EP0936267A2 - Alkali metal silicate/ nonionic surfactant compound - Google Patents

Abstract

Production of a powdery mixture containing an alkali metal silicate with mole ratio SiO2:M2O of 1.8-4. M = Na and/or K and a nonionic surfactant. Production of a powdery mixture containing an alkali metal silicate with mole ratio SiO2:M2O of 1.8-4.0. M = Na and/or K and a nonionic surfactant by: (i) drying an aqueous solution of the silicate; (ii) pulverizing the solid product if necessary and isolating the fraction of size 0.2 - 0.6 mm; and (iii) contacting this fraction with the nonionic surfactant such that the wt. ratio nonionic surfactant:solid product in step (i) is above 0.5.

Description

The invention is in the field of detergents and cleaning agents. It affects the production and use of solid, water-soluble alkali metal silicates, optionally as a compound with other components containing such Amount of nonionic surfactants are loaded that the weight ratio non-ionic surfactants for solid product serving as carrier is greater than 0.5. In spite of this high loading with the liquid or waxy nonionic This compound is flowable to tensides and can therefore be more solid as a component Detergents, washing aids and cleaning agents are used. The water soluble Alkali metal silicate has a double function: it serves as a Backing material for absorbing liquid to waxy nonionic Surfactants. Secondly, it itself has builder and anti-corrosion properties and thus contributes to the performance of detergents and cleaning agents.

Nonionic surfactants are an essential component of current laundry and Detergent. In the manufacture of detergents and cleaning agents in solid form, for example as powder, granules, compactates or extrudates the problem, a sufficient amount of liquid to waxy or paste-like nonionic surfactants in the washing or cleaning agent to be introduced without this losing its flowability. Therefore, it is required, the liquid, waxy or pasty nonionic Apply surfactants to a suitable carrier material. For this you use usually inorganic carrier materials, but only up to one certain maximum limit can be loaded with the nonionic surfactants, without getting sticky. If you set as carrier materials, for example, as in Known in the art, sodium carbonate or sodium sulfate can be if necessary, produce compounds that contain up to 30% by weight of nonionic surfactants contain. When using pore-rich carrier materials such as water-insoluble silicates and aluminosilicates such as, in particular, zeolites can be Compounds containing up to 65 wt .-% nonionic surfactants. The However, the carrier materials mentioned have the disadvantage of not being water-soluble be.

WO 97/28240 provides a dispersion, its continuous phase is a concentrated aqueous solution of an alkali metal silicate in which Droplets or particles of the nonionic surfactants are dispersed. This Dispersion can be dried in the form of a thin film, for example, which you can then break up into a powder. This gives you a free-flowing powder from sodium silicates, in the particles of which are droplets nonionic surfactants are included. The content of the compound nonionic surfactants can be over 50% by weight, i. H. the Weight ratio of nonionic surfactants to alkali metal silicates can be greater than 1 be.

The object of the present invention is a water-soluble compound from alkali metal silicates and nonionic surfactants with a high proportion of to provide nonionic surfactants, the nonionic Surfactants on the particles of sodium silicate used as carriers are upset. The compound is said to flow freely and as a component of solid washing and Detergent can be used.

a) eine wäßrige Lösung, welche die Alkalimetallsilicate enthält, zu einem Festprodukt trocknet,

b) das im Teilschritt a) erhaltene Festprodukt pulverisiert, sofern es nicht bereits als Pulver vorliegt, und die Fraktion mit einer Teilchengröße im Bereich von 0,2 bis 0,6 mm isoliert, sofern das Pulver nicht bereits ausschließlich aus dieser Fraktion besteht, und

c) auf das Pulver mit einer Teilchengröße im Bereich von 0,2 bis 0,6 mm die nichtionischen Tenside in einer solchen Menge aufbringt, daß das Gewichtsverhältnis nichtionische Tenside : dem in Teilschritt a) erhaltenen Festprodukt größer ist als 0,5.

