EP0804529B1 - Amorphous alkaline silicate compound - Google Patents

Abstract

A spray-dried amorphous alkali metal silicate compound which provides multiple-cycle washing performance. The silicate compound has a molar ratio of M2O to SiO2 of 1:1.5 to 1:3.3 wherein M represents an alkali metal. The compound contains 0.5 to less than 30% by weight of anionic surfactant and has an absorption capacity for liquid components which is at least 20% higher than that of the same quantity of the alkali metal silicate compound which is free from anionic surfactant.

Description

The invention relates to an amorphous alkali silicate compound with secondary washing power, that as a water-soluble builder substance in detergents or cleaning agents can be used, as well as the use of such Alkali silicate compounds in washing or cleaning agents, extruded Detergents or cleaning agents and a process for their production.

Modern, compressed washing or cleaning agents generally have the Disadvantage that they have a poorer because of their compact structure Dissolving behavior in aqueous liquor is shown, for example, as lighter one spray-dried washing or cleaning agents of the prior art. Washing or cleaning agents generally tend to do so poorer dissolving speed in water, the higher their degree of compaction is. Zeolites used in detergents or cleaning agents as builders are usually included due to their water insolubility in addition to the worsened dissolving behavior.

A water-soluble alternative for the zeolite are amorphous alkali silicates with secondary washing ability.

Spray or roller drying of water glass solutions is known to be possible obtain hydrated water-soluble silicates in powder form, which still contain about 20% by weight of water (cf. Ullmann's Encyclopedia of technical chemistry, 4th edition 1982, volume 21, page 412). Such products are in the trade for various purposes. Such powders are due to spray drying has a very loose structure; their bulk weights are generally well below 700 g / l.

Alkali silicates in granular form with higher bulk densities can according to the teaching of European patent application EP-A-0 526 978 can be obtained, whereby an alkali silicate solution with a solids content between 30 and introduces 53% by weight into a heated drum, one in the longitudinal axis Shaft with a variety of close to the inner surface of the drum Arms rotates, the drum wall having a temperature between 150 and 200 ° C and the drying process by a fed into the drum Supported gas with a temperature between 175 and about 250 ° C becomes. According to this process, a product is obtained, the middle one Particle size is in the range between 0.2 and 2 mm. A preferred one Drying gas is heated air.

European patent application EP-A-0 542 131 describes a process in which a product which is completely soluble in water at room temperature and has a bulk density of between 500 and 1200 g / l is obtained. Drying is preferably carried out using heated air. Here, too, a cylindrical dryer with a heated wall (160 to 200 ° C.) is used, in the longitudinal axis of which a rotor with blade-shaped blades rotates at such a speed that the silicate solution has a solids content of between 40 and 60% by weight pseudoplastic mass with a free water content between 5 and 12 wt .-% arises. Drying is supported by a hot air stream (220 to 260 ° C).

The older, unpublished application P 44 19 745.4 describes also a water-soluble, amorphous and granular alkali silicate, which is prepared in a manner similar to that described in EP-A-0 526 978 is, but contains silicic acid. With the term "amorphous" is "X-ray amorphous" meant. This means that the alkali silicates in X-ray diffraction not deliver sharp reflections, but at best one or more broad maxima, the width of which is several degree units of the Diffraction angle. However, this does not rule out the fact that Electron diffraction areas can be found that are sharp Provide electron diffraction reflections. This is to be interpreted as meaning that Substance microcrystalline areas in the order of magnitude up to approx. 20 nm (max. 50 nm).

Granular amorphous sodium silicates, which by spray drying aqueous Water glass solutions, subsequent grinding and subsequent compacting and Rounding can be obtained with additional removal of water from the ground material, are the contents of US Pat. Nos. 3,912,649, 3,956,467, 3,838,193 and 3,879,527. The water content of the products obtained is at about 18 to 20 wt .-% with bulk weights well above 500 g / l.

Other granular alkali silicates with secondary washing ability are from the European patent applications EP-A-0 561 656 and EP-A-0 488 868 are known. These are compounds of alkali silicates with certain Q distributions and alkali carbonates. The products are manufactured by that using powdered anhydrous sodium carbonate granulated a sodium silicate solution (water glass solution) and the Dries products in such a way that they have a specific bond to the silicate Have residual water content.

Absorbent alkali silicate compounds are known from German patent application DE-A-44 06 592 known which exist as a multi-component mixture and by spray drying an aqueous preparation of the multicomponent mixture with superheated steam. Such Compounds can be used as carriers for liquid preparations in particular Serve surfactants.

