DK151231B - PROCEDURE FOR CLEANING, INCLUDING WASHING, PRE-WASHING AND PLEASING WASHING, WASTE MATERIALS, ISAARY TEXTILES, AS WELL AS EXERCISE OF THE PROCEDURE AND PROCEDURE FOR MANUFACTURING THE AGENT - Google Patents

Description

151231

As is well known, detergents used in the household, in industrial laundries and in the industry often contain large amounts of condensed phosphates, especially tripolyphosphates, which are largely responsible for the good cleaning performance of the product. The phosphate content in these funds is criticized by the public on environmental protection issues. It is often expressed that this phosphate via the water in rivers and lakes leads to eutrophication of the water, i.e. for an increase in algae growth and oxygen consumption. Therefore, it is sought to remove or substantially reduce the amount of phosphate 10 in washing and cleaning processes or from the agents used.

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It is known from German Publication Publication No. 1,617,058 to use water-insoluble cellulose derivatives, especially phosphorylated cotton, in the washing process to cure the water. However, this proposal does not provide a technically viable solution to the problem because too many 5 phosphorylated cotton must be used to bind the hardness of the water completely except for cellulose derivatives with poorer calcium binding capacity, such as sulfatoxycellulose, carboxymethyl cellulose or succinic acid = esters of cellulose.

It is further known from German Publication No. 2,055,423 to powdered to granular detergents in water and in alkaline solutions to insert insoluble cation-exchanging, cross-linked polymeric agents such as e.g. a crosslinked polymeric divinylbenzene and polyacrylic acid or polymethacrylic acid. Adding these water-insoluble cation exchangers, in the form of fine particles, to the wash water, they disperse into the textile materials to be washed, and can only be very incompletely rinsed out. For this reason, it has also been proposed to put the granular polymerisates into the wash water sewn into permeable bags. Thereby, however, contact 20 with the wash water and thus also the effect of the polymerisates is severely limited.

Finally, from Lesser, Soap and Sanitary Chemicals, October 1945, pages 37 - 45, it is known to combine bentonite (a finely divided aluminum silicate) 25 ° 9 a synthetic surfactant. However, bentonite can be deposited in the washed clothing and its washing ability is poor.

The invention relates to a process for cleaning, including washing, prewashing and bleaching, of solid materials, especially textiles, by treating these materials with an aqueous float containing water-insoluble, finely divided aluminum silicate having builder effect, and at least one compound. selected from surfactants, builder fabrics and optionally a bleach. The method is peculiar to the characterizing part of claim 1.

35

The invention provides that the use of the harmful phosphates can be avoided or reduced.

The calcium binding capacity may have values of up to 200 mg CaO / g AS and is preferably in the range 100-200 mg CaO / g AS.

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As a cation, sodium is especially important. However, it may also be replaced by lithium, potassium, ammonium or magnium and, by virtue of the cations, water-soluble organic bases, e.g. bases of primary, secondary or tertiary amines or alkylolamines having a maximum of 2 C-5 atoms per alkyl residue or not more than 3 C atoms per alkylolrest.

These compounds are hereinafter referred to as "aluminum silicates" for simplicity. Preferably, sodium aluminum silicates are used. All statements on their preparation and use are similarly applied to the other compounds.

The aluminum silicates defined above can be synthetically prepared in a simple manner, e.g. by reaction of water-soluble silicates with water-soluble aluminates in the presence of water. For this purpose, 15 aqueous solutions of the starting materials may be mixed with one another or a solid state component may be reacted with the other component present as the aqueous solution. Also, by mixing the two solid state components, the desired aluminum silicates are obtained in the presence of water. Aluminum silicates can also be prepared by reaction with alkali silicate or aluminate solutions of 20 Al (OH) j, A120j or SiC> 2. Finally, such substances can also be formed by melting, but this process is, however, economically less interesting due to the high melting temperature required and the need to convert the melt into finely divided products. Admittedly, the cation-exchanging aluminum silicates to be used in accordance with the invention are formed only by adherence to special precipitation conditions, as otherwise products which have no or only insufficient cation-exchange ability are formed. The preparation of aluminum silicates usable according to the invention is described in the experimental part.

