EP0804529A1

EP0804529A1 - Amorphous alkaline silicate compound

Info

Publication number: EP0804529A1
Application number: EP96900573A
Authority: EP
Inventors: Kathrin Schnepp; Rene-Andres Artiga Gonzalez; Katrin Erbs; Hubert Freese; Manfred Greger; Bernd Larson; Volker Bauer; Peter Sandkühler; Wilfried Rähse
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1995-01-18
Filing date: 1996-01-09
Publication date: 1997-11-05
Anticipated expiration: 2016-01-09
Also published as: ES2144721T3; EP0804529B1; CN1168154A; RU2168542C2; US20020002130A1; HUP9702001A2; JPH10512321A; HUP9702001A3; KR19980701494A; DE59604687D1; US6458755B2; SK96297A3; CZ226797A3; DE19501269A1; ATE190645T1; PT804529E; US6191096B1; WO1996022349A1; PL324033A1

Abstract

Water-soluble builder substances are to be prepared for the partial or complete replacement of zeolith in washing or cleaning agents. In addition, said water-soluble builder substances are also to be capable of absorbing constituents of washing or cleaning agents which are liquid to waxy at the operating temperature. Thus extruded washing or cleaning agents and a process for producing them is to be prepared which contain the water-soluble builder substances to the extent where zeolith may be partly or completely excluded not only for application but also for processing reasons, These aims are achieved by spray-dried amorphous alkaline silicate compounds with secondary washing power and a mol ratio of M2O : SiO2 (M = alkaline metal) or between 1:1.5 and 1:3.3, containing anionic tensides in proportions of 0.5 to less than 30 wt.%.

Description

"Amorphous alkali silicate compound"

The invention relates to an amorphous alkali silicate compound with secondary washability, which can be used as a water-soluble builder in detergents or cleaners, and to the use of such alkali silicate compounds in detergents or cleaners, extruded detergents or cleaners and a process for their manufacture.

Modern, compacted detergents or cleaning agents generally have the disadvantage that, owing to their compact structure, they show poorer dissolving behavior in aqueous liquors than, for example, lighter spray-dried detergents or cleaning agents of the prior art. Washing or cleaning agents generally tend to have a poorer rate of dissolution in water, the higher their degree of compaction. Zeolites, which are usually contained in washing or cleaning agents as powder substances, can additionally contribute to the deterioration in dissolution behavior due to their insolubility in water.

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

As is known, hydrated water-soluble silicates can be obtained in powder form by spray or roller drying of water glass solutions, which still contain about 20% by weight of water (cf. Ullmann's Encyclopedia of Industrial Chemistry, 4th edition 1982, volume 21, page 412). Such products are commercially available for various purposes. Such powders have a very loose structure due to spray drying; their bulk weights are generally well below 700 g / 1.

Alkali silicates in granular form with higher bulk densities can be obtained according to the teaching of the European patent application EP-A-0526978, wherein an alkali silicate solution with a solids content of between 30 and 53% by weight is introduced into a heated drum, in the longitudinal axis of which a shaft rotates with a plurality of arms reaching close to the inner surface of the drum, the drum wall having a temperature between 150 and 200 ° C and the drying process is supported by a gas fed into the drum with a temperature between 175 and about 250 ° C. This process gives a product whose average particle size is in the range between 0.2 and 2 mm. A preferred 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 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 scoop-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 19745.4 also describes a water-soluble, amorphous and granular alkali silicate, which is prepared in a similar manner to that described in EP-A-0 526 978, but contains silica. The term "amorphous" means "X-ray amorphous". This means that the alkali silicates do not provide sharp reflections in X-ray diffraction recordings, but at most one or more broad maxima, the width of which is several degree units of the diffraction angle. However, this does not rule out the possibility that areas are found in electron diffraction experiments which give sharp electron diffraction reflections. This is to be interpreted in such a way that the substance has microcrystalline areas in a range of up to approx. 20 n (ax. 50 nm).