This object is achieved by a process for producing a powdery mixture which contains at least alkali metal silicates with a molar ratio of SiO ₂ : M ₂ O, M = sodium and / or potassium, in the range from 1.8 to 4.0 and nonionic surfactants , that he

a) drying an aqueous solution which contains the alkali metal silicates to give a solid product,

b) pulverizing the solid product obtained in sub-step a), if it is not already in the form of a powder, and isolating the fraction with a particle size in the range from 0.2 to 0.6 mm, unless the powder already consists exclusively of this fraction, and

c) the nonionic surfactants are applied to the powder with a particle size in the range from 0.2 to 0.6 mm in such an amount that the weight ratio of nonionic surfactants: the solid product obtained in sub-step a) is greater than 0.5.

For this purpose, preference is given to using alkali metal silicates in which the molar ratio SiO ₂ : M ₂ O, M = sodium and / or potassium is in the range from about 2.0 to about 3.4. Alkali metal silicates in the specified ranges of the molar ratio have builder properties in detergents and cleaning agents, combined with an anti-corrosion effect.

For economic reasons, preference is given to using alkali metal silicates which contain only sodium as alkali metal. Potassium silicates are more expensive than Sodium silicates, but more soluble in water. So you put on a particularly high one Water solubility value, it is recommended that the sodium at least partially to be replaced by potassium.

In step a), the aqueous solution containing the alkali metal silicates can to any solid product known in the art be dried. The drying takes place so far that the obtained Solids still have a residual water content by measuring the weight loss is determinable at 800 ° C, in the range of about 3 to about 25 wt .-%. The Drying to a solid product can, for example, in an oven, with a Contact dryers, in a fluidized bed or by spray drying.

Spray Drying Handbook", 4. Auflage, George Godwin, London (1985). Auf die Trocknungsbedingungen für Natriumsilicatlösungen wird auf dessen Seiten 566 und 567 näher eingegangen. Weiterhin wird die Sprühtrocknung von Alkalimetallsilicatlösungen beispielsweise beschrieben in US-A-3 8398 192.The preferred drying method is spray drying. The spray drying process is widely used in the prior art. For example, it is extensively described in K. Masters:

Spray Drying Handbook ", 4th edition, George Godwin, London (1985). The drying conditions for sodium silicate solutions are discussed in more detail on pages 566 and 567 thereof. Furthermore, spray drying of alkali metal silicate solutions is described, for example, in US Pat. No. 3,8398,192.

The aqueous solution, which contains the alkali metal silicates and which is dried to a solid product in sub-step a), can contain and / or disperse further ingredients of washing, washing aids and cleaning agents in such an amount that the proportion of alkali metal silicates in the total solids content the aqueous solution is between 99.9 and 50% by weight. The further ingredients of washing, washing aids and cleaning agents can be selected from
inorganic salts such as sodium phosphates, sodium sulfate, sodium hydrogen carbonate and sodium carbonate. Sodium carbonate is particularly preferred
Complexing agents such as salts of citric acid, 1-hydroxyethane-1,1-diphosphonic acid and phosphonobutane tricarboxylic acid,
organic polymers with builder properties such as, for example, polymers and copolymers of acrylic acid, methacrylic acid and maleic acid,
anionic surfactants such as alkyl sulfates and alkyl sulfonates. These surfactants are preferably added to the aqueous solution in amounts such that their share in the total solids content of the solution is not greater than 20% by weight.

In sub-step b) the solid product obtained in sub-step a) is pulverized, provided that it is not already in powder form. The sub-step of pulverization can therefore for example omitted if the solid product by spray or Fluid bed drying was obtained. It is then already in the desired one Powder form. However, in step a) the aqueous solution is closed in a way a solid product has been dried so that it is not in powder form, so it has to be ground to a powder. This is the case, for example, if you use oven or contact drying. The powder becomes the fraction isolated with a particle size in the range of 0.2 to 0.6 mm, provided that The powder was not produced in such a way that it was at least 90 % By weight consists of this fraction. For example, it is after a spray or Fluid bed drying required, from the powder obtained the above Isolate fraction. This is preferably done by screening, but it is also possible, for example, by wind sighting.

In step c), the powder with a particle size in the range of 0.2 to 0.6 mm the nonionic surfactants in such an amount that the Weight ratio of nonionic surfactants: that obtained in substep a) Solid product is greater than 0.5. The nonionic surfactants are preferably used in an amount such that the weight ratio is greater than 0.8 and is preferably greater than 1.0. The nonionic surfactants can contain up to 25 % By weight, based on the mass of the nonionic surfactants, anionic surfactants or contain other substances that are good in non-ionic Dissolve or disperse surfactants.

