bepex extruder. The temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is preferably designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded. The duration of the temperature influence in the compression range of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.

Another method for producing the surfactant granules, the granulation and compacting, can be carried out in the manner known for detergents. It is particularly possible to compact the granules before, during or after the granulation. From an application point of view, it has proven to be very favorable if the surfactant granules used have a grain size in the range from 0.01 to 6, preferably 0.1 to 5 mm, and in particular the proportion which is not in the range from 0.1 to 5 mm is less than 25% by weight.

The surfactant granules can be produced by means of roller compaction . Here, the premix is metered in between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe. The rollers exert a high line pressure on the premix and can be additionally heated or cooled as required. When using smooth rollers, smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which, for example, certain shapes of the later detergent particles can be specified. The sliver belt is subsequently broken up into smaller pieces by a knocking-off and crushing process and can be processed into granules in this way, which can be refined by further known surface treatment processes, in particular in an approximately spherical shape. In the case of roller compaction, too, the temperature of the pressing tools, that is to say the rollers, is preferably at a maximum of 150 ° C., preferably at a maximum of 100 ° C. and in particular at a maximum of 75 ° C. Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder. It is further preferred here that the duration of the temperature effect in the compression range of the smooth rollers or with depressions of a defined shape is a maximum of 2 minutes and in particular ranges between 30 seconds and 1 minute.

The surfactant granules can also be produced by pelleting . The premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization. In conventional embodiments of pellet presses, the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device. The most varied configurations of the pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers. The press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation.

An apparatus suitable for carrying out the method is described, for example, in German laid-open specification DE 3816842 A1 . The ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge. Here, the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved. Of course, it is also possible to work with heatable or coolable rollers in the pelletizing in order to set a desired temperature of the premix. In pelletizing, too, the temperature of the pressing tools, that is to say the pressure rollers or pressure rollers, is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at most 75 ° C. Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.

All processes have in common that the premix is compressed and plasticized under pressure and the individual particles are pressed together and the porosity is reduced be liable. In all processes, the tools can be heated to higher temperatures or cool to dissipate the heat generated by shear forces.

The dropletization is a process for the production of surfactant granules, in which a stream of an aqueous surfactant preparation is dripped by vibration with the aid of a pouring plate and the drops are directed towards a gaseous drying agent which evaporates the water components and thereby dries the granules.
Granulation by dropping using a vibrating pouring plate is already known for the processing of synthetic waxes, resins and low-viscosity polyesters. Corresponding components are sold, for example, by Rieter-Automatik under the name "Droppo Line" for use in textile technology. Casting plates are preferred which are shaped as perforated disks, through the openings of which the drops can then drip into the spray tower. The performance of such perforated disks can preferably be in the range from 100 to 800 kg / h and is in particular about 500 kg / h, the diameter of the bores is between 0.5 (average diameter of the granules 0.8 mm) and 1.4 mm (Average diameter of the granules 2.5 mm). The oscillation frequency which is imposed on the aqueous surfactant preparations is typically in the range from 100 to 1000 and preferably 500 to 800 Hz. In comparison with the conventional processes, only a slight excess pressure (typically: 10 to 100 mbar) is used. Drying within the spray tower can be carried out with hot air or hot combustion gases at temperatures, for example in the range from 100 to 150 ° C., in countercurrent, as is adequately described in the prior art. The granules are approximately spherical and then have an average diameter in the range from 1 to 2.5 mm, depending on the openings in the perforated plate and the frequency. The proportion of dust, ie particles with particle sizes smaller than 0.5 mm, is practically zero.

Industrial applicability

(a) 75 - 97 Gew. %, vorzugsweise 85 - 95 Gew.% eines Alkylsulfates,

(b) 3 - 25 Gew. %, vorzugsweise 5 - 15 Gew.% eines Alkenylsulfates
mit der Maßgabe, dass sich die Mengenangaben mit Wasser und gegebenenfalls Elektrolytsalzen zu 100 Gew. % ergänzen

Ein weiterer Gegenstand der Erfindung betrifft die Verwendung der Tensidgranulate zur Herstellung von festen Wasch-, Spül- und Reinigungsmittel, in denen sie in Mengen von 1 bis 90, vorzugsweise 5 bis 50 und insbesondere 10 bis 25 Gew.-% - bezogen auf die Mittel - enthalten sein können. Die Mittel können dabei sowohl in Form von Pulvern, Granulaten, Extrudaten, Agglomeraten oder insbesondere Tabletten vorliegen und weitere typische Inhaltsstoffe beinhalten.
Vorzugsweise finden sie Verwendung zur Herstellung von Waschmittelfestkörpern, da gerade in Festkörperformulierungen die Auflösegeschwindigket eine kritische Größe darstellt.The surfactant granules according to the invention contain