The aluminum silicates transferred by precipitation or otherwise in finely divided state in aqueous suspension can, from heating to temperatures of 50-200 ° C, be converted from amorphous to aged or crystalline, but there is hardly any difference between these two forms. in terms of calcium binding capacity. Except for the drying conditions, this is proportional to the amount of aluminum contained in the aluminum silicates. Still, it is preferred to use the crystalline aluminum silicates for the purposes of the invention. The preferred calcium binding capacity, ranging from 100 to 200 mg CaO / g AS, is found especially in compounds of the composition 0.7 - 1.1 Ha 2 O · AL 2 O 3 · 1.3 - 3, 3 SiO 2 <5

This sum formula includes two types of different crystal structures (their non-crystalline precursors, respectively) that also differ by their sum formulas. It is: a) 0.7-1.1 Ka2 O · 20120 ^ · 1.3 - 2.4 SiO £ b) 0.7 - 1.1 ITa20 · A1203 ·> 2.4 - 3.3 SiO2.

The various crystal structures are shown in the X-ray bending diagram. The d-values thus obtained are set out below in connection with the description of the preparation of the aluminum silicates.

The amorphous or crystalline aluminum silicate in aqueous suspension can be separated by filtration from the remaining aqueous solution and dried at temperatures of e.g. 50-800 ° C. All according to the drying conditions, the product contains more or less bound water. Non-free products are obtained at 800 ° C. If you want to spread. If the water is completely watered, this is possible at 1 hour heating to 800 ° C. In this way, the AS content of the aluminum silicates is also determined.

Such high drying temperatures are not recommended for the aluminum silicates to be used in the invention. Conveniently does not exceed 400 ° C. It is a particular advantage that even products which have dried at substantially lower temperatures of e.g. 80-30 200 ° C to remove the adherent liquid water are useful for the purposes of the invention. The aluminum silicates thus prepared containing alternating amounts of bound water appear after decomposition of the dried filter cake as fine powder, whose primary particle size is at most 0.1 mm, but for the most part is substantially lower, and which goes all the way down to dust fineness, f. eg. up to 0.1 µi. It should be borne in mind that the primary particles may be agglomerated for larger assemblies. For many manufacturing methods, primary particle sizes are obtained in the range of 50-1 µ.

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With particular advantage, aluminum silicates are used which, for at least 80% by weight, consist of particles having a size of 10-0.01 µ, preferably from 8 to 0.1 µ. Preferably, these aluminum = silicates contain no primary particles or secondary particles. over 40 µ.

5 In the case of crystalline products, for the sake of simplicity, these are referred to as microcrystalline.

Already, the precipitation conditions can "contribute to the formation of small particle sizes by exposing the mixed aluminate 10 and silicate solutions, which can also be applied to the reaction vessel simultaneously, for strong shear forces. Preparation of the crystallized aluminum silicates preferably used according to the invention prevents the formation of large, possibly growing crystals by slow stirring of the crystallizing mass.

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Nevertheless, upon drying, an unwanted agglomeration of crystal lithic particles may occur, so it is recommended to remove these secondary particles appropriately, e.g. at wind sifting. Also aluminum = silicates which appear coarser and which must be ground to the desired grain size can be used. For example, suitable for this purpose. wind turbines and / or windscreens or combinations thereof. The latter is described, among other things. by Ullmann "Enzyklopådie der technischen Chemie", Volume 1, 1951, pages 632-634.

Of the sodium aluminum silicates, the aluminum silicates of other cations, e.g. of potassium, magnesium or water-soluble organic bases are prepared simply by base exchange. The use of these compounds in place of sodium aluminum silicates may be convenient if a particular effect is achieved upon delivery of said cations, e.g. will affect the dissolution state of co-present surfactants.

These pre-formed, i.e. prior to their use, aluminum silicates are used for the purposes of the invention.

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The amount of aluminum silicate needed to achieve a good washing or cleaning effect depends, on the one hand, on its calcium binding capacity, on the other, on the amount and degree of dirtiness of the treated material and on the hardness and amount of s used. water. When using hard water, it is convenient to measure the amount of aluminum silicate so that the residual hardness of the water is not more than 5 ° dH (corresponding to 50 mg CaO / l), preferably 0.5-2 ° dH (5-20 mg CaO / L). In order to achieve an optimal washing or cleaning effect, it is recommended, especially in the case of heavily soiled materials, to use a certain excess of aluminum silicates to also completely or partially retard the hardness formers contained in the released dirt. Therefore, the concentration of aluminum silicate used may be in the range of preferably 0.2-10 g'AS / l, especially 10 1-6 g AS / l.