The invention is based on the surprising finding that especially after Spray drying the absorption capacity of the alkali metal silicates for liquid, wax-like or paste-like non-ionic surfactants do not work as expected increasing particle size of the alkali metal silicate particles decreases. Rather it has Surprisingly, it has been shown that the sodium silicate particles are particularly special can absorb a lot of non-ionic surfactants if that by sieve analysis certain particle size is in the range of 0.2 to 0.6 mm. At a Particle size in the range of about 0.4 mm becomes a maximum Absorption capacity observed for nonionic surfactants, that to larger and smaller particle sizes.

This finding is surprising since it is usually assumed that the nonionic Surfactants the particles of the carrier material with a certain layer thickness envelop. However, since the specific surface of the carrier material is smaller Particle size increases, it would be expected that the carrier material one can absorb larger amounts of nonionic surfactants, the smaller its particles and the larger its specific surface is. So it is in the field of detergents, for example, is known to occur in smaller particles Zeolite P has a higher surfactant absorption capacity than that with larger ones Particle size of zeolite A. Comparative experiments with carrier materials with smooth surface such as glass balls show that these carrier materials also have the expected behavior, the more nonionic surfactants the smaller the particle size.

a) alkoxylierten Alkoholen mit 8 bis 22 C-Atomen im Alkylrest mit 1 bis 25 Alkylenoxideinheiten,

b) Alkylglycosiden mit Alkylresten mit 8 bis 22 C-Atomen,

c) Alkylaminoxiden mit zumindest einem Alkylrest mit 8 bis 22 C-Atomen,

d) Polyhydroxyfettsäureamiden von Fettsäuren mit 6 bis 22 C-Atomen, die am N-Atom zumindest einen Polyhydroxyalkylrest mit 3 bis 10 C-Atomen und mit 3 bis 10 Hydroxylgruppen tragen,

e) Alkoxylierten Fettsäuren mit 8 bis 22 C-Atomen in der Fettsäure mit 5 bis 25 Alkylenoxideinheiten,

f) Alkoxylierten Fettsäureamiden mit 8 bis 22 C-Atomen in der Fettsäure mit 5 bis 25 Alkylenoxideinheiten

g) Alkoxylierten Fettaminen mit zumindest einer Alkyl- oder Alkenylgruppe mit 8 bis 22 C-Atomen mit 5 bis 25 Alkylenoxideinheiten.

The nonionic surfactants are preferably selected from

a) alkoxylated alcohols with 8 to 22 carbon atoms in the alkyl radical with 1 to 25 alkylene oxide units,

b) alkyl glycosides with alkyl radicals with 8 to 22 carbon atoms,

c) alkylamine oxides with at least one alkyl radical having 8 to 22 carbon atoms,

d) polyhydroxy fatty acid amides of fatty acids with 6 to 22 C atoms which carry at least one polyhydroxyalkyl radical with 3 to 10 C atoms and with 3 to 10 hydroxyl groups on the N atom,

e) alkoxylated fatty acids with 8 to 22 carbon atoms in the fatty acid with 5 to 25 alkylene oxide units,

f) Alkoxylated fatty acid amides with 8 to 22 carbon atoms in the fatty acid with 5 to 25 alkylene oxide units

g) Alkoxylated fatty amines with at least one alkyl or alkenyl group with 8 to 22 carbon atoms with 5 to 25 alkylene oxide units.

Examples of suitable nonionic surfactants are 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 alcohols 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. The alcohol ethoxylates can 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 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (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 is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of them.

in der R²CO 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 the R ² CO for an aliphatic acyl radical having 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.

Further examples of suitable nonionic surfactants are in WO 97/28240 included, thus made the subject of the present disclosure becomes.

To apply the nonionic surfactants in sub-step c), the im State of the art use mixing and agglomeration units. Examples include slow rotating and preferably mixing ones Built-in drums, for example ploughshare mixers from the company Lödige. Also suitable are, for example, granulating plates, which are a preferably turn the axis inclined to the vertical. Furthermore, that Application of the nonionic surfactants in a fluidized by a gas stream Fluid bed of the solid take place. All procedures have in common that the nonionic surfactants or a solution thereof sprayed onto the solid while its particles are in motion.