Granular amorphous sodium silicates, which by spray drying aqueous water glass solutions, subsequent grinding and subsequent compression and Rounding off with additional removal of water from the millbase are contained in the US Pat. Nos. 3,912,649, 3,956,467, 3,838,193 and 3,879,527. The water content of the products obtained is approximately 18 to 20% by weight with bulk weights significantly above 500 g / l.

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

German patent application DE-A-44 06 592 discloses absorbent alkali silicate compounds which are present as a multicomponent mixture and have been prepared by spray drying an aqueous preparation of the multicomponent mixture with superheated steam. Such compounds can serve as carriers for liquid preparations of surfactants in particular.

Spray-dried surfactant-rich granules are known from European patent application EP-A-0219 314, which (a) 30 to 60% by weight of a mixture of alkylbenzenesulfonate and Ci2-Ci6-alkyl sulfate in a weight ratio of 4: 1 to 1: 4 and (b) Contain alkali metal silicates in the weight ratio (a) to (b) of 1.5: 1 to 6: 1.

EP-A-0 651 050 describes a process for producing agglomerates, a salt, for example silicate or carbonate, with an aqueous "binder" containing at least 20% by weight of silicate and at least 30% by weight of anionic surfactant contains, is processed. From the European patent EP 486 592 a process for the production of extrudates with high density is known, whereby a solid and free-flowing premix is extruded under pressure. The solid and free-flowing premix contains a plasticizer and / or lubricant, which has the effect that the premix plastically softens under the pressure or the entry of specific work and thus becomes extrudable. After exiting the hole shape, the system is no longer subjected to shear forces and the viscosity of the system increases in such a way that the extruded strand can be cut to predeterminable extrudate dimensions. From international patent application WO-A-94/09111 it is now known that the premix to be extruded must contain both constituents which have a structurally viscous behavior and constituents which have dilatant properties. If only components with a structure-viscous action were present in the premix, it would soften, in fact become almost liquid, owing to the strong shear gradient, so that the strand would no longer be able to be cut after leaving the hole shape. Therefore, components with a latent action are used, which have increasing plasticity with increasing shear rate and thereby ensure the cutting ability of the extruded strand. Most of the ingredients in detergents or cleaning agents show structurally viscous behavior. Dilated behavior tends to be the exception. However, a common component of conventional washing or cleaning agents has dilated properties; it is the water-insoluble aluminum silicates such as zeolite that are used as builder and phosphate substitute. Extruded washing or cleaning agents are known from international patent application W0-A-94/09111, which contain 19% by weight of zeolite (based on anhydrous active substance) as well as 12.5% by weight of sodium carbonate and 2.2% by weight. contain amorphous sodium silicate; However, it was not known that, from a process engineering point of view, zeolite can be partially or even completely replaced by water-soluble inorganic builder substances, such as amorphous alkali silicates, if these are used in a specific form. It has been shown, however, that some alkali silicate compounds with a secondary washing ability lose some of this when processed under the action of water, high shear forces and / or (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, as a result of which the dissolving behavior, in particular of heavy detergents or cleaning agents, should be improved. In addition, these water-soluble builder substances should also have an absorption capacity for ingredients of detergents or cleaning agents which are liquid to waxy at the processing temperature. Likewise, builder substances should be provided that do not lose the secondary washing ability during processing. Another object of the invention was to provide extruded detergents or cleaning agents and a process for their preparation which contain the water-soluble builder substances to the extent that zeolite can be dispensed with partially or entirely not only from an application point of view but also from a process point of view .

Accordingly, the invention relates in a first embodiment to a spray-dried amorphous alkali silicate compound with secondary washability and a molar ratio M2O: SiO 2 (M = alkali metal) between 1: 1.5 and 1: 3.3, which is anionic surfactants contains in amounts of 0.5 to less than 30 wt .-%.