Furthermore, it has been found that the dirt is removed substantially faster and / or more completely when adding to the treatment float a compound which exerts a complexing and / or precipitating effect on the calcium present in the water as hardness. Compounds of calcium suitable for the purposes of the invention are also substances with so little complexing ability that they have not hitherto been regarded as typical calcium complexers, but such compounds often have the ability to delay the precipitation of calcium carbonate from aqueous 2O solutions.

Preferably, small amounts added are used, e.g. 0.05-2 g / l complexing agent or calcium precipitating agent to noticeably accelerate or improve the removal of the contaminants. In particular, 25 are employed with added amounts of 0.1-1 g / l. Significantly larger amounts can also be used, but when using phosphorus-containing complexing agents or precipitants, such amounts must be chosen so that the phosphorus loading of the wastewater is clearly less than using the currently usual triphosphate-based detergents.

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The complexing or precipitating agents include those of an inorganic nature, such as e.g. pyrophosphate, triphosphate, higher polyphosphates and metaphosphates.

Organic compounds which serve as complexing or precipitating agents for calcium are found among the polycarboxylic acids, hydrocycarboxylic acids, aminocarboxylic acids, carboxyalkyl ethers, polyanionic polymers, especially the polymeric carboxylic acids and phosphonic acids, these compounds being mostly soluble in their salts.

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Examples of polycarboxylic acids are dicarboxylic acids of the general formula H00C- (CH2) n-C00H, where n is 0-8, in addition maleic acid, methylene malonic acid, citraconic acid, mesaconic acid, itaconic acid, non-cyclic polycarboxylic acids having at least 3 carboxyl groups in the molecule such as . tricarbalic acid, aconitic acid, ethylene tetracarboxylic acid, 1,1,3 »3-propane tetracarboxylic acid, 1,1,3,3,5,5-pentane hexacarboxylic acid, hexane hexacarboxylic acid, cyclic di- or polycarboxylic acids such as cyclopentane tetracarboxylic acid, cyclohexane hexacarboxylic acid, tea trahydrofurant tracarboxylic acid, phthalic acid, terephthalic acid, benzoltri, tetra or pentacarboxylic acid and mellit = 10 acid.

Examples of hydroxymono or polycarboxylic acids are glycolic acid, lactic acid, malic acid, tartaric acid, methyl tartaronic acid, gluconic acid, glyceric acid, citric acid, tartaric acid, salicylic acid.

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Examples of aminocarboxylic acids are glycine, glycylglycine, alanine, asparagine, glutamic acid, aminobenzoic acid, iminodic or triacetic acid, hydroxyethyl dimino diacetic acid, ethylene diamine tetraacetic acid, hydroxy Ridylcarbon acid derivatives, e.g. of acetic acid, succinic acid, tricarbalyl = acid and subsequent saponification, or by condensation of polyamines with a molecular weight of 500-10,000 with chloroacetic or bromoacetic salts.

25

Examples of carboxyalkyl ethers are 2,2-oxydiruccinic acid and other ethers = polycarboxylic acids, especially polycarboxylic acids containing carboxymethyl ethers = groups to which derivatives of the following polyhydric alcohols or hydroxycarboxylic acids, which may be fully or partially etherified with glycolic acid, glycolic acid, glycolic acid, glycerine, di- or triglycerine, glycerine monomethyl ether, 2,2-dihydroxymethyl propanol, 1,1,1-trihydroxymethyl ethanol, 1,1,1-trihydroxymethylpropane, erythrite, pentaerythritite, glycolic acid, lactic acid, tartaric acid, methyl tartaric acid, methyl tartaric acid, erythronic acid, malic acid, citric acid, tartaric acid, trihydroxyglutaric acid, sugar acid, mucic acid.

As the types of transition to the polymeric carboxylic acids, mention is made of the carboxy methyl ethers of sugar, starch and cellulose.

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Among the polymeric carbonic acids, e.g. the polymers of acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, methylene malonic acid, citraconic acid and the like, the copolymers of the aforementioned carboxylic acids mutually or with ethylenically unsaturated compounds such as ethylene, vinylene, ethylene, propylene, propylene, propylene, , vinyl acetate, acrylamide, acrylonitrile, methacrylic acid, crotonic acid, etc., and e.g. The 1: 1 mixture polymers of maleic anhydride and ethylene or propylene or furan have a special role.