If by applying solutions of nonionic surfactants on the Solids in sub-step c) the total water content of that obtained in sub-step c) Compounds increased above the desired upper limit, can in step c) Compound obtained by heating to the desired water content be dried.

In a further aspect, the invention relates to the use of an after product produced above process as part of solid washing, Washing aids or cleaning agents. The washing, auxiliary washing and Detergents contain other ingredients that are common in the prior art are shown below as examples:

Anionic surfactants which are used in or together with the alkali silicate / surfactant 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 washing, washing aids or cleaning agent therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C ₁₂ C ₁₄ or C ₁₂ -C ₁₈ -Fettalkylsulfaten -Fettalkylsulfaten with C ₁₆ -C ₁₈ and more particularly -Fettalkylsulfaten 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 sulfonated 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.

The sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 mol ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol ethylene oxide (EO) or C ₁₂ - C ₁₈ fatty alcohols with 1 to 4 EO 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.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which Represent mono-, di- and triesters and their mixtures as they are in the Production by esterification by a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol become.

Suitable surfactants of the sulfate type are the aforementioned sulfuric acid monoesters from primary alcohols of natural and synthetic origin and, if appropriate, their alkoxylated, preferably ethoxylated, derivatives. 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 be soaps, preferably in amounts of 0.2 to 5% by weight. 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 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 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 surfactants are preferably in the form their sodium or potassium salts, especially in the form of the sodium salts.

In addition to the alkali silicate / surfactant compounds produced according to the invention, the washing, washing aids and cleaning agents 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 agents. 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 can contain small 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 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 detergents, auxiliary washing agents 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 contain washing or Cleaning agents, however, 10 to 16 wt .-% zeolite (based on anhydrous Active substance) and 10 to 30% by weight of an alkali silicate compound produced according to the invention.

Included in a further particularly preferred embodiment of the invention the washing or cleaning agents, however, 0 to 5 wt .-% zeolite (based on anhydrous active substance) and 15 to 40% by weight of one according to the invention Alkali silicate compounds produced. It is possible that the zeolite at Application of an extrusion process is not only co-extruded, but that the zeolite partially or completely retrospectively, i.e. after the extrusion step into the Detergent or cleaning agent is introduced. Are particularly preferred here Detergents or cleaning agents that contain an extrudate that is inside the Extrudate grain is free of zeolite.

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

Crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, and are preferred as crystalline layered silicates 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 phyllosilicates of the formula given are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

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 mass from 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As Copolymers of acrylic acid with maleic acid have been particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain. Their relative molecular mass, based on free acids, is in 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 according to DE-A-43 00 772 as monomers salts acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.

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 for ecological reasons is not objectionable, 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 ones Polyglucosans and / or their water-soluble salts as they described for example in the international patent application WO-A-93/08251 be or their production, for example, in the international Patent application WO-A-93/16110 is described.

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 at least 3 have hydroxyl groups, for example as in the European Patent application EP-A-0 280 223 can be obtained. Preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as Obtain 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 wt .-% in the finished washing, auxiliary washing or Detergents may be included.

In addition, the agents can also contain components that the oil and Influencing fat washability from textiles positively. This effect will particularly clear if a textile is soiled that has already been used several times with a detergent according to the invention that this oil and fat-dissolving Contains 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 of methoxyl groups from 15 to 30% by weight and hydroxypropoxyl groups from 1 to 15 % By weight, based in each case on the nonionic cellulose ether, and that from the Polymers of phthalic acid and / or of known in the art Terephthalic acid or its derivatives, in particular polymers Ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof.

The agents can also contain components which have solubility further improve especially of heavy granules. Such components and the introduction of such components are, for example, in the international Patent application WO-A-93/02176 and in the 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 EO, but also Fatty alcohols with 14 EO and polyethylene glycols with a relative molecular weight between 200 and 2000.

