EP0777721B1 - Process for producing tablets of washing or cleaning agents - Google Patents

Abstract

PCT No. PCT/EP95/03169 Sec. 371 Date Mar. 26, 1997 Sec. 102(e) Date Mar. 26, 1997 PCT Filed Aug. 10, 1995 PCT Pub. No. WO96/06156 PCT Pub. Date Feb. 29, 1996A process for producing detergent tablets containing more than 10% by weight of anionic surfactant wherein the detergent tablets contain detergent components which are at least partly in hydrated form and the anionic surfactant is present in the form of one or more compounds containing up to 95% by weight of surfactants, by exposing a mixture of the detergent components and the anionic surfactant to microwaves in the frequency range from 3 to 300,000 MHz.

Description

The invention relates to a process for producing surfactant-containing washing or detergent tablets using microwave technology.

The disadvantage of conventional detergent tablets, in particular of detergent tablets, usually by pressing were made, was that these tablets due to their Compactness did not dissolve quickly enough and the active substances in the wash were released too slowly. Additionally owned in particular Detergent tablets have too slow a disintegration rate.

The older, non-prepublished international application WO-A-94/25563, the disclosure of which is expressly referred to, describes in detail the manufacture of washing and cleaning-active tablets using microwave technology, which have an extremely high dissolution or disintegration rate. An essential prerequisite for the production of tablets from powdered or granular raw materials using microwaves is that at least some of these starting materials are in hydrated form, being hydrated under "hydrated" under certain conditions with regard to temperature, pressure or relative humidity of the atmosphere which the raw material is exposed to or with which the raw material is in equilibrium "is understood. In the context of this invention, “microwaves” is understood to mean the entire frequency range between 3 and 300,000 MHz, which thus also includes the radio wave range of 3 to 300 MHz in addition to the actual microwave range of above 300 MHz. This technique can be used to produce so-called macrosolids, which in addition to tablets also include blocks, for example, which can usually contain up to 40% by weight of surfactants. If one of the raw materials used in substantial amounts is a crystalline layered silicate, in particular of the type SKS-6 ^(R) (crystalline sodium disilicate; commercial product from Hoechst AG, Germany), the surfactant content can even be up to 60% by weight. Other possible ingredients are on the one hand the microwave-active hydrated inorganic or organic salts such as alkali phosphate, alkali carbonate, alkali bicarbonate, alkali sulfate and citrate, but also zeolite and even peroxy bleaching agents such as perborate or percarbonate. These are preferably used in encased form.

The German patent application DE-A-23 27 956 describes a process for the production of Granules in which a raw granulate with at least one is capable of hydration Component and water inflated by means of microwave radiation without it Caking comes.

The German published patent application DE-A-31 04 371 describes detergent tablets with high Dissolving rate of 10 to 55% by weight of surfactants, 80 to 25% by weight of phosphates, 5 to 20 % By weight polyvenülpolypyrolidon, 0.1 to 2% by weight of silica and optionally pasty contain nonionic surfactant, sticking to the mixing or Pressing tools are prevented by placing the connections in water-free low water form.

Difficulties still exist in the manufacture of microwave tablets, which anionic surfactants in substantial quantities, for example in quantities above 10% by weight and inorganic salts in amounts below 60 % By weight. Such tablets can be technically according to the Manufacture teaching of WO-A-94/25563; especially those containing sulfate and sulfonate However, anionic surfactants tend to increase in such high concentrations Browning, which does not affect the washing performance, which, however, are not accepted by the consumer. It also worsened the dissolving behavior of the tablets increases with the surfactant content.

It has now been found that the dissolving behavior of microwave tablets containing surfactants can be increased by a substantial part of the surfactants is not incorporated into the tablets as a single raw material.

The invention accordingly relates to a process for the production Detergent tablets containing anionic surfactants using microwave technology with microwaves of the frequency range 3 to 300 000 MHz from source materials, which are at least partially in Hydralized form are present, characterized in that the anionic surfactants in the form one or more compounds are introduced into the process, the compounds contain up to 95% by weight of surfactants.