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Other polymeric carbonic acids of the type polyhydroxypolycarboxylic acids or polyaldebydopolycarboxylic acids are essentially substances made up of acrylic acid and acrolein units or acrylic acid and vinyl alcohol units which can be obtained by copolymerization of acrylic acid and acrolein or by the eventual reaction of acrylic acid and acrylic anhydride. .

Examples of phosphorus-containing organic complexing agents are alkane polyphosphonic acids, amino and hydroxyalkane polyphosphonic acids, and phosphonic carbonic acids such as e.g. the compounds methane diphosphonic acid, propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 1-amino-1-phenyl-1,1 -diphosphonic acid, aminotrimethylene = triphosphonic acid, methylamino or ethylaminodimethylenediphosphonic acid, ethylenediaminotetramethylenetetrafosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, phosphonacetic acid, phosphonic acetic acid, phosphonic acetic acid, phosphonic acetic acid , 3-dicarboxylic acid, 2-phosphonbutane-1,2,4-tricarboxylic acid, 2-phosphonbutane-2,3,4-tricarboxylic acid, and blend polymers of vinylphosphonic acid and acrylic acid.

The 30-g use according to the invention of the aluminum silicates described above, even with the use of phosphorous, inorganic or organic complexing agents or calcium precipitating agents, it is possible to maintain the phosphorous content of the treatment fleet at a maximum of 0.6 g / l, preferably not more than 0.3 g / l of organic and / or inorganically bound phosphorus. However, good results can also be worked on completely phosphorus-free.

The process of the invention, which works using aluminum silicates, can be used in numerous areas of the art and household for the most diverse purification tasks. Examples of such applications are cleaning of apparatus, pipelines and containers of wood, plastic, metal, ceramics, glass, etc. in industry or other industries, cleaning of furniture, walls, floors, 5 items of ceramics, glass, metal, wood, plastics, cleaning of polished or varnished surfaces in the household, etc. A particularly important area of application is the washing and bleaching of fabrics of any kind in the industry ,! commercial laundries and in the household.

10 The textiles to be washed may consist of the most diverse taverns of natural or synthetic origin. These include, for example. cotton, regenerated cellulose or flax, and textiles containing highly processed cotton sticks or synthetic chemical taverns such as polyamide, polyester, polyacrylonitrile, polyurethane, polyvinyl chloride or polyvinylidene chloride taverns. The detergents of the invention can also be used for laundry of synthetic fabrics fabrics and synthetic fabrics and cotton blend fabrics of the kind termed ironing.

By washing and purifying such substrates using aqueous 20 cleaning floats containing suspended aluminum silicates, the washing or cleaning effect can be enhanced by the usual constituents of such treatment floats. These include e.g. surfactants, surfactant or non-surfactant foam stabilizers or inhibitors, textile softeners, neutral or alkaline reacting substances, chemical bleaches and their stabilizers and / or activators, soil carriers, corrosion inhibitors, antimicrobials, enzymes, enzymes, dyes and fragrances.

30 When using one or more of the above-mentioned substances usually present in washing and cleaning floats, the following concentrations are suitably adhered to: 0-2.5 g / l surfactants 35 0-6 g / l buildup 0-0.4 g / l active oxygen or equivalent amounts of active chlorine.

Depending on the substrate to be washed or purified, the pH of the treatment float may range from 6 to 13, preferably 8.5-12.

For a long time, a useful phosphate replacement has been sought, 5 which can not only bind calcium but can also be biodegraded in the wastewater. Therefore, the most diverse organic compounds such as phosphate replacements have been proposed. Therefore, the technical teachings of the present invention for using water-insoluble cation-exchange aluminum silicates for this purpose are a complete departure from the working world of the overall art. It is particularly surprising that the water-insoluble aluminum silicates can be completely flushed out of textile materials. The use of aluminum silicates causes a double discharge of the wastewater. The amounts of phosphorus entering the wastewater are greatly reduced or completely eliminated, and besides, the aluminum silicates do not require any ill-treatment for the biodegradation. They are of a mineral nature, eventually settle in clearing plants or in natural streams and therefore fulfill the ideal requirements for a phosphate replacement.

20 But also washing and cleaning techniques have advantages over other phosphate replacements already proposed: They adsorb colored contaminants and thereby save chemical-acting bleaches.