Preferred amorphous alkali silicates have a molar ratio M2O: 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. The sodium silicates are preferred for economic reasons. If, however, value is attached to a particularly high dissolving rate in water for reasons of application technology, it is advisable to at least partially replace sodium with potassium. For example, the composition of the alkali silicate can be chosen so that the silicate has a potassium content, calculated as K2O, of up to 5% by weight. Preferred alkali silicates are a compound with alkali carbonate, preferably sodium and / or Potassium carbonate, before. 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 according to the invention are obtained by spray drying an aqueous slurry containing alkali silicates and anionic surfactants, alkali silicate compounds in particular having water contents of 14 to 19% by weight being formed. In particular, aqueous slurries are sprayed which additionally have 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 Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates as well as disulfonates, such as those obtained from Ci2-Cl8 ~ ^mono "olefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products, alkane sulfonates obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, are also suitable 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 Ci2-Ci8 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl alcohol, Myristyl, cetyl or stearyl alcohol or the Cιo-C2θ " ^0xoa ^ ^ono ^ ^{e and} those ^{half-esters of} secondary alcohols of this chain length preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. Ci6-Ci8 ~ alk (en) yl sulfates are of particular interest in washing technology. prefers. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use Ci6-Ci8-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 at relatively low washing temperatures of for example, room temperature to 40 ^β C show a low tendency to crystallize. In a preferred embodiment of the invention, the compounds therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of Ci2Ci4-fatty alkyl sulfates or Ci2-Ci8-fatty alkyl sulfates with Ciö-Ciβ-fatty alkyl sulfates and in particular C12-C16-fatty alkyl sulfates with Cjs-Ciβ-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 C15 to C22 are used. Mixtures of saturated sulfated fatty alcohols consisting predominantly of C15 and unsaturated sulfated fatty alcohols consisting predominantly of CQ are preferred in particular, for example those which differ from solid or liquid fatty alcohol mixtures of the HD-ocenol ( ^R ) type (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 C7-C2i alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-C ^ alcohols with an average of 3.5 mol of ethylene oxide (E0) or Ci2- C _j 8 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 of alkali silicates, 1 to 25% by weight of anionic surfactants, preferably up to 20% by weight of anionic surfactants and 10 to 22% by weight, preferably 12 to 19 % By weight and in particular 14 to 19% by weight of water. It has been shown that amounts above 25% by weight of anionic surfactants, sometimes even above 20% by weight of anionic surfactants in the compounds, can again lead to a deterioration in the secondary washing ability of the entire detergent. The applicant suspects - without wishing to restrict himself to this theory - that the compounds with higher anionic surfactants are so quickly soluble that there are negative interactions between the anionic surfactants and the hardness formers of the water before the latter can be eliminated by the silicate .

In a further preferred embodiment of the invention, the compounds according to the invention contain 15 to 50% by weight, preferably 20 to 40% by weight of alkali silicates, 30 to 70% by weight, preferably 40 to 65% by weight of alkali metal carbonates, 1.5 up to 15% by weight and in particular 2 to 12% by weight of anionic surfactants, advantageously alkylbenzenesulfonates and / or alk (en) yl sulfates, and 12 to 19% by weight of water.

The alkali silicate compounds can additionally contain further ingredients of washing or cleaning agents, preferably in amounts of up to 10% by weight and in particular in amounts not exceeding 5% by weight. 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 ingredients of washing or cleaning agents which are liquid to wax-like at the usual processing temperatures. Alkali silicate compounds can also absorb certain amounts of liquid components without the addition of anionic surfactants; However, it has been shown that the addition capacity of anionic surfactants increases the absorption capacity of the alkali silicate compounds and improves the flow behavior. In a preferred training In an embodiment of the invention, the alkali silicate compounds containing anionic surfactants according to the invention have an absorption capacity for liquid components which is at least 20% higher than that of the same amount of alkali silicate compounds without anionic surfactants. In particular, compounds are preferred whose absorption capacity for liquid components has been increased by at least 30% and advantageously even by at least 50%, in each case based on the absorption capacity of the corresponding quantitative alkali silicate compounds without anionic surfactants.