(a) 75-97% by weight, preferably 85-95% by weight of an alkyl sulfate,

(b) 3 to 25% by weight, preferably 5 to 15% by weight of an alkenyl sulfate
with the proviso that the quantities with water and possibly electrolyte salts add up to 100% by weight

Another object of the invention relates to the use of the surfactant granules for the production of solid washing, rinsing and cleaning agents, in which they are present in amounts of 1 to 90, preferably 5 to 50 and in particular 10 to 25% by weight, based on the agent - May be included. The agents can be in the form of powders, granules, extrudates, agglomerates or in particular tablets and can contain other typical ingredients.
They are preferably used for the production of detergent solids, since the dissolution rate is a critical parameter, especially in solid formulations.

Auxiliaries and additives

In addition to the aforementioned, the detergent compactates can also contain other typical ingredients, for example Builders, bleaches, bleach activators, detergent boosters, enzymes, enzyme stabilizers, Graying inhibitors, optical brighteners, soil repellants, foam inhibitors, inorganic salts as well as fragrances and dyes.

In particular, finely crystalline, synthetic and bound water-containing zeolite such as zeolite NaA in detergent quality is used as the solid builder . However, zeolite NaX and mixtures of NaA and NaX are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water. Suitable substitutes or partial substitutes for zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A. Preferred crystalline layered silicates are those in which M in the general formula stands for sodium and x assumes the values 2 or 3. In particular, both β- and γ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171 . The powder detergents according to the invention preferably contain 10 to 60% by weight of zeolite and / or crystalline layered silicates as solid builders, mixtures of zeolite and crystalline layered silicates in any ratio being particularly advantageous. In particular, it is preferred that the agents contain 20 to 50% by weight of zeolite and / or crystalline layered silicates. Particularly preferred agents contain up to 40% by weight of zeolite and in particular up to 35% by weight of zeolite, in each case based on anhydrous active substance. Other suitable ingredients of the agents are water-soluble amorphous silicates; they are preferably used in combination with zeolite and / or crystalline layered silicates. Particularly preferred are agents which contain, above all, sodium silicate with a molar ratio (module) of Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5. The content of amorphous sodium silicates in the agents is preferably up to 15% by weight and preferably between 2 and 8% by weight. Phosphates such as tripolyphosphates, pyrophosphates and orthophosphates can also be present in small amounts in the compositions. The content of the phosphates in the compositions is preferably up to 15% by weight, but in particular 0 to 10% by weight. In addition, the agents can also contain layered silicates of natural and synthetic origin. Layered silicates of this type are known, for example, from patent applications DE 2334899 B , EP 0026529 A and DE 3526405 A. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable sheet silicates, which belong to the group of water-swellable smectites, are, for example, those of the general formulas (OH) ₄ Si _8-y Al _y (Mg _x Al _4-x ) O ₂₀ montmorrilonite (OH) ₄ Si _8-y Al _y (Mg _6-z Li _z ) O ₂₀ hectorite (OH) ₄ Si _8-y Al _y (Mg _6-z Al _z ) O ₂₀ saponite with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Furthermore, due to their ion-exchanging properties, the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na ⁺ and Ca ²⁺ . The amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing. Useful sheet silicates are known, for example, from US 3,966,629, US 4,062,647, EP 0026529 A and EP 0028432 A. Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment. Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these , Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. The use of polymeric polycarboxylates is not absolutely necessary. However, if polymeric polycarboxylates are used, agents are preferred which are biodegradable polymers, for example terpolymers, the monomers acrylic acid and maleic acid or salts thereof, and vinyl alcohol or vinyl alcohol derivatives or the monomers acrylic acid and 2-alkylallylsulfonic acid or salts thereof as well as sugar derivatives. Terpolymers which are obtained according to the teaching of German patent applications DE 4221381 A and DE 4300772 A are particularly preferred. Further suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0280223 A. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Among the compounds which serve as bleaching agents and which supply hydrogen peroxide in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents are, for example, peroxy carbonate, citrate perhydrates and salts of peracids, such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight. The use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. Due to its ability to bind free water with the formation of the tetrahydrate, it contributes to increasing the stability of the agent.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl or O-acyl compounds which form organic peracids with hydrogen peroxide, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. The bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. 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. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. In addition to the mono- and polyfunctional alcohols and the phosphonates, the agents can contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B4O ₇ ), is particularly advantageous.