The invention further relates to a detergent, including detergent, prewash detergent and bleach detergent, for carrying out the process according to claims 1-15, containing a water-insoluble, finely divided aluminum silicate and at least one compound of the group of surfactants, builder fabrics and bleaching agents and a partial substitute substance. or complete replacement of condensed phosphates. The agent is characterized in that it contains as a phosphate substitute a crystalline or X-ray-grafted aluminum silicate of the general formula as set forth in claim 1 and with the calcium binding capacity of claim 1.

The aluminum silicate content of such agents may range from 5 to 95, preferably 15 to 60%.

The compositions of the invention may further contain complexing agents or precipitating agents. calcium, whose effect according to the chemical nature of the agent is preferably recognized by content of 2-15%.

The amount of inorganic phosphates and / or organic phosphorus compounds present in the compositions of the invention should not be greater than a total P content of the agent of $ 6, preferably $ 3.

5 All of these percentages are percentages by weight and are based on the anhydrous active substance (= AS).

Among the washing, bleaching or cleansing compounds contained in the detergents or cleaning agents, for example. surfactants, surfactant or non-surfactant foam stabilizers or inhibitors, textile softeners, neutral or alkaline reacting, build-up agents, chemically acting bleaches such as stabilizers and / or activators thereof. Other auxiliaries and additives, which are mostly present in small quantities, are e.g. corrosion inhibitors, antimicrobials, dirt carriers, enzymes, brighteners, dyes and fragrances.

The composition of typical textile detergents for use at temperatures in the range of 50-100 ° C is within the range of the following prescriptions: 5 - 30 $ anionic and / or nonionic and / or zwitterionic surfactants 5 - 70 $ aluminum silicates (calculated on AS) 25 2 - 45 $ complexing agents for calcium O - 50 $ washing alkali incapable of complexing (alkaline build-up agents) 30 0 - $ 50 bleaches and other additives, mostly present only in small quantities in laundry detergents.

In the following, the substances suitable for use in the compositions of the invention are enumerated.

The surfactants contain in the molecule at least one hydrophobic, organic residue and a water-solubilizing, anionic, zwitterionic or nonionic group. The hydrophobic residue is mostly an aliphatic carbon of 8-26, preferably 10-22 and most preferably 12-18 carbon atoms or an alkyl aromatic residue of 6-18, preferably 8-16 aliphatic carbon atoms.

As anionic surfactants, e.g. soaps are used of natural or synthetic, preferably saturated fatty acids, optionally also of resin acids or naphthenic acids. Suitable synthetic anionic surfactants are those of the sulfonate type, the sulfate type and the synthetic carboxylates.

As the sulfonate-type surfactants, these may be alkylbenzene sulfonates (C ^^ ^^ - alkyl), mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as e.g. may obtain those of terminal or internal double bond monoolefins by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Furthermore, alkanesulfonates obtainable from alkanes are suitable for sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Other useful surfactants of the sulfonate type are esters of alpha-sulfo fatty acids, e.g. α-sulfonic acids of hydrated methyl or ethyl = 2o esters of coconut fatty acid, palm kernel fatty acid or tallow fatty acid.

Suitable surfactant surfactants are sulfuric acid monoesters of primary alcohols (for example, of coconut fatty alcohols, sebum fatty alcohols or oleyl alcohols) and of secondary alcohols. In addition, sulfated 25 fatty acid alkanolamides, fatty acid monoglycerides or reaction products of 1-4 moles of ethylene oxide with primary or secondary fatty alcohols or alkyl phenols are suitable.

Other suitable anionic surfactants are the fatty acid esters or amides of hydroxy or aminocarboxylic acids or sulfonic acids such as e.g. fat = acid sarcosides, glycolates, lactates, taurids or isothionates.

The anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or triethanolamine.

As nonionic surfactants can be used preparation products of 4-40, preferably 4-20 moles of ethylene oxide to 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide. Particularly important are preparation products of 5-16 moles of ethylene oxide for coconut or tallow fatty alcohols, for oleyl alcohol or for secondary alcohols having 8-18, preferably 12-18 carbon atoms, and for mono or dialkyl phenols having 6-14 carbon atoms. in the alkyl residue. In addition to these water-soluble, nonionic substances, non-water-soluble or non-completely water-soluble polyglycol ethers having 1-4 ethylene = glycol ether residues also have molecular interest, especially when used with water-soluble, nonionic or anionic surfactants.