In a further embodiment of the invention, spray-dried alkali silicate compounds are therefore claimed, which have been aftertreated with liquid components, which include liquid to waxy ingredients of detergents or cleaning agents in the context of this invention at the processing temperature. 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, particularly preferred are nonionic surfactants, for example alkoxylated, preferably ethoxylated and / or ethoxylated and propoxylated, aliphatic C8-C22 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 linear and methyl-branched radicals in the Can contain mixture, as they are 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, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cu alcohol with 7 EO, Ci3-Ci5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-Ci8 ~ Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Cχ2 ~ Cj4 alcohol with 3 EO and Ci2-Ci8 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Loading 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferably used nonionic surfactants, which are used 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, in particular Fatty acid methyl esters as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.

Even the primary spray-dried compounds according to the invention have a stabilized secondary washing power when processed into detergents in comparison with alkali silicate compounds free of anionic surfactants. In particular, however, such compounds according to the invention have a stable secondary washing power, the surface of which has subsequently been rendered hydrophobic, advantageously with nonionic surfactants.

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

In a further embodiment of the invention, the compounds according to the invention are produced by spray drying an aqueous preparation of the multicomponent mixture in accordance with the process engineering teaching of German patent application DE-A-44 06 592 with superheated steam. 11

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

The amorphous alkali silicate compounds with secondary washing ability can be used as an admixture component for powdery to granular washing or cleaning agents or as a component in the production of the granular washing or cleaning agents, preferably in the granulation and / or compacting. Depending on the way in which they are produced, the bulk densities of the alkali silicate compounds can vary between 50 and, for example, 850 g / l. The washing or cleaning agents according to the invention, however, can have a bulk density between 300 and 1200 g / 1, preferably from 500 to IOC g / 1, and preferably contain the alkali silicate compounds according to the invention in amounts of 5 to 50% by weight ¬ others in amounts of 10 to 40 wt .-%. They can be produced by any of the known methods such as mixing, spray drying, granulating, compacting such as roller compaction and extrusion. Processes in which several partial components, for example spray-dried components and granulated and / or extruded components, are mixed with one another are particularly suitable. It is also possible for spray-dried or granulated components to be subsequently treated in the preparation, for example with nonionic surfactants, in particular ethoxylated fatty alcohols, by the customary processes. In granulation and extrusion processes in particular, it is preferred to use the further anionic surfactants, if any, in the form of a spray-dried, granulated or extruded compound, either as an additive component in the process or as an additive to other granules. It is also possible and, depending on the recipe, to be advantageous if further individual constituents 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, are subsequently mixed into spray-dried, granulated and / or extruded components, which may have nonionic surfactants and / or other ingredients which are liquid to wax-like at processing temperature added to them. A method is preferred in which the surface of partial components of the agent or of the entire agent is subsequently treated to reduce the stickiness of the granules and / or to improve their solubility. Suitable surface modifiers are known from the prior art. In addition to other suitable ones, finely divided zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts, for example calcium stearate, but above all mixtures of zeolite and silicic acid, in particular in the weight ratio of zeolite to silica of at least 1: 1, or zeolite and Calcium stearate is particularly preferred.

Particularly preferred embodiments of the invention are extruded washing or cleaning agents with a bulk density above 600 g / l, which contain anionic and optionally nonionic surfactants and an amorphous alkali silicate compound of the type specified in the extrudate. For the production of these extruded washing or cleaning agents, reference is made to the known methods for extrusion, in particular to the European patent EP-B-0486592. Here, a solid and free-flowing premix is extruded at pressures of up to 200 bar, the extrudate is cut to the predetermined granulate dimension after exiting the hole shape by means of a cutting device, and the plastic and, if necessary, still moist crude extrudate is fed to a further shaping processing step and then dried, the alkali silicate compounds according to the invention being used in the premix.