Spray-dried surfactant-rich granules are known from European patent application EP-A-0 219 314, which (a) 30 to 60 wt .-% of a mixture of alkylbenzenesulfonate and C ₁₂ -C ₁₆ alkyl sulfate in a weight ratio of 4: 1 to 1: 4 and (b) Alkali metal silicates in the weight ratio (a) to (b) from 1.5: 1 to 6: 1 contain.

EP-A-0 651 050 describes a process for producing agglomerates, where a salt, for example silicate or carbonate, with a aqueous "binder" containing at least 20% by weight of silicate and at least 30 Contains wt .-% anionic surfactant is processed.

A process for the production is known from the European patent EP 486 592 known from extrudates with high density, being a solid and free-flowing Premix is extruded under pressure. The solid and free-flowing premix contains a plasticizer and / or lubricant, which causes the premix under the pressure or the entry more specific Work softens plastically and thus becomes extrudable. After this Exit from the hole shape no longer affects the system with shear forces and the viscosity of the system increases such that the extruded one Strand can be cut to predetermined extrudate dimensions can. From international patent application WO-A-94/09111 it is now known that in the premix to be extruded both components which have a structurally viscous behavior, as well as components which have dilatant properties, must be included. Layers only structurally viscous active ingredients in the premix, it would be due soften the strong shear gradient, become almost fluid, that the strand no longer exits the hole shape would be able to be cut. It therefore also has dilating components used, which with increasing shear rate an increasing plasticity and thereby ensure the cutting ability of the extruded strand. Most of the ingredients in washing or cleaning agents show structurally viscous behavior. A dilatante behavior poses rather the exception. A common part of conventional laundry or detergent has dilatant properties; they are water-insoluble used as builder and phosphate substitute Aluminosilicates such as zeolite. From international patent application WO-A-94/09111 extruded detergents or cleaning agents are known, which 19% by weight zeolite (based on anhydrous active substance) and Contain 12.5% by weight sodium carbonate and 2.2% by weight amorphous sodium silicate; however, it was not known that zeolite from process engineering Partially or even completely visible through water-soluble inorganic Builder substances like amorphous alkali silicates can be replaced, though these are used in a specific form. However, it did shown that some alkali silicate compounds with secondary washing ability this when processing under the influence of water, high shear forces and / or partially lose (slightly) elevated temperatures.

An object of the invention was to provide water-soluble builder substances for the partial or complete replacement of zeolite in detergents or cleaning agents To provide, whereby the detachment behavior, especially of heavy washing or Detergents should be improved. In addition, these should be water soluble Builder substances also have a holding capacity for at the processing temperature have liquid to waxy ingredients in washing or cleaning agents. Likewise, builder substances should be provided, which are also used during processing Do not lose secondary washing power. Another object of the invention was therein, extruded washing or cleaning agents and a process for their production to provide, which contain the water-soluble builder substances to the extent that on zeolite not only from an application technology perspective but also from a process technology perspective View can be partially or completely omitted.

Accordingly, the invention relates in a first embodiment to a spray-dried amorphous alkali silicate compound with secondary washing power and a molar ratio M ₂ O: SiO ₂ (M = alkali metal) between 1: 1.5 and 1: 3.3, which anionic surfactants in amounts of Contains 0.5 to less than 30 wt .-%, has an absorption capacity for liquid components, which is at least 20% higher than that of the same amount alkali silicate compounds without anionic surfactants and with liquid components, the ingredients of detergents or cleaning agents, especially nonionic surfactants , are aftertreated.

Preferred amorphous alkali silicates have a molar ratio M ₂ O: SiO ₂ (M = alkali metal) between 1: 1.9 and 1: 3, in particular up to 1: 2.5. Sodium and / or potassium silicate are particularly suitable here. Sodium silicates are preferred for economic reasons. However, if, for reasons of application technology, a particularly high dissolution rate in water is important, it is advisable to replace sodium at least partially with potassium. For example, the composition of the alkali silicate can be chosen so that the silicate has a potassium content, calculated as K ₂ O, of up to 5% by weight. Preferred alkali silicates are present as a compound with alkali carbonate, preferably sodium and / or potassium carbonate. The water content of these preferred amorphous alkali silicate compounds is advantageously between 10 and 22% by weight, in particular between 12 and 20% by weight. Water contents of 14 to 19% by weight can be particularly preferred.

The compounds of the invention are obtained by spray drying an aqueous Slurry containing alkali silicates and anionic surfactants obtained, wherein especially alkali silicate compounds with water contents from 14 to 19 Wt .-% arise. In particular, aqueous slurries are sprayed the additional alkali carbonates, advantageously sodium carbonate and / or potassium carbonate.