Further, as non-ionic surfactants, the water-soluble additive ethylene oxide ring products can be used for polypropylene glycol (= Pluronics®) containing 20-250 ethylene glycol ether groups and 10-100 propylene glycol ether groups, alkylenediamine polypropylene glycol (= Tetronics®) and alkyl 1-10 carbon atoms in the alkyl chain, wherein the polypropylene glycol chain acts as a hydrophobic residue.

Non-ionic surfactants of the amine oxide or sulfoxide type are also useful.

The foaming ability of surfactants can be increased or decreased by combining suitable surfactant types. A reduction can also be obtained by the addition of non-surfactant-like organic substances.

Suitable as foam stabilizers are particularly suitable for surfactants of the sulfonate or sulfate type capillary active carboxy or sulfobetaine and the aforementioned non-ionic substances of the alkylolamide type. In addition, fatty alcohols or higher end diols have been proposed for this purpose.

A diminished foaming capability that is desirable when working in machinery 3q is often achieved by combining different surfactant types, e.g. sulfates and / or sulfonates with non-ionic substances and / or with soaps. With soaps, the foam attenuation increases with the degree of saturation or total in the fatty acid residue. Therefore, soaps of saturated C 2Q 2 -acetic acids are particularly suitable as antifoam.

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The non-surfactant-like foam inhibitors optionally include chlorine-containing N-alkylated aminotriazines, which can be obtained by reacting 1 mole of cyanuric chloride with 2-3 moles of a mono- and / or dialkylamine with 6-20, preferably 8-18 carbon atoms in the alkyl residue. Similarly, propoxylated and / or butoxylated aminotriazines, e.g. products obtained by adding 5-10 moles of propylene oxide to 1 mole of melamine and additionally adding 10-50 moles of butylene oxide to this propylene oxide derivative.

Also suitable as a non-surfactant foam inhibitor are water-insoluble organic compounds such as paraffins or halogen paraffins having melting points below 100 ° C, aliphatic C C- to C ^ ketones, and aliphatic carbonic esters, as in the acid residue. or in the alcohol residue, possibly also in both of these residues, contains at least 18 carbon atoms (e.g., triglycerides or fatty fatty alcohol esters). In particular, they can be used in combinations of surfactants of the sulfate and / or sulfonate type with soaps to soften the foam.

Particularly weakly foaming non-ionic substances which can be used both alone and in combination with anionic, zwitterionic and nonionic surfactants, and which reduce the foaming ability of highly foaming surfactants are propylene oxide adhesives for the capillary active polyethylene glycol ether already mentioned and the also 0 addition products of ethylene oxide already described for polypropylene glycols and for alkylenediamine polypropylene glycols or for C- Q Q alkyl alkylpropylene = glycols.

As the building materials, slightly acidic, neutral or alkaline reacting, inorganic or organic salts are suitable.

According to the invention, usable weakly acidic, neutral or alkaline reacting salts are e.g. the bicarbonates, carbonates, borates or silicates of alkalis, alkali sulfates, and alkali salts of organic, 0 non-capillary active sulfonic acids, carbonic acids and sulfocarboxylic acids containing 1-8 carbon atoms. These include, for example. water-soluble salts of benzene, toluene or xylolsulfonic acid, water-soluble salts of sulfoacetic acid, sulfobenzoic acid or sulfodicarboxylic acids.

The compounds mentioned above as complexing agents or precipitating agents for calcium are generally useful as building agents. Therefore, they may also be present in the agents of the invention in greater amounts than are necessary to fulfill their function as complexing agents or calcium precipitants.

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The constituents of the products which are preferably used as detergents or as household cleaners, especially the build-up substances, are mostly selected such that the compositions react neutrally to strongly alkaline, so that the pH of a 1 $ solution of the composition for the most are in the range 7-12. Detergents have e.g. mostly neutral to slightly alkaline reaction (pH 7-9.5), while soaking, prewash and boiling detergents are more strongly alkaline (pH 9.5-12, preferably 10-11.5). If, for special purification purposes, higher pH values are required, these 10 can easily be adjusted using alkali silicates with suitable ratios of 1a 2 O to SiO 2 or etching alkalis.