Particularly in the production of extruded detergents or cleaning agents, the alkali silicate compounds containing anionic surfactants surprisingly have advantages over the alkali silicate compound alternatives which are free from anionic surfactants, not only from the point of view of the application technology, but also from the point of view of process engineering. It has been shown that extrusion sion processes, in which in particular anionic surfactant-free alkali silicate carbonate compounds were used, could not be interrupted, since the extrusion mixture lost its plasticity and lubricity so quickly in the resting phase that restarting the system brought with it technical safety problems. This problem was solved by replacing the anionic surfactant-free alkali silicate compounds containing anionic surfactant, in particular alkali silicate compounds containing anionic surfactant and carbonate.

The finished washing or cleaning agents can additionally contain the following ingredients.

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

Suitable anionic surfactants of the sulfonate type are the alkylbenzenesulfonates, olefin sulfonates and alkanesulfonates already mentioned above. However, the esters of oc-sulfofatty acids (ester sulfonates), e.g. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Further suitable anionic surfactants are the α-sulfofatty acids obtainable by ester splitting of the α-sulfofatty acid alkyl esters or their di-salts. The mono-salts of the oc-sulfofatty acid alkyl esters are obtained 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 are mono-, di- and triesters as well as their mixtures, such as those produced 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 of glycerol be preserved. 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 optionally 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 CQ to Ci8 ~ 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, the fatty alcohol residues of which 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 in amounts of 0.2 to 5% by weight. Saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants and soaps can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanola in. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

In one embodiment of the invention, washing or cleaning agents, in particular extruded washing or cleaning agents, which contain 10 to 30% by weight of anionic surfactants are preferred. Advantageously are preferably at least 3% by weight and in particular at least 5% by weight of sulfate surfactants. In an advantageous embodiment, the compositions — based on the anionic surfactants as a whole — contain at least 15% by weight, in particular 20 to 100% by weight, of sulfate surfactants.

The non-ionic surfactants used are preferably the above-described alkoxylated, advantageously ethoxylated alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol.

The alkoxylated fatty acid alkyl esters mentioned above can also be used.

In addition, alkyl glycosides of the general formula R0 (G) _x can also be used as further nonionic surfactants, in which R is 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 C atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

R3

I.

R2_CO-N- [Z] (I) in which R ^{2 is} C0 for an aliphatic acyl radical with 6 to 22 carbon atoms, R3 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 is up to 10 hydroxyl groups. 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 contained in the agents according to the invention preferably 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 washability, the compositions can also contain further, additional builder substances and co-builders. For example, customary builder substances such as phosphates, zeolites and crystalline layered silicates can be included in the compositions. The synthetic zeolite used is preferably finely crystalline and contains bound water. Suitable are, for example, zeolite A, but also zeolite X and zeolite P and mixtures of A, X and / or P. 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 can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated Ci2-Ci8 fatty alcohols with 2 to 5 ethylene oxide groups - Pen, Ci2-Ci4 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).

In a particularly preferred embodiment of the invention, however, washing or cleaning agents contain 10 to 16% by weight of zeolite (based on anhydrous active substance) and 10 to 30% by weight of an alkali silicate compound according to the invention.

In a further particularly preferred embodiment of the invention, however, the washing or cleaning agents contain 0 to 5% by weight of zeolite (based on anhydrous active substance) and 15 to 40% by weight of an alkali silicate compound according to the invention. It is possible for the zeolite not only to be coextruded, but for the zeolite to be introduced into the washing or cleaning agent partially or completely subsequently, that is to say after the extrusion step. Washing or cleaning agents which contain an extrudate which is free of zeolite in the interior of the extrudate grain are particularly preferred.

Crystalline phyllosilicates and / or conventional phosphates can also be used as substitutes for the zeolite. However, it is preferred that the detergents or cleaning agents contain only small amounts, in particular up to 10% by weight, of phosphates.

Crystalline layered silicates are, in particular, crystalline, layered sodium silicates of the general formula aMSi _x θ2χ + yH2θ, 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 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 is sodium and x is 2 or 3. In particular, both beta and ZT sodium disilicate Na2Sι ^* 2θ5'yH2θ are preferred. These crystalline layered silicates are, however, preferably only in the extrudates according to the invention only in amounts of not more than 10% by weight, in particular those of less than 8% by weight, advantageously of at most 5% by weight.