Anionic surfactants used in the alkali silicate compounds are, above all, surfactants of the sulfonate and / or sulfate type. Preferred surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C ₁₂ -C ₁₈ monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin. As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. C ₁₆ -C ₁₈ alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C ₁₆ -C ₁₈ -alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize. In a preferred embodiment of the invention, the compounds therefore mixtures of short and long-chain fatty alkyl sulfates, preferably mixtures of C ₁₂ C ₁₄ or C ₁₂ -C -Fettalkylsulfaten contain ₁₈ -Fettalkylsulfaten with C ₁₆ -C ₁₈ -Fettalkylsulfaten and in particular C ₁₂ -C ₁₆ - Fatty alkyl sulfates with C ₁₆ -C ₁₈ fatty alkyl sulfates. In a further preferred embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C ₁₆ to C ₂₂ are used. Mixtures of saturated sulfated fatty alcohols predominantly consisting of C ₁₆ and unsaturated sulfated fatty alcohols predominantly consisting of C ₁₈ are particularly preferred, for example those derived from solid or liquid HD-Ocenol ^(R) fatty alcohol mixtures (commercial product of the applicant) . Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.

2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN ^(R) , are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol of ethylene oxide (E0) or C ₁₂ - C ₁₈ fatty alcohols with 1 to 4 E0 are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

In a preferred embodiment of the invention, the compounds contain 15 to 80 % By weight alkali silicates, 1 to 25% by weight anionic surfactants, preferably up to 20% by weight Anionic surfactants and 10 to 22% by weight, preferably 12 to 19% by weight and in particular 14 up to 19% by weight of water. It has been shown that amounts above 25% by weight Anionic surfactants, sometimes even above 20 wt .-% of anionic surfactants in the Compounds again deteriorate in the secondary washing ability of the can carry all detergent. The applicant suspects - without relying on this Wanting to limit theory- that the compounds with higher amounts of anionic surfactants are soluble so quickly that there are negative interactions between the Anionic surfactants and the hardness formers of the water comes before the latter comes from the silicate can be eliminated.

In a further embodiment of the invention, the spray-dried, amorphous alkali silicate compounds with secondary washability and a molar ratio M ₂ O: SiO ₂ (M = alkali metal) between 1: 1.5 and 1: 3.3 contain 15 to 50% by weight, preferably 20 to 40% by weight alkali silicates, 30 to 70% by weight, preferably 40 to 65% by weight alkali carbonates, 1.5 to 15% by weight and in particular 2 to 12% by weight anionic surfactants, advantageously alkylbenzenesulfonates and / or alk (en) yl sulfates, and 12 to 19% by weight of water.

The alkali silicate compounds can also contain other ingredients from washing or cleaning agents, preferably in amounts of up to 10% by weight and in particular in Amounts do not contain above 5 wt .-%. These include, for example, neutral salts such as sodium or potassium sulfates, but also graying inhibitors or nonionic Surfactants such as alkyl polyglycosides.

The alkali silicate compounds according to the invention have a significant absorption capacity for liquid up to the usual processing temperatures wax-like ingredients of washing or cleaning agents. You can too Alkali silicate compounds without the addition of anionic surfactants have certain amounts of liquid components take up; however, it has been shown that the addition of Anionic surfactants increase the absorption capacity of the alkali silicate compounds and that Trickle behavior is improved. In a preferred embodiment of the invention have the anionic surfactant according to the invention Alkali silicate compounds have a capacity to absorb liquid components is at least 20% higher than that of the equal-quantity alkali silicate compounds without Anionic surfactants. In particular, compounds whose absorption capacity are preferred for liquid components even by at least 30% and advantageously even by at least 50%, each based on the absorption capacity of the same quantity corresponding alkali silicate compounds without anionic surfactants.

In a preferred embodiment, the spray-dried alkali silicate compounds are aftertreated with liquid components, which include liquid to waxy ingredients of detergents or cleaning agents at processing temperature in the context of this invention. Suitable liquid components which can be absorbed by the alkali silicate compounds according to the invention are, for example, nonionic surfactants, cationic surfactants and / or foam inhibitors such as silicone oils and paraffin oils. However, nonionic surfactants are particularly preferred, for example alkoxylated, preferably ethoxylated and / or ethoxylated and propoxylated, aliphatic C ₈ -C ₂₂ alcohols. These include in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be methyl-branched linearly or preferably in the 2-position or contain linear and methyl-branched radicals in the mixture can, as is usually present in oxo alcohol residues. However, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are also preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohol with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 E0, 25 E0, 30 EO or 40 E0.