Among the compounds which serve as bleaching agents and which in water give H 2 O 2, sodium perborate tetrahydrate (liaB02, H202, 3H2O) and mono = 15 hydrate (NaBO2, H20r>) are of particular importance. But other borates that give H202 are also useful, e.g. These compounds may be partially or completely replaced by other active oxygen carriers, especially by peroxyhydrates such as peroxycarbonates (Na 2 CO 2, 1.5 H 2 O 2), peroxypyrophosphates, citrate perhydrates, urea H 2 O 2-20, or melamine. H 2 O 2 compounds, as well as of persure salts, which give H 2 O 2, e.g. carbohydrates (KHSO4), perbenzoates or peroxyphthalates.

It is convenient to incorporate conventional water-soluble and / or water-insoluble stabilizers for the peroxy compounds together with these in amounts of 0.25 to 10 weight percent. As water-insoluble stabilizers, e.g. constituting 1-8, preferably 2-7 $, by weight of the total composition, the magnesium silicates Mg0 obtained by precipitation of aqueous solutions are suitable; SiO2 = 4: 1 to 1: 4, preferably 2: 1 to 1: 2, and especially 1 : 1st Other alkaline earth silicates, cadmium silicates or tin silicates of similar composition may be used instead. Also aqueous oxides of tin are suitable as stabilizers. Tooth-soluble stabilizers that may be present with water-insoluble are organic complexing agents, the amount of which may be 0.25-5, preferably $ 0.5-2.5, of the total composition weight.

In order to achieve a satisfactory bleaching effect on washing already at temperatures below 80 ° C, especially in the range of 60-40 ° C, activator-containing bleaching components are preferably incorporated into the compositions.

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As activators for per-compound imparting in water, certain U-acyl, O-acyl compounds which form organic peracids with this H 1 C 2, in particular acetyl, propionyl or benzoyl compounds such as carbonic or pyrocarbon esters, are used. Useful compounds include: 5 N-diacylated and Ν, ΪΓ'-tetraacylated amines such as e.g. IT, ΪΓ, 1β, IT * - tetraacetylmethylenediamine or ethylenediamine, ΪΓ, Ν-diacetylaniline and ΕΓ, ΪΓ-diacetyl-p-toluidine or 1,3-diacylated bydantoins, alkyl-N-sulfonylcarbonamides, e.g. H-methyl-N-mesylacetamide, N-methyl-N-mesyl = benzamide, N-methyl-N-mesyl-p-nitrobenzamide and N-methyl-H-meyl-p-me toxy = LO benzamide, H- acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. monoacetylmaleic acid hydrazide, O, N, B-trisubstituted hydroxylamines, e.g. O-benzoyl-N, N-succinyl-hydroxylamine, 0-acetyl-ΪΓ, N-sucinyl-hydroxylamine, 0-p-methoxybenzoyl-H, H-succinyl-hydroxylamine, Op-nitrobenzoyl-NjN-succinyl-hydroxylamine and Ο, Ν, Ν-L5 triacetyl-hydroxylamine, JfILF'-diacylsulfurylamides such as NjlP-dimethyl-ΪΤ, ΪΓ'-diacetylsulfurylamide and H, IT-diethyl-N, ΪΓ'-dipropionylsulfurylamide, triacylcyanurates, e.g. triacetyl or tribenzoyl cyanurate, carbon = acid anhydrides, e.g. benzoic anhydride, m-chlorobenzoic anhydride, phthalic anhydride, 4-chlorophthalic anhydride, sugar esters such as glucose pentaacetate, 1,3-diacyl-4,5-diacyloxyimidazolines, e.g. the compounds 1,3-diformyl-4,5-diacetoxyimidazoline, 1,3-diacetyl-4,5-diacet = oxyimidazoline, 1,3-diacetyl-4,5-dipropionyloxyimidazoline, acylated glycoluriles, e.g. tetrapropionylglycoluril or diacetyl dibenzoyl = glycoluril, diacylated 2,5-diketopiperazines such as e.g. 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine, 1,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine, acetylation products and benzoylation products of propylenediurea or 2,2-dimethylpropylenediurea (2,4,6,8-tetraazabicyclo (3.3, 1) -nonane-3,7-dione or its 9,9-dimethyl derivative), sodium salts of p- (ethoxycarbonyloxy) - 30 benzoic acid and p- (propoxycarbonyloxy) benzene sulfonic acid.

The active chlorine compounds which serve as bleach may be inorganic or organic in nature.