For example, polymeric polycarboxylates can be used as cobuilders. 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. Terpolymers are also particularly preferred, for example those which, according to DE-A-43 00772, are monomers, salts of acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomers contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives. Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and P 44 17 734.8 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Other useful organic cobuilders are 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), provided that 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.

Other suitable builder systems are oxidation products of carboxyl-containing polyglucosans and / or their water-soluble ones Salts as described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application W0-A-93/16110.

The known polyaspartic acids or their salts and derivatives are also to be mentioned as further preferred buder substances.

Other 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-A-0 280 223 . 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.

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

In addition, the agents can also contain components which have a positive effect on the ability to wash off fat and fat from textiles. This effect is particularly evident when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. The agents can also contain constituents which further improve the solubility, in particular of the heavy granules. Such components and the introduction of such components are described, for example, in international patent application WO-A-93/02176 and in German patent application DE-A-4203031. The components preferably used 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 E0 and tallow alcohol with 40 E0, but also fatty alcohols with 14 E0 and polyethylene glycols with a relative molecular weight between 200 and 2000. Among the bleaching agents The sodium perborate monohydrate serving in water H2O2 compounds is of particular importance. Further bleaching agents that can be used are, for example, sodium perborate tetrahydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-delivering persic acid 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 H2O2, 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 525239. The bleach activator content of the bleach-containing agents is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), l, 5-diacetyl-2,4-dioxo-hexahydro-l, 3,5-triazine (DADHT) and acetylated sorbitol mannitol Mixes (S0RMAN). It can be advantageous to add conventional foam inhibitors to the compositions. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci8 ~ C24 fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally signed silica, and also 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.

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, Streptomyces griseus and Humicola insolens, are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but especially protease- and / or lipase-containing mixtures of of special interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

The salts of polyphosphonic acids, in particular l-hydroxyethane-l, l-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or, come as stabilizers, in particular for per compounds and enzymes 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 (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying. Water-soluble colloids of mostly organic nature are suitable for this, 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, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers, such as carboxymethyl cellulose (sodium salt), 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 used.

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-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which contain an replace the morpholino group with a diethanolamino group, a methylamino group, an 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) diphenyl. Mixtures of the aforementioned brighteners can also be used.

In addition to the alkali silicate compounds, which in a preferred embodiment also contain alkali carbonates, the agents can contain further inorganic salts, also further amorphous alkali silicates of the type described above and alkali carbonates of the type described above. Other inorganic salts which can be considered as ingredients are neutral salts such as sulfates and possibly also chlorides in the form of their sodium and / or potassium salts.

Of course, the dyes and fragrances usually contained in detergents or cleaners can also be present.

Examples

Example 1: Production of alkali silicate compounds

The alkali silicate compounds C1 to C4 according to the invention and the comparative compound VC were obtained by conventional spray drying of an aqueous slurry. The composition of the compounds (in weight) was as follows:

Cl C2 C3 C4 VC

amorphous sodium disilicate 28.1 28.1 27.3 24.65 29.0

Sodium carbonate 53.4 53.4 51.7 46.75 55.0

Ci2-Ci8 ~ alkyl sulfate (sodium salt) 3.0

Ci2 ~ alkylbenzenesulfonate (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 compared to the comparative compound VC used in the same amount was determined using a nonionic surfactant which consists of 80% by weight of Ci2 ~ Ci8- Fatty alcohol with 5 E0 and 20% by weight consisted of Ci2-Ci4 fatty alcohol with 3 E0. The nonionic surfactant absorption 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 nonionic 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

Cl 97

C2 110

C3 128

C4 130

VC 57

Example 3: Extrusion Ability

In accordance with 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 problems. The comparable product VE could only be manufactured 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 / 1. 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 EV (in% by weight).