Another class of preferred non-ionic surfactants that either as the sole nonionic surfactant or in combination with the other nonionic surfactants mentioned are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the Alkyl chain, especially fatty acid methyl esters, as described, for example, in Japanese Patent Application JP 58/217598 are described or the preferably according to that in international patent application WO-A-90/13533 described methods are produced.

The primary spray-dried compounds according to the invention already show a stabilized secondary washing ability when processed into detergents compared to alkali silicate compounds free of anionic surfactants. In particular, however, such compounds according to the invention show a stable Secondary washing ability, the surface of which subsequently becomes hydrophobic, was advantageously treated with nonionic surfactants.

The alkali silicate compounds according to the invention are spray dried manufactured. In particular, a method is preferred in which the Alkali silicate compounds by spray drying an aqueous slurry, which all components (with the exception of the liquid components, with which the compounds can be post-treated) of the alkali silicate compounds contains.

In a further embodiment of the invention, the invention Compounds by spray drying an aqueous preparation of the Multi-component mixture according to the process engineering teaching of German patent application DE-A-44 06 592 made with superheated steam.

The alkali silicate compounds with ingredients produced in this way can subsequently be used be treated by detergents or cleaning agents. This can can be carried out in a conventional manner, for example by mixing or by spraying in a mixer / granulator, optionally with a subsequent one Heat treatment.

The amorphous alkali silicate compounds with secondary washing ability can be used as Additive component to powdery to granular detergents or cleaning agents or as a component in the manufacture of granular washing or cleaning agents, preferably during granulation and / or compacting, be used. Depending on the type of manufacture, the Bulk weights of the alkali silicate compounds between 50 and for example Vary 850 g / l. The washing or cleaning agents according to the invention can, however, a bulk density between 300 and 1200 g / l, preferably from 500 to 10G ,: g / l, contain and contain the alkali silicate compounds according to the invention preferably in amounts of 5 to 50% by weight, in particular in amounts of 10 to 40% by weight. Their manufacture can be done according to any of the known processes such as mixing, spray drying, granulating, compacting such as roller compaction and extrusion. Are particularly suitable such processes in which several sub-components, for example spray-dried Components and granulated and / or extruded components be mixed together. It is also possible that spray-dried or granulated components afterwards in the preparation, for example with nonionic surfactants, especially ethoxylated fatty alcohols, be applied according to the usual procedures. In particular in granulation and extrusion processes it is preferred to optionally existing further anionic surfactants in the form of a spray-dried, granulated or extruded compounds either as admixture components in using the process or as an additive to other granules. It is also possible and can depend on the recipe be advantageous if further individual components of the agent, for example Carbonates, citrate or citric acid or other polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, zeolite and / or Layered silicates, for example layered crystalline disilicates, subsequently to spray-dried, granulated and / or extruded Components, if necessary, with nonionic surfactants and / or others at processing temperature liquid to waxy ingredients are added to be mixed. A is preferred Method in which the surface of partial components of the agent or of the entire agent for reducing the stickiness of the granules and / or is subsequently treated for their improved solubility. Suitable Surface modifiers are known from the prior art. Next further suitable are finely divided zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts, for example calcium stearate, but above all mixtures of zeolite and silica, in particular in a weight ratio of zeolite to silica of at least 1: 1, or zeolite and calcium stearate are particularly preferred.

Particularly preferred embodiments of the invention are extruded Detergents or cleaning agents with a bulk density above 600 g / l, which anionic and optionally nonionic surfactants and a Amorphous alkali silicate compound of the specified type contained in the extrudate. To produce these extruded detergents or cleaning agents, the known processes for extrusion, in particular to the European Patent EP-B-0 486 592. This will be a solid and free-flowing Premixed at a pressure of up to 200 bar, the strand after the exit from the hole shape by means of a cutting device on the predefined granule dimension cut as well as the plastic and if necessary raw extrudate still moist in a further shaping processing step fed and then dried, the inventive Alkali silicate compounds are used in the premix.

Especially in the production of extruded washing or cleaning agents have surprisingly the alkali silicate compounds containing anionic surfactants not only from an application perspective, but also from procedural point of view Advantages over the anion-surfactant-free Al-potassium silicate compound alternatives on. It has been shown that extrusion processes, in which in particular anionic surfactant-free alkali silicate carbonate compounds were not allowed to be interrupted because the Extrusion mixture in the resting phase its plasticity and lubricity lost so quickly that restarting the system safety-related Brought problems. This problem was replaced by the the anionic surfactant-free alkali silicate compounds containing anionic surfactants, especially through alkali silicate compounds containing anionic surfactants and carbonate solved.