The use of such surfactant compounds, even highly concentrated ones Surfactant compounds with contents of up to about 95 wt .-% of surfactants local surfactant concentration differences in the tablet, which is not only as an advantage in processing, but also in later decay of the tablet in the wash liquor.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as those obtained from C ₁₂ -C ₁₈ monoolefins with an end or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under Fatty acid glycerol esters are the mono-, di- and triesters as well as their To understand mixtures as they are produced by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of Triglycerides with 0.3 to 2 moles of glycerin can be obtained. Preferred sulfated Fatty acid glycerol esters are the sulfonation products of saturated Fatty acids with 6 to 22 carbon atoms, for example the Caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, Stearic acid or behenic acid. If you start from fats and Oils, i.e. natural mixtures of different fatty acid glycerol esters off, it is necessary to in the feed products before sulfonation to become saturated with hydrogen to a large extent, i.e. on Iodine numbers less than 5, advantageously less than 2 to harden. Typical Examples of suitable feedstocks are palm oil, palm kernel oil, palm stearin, Olive oil, rape oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, Linseed oil, lard oil or lard. Because of their high natural content in terms of saturated fatty acids, however, it has proven to be particularly advantageous proven to start from coconut oil, palm kernel oil or beef tallow. The Sulfation of saturated fatty acids with 6 to 22 carbon atoms or of mixtures of fatty acid glycerol esters with iodine numbers less than 5, the Containing fatty acids with 6 to 22 carbon atoms is preferably done by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as described in the international patent application WO-A-91/09009 is indicated. The sulfonation products represent a complex Mixture, the mono-, di- and triglyceride sulfonates with α-permanent and / or internal sulfonic acid grouping. As by-products sulfonated fatty acid salts, glyceride sulfates, glycerol sulfates, Glycerin and soaps. If you go from the sulfation of saturated Fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of α-sulfonated fatty acid disalts can vary depending on the procedure can be up to about 60% by weight.

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 especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil 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 compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably C ₁₂ -C ₁₈ fatty alkyl sulfates or mixtures of C ₁₂ -C ₁₄ fatty alkyl sulfates or C ₁₂ -C ₁₈ fatty alkyl sulfates with C ₁₆ -C ₁₈ -Fatty alkyl sulfates and especially C ₁₂ -C ₁₆ fatty alkyl sulfates with C ₁₆ -C ₁₈ fatty alkyl sulfates. In a further preferred embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C ₁₆ to C ₂₂ are used. Mixtures of saturated sulfated fatty alcohols predominantly consisting of C ₁₆ and unsaturated sulfated fatty alcohols predominantly consisting of C ₁₈ are particularly preferred, for example those derived from solid or liquid HD-Ocenol ^(R) fatty alcohol mixtures (commercial product of the applicant) . Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.

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

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially 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 in themselves are nonionic surfactants (description see below). 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.

Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C ₁₂ -C ₂₄ fatty acid soaps and 0 to 50% by weight of oleic acid soap.

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

In addition to anionic surfactants, the tablets, optionally also in the anionic surfactant-containing compounds also non-ionic, cationic, zwitterionic or amphoteric surfactants can be used. Here are in particular nonionic surfactants preferred.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (E0) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2 position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of 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 E0 per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 E0 or 4 E0, C ₉ -C ₁₁ alcohol with 7 E0, C ₁₃ -C ₁₅ alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C ₁₂ -C ₁₈ alcohols with 3 E0, 5 E0 or 7 E0 and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 E0 and C ₁₂ -C ₁₈ alcohol with 5 E0. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 E0 can also be used. Examples include tallow fatty alcohol with 14 E0, 25 E0, 30 E0 or 40 E0.

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; x is preferably 1.2 to 1.4.

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

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

in der 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.