The detergents, auxiliary washing agents and cleaning agents can furthermore contain bleaches. Sodium perborate monohydrate is of particular importance among the compounds which serve as bleaching agents and produce H ₂ O ₂ in water. Further bleaching agents which can be used are, for example, sodium perborate tetrahydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing 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 O-acyl compounds which form organic peracids with H ₂ O 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. Bacterial strains are particularly suitable or mushrooms, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens enzymatic active ingredients obtained. Proteases of the subtilisin type and in particular proteases are preferably which are obtained from Bacillus lentus. Here are enzyme mixtures, for example from 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 protease and / or Mixtures of lipase of particular interest. Peroxidases too or oxidases have been found 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 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 salts come as stabilizers, in particular for per-compounds and enzymes 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 BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous.

Graying inhibitors have the task of removing the dirt detached from the fiber keep suspended in the fleet and thus prevent graying. For this are water-soluble colloids mostly of an organic nature, 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. Also water soluble, polyamides containing acidic groups are suitable for this purpose. Farther soluble starch preparations and other than the above Use starch products, e.g. degraded starch, aldehyde starches, etc. Also Polyvinyl pyrrolidone is useful. However, cellulose ethers such as Carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and Mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, Methyl carboxymethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone for example in amounts of 0.1 to 5 wt .-%, based on the agent used.

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 compounds of the same structure, which instead of the morpholino group Diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group carry. Brighteners of the type of substituted diphenylstyryl, 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 be used.

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

The invention further relates to a method for producing a washing, Detergent or cleaning agent, in which one after the Powdered mixture produced according to the method of the invention Alkali metal silicates and non-ionic surfactants with the remaining ingredients of the detergent, auxiliary washing agent or cleaning agent. Examples of such remaining ingredients were listed above.

The washing, manufactured by mixing the components mentioned Detergents or cleaning agents can be used in the prior art known measures such as granulation, compacting or Extrusion can be brought into a low-dust form and / or compressed. To this In this way, compact detergents with bulk weights can be obtained for example in the range from 500 to 1000 g / l.

Finally, the invention relates to solid washing, auxiliary washing or cleaning agents, which is a powdery prepared by the inventive method Contain a mixture of alkali metal silicates and nonionic surfactants. Of the Share of this process product in the washing, auxiliary washing or Detergent is in the amount range between about 5 and about 50 wt .-%. The remainder to 100 wt .-% form those listed above by way of example remaining components of washing, washing aids or cleaning agents.

Embodiments Determination of the nonionic surfactant absorption capacity

The surfactant absorption capacity was analogous to the standard DIN ISO 787 General test methods for pigments and fillers, determination of the oil number "in the version from 1983, wherein the coating oil was replaced by nonionic surfactant (C _12-18 fatty alcohol x 7 mol ethylene oxide).

In the standard it is pointed out that the determined number of oils by the processor depends and values from different laboratories are not necessarily comparable are. In round robin tests, absolute values differed by up to 60%, yet the Method reproducible within a laboratory.

The determination is made as follows:
The sample is placed on a glass plate (in the case of the glass balls, a watch glass is used) and weighed out. 4 to 5 drops of nonionic surfactant (C _12-18 fatty alcohol x 7 mol ethylene oxide) are slowly added from a Pasteur pipette. After the addition, the surfactant is worked into the sample with a spatula. The addition of the surfactant continues accordingly until the agglomeration of surfactant and sample forms. Then a drop of surfactant is added and rubbed in thoroughly with a spatula until a soft paste suddenly forms. The paste should stick to the plate without tearing or crumbling. The amount of surfactant absorbed is determined by weighing again.

As a sample, a sodium silicate powder was used, which was obtained by spray drying an aqueous solution of sodium silicate with a molar ratio of SiO ₂ : Na ₂ O = 2.4. The different grain size fractions, the surfactant absorption capacity of which was determined as above, were separated by sieving the powder. The results are shown in Table 1. Spray-dried Na water glass, molar ratio 2.4 Particle size (µm) Surfactant number (g / 100) g 32-50 47.4 ± 1.7 50-63 46.4 ± 1.3 63-100 48.2 ± 1.1 100-200 60.6 ± 2.1 200-315 128.5 ± 4.7 315-500 172.9 ± 4.6 500-630 153.7 ± 2.9 630-100 72.5 ± 3.6