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

As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brighteners can also be used. Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example ^Contain 10 ^-6 to 10 ^-3 wt .-%, preferably by 10 ^-5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).
Suitable soil repellants are substances which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10. The molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100. The polymers are characterized by an average molecular weight of about 5000 to 200,000 and can have a block, but preferably a random structure. Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers which have linking polyethylene glycol units with a molecular weight of 750 to 5000, preferably of 1000 to about 3000 and a molecular weight of the polymer from about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Soaps of natural or synthetic origin, for example, which have a high proportion of C ₁₈ -C ₂₄ fatty acids, are suitable for this. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone- or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

Examples

Application test. A quantity of the granules, corresponding to 10 g of surfactant in each case, was stirred into 1 | Water (25 ° C). After 30 s (T1), 60 s (T2) and 180 s (T3), the solution was filtered through a sieve (mesh size: 0.2 mm). The filter residue was briefly washed with acetone, dried and then weighed. The results are summarized in Table 1: Example for improving the solubility of the raw material (data in% by weight) composition C _16/18 alkyl sulfate 100 95 90 85 80 75 C _16/18 alkenyl sulfate 0 5 10 15 20 25 Solubility hand wash test (% residue) at 25 ° C 50.6 32.4 32.2 28 22.3 12.4

The surfactant granules according to the invention were used in detergent tablets (formulations R1 to R3) to evaluate further application properties. These detergent tablets were compared with two examples of conventional detergent tablets (V1 and V2) in terms of their dissolution rate. The preparations were pressed into tablets (weight 40 g, constant hardness), packed airtight and then stored at 40 ° C. for 2 weeks. The composition of the detergent tablets is shown in Table 2. Formulations 1, 2 and 3 are according to the invention, formulations V1 and V2 are used for comparison. To assess the dissolution behavior, the tablets were placed on a wire frame which was in water (0 ° d, 25 ° C). The tablets were completely surrounded by water. The disintegration time from immersion to complete disintegration was measured. The disintegration times are also shown in Table 2. Example of improving the solubility of a detergent tablet (in% by weight) composition R1 R2 R3 V1 V2 Granules according to the invention 15 10 15 Coconut alcohol sulfate Na 15 15 C _12/14 alkyl polyglucoside 5 C _12/18 coconut _fatty alcohol + 7 EO 1 1 1 1 1 sodium silicate 2 2 2 2 2 Sodium percarbonate 12 12 12 12 12 Disintegrant Arbocel G350 15 15 15 15 15 sodium tripolyphosphate 29 29 Zeolite A 25 25 25 25 polycarboxylate 4 4 4 TAED 4 4 4 4 4 defoamers 5 5 5 5 5 sodium 7 7 7 7 7 Water (residual moisture) ad 100 ad 100 ad 100 ad 100 ad 100 Dissolution rate decay [s] 55 35 40 120 100

Claims (9)

Surfactant granules consisting of (a) 75-97% by weight of an alkyl sulfate, (b) 3 - 25% by weight of an alkenyl sulfate,
with the proviso that the quantities with water and possibly electrolyte salts add up to 100% by weight. Surfactant granules according to claim 1, characterized in that they have as component (a) compounds of the formula R ¹ O-SO ₃ X in which R ^{1 represents} a linear or branched, aliphatic alkyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Surfactant granules according to at least one of claims 1 and 2, characterized in that they contain , as component (b), compounds of the formula R ² O-SO ₃ X in which R ^{2 represents} a linear or branched, mono- or polyunsaturated aliphatic alkenyl radical having 12 to 22, preferably 16 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Surfactant granules according to at least one of claims 1 to 3, characterized in that they contain alkenyl sulfates with iodine numbers in the range 5 to 60 as component (b). Process for the preparation of surfactant granules according to Claim 1, characterized in that aqueous pastes of component (a) are subjected to drying and simultaneous granulation in the presence of component (b). Process for the production of surfactant granules according to Claim 5, characterized in that the granulation is carried out in a fluidized bed, Use of surfactant granules according to claim 1 in washing, rinsing and cleaning agents. Use of surfactant granules according to claim 1 for the production of detergent solids. Use of surfactant granules according to claim 1 to support the tablet disintegration of Detergent tablets.