In a preferred embodiment of the invention, those containing anionic surfactants are used Compounds used, which different anionic surfactants - for example Alkyl sulfates and alkyl benzene sulfonates and / or soap or alkyl sulfates and sulfonated fatty acid glycerol ester and / or anionic surfactants in combination with nonionic surfactants - for example alkyl sulfates and ethoxylated Fatty alcohols or alkyl sulfates, alkylbenzenesulfonates, ethoxylated fatty alcohols and / or alkyl glycosides or alkyl sulfates, soap, ethoxylated Fatty alcohols and glucamides - included. It is preferably to compounds which contain anionic surfactants and nonionic surfactants in a weight ratio of 10: 1 to 1: 1 included.

Compounds used with preference have a surfactant content of at least 10% by weight. In a further preferred embodiment of the invention compounds are used which contain at least 40% by weight, preferably 60 up to 95% by weight, based on the compound, of anionic surfactants.

Another preferred embodiment of the invention provides that at least 2 different types of compounds are used in the process. For example, it is possible to use anionic surfactants and nonionic surfactants to be spatially separated from one another as much as possible, i.e. in different To house compounds. Compounds containing nonionic and nonionic surfactants can, for example, 40 to 70 wt .-% of the nonionic surfactants mentioned and silicates of the known type, organic builder substances such as polymers Contain polycarboxylates and / or phosphonates.

Particularly advantageous embodiments of the invention provide that at least 35% by weight, preferably at least 50% by weight and in particular at least 70% by weight of the total formulation of the washing or cleaning agent tablet consist of one or more different types of compounds. Here, a method can be particularly advantageous in which at least 75% by weight and up to 100% by weight of the total formulation as a compound, which may have been post-treated.

In this way, conventional and commercially available washing or Cleaning agents which contain at least one compound containing anionic surfactants, convert into tablets in the manner according to the invention. Examples for this are spray-dried detergents with bulk weights of around 300 up to 600 g / l, preferably 5 to 40 in the spray-dried proportions % By weight of anionic surfactants. These spray-dried granules can also with additional ingredients from washing or cleaning agents sprayed or powdered under granulating conditions, which increases the bulk weight. As preferred liquid ingredients are nonionic surfactants, for example as powdering agents finely divided zeolites, silicas, sulfates and / or calcium stearates to call. In other preferred detergents or cleaning agents spray-dried granules containing anionic surfactant lie next to spray-dried granules or granulated compounds, which consist of carrier materials such as Zeolite, crystalline layered silicates, polymeric polycarboxylates, carbonates and possibly also silicates and with liquid up pasty or waxy ingredients such as nonionic surfactants and / or impregnated with foam inhibitors or conventional textile softeners are.

In a further embodiment of the invention, not only are spray-dried Detergents or cleaning agents, but also granulated or extruded Detergents or cleaning agents, which, for example, according to Process according to European patent applications EP-A-0 339 996, EP-A-0 420 317 or international patent applications WO-A-93/23523 or WO-A-91/02047 were claimed.

Of course it is also possible and even within the scope of this invention preferred, not only such existing agents in the specified Kind of tableting, but separately manufactured compounds if necessary to mix with relatively small amounts of individual components and to be tabletted using microwave technology. So spray-dried anionic surfactant-containing granules with zeolite-containing granules, the are sprayed with nonionic surfactants and / or individual extrudates, for example enzyme or bleach activator-containing, but also peroxy bleaching agents Extrudates tabletted together using microwave technology will. It is also possible to use different extrudates, for example, those that follow the procedure according to the older German Application DE-A-44 06 210 were made for microwave tableting to use. Compounds can also be used as by means of steam drying or drying by means of microwave radiation were manufactured.

In a preferred embodiment of the invention, however, at least used as one of several compounds with high levels of anionic surfactants, which anionic surfactant contents are above 40% by weight, preferably up to Have above 90 wt .-% and in particular by granulation with simultaneous drying possibility, advantageously after an in a fluidized bed process, as it is in the international Application WO-A-93/04162 is made.