El E2 E3 E4 EV

Cg-Ci3-alkylbenzenesulfonate 11.5 11.5 11.5 11.5 11.5 Ci2-Ci8-alkyl sulfate 10.5 10.5 10.5 10.5 10.5 Ci2-C _j 8-alcohol with 7 EO 4.0 4.0 4.0 4.0 4.0 Ci2-Ci8 ~ fatty acid soap 1.0 1.0 1.0 1.0 1.0 polyethylene glycol with a 1.5 1.5 1.5 1.5 1.5 molecular weight of 400

Zeolite (anhydrous active substance) 1 199, 00 19.0 19.0 19.0 19.0 Acrylic acid-maleic acid copolymer 6.0 6.0 6.0 6.0 6.0 (sodium salt)

Alkali silicate compound Cl 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

claims

1. Spray-dried, amorphous alkali silicate compound with secondary washing ability and a molar ratio M2O: SiO 2 (M = alkali metal) between 1: 1.5 and 1: 3.3, characterized in that it contains anionic surfactants in amounts of 0.5 contains up to less than 30% by weight.

2. alkali silicate compound according to claim 1, characterized in that there are 15 to 80 wt .-% alkali silicates, 1 to 25 wt .-% anionic surfactants, preferably up to 20 wt .-% anionic surfactants, and 10 to 22 wt .-% % Contains water.

3. alkali silicate compound according to claim 1 or 2, characterized in that it 15 to 50 wt .-%, preferably 20 to 40 wt .-% alkali silicates, 30 to 70 wt .-%, preferably 40 to 65 wt .-% Contains alkali metal carbonates, 1.5 to 15% by weight and in particular 2 to 12% by weight of anionic surfactants, advantageously alkylbenzenesulfonates and / or alk (en) yl sulfates, and 12 to 19% by weight of water.

4. alkali silicate compound according to one of claims 1 to 3, characterized ge indicates that it has an absorption capacity for liquid components which is at least 20%, preferably at least 30% and in particular at least 50% higher than that of equal-quantity alkali silicate compounds without anionic surfactants.

5. alkali silicate compound according to any one of claims 1 to 4, characterized ge indicates that it has been aftertreated with liquid components, the ingredients of detergents or cleaning agents, in particular nonionic surfactants.

6. A process for the preparation of an amorphous alkali silicate compound with secondary washing power according to one of claims 1 to 5, characterized ge indicates that the co pound are produced by spray drying an aqueous slurry which contains all the constituents of the alkali silicate compound.

7. The method according to claim 6, characterized in that the compound is produced by spray drying an aqueous preparation of the Mehrkompon¬ mixture with superheated steam.

8. The method according to claim 6 or 7, characterized in that the spray-dried alkali silicate compound is subsequently treated with liquid ingredients of detergents or cleaning agents, in particular with nonionic surfactants.

9. Use of an alkali silicate compound with secondary washing ability according to one of claims 1 to 5 in detergents or cleaning agents, the latter being produced by spray drying, granulation, compacting such as roller compaction or extrusion or by mixing processes.

10. washing or cleaning agent containing 10 to 16 wt .-% zeolite (based on anhydrous active substance) and 10 to 30 wt .-% of an alkali silicate compound according to any one of claims 1 to 5.

11. washing or cleaning agent containing 0 to 5% by weight zeolite (based on anhydrous active substance) and 15 to 40% by weight of an alkali silicate compound according to any one of claims 1 to 5.

12. Extruded washing or cleaning agent with a bulk density above 600 g / 1, containing anionic and optionally non-ionic surfactants and an amorphous alkali silicate, characterized in that it is an amorphous alkali silicate compound with secondary washing capacity according to one of claims 1 contains up to 5.

13. A process for the production of a detergent or cleaning agent, a solid and free-flowing premix being pressed into strands at pressures of up to 200 bar, the strand after exiting the hole shape by means of a cutting device to the predetermined size of the granulate cut and the plastic, optionally moist crude extrudate is fed to a further shaping processing step and then dried, characterized in that an amorphous alkali silicate compound according to one of Claims 1 to 5 is used in the premix.