The finished detergents or cleaning agents can also do the following Contain ingredients.

These include in particular surfactants, especially anionic surfactants and, if appropriate nonionic surfactants, but also cationic, amphoteric or zwitterionic surfactants.

The anionic surfactants of the sulfonate type include those already mentioned above Alkylbenzenesulfonates, olefinsulfonates and alkanesulfonates can be considered. Suitable but are also the esters of α-sulfo fatty acids (ester sulfonates), e.g. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or Tallow fatty acids. Other suitable anionic surfactants are those by ester cleavage the α-sulfofatty acid alkyl esters obtainable α-sulfofatty acids or their di-salts. The mono-salts of the α-sulfofatty acid alkyl esters are already falling in their industrial production as an aqueous mixture with limited Amounts of di-salts. The disalt content of such surfactants is usually below 50% by weight of the anionic surfactant mixture, for example up to about 30 % By weight.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which represent mono-, di- and triesters and their mixtures as they do in the production by esterification by a monoglycerol with 1 to 3 Moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles Glycerin can be obtained.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters mentioned from primary alcohols of natural and synthetic origin, 2,3-alkyl sulfates and, if appropriate, alkoxylated, preferably ethoxylated, derivatives of the sulfuric acid monoesters. Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves. Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

In addition to the anionic surfactants, the agents can also contain soaps, preferably contained in amounts of 0.2 to 5 wt .-%. Saturated ones are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, Palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid as well especially from natural fatty acids, e.g. Coconut, palm kernel or Tallow fatty acids, derived soap mixtures.

The anionic surfactants and soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, Di- or triethanolamine. The anionic are preferably located Surfactants in the form of their sodium or potassium salts, especially in the form of Sodium salts.

In one embodiment of the invention, detergents or cleaning agents, especially preferred extruded washing or cleaning agents, which contain 10 to 30% by weight of anionic surfactants. Advantageously are preferably at least 3% by weight and in particular at least 5% % By weight of sulfate surfactants. In an advantageous embodiment, in the means - based on the total anionic surfactants - at least 15 wt .-%, in particular 20 to 100 wt .-% sulfate surfactants.

Preferred nonionic surfactants are those already described above alkoxylated, advantageously ethoxylated alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (E0) used per mole of alcohol.

The alkoxylated ones mentioned above can also be used Fatty acid alkyl esters are used.

In addition, alkyl glycosides of the general formula R0 (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10.

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

in der R²C0 für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R³ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

in which R ^{2 is} C0 for an aliphatic acyl radical with 6 to 22 carbon atoms, R ³ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

Nonionic surfactants are preferred in the agents according to the invention in amounts of 0.5 to 15% by weight, in particular in amounts of 2 to 10 % By weight.

In addition to the amorphous alkali silicate compounds with secondary washing ability, the detergents can also contain further, additional builder substances and cobuilders. For example, customary builder substances such as phosphates, zeolites and crystalline layered silicates can be contained in the compositions. The synthetic zeolite used is preferably finely crystalline and contains bound water. Zeolite A, for example, but also zeolite X and zeolite P and mixtures of A, X and / or P are suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. It is also possible to use zeolite suspensions and zeolite powder. Suitable zeolite powders have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. Zeolite can be contained in the washing or cleaning agents in amounts of up to about 40% by weight (based on anhydrous active substances).

Included in a particularly preferred embodiment of the invention Washing or cleaning agents, however, 10 to 16 wt .-% zeolite (based on anhydrous active substance) and 10 to 30 wt .-% of an inventive Alkali silicate compounds.

In a further particularly preferred embodiment of the invention however, the detergents or cleaning agents contain 0 to 5% by weight of zeolite (based on anhydrous active substance) and 15 to 40 wt .-% of an inventive Alkali silicate compounds. It is possible that the zeolite is not only co-extruded, but that the zeolite is partially or completely afterwards, i.e. after the extrusion step into the washing or Detergent is introduced. Washing machines are particularly preferred. or cleaning agents that contain an extrudate that is inside the Extrudate grain is free of zeolite.

Crystalline layered silicates can also be used as substitutes for the zeolite and / or conventional phosphates are used. However, it is preferred that phosphates only in small amounts, in particular up to a maximum 10% by weight, are contained in the washing or cleaning agents.