According to the above-mentioned compound-containing mixtures microwaves exposed to international patent application WO-A-94/25563 the compounds by local melting / sintering at the contact points interconnected. The voids between the individual compounds before exposure to microwaves cause a high Porosity of the resulting tablet and thus contribute to the improvement of the Dissolving properties of the tablet.

So that local sintering of the compounds is possible, at least some of them have sintering properties on the surface. This requires that the compounds themselves or their surface contain enough water so that by heating this water a The contact points on the compounds are merged. According to the teaching International patent application WO-A-94/25563 must include at least a part the mixture to be irradiated with microwaves is in hydrated form, being under "hydrated" means hydrated under certain conditions regarding temperature, pressure or relative humidity of the atmosphere, which the raw material is exposed to or with which the raw material is in balance "is understood.

In one embodiment of the invention, compounds are therefore used which contain proportions of starting materials that are in hydrated Form. Are these water-containing components in the compounds not or not available in sufficient quantities for sintering, so can use the compounds prior to tableting using microwave technology such substances are partially or completely encased in sufficient quantity will. Enveloping substances are particularly preferably used amorphous silicates such as metasilicates or water glasses, alkali carbonates and Alkali sulfates, zeolites such as zeolite A, X, Y or P, in particular zeolite A. and P or mixtures of these, but also organic components such as hydrated citrates, for example sodium citrate dihydrate, or hydrated ones Acetates, for example sodium acetate trihydrate. These coating substances are advantageously used in amounts of 1 to 30% by weight, based on the overall recipe, introduced into the process.

The overall recipe, consisting of the individual compounds as well as any other ones individual non-surfactant raw materials, which are not a compound must be present, is filled into a shaped body according to WO-A-94/25563 and irradiated with microwaves. The radiation leads to increased Temperatures and the local sintering of the compounds at the contact points, whereby the cavities in the molded body are retained, that is, one complete fusion of the compounds with one another is avoided. The Compounds themselves are not burdened by higher temperatures. This type of sintering leads to a surprisingly high breaking strength the tablet so that it can be handled without problems and in particular also can be transported.

If, despite this, tablets also result in this method, depending on the recipe, which do not have sufficient stability and strength, this problem may have arisen in that the filling density of the mold was not high enough, i.e. the compounds were not filled by filling the mold as usual had a sufficient number of contact points with one another. In this case, a method can be used to remedy the situation, in which the filled mold is subjected to pre-compression at low pressure before irradiation with microwaves. All the (pre-) compression methods known to the person skilled in the art are suitable for this. The pre-pressing is preferably carried out at pressures of 0.1 to 5 bar and in particular at 0.1 to 2 bar, corresponding to 1 to 50 N / cm ² or 1 to 20 N / m ² . This achieves sufficiently large contact points for the individual compounds in the tablet.

In a further preferred embodiment, the invention provides that disintegrants are incorporated into the tablets, which break up the Take the tablet after it has come into contact with water. Typical disintegrants which are preferably used in this process are, for example, citric acid or citrates, bicarbonates and carbonates, Bisulfate, but also percarbonate. Because of this procedure Occurring relatively low temperatures, it is possible to use peroxy bleach like incorporating perborate and even percarbonate into the tablets. Other preferred disintegrants are microcrystalline cellulose, sugar, especially sorbitol, but also layered silicates, especially fine particles and swellable layered silicates of the bentonite or smectite type. Explosives of the type described can be used in quantities of 0.5 to 30 % By weight, preferably from 1 to 25% by weight, based on the total recipe, be used. It is possible to use the explosives as a single raw material or also used as a compound.

Should the residual moisture in the total mixture to be used have a value of about 5 to 10 wt .-%, it is recommended to use the disintegrants to protect against this moisture. In a preferred embodiment The invention therefore uses explosives that are used before were coated with known hydrophobic components. Just for example are used here as coating substances paraffin oil or called silicone oil, the use of which is also preferred.