In comparison, the surfactant absorption capacity of glass spheres was determined as a function of the particle size range. The results are summarized in Table 2. Comparison: glass balls Particle size (µm) Surfactant number (g / 100 g) 100-110 17.7 ± 0.8 170-180 15.2 ± 0.6 250-300 12.9 ± 0.7 450-500 8.8 ± 0.6 1000 5.5 ± 0.3 1500-2000 2.5 ± 0.1

A comparison of Tables 1 and 2 shows that the glass spheres are so far behave as expected, as the surfactant uptake with falling Particle size and thus increases with increasing specific surface area. In contrast, the spray-dried water glass powder shows a remarkable Maximum surfactant absorption in the particle size range between about 200 and about 630 µm.

Claims (11)

Process for the preparation of a powdery mixture which contains at least alkali metal silicates with a molar ratio SiO ₂ : M ₂ O, M = sodium and / or potassium, in the range from 1.8 to 4.0 and nonionic surfactants, characterized in that a) drying an aqueous solution which contains the alkali metal silicates to give a solid product, b) pulverizing the solid product obtained in sub-step a), if it is not already in the form of a powder, and isolating the fraction with a particle size in the range from 0.2 to 0.6 mm, unless the powder already consists exclusively of this fraction, and c) the nonionic surfactants are applied to the powder with a particle size in the range from 0.2 to 0.6 mm in such an amount that the weight ratio of nonionic surfactants: the solid product obtained in sub-step a) is greater than 0.5. A method according to claim 1, characterized in that the molar ratio SiO ₂ : M ₂ O, M = sodium and / or potassium is in the range from 2.0 to 3.4. Method according to one or both of claims 1 and 2, characterized characterized in that the aqueous solution in sub-step a) by spray drying is dried to a solid product. Method according to one or more of claims 1 to 3, characterized characterized in that the aqueous solution in sub-step a) further ingredients of detergents, washing aids and cleaning agents dissolved in such an amount and / or dispersed contains that the proportion of alkali metal silicates on Total solids content of the aqueous solution is between 99.9 and 50% by weight. A method according to claim 4, characterized in that the further Ingredients of washing, washing aids and cleaning agents are selected from inorganic salts, complexing agents, organic polymers with Builder properties and anionic surfactants. Method according to one or more of claims 1 to 5, characterized characterized in that in sub-step c) the nonionic surfactants in a such an amount that the weight ratio of nonionic surfactants: the solid product obtained in sub-step a) is greater than 0.8. Method according to one or more of claims 1 to 6, characterized in that the nonionic surfactants are selected from a) alkoxylated alcohols with 8 to 22 carbon atoms in the alkyl radical with 1 to 25 alkylene oxide units, b) alkyl glycosides with alkyl radicals with 8 to 22 carbon atoms, c) alkylamine oxides with at least one alkyl radical having 8 to 22 carbon atoms, d) polyhydroxy fatty acid amides of fatty acids with 6 to 22 C atoms which carry at least one polyhydroxyalkyl radical with 3 to 10 C atoms and with 3 to 10 hydroxyl groups on the N atom, e) alkoxylated fatty acids with 8 to 22 carbon atoms in the fatty acid with 5 to 25 alkylene oxide units, f) Alkoxylated fatty acid amides with 8 to 22 carbon atoms in the fatty acid with 5 to 25 alkylene oxide units g) Alkoxylated fatty amines with at least one alkyl or alkenyl group with 8 to 22 carbon atoms with 5 to 25 alkylene oxide units. Use one according to the method of one or more of the Claims 1 to 7 manufactured product as part of solid washing, Washing aids or cleaning agents. Process for the production of a detergent, auxiliary washing agent or cleaning agent, characterized in that one according to the method according to one or several of claims 1 to 7 manufactured product with the rest Components of the detergent, auxiliary washing or cleaning agent mixed. A method according to claim 9, characterized in that one according to the Method according to one or more of claims 1 to 7 manufactured product with the remaining components of the detergent, auxiliary washing agent or cleaning agent mixed and the mixture obtained by granulation, compacting or by extrusion into a low-dust form and / or compacted. Solid detergent, auxiliary washing agent or cleaning agent, which is an after the procedure contains product manufactured according to one or more of claims 1 to 7.