The crystalline layered silicates are, in particular, crystalline, layered sodium silicates of the general formula NaMSi _x 0 _{2x + 1} .yH ₂ 0, 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 is preferred Values for x 2, 3 or 4 are suitable. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ 0 ₅ .yH ₂ 0 are preferred. However, these crystalline layered silicates are preferably contained in the extrudates according to the invention only in amounts of not more than 10% by weight, in particular less than 8% by weight, advantageously not more than 5% by weight.

Polymeric polycarboxylates, for example, can be used as cobuilders become. Suitable polymeric polycarboxylates are, for example, the sodium salts polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of Acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with Maleic acid. Copolymers of acrylic acid have proven particularly suitable proven with maleic acid, the 50 to 90 wt .-% acrylic acid and 50 to 10 % By weight of maleic acid. Their relative molecular mass, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. Particularly preferred also terpolymers, for example those which according to DE-A-43 00 772 as Monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of Acrylic acid and the 2-alkylallylsulfonic acid as well as sugar derivatives. Other preferred copolymers are those described in the German Patent applications DE-A-43 03 320 and P 44 17 734.8 are described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or Have acrolein and vinyl acetate.

Other usable organic cobuilders are preferred in the form of their Sodium salts used polycarboxylic acids, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided such use ecological reasons are not objectionable, as well as 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.

Other suitable builder systems are oxidation products from carboxyl-containing polyglucosans and / or their water-soluble Salts such as those used in the international patent application WO-A-93/08251 are described or their production, for example, in of international patent application WO-A-93/16110.

Also known are the other preferred builder substances To name polyaspartic acids or their salts and derivatives.

Other suitable builder substances are polyacetals, which by reaction of dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and have at least 3 hydroxyl groups, for example as in European Patent application EP-A-0 280 223 can be obtained. Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

These cobuilders can be used in amounts of, for example, 0.5 to 20% by weight, preferably from 2 to 15% by weight in the finished washing or cleaning agents be included.

In addition, the agents can also contain components that the oil and Influencing fat washability from textiles positively. This effect becomes particularly clear when a textile that is already soiled is soiled previously several times with a detergent according to the invention that this oil and contains fat-dissolving component, is washed. Among the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion on methoxyl groups from 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ether, as well as the polymers known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these.

The agents can also contain constituents which further improve the solubility, particularly of the heavy granules. Such components and the incorporation of such components are described, for example, in international patent application WO-A-93/02176 and in German patent application DE-A-42 03 031. The preferred ingredients include, in particular, fatty alcohols with 20 to 80 moles of ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol with 30 EO and tallow fatty alcohol with 40 E0, but also fatty alcohols with 14 EO and polyethylene glycols with a relative molecular weight between 200 and 2000. Among the bleaching agents serving, in water H ₂ 0 ₂ providing compounds, the sodium perborate monohydrate is of particular importance. Further bleaching agents which can be used are, for example, sodium perborate tetrahydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ 0 ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used. Percarbonate is also preferred as an ingredient. However, percarbonate is preferably not co-extruded, but optionally mixed in subsequently.

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 0-acyl compounds which form organic peracids with H ₂ 0 ₂ , preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239. 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'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).

It can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone and / 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.

Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Are particularly well suited Bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymatic Active ingredients. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Enzyme mixtures, for example of protease and amylase or Protease and lipase or protease and cellulase or from cellulase and Lipase or from protease, amylase and lipase or protease, lipase and Cellulase, but especially mixtures containing protease and / or lipase of special interest. Also have peroxidases or oxidases proved to be suitable in some cases. The enzymes can on carriers adsorbed and / or embedded in enveloping substances around them protect against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

The stabilizers come in particular for per-compounds and enzymes Salts of polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or Ethylenediaminetetramethylenephosphonic acid into consideration.

The agents can also 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 B0 ₃ ), metaboric acid (HB0 ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ 0 ₇ ), is particularly advantageous.

Graying inhibitors have the task of detaching from the fiber Keep dirt suspended in the fleet and prevent graying. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, Glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Furthermore, soluble ones Use starch preparations and other starch products than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, cellulose ethers such as Carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their Mixtures and polyvinylpyrrolidone, for example in amounts from 0.1 to 5 % By weight, based on the composition.

The agents can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed connections that instead the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group.

Brighteners of the substituted diphenylstyryl type may also be present be, e.g. 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) diphenyl. Mixtures of the aforementioned brighteners can also be used.