The tablets can - as in the earlier application WO-A-94/25563 described - with other substances, preferably ingredients from Detergents or cleaning agents and especially ingredients that counter Microwaves are sensitive to be treated. Here are to name in particular enzymes and perfumes. Is particularly advantageous but consider that enzymes because of the better possible temperature control or the lower temperature load of the overall mixture the procedure according to the invention can also be irradiated with and no longer have to be added subsequently.

The tablets can contain all the usual ingredients of washing or cleaning agents included in their overall recipe. In addition to the surfactants already described in detail, especially inorganic and organic builder substances, components that prevent re-contamination prevent the textile fabric (soil repellents), and graying inhibitors, alkaline salts, bleaches and bleach activators, foam inhibitors, fabric softening agents, neutral salts as well as colors and fragrances contain.

In addition to the conventional ones, inorganic builders are suitable Phosphates, in particular aluminosilicates of the zeolite type. The one used finely crystalline, synthetic and bound water containing zeolite is preferably detergent grade zeolite NaA. However, are suitable also zeolite X and zeolite P and mixtures of A, X and / or P.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Useful organic builder substances are preferred, for example polycarboxylic acids 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 such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Suitable polymeric polycarboxylates are, for example, the sodium salts 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 acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven 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 generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. Organic are also particularly preferred Degradable terpolymers, for example those which are salts of the monomers Acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives (DE-A-43 00 772.4) or the monomers as salts of acrylic acid and Contain 2-alkylallylsulfonic acid and sugar derivatives (DE-A-42 21 381).

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

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

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

The inorganic and / or organic builder substances are preferred in amounts of about 10 to 60% by weight, in particular from 15 to 50 % By weight, used in the tablets.

In addition, the agents can also contain components which and grease washability from textiles positively. This effect becomes particularly clear when a textile that is already soiled is soiled previously several times with a detergent according to the invention that this oil and contains fat-dissolving component, is washed. Among the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and especially methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ether, as well as the polymers known from the prior art phthalic acid and / or terephthalic acid or their derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionic and / or nonionic modified Derivatives of these. You can already in small quantities be effective. Their content is therefore preferably 0.2 to 10% by weight and in particular up to 5% by weight.

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

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; In particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used. The sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight. The sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.

In the context of the invention, the term “amorphous” also means “X-ray amorphous” Understood. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections as they do for crystalline ones Substances are typical, but at most one or more maxima scattered x-rays that are several units wide of the diffraction angle. However, it is very possible and can that the silicate particles even lead to particularly good builder properties washed out or even sharp in electron diffraction experiments Deliver diffraction maxima. This is to be interpreted as the products have microcrystalline regions of size 10 to a few hundred nm.

These X-ray amorphous silicates are just like some commercially available Compounds made of carbonates and amorphous silicates are suitable, the usual Builder substances such as phosphate, zeolite and crystalline layered silicates to replace partially or completely. If such substances are used, so their content can also exceed the amounts given above for Go beyond carbonates and amorphous silicates. Levels here are up to 40 % By weight or even 60% by weight within the scope of the invention.

According to the teaching of the older German patent application DE-A-43 19 578 Alkali carbonates also by sulfur-free, 2 to 11 carbon atoms and optionally having a further carboxyl and / or amino group Amino acids and / or their salts are replaced. Within the scope of this invention it is preferred that a partial to complete exchange the alkali carbonates are made by glycine or glycinate.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid 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, advantageously using perborate monohydrate and / or percarbonate.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl or 0-acyl compounds which form organic peracids with H ₂ O ₂ , preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonate, also carboxylic 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).

When used in machine washing processes, 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 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.

The salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, Diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate used in amounts of 0.1 to 1.5 wt .-%.

Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Are particularly well suited Strains of bacteria or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably become proteases of the subtilisin type and in particular proteases that 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 Mixtures of cellulase of particular interest. Peroxidases too or oxidases have been found to be suitable in some cases. The enzymes can be adsorbed on carrier substances and / or in coating substances embedded to protect them against premature decomposition. The amount the 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 tablets or compounds can be used as optical brighteners Contain diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed connections that instead of Morpholino group a diethanolamino group, a methylamino group, a Wear anilino group or a 2-methoxyethylamino group. Can continue Present brighteners of the substituted diphenylstyryl type, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

In a preferred embodiment of the invention tablets are produced which contain 15 to 40% by weight, preferably 18 to 35% by weight and in particular 20 to 30% by weight of anionic or anionic and nonionic surfactants, the content of anionic surfactants is preferably above 10% by weight and the weight ratio of anionic surfactants: nonionic surfactants is 5: 1 to 1: 2. Particularly preferred anionic surfactants are alkyl benzene sulfonates and alkyl sulfates and soaps. Preferred nonionic surfactants are ethoxylated C ₁₂ -C ₁₈ fatty alcohols or oxo alcohols and alkyl glycosides. Furthermore, tablets produced preferably contain 10 to 60% by weight, preferably 15 to 50% by weight and in particular 20 to 40% by weight of builder substances such as zeolite A and / or zeolite P, crystalline layered silicates of the SKS-6 type ^{(R. )} or amorphous or X-ray amorphous silicates and carbonate-silicate compounds with a correspondingly high calcium binding capacity.

In a further preferred embodiment of the invention, tablets produced, which contain 40 to 60 wt .-% compounds that 10 to 90 wt .-% of anionic surfactants, advantageously from Alkylbenzenesulfonates and / or alkylsulfates, as well as 10 to 90% by weight consist of builder substances, hydrated salts and / or disintegrants.

Other advantageous tablets additionally have compounds which are free of anionic surfactants and builder substances, advantageously zeolite A and / or zeolite P and 10 to 40 wt .-% nonionic surfactants.

Examples Example 1:

A tablet was produced from the compounds, powders and liquids listed below in accordance with the teaching of international patent application WO-A-94/25563. For this purpose, a homogeneous overall mixture was produced from the components in a mixer, which was then filled into a shaped body and pre-pressed for 10 seconds with a pressure of 13 N / cm ² (the force exerted on the circular area was 35 N on an area of 2.7 cm ² ). The microwave radiation was then carried out at 2450 MHz and 700 watts. The radiation lasted 7 seconds. A temperature of 60 ° C was not exceeded during the irradiation process.

Composition:

3% by weight Anionic surfactant compound (consisting of 90.5% by weight C ₁₂ -C ₁₈ alkyl sulfate, 5% by weight sodium sulfate, balance water) 41% by weight spray-dried granules (consisting of 10% by weight sodium dodecylbenzenesulfonate, 3% by weight C ₁₂ -C ₁₈ sodium fatty acid soap, 1.5% by weight tallow fatty alcohol with 5 ethylene oxide groups, 60% by weight zeolite (calculated as anhydrous Active substance), 5% by weight sodium carbonate, 2.5% by weight sulfate and other salts from solutions and raw materials and 18% by weight water) 3% by weight a granular foam inhibitor based on silicone oil (15% by weight) 14% by weight Sodium perborate monohydrate 7% by weight a granular bleach activator based on tetraacetylethylenediamine 1% by weight Sodium carbonate (soda ash) 1% by weight Silica 2% by weight Zeolite powder 1% by weight copolymeric salt of acrylic acid and maleic acid 3% by weight a 30% aqueous solution of this copolymer 11% by weight Sodium bicarbonate 9% by weight Citric acid 1% by weight of an enzyme granulate based on protease 2% by weight C ₁₂ -C ₁₈ alcohol with 7 ethylene oxide groups 1% by weight Perfume

The tablet had good breaking strength at pressures between 7.4 to 37 N / cm ² .

The tablet also had a high rate of disintegration in water on: Large parts of the tablet had disintegrated after just 1 minute; after The tablet was 100% disintegrated in 5 minutes.

Percarbonate could also be used instead of the perborate. As well it was possible to use the soap as separate soap granules containing more as 80 wt .-% soap and also to use soda and polymeric polycarboxylates.

Example 2:

A tablet was produced from the compounds, powders and liquids listed below in accordance with the teaching of international patent application WO-A-94/25563. For this purpose, a homogeneous total mixture was produced from the components in a mixer, which was then filled into a shaped body and pre-pressed for 10 seconds at a pressure of 2.6 N / cm ² (the force exerted on the circular area was 7 N on an area of 2 , 7 cm ² ). The microwave radiation was then carried out at 2450 MHz and 700 watts. The radiation lasted 7 seconds. A temperature of 65 ° C was not exceeded during the irradiation process.

Composition:

3% by weight Anionic surfactant compound (consisting of 90.5% by weight C ₁₂ -C ₁₈ alkyl sulfate, 5% by weight sodium sulfate, balance water) 48% by weight spray-dried granules (consisting of 10.3% by weight sodium dodecylbenzenesulfonate, 2.9% by weight C ₁₂ -C ₁₈ sodium fatty acid soap, 1.5% by weight tallow fatty alcohol with 5 ethylene oxide groups, 56.4% by weight % Zeolite (calculated as anhydrous active substance), 3.4% by weight sodium carbonate, 2.3% by weight polyvinylpyrrolidone, 5.4% by weight copolymeric salt of acrylic acid and maleic acid, 1% by weight other salts Solutions and raw materials as well as 16.8% by weight water) 3% by weight a granular foam inhibitor based on silicone oil (15% by weight) 3% by weight Sodium carbonate (soda ash) 1% by weight Silica 3% by weight Zeolite powder 2% by weight copolymeric salt of acrylic acid and maleic acid 11% by weight Sodium bicarbonate 14% by weight Sodium citrate 1% by weight of an enzyme granulate based on protease 5% by weight C ₁₂ -C ₁₈ alcohol with 7 ethylene oxide groups 1% by weight Perfume 5% by weight Sodium silicate (Na ₂ O: SO ₂ , 1: 2.0 with 18% by weight water).

The tablet had good breaking strength at pressures between 7.4 to 22 N / cm ² .

The tablet also had a high rate of disintegration in water on: Large parts of the tablet had disintegrated after only 0.5 minutes; after 4 minutes the tablet was 100% disintegrated.

Claims (10)

1. A process for the production of detergent or cleaning tablets containing anionic surfactants using microwaves in the frequency range from 3 to 300,000 MHz from starting materials which are at least partly present in hydrated form, characterized in that the anionic surfactants are introduced into the process in the form of one or more compounds, the compounds containing up to 95% by weight of surfactants.
2. A process as claimed in claim 1, characterized in that anionic surfactant compounds containing various anionic surfactants and/or anionic surfactants in combination with nonionic surfactants are used.
3. A process as claimed in claim 1 or 2, characterized in that compounds of at least two different types are used.
4. A process as claimed in any of claims 1 to 3, characterized in that at least 35% by weight, preferably at least 50% by weight and more preferably at least 70% by weight of the overall formulation of the detergent or cleaning tablet consists of one or more compounds of different types.
5. A process as claimed in any of claims 1 to 4, characterized in that the compounds used contain starting materials present in hydrated form.
6. A process as claimed in any of claims 1 to 5, characterized in that one, several or all of the compounds are completely or partly encapsulated before microwave tabletting with hydrated substances and preferably with amorphous alkali metal silicates, alkali metal carbonates and bicarbonates, alkali metal sulfates and bisulfates, zeolite, citrates and acetates.
7. A process as claimed in claim 6, characterized in that the encapsulating materials are used in quantities of 1 to 30% by weight, based on the formulation as a whole.
8. A process as claimed in any of claims 1 to 7, characterized in that the filled mold is subjected to precompression before the microwave treatment.
9. A process as claimed in any of claims 1 to 8, characterized in that disintegrating agents which cause the tablet to break up after coming into contact with water are used in quantities of 0.5 to 30% by weight and preferably in quantities of 1 to 25% by weight.
10. A process as claimed in claim 9, characterized in that the disintegrating agents are used in encapsulated form, paraffin oils and silicone oils being preferred encapsulating materials.