In addition to the alkali silicate compounds in a preferred embodiment the agents may also contain alkali metal carbonates inorganic salts, also other amorphous alkali silicates of those described above Contain type and alkali carbonates of the type described above. Further inorganic salts which can be considered as ingredients Neutral salts such as sulfates and possibly also chlorides in the form of their sodium and / or potassium salts.

Of course, they can also be used in washing or cleaning agents contained dyes and fragrances.

Examples Example 1: Production of alkali silicate compounds

The alkali silicate compounds C1 to C4 according to the invention and the comparison compound VC were obtained by conventional spray drying of an aqueous slurry. The composition of the compounds (in% by weight) was as follows: C1 C2 C3 C4 VC amorphous sodium disilicate 28.1 28.1 27.3 24.65 29.0 sodium 53.4 53.4 51.7 46.75 55.0 C ₁₂ -C ₁₈ alkyl sulfate (sodium salt) 3.0 ---- ---- ----- ---- C ₁₂ alkyl benzene sulfonate (sodium salt) ---- 3.0 6.0 15.0 ---- water 15.5 15.5 15.0 13.6 16.0

Example 2: Absorption capacity of the alkali silicate compounds (trickle test)

The absorption capacity of the alkali silicate compounds C1 to C4 according to the invention was compared to the comparative compound VC used with the same quantity using a nonionic surfactant which was 80% by weight of C ₁₂ -C ₁₈ fatty alcohol with 5 EO and 20% by weight of C Passed ₁₂ -C ₁₄ fatty alcohol with 3 E0. The nonionic surfactant absorption capacity was determined in accordance with DIN ISO 787, the above-mentioned nonionic surfactant being used instead of the linseed oil specified there. For this determination, a weighed amount of sample is placed on a plate. Slowly add 4 or 5 drops of nonionic surfactant from a burette. After each addition, the nonionic surfactant is rubbed into the powder with a spatula. The addition of the nonionic surfactant continues accordingly until aggregations of nonionic surfactant and powder have formed. From this point on, a drop of nonionic surfactant is added and rubbed with the spatula. The non-ionic surfactant addition is stopped when a soft paste has formed.

This paste should just be able to spread without tearing or crumbling and just stick to the plate. The amount of nonionic surfactant added is read off the burette and converted to ml nonionic surfactant per 100 g sample. The following results were obtained: ml nonionic surfactant per 100 g carrier C1 97 C2 110 C3 128 C4 130 VC 57

Example 3: Extrusion ability

According to the teaching of international patent application WO-A-94/02047, the following extrudates E1 to E4 according to the invention and the comparative extrudate VE were produced. The extrusion mixtures of agents E1 to E4 could be extruded without any process engineering problems. The comparative product VE could only be produced as long as the production process did not last longer than 60 minutes. was interrupted. The compositions of the extrudates were as listed in Table 1. The bulk density of the extrudates was between 750 and 780 g / l. Both the extrudates according to the invention and the comparative extrudate showed good dissolving behavior: only slight residues were obtained in the flushing-in behavior and in the solubility test. Compositions from E1 to E4 and VE (in% by weight): E1 E2 E3 E4 VE C ₉ -C ₁₃ alkylbenzenesulfonate 11.5 11.5 11.5 11.5 11.5 C ₁₂ -C ₁₈ alkyl sulfate 10.5 10.5 10.5 10.5 10.5 C ₁₂ -C ₁₈ alcohol with 7 EO 4.0 4.0 4.0 4.0 4.0 C ₁₂ -C ₁₈ fatty acid soap 1.0 1.0 1.0 1.0 1.0 Polyethylene glycol with a molecular weight of 400 1.5 1.5 1.5 1.5 1.5 Zeolite (anhydrous active substance) 19.0 19.0 19.0 19.0 19.0 Acrylic acid-maleic acid copolymer (sodium salt) 6.0 6.0 6.0 6.0 6.0 Alkali silicate compound C1 14.0 ---- ---- ---- ---- Alkali silicate compound C2 ---- 14.0 ---- ---- ---- Alkali silicate compound C3 ---- ---- 14.0 ---- ---- Alkali silicate compound C4 ---- ---- ---- 14.0 ---- Alkali silicate compound VC ---- ---- ---- ---- 14.0 Perborate monohydrate 21.0 21.0 21.0 21.0 21.0 Phosphonate 0.7 0.7 0.7 0.7 0.7 Sodium sulfate 1.5 1.5 1.5 1.5 1.5 Water and salts from solutions rest rest rest rest rest

Claims (13)

1. A spray-dried amorphous alkali metal silicate compound with multiple-cycle washing performance and a molar ratio of M₂O to SiO₂ (M = alkali metal) of 1:1.5 to 1:3.3, characterized in that it contains anionic surfactants in quantities of 0.5 to less than 30% by weight, has an absorption capacity for liquid components which is at least 20% higher than that of the same quantity of alkali metal silicate compounds free from anionic surfactants and has been aftertreated with liquid components which are ingredients of detergents, more particularly nonionic surfactants.
2. An alkali metal silicate compound as claimed in claim 1, characterized in that it contains 15 to 80% by weight of alkali metal silicates, 1 to 25% by weight of anionic surfactants, preferably up to 20% by weight of anionic surfactants, and 10 to 22% by weight of water.
3. A spray-dried amorphous alkali metal silicate compound with multiple-cycle washing performance and a molar ratio of M₂O to SiO₂ (M = alkali metal) of 1:1.15 to 1:3.3, characterized in that it contains 15 to 50% by weight and preferably 20 to 40% by weight of alkali metal silicates, 30 to 70% by weight and preferably 40 to 65% by weight of alkali metal carbonates, 1.5 to 15% by weight and, more particularly, 2 to 12% by weight of anionic surfactants, advantageously alkyl benzene sulfonates and/or alk(en)yl sulfates, and 12 to 19% by weight of water.
4. An alkali metal silicate compound as claimed in claim 3, characterized in that it has an absorption capacity for liquid components which is higher by at least 20%, preferably at least 30% and, more preferably, at least 50% than that of the same quantity of alkali metal silicate compounds without anionic surfactants.
5. An alkali metal silicate compound as claimed in claim 3 or 4, characterized in that it has been aftertreated with liquid components which are ingredients of detergents or cleaning formulations, more particularly nonionic surfactants.
6. A process for the production of the amorphous alkali metal silicate compound with multiple-cycle washing performance claimed in any of claims 1 to 5, characterized in that the compound is produced by spray drying of an aqueous slurry containing all the constituents of the alkali metal silicate compound.
7. A process as claimed in claim 6, characterized in that the compound is produced by spray drying of an aqueous preparation of the multiple component mixture with superheated steam.
8. A process as claimed in claim 6 or 7, characterized in that the spray-dried alkali metal silicate compound is subsequently treated with liquid ingredients of detergents or cleaning formulations, more particularly with nonionic surfactants.
9. The use of the alkali metal silicate compound with multiple-cycle washing performance claimed in any of claims 1 to 5 in detergents or cleaning formulations, the detergents or cleaning formulations being produced by spray drying, granulation, compacting, such as roll compacting, or extrusion or by mixing processes.
10. A detergent or cleaning formulation containing 10 to 16% by weight of zeolite (based on water-free active substance) and 10 to 30% by weight of a spray-dried amorphous alkali metal silicate compound with multiple-cycle washing performance and a molar ratio of M₂O to SiO₂ (M = alkali metal) of 1:1.5 to 1:3.3 which contains anionic surfactants in quantities of 0.5 to less than 30% by weight, preferably the alkali metal silicate compound claimed in any of claims 1 to 5.
11. A detergent or cleaning formulation containing 0 to 5% by weight of zeolite (based on water-free active substance) and 15 to 40% by weight of the alkali metal silicate compound claimed in any of claims 1 to 5.
12. An extruded detergent or cleaning formulation with an apparent density above 600 g/l containing anionic and optionally nonionic surfactants and an amorphous alkali metal silicate, characterized in that it contains a spray-dried amorphous alkali metal silicate compound with multiple-cycle washing performance and a molar ratio of M₂O to SiO₂ (M = alkali metal) of 1:1.5 to 1:3.3, which contains anionic surfactants in quantities of 0.5 to less than 30% by weight, and preferably the alkali metal silicate compound claimed in any of claims 1 to 5.
13. A process for the production of a detergent or cleaning formulation in which a solid free-flowing premix is extruded under pressures of up to 200 bar to form a strand, the strand is cut to a predetermined granule size by means of a cutting unit after leaving the extrusion die and the plastic and optionally still moist crude extrudate is subjected to another shaping or forming step and is subsequently dried, characterized in that the premix contains contains a spray-dried amorphous alkali metal silicate compound with multiple-cycle washing performance and a molar ratio of M₂O to SiO₂ (M = alkali metal) of 1:1.5 to 1:3.3, which contains anionic surfactants in quantities of 0.5 to less than 30% by weight, and preferably the alkali metal silicate compound claimed in any of claims 1 to 5.