35 The inorganic active chlorine compounds include alkali hypochlorites which may be used in particular in the form of their mixing salts or additives for orthophosphates or condensed phosphates such as pyro and polyphosphates or alkali silicates. If the detergents and detergents contain monopersulfates and chlorides, active chlorine is formed in aqueous solution.

i7 151231

Particularly useful as organic active chlorine compounds are N-chlorine compounds in which 1 or 2 chlorine atoms are bonded to a nitrogen atom, preferably the third valence of the nitrogen atom leading to a negative group, especially to a CO or SO 2 group. These compounds include dichloro and trichloro cyanuric acid or their salts, chlorinated alkyl guanides or alkyl biguanides, chlorinated hydantoins and chlorinated melamines.

Further, in the compositions of the invention, there may be dirt carriers which keep the dirt released from the taverns suspended in the float, thereby preventing graying. For this purpose, water-soluble colloids, mostly organic, such as e.g. the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carbonic or ether sulfonic acids of starch or cellulose or salts of acidic sulfur = 15 acid esters of cellulose or starch. Also water-soluble polyamides containing acidic groups are suitable for this purpose. Further, soluble starch preparations and other than the above starch products, e.g. degraded starch, aldehyde starch, etc. Polyvinylpyrrolidone is also useful.

20

The enzyme preparations to be used are mostly a mixture of enzymes having different effects, e.g. of proteases, carbohydrates, esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases, transferases, desmolases or nucleases. Of particular interest are the enzymes extracted by bacterial strains or fungi such as Bacillus subtilis or Streptomyces griseus, especially proteases or amylases, which are relatively durable to per-compounds and anionic surfactants and are effective even at temperatures up to 70 ° C.

30

Enzyme preparations are mostly marketed by the manufacturers as aqueous solutions of the active substances or as powders, granules or as cold-sprayed powders. As a diluent, they often contain sodium sulfate, sodium chloride, alkali orthophosphate, pyrophosphate or polyphosphate, especially tripolyphosphate. Special emphasis is placed on dust-free preparations. They can be obtained in a manner known per se by incorporation of oily or paste-shaped, nonionic substances or by granulation by melting of crystalline salts in their own crystal water.

18 151231

Enzymes specific to a particular kind of debris may be incorporated, e.g. proteases or amylases or lipases. Preferably, combinations of enzymes with different effects are used, especially combinations of proteases and amylases.

5

The detergents may, as optical brighteners for cotton, contain, in particular, derivatives of diaminostilbendisulfonic acid or its alkali metal salts. Suitable are e.g. salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilben-2,2'-disulfonic acid or similarly constructed compounds which, instead of the morpholino group, carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. As polyamide toner clearing agents, they may be of the type 1,3-diaryl-2-pyrazoline, e.g. the compound 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, as well as compounds built in a similar manner which, instead of the sulfamoyl group, carry e.g. methoxycarbonyl, 2-methoxyethoxycarbonyl, acetylamino or vinylsulfonyl group. Useful polyamide clarifiers are also the substituted amino coumarins, e.g. 4-methyl-7-dimethylamino or 4-methyl-7-diethylamino coumarin. Furthermore, as polyamide clarifiers, compounds 2- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) -ethylene and 1-ethyl-3-phenyl-7-diethylaminocarbostyril can be used. Compounds suitable for polyester and polyamide taps are the compounds 2,5-di- (2-benz = oxazolyl) -thiophene, 2- (2-benzoxazolyl) -naphtho / 2,3-b / -thiophene and 1,2-di - (5-methyl-2-benzoksazolyl) -ætylen. Furthermore, clarifiers of the substituted 4,4'-distyryldiphenyl type, e.g. compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned clarifiers may also be used.

Of particular practical interest, according to the invention, agents of powder-3Q are molded to grainy character which can be prepared by any method known in the art.

Thus, e.g. the powdered aluminum silicates are simply mixed with the other components of the detergent, with oily or pasty products such as e.g. non-ionic substances are sprayed onto the powder. Another manufacturing option lies in the incorporation of the powdered aluminum silicates into the other constituents of the agent, which exists as an aqueous porridge which is then converted into a powder by crystallization or by drying the water. After hot drying, e.g. Then, on rollers or atomisers, heat-sensitive and moisture-sensitive components such as bleach components and activators thereof, enzymes, antimicrobials, etc. can be incorporated. The invention also relates to a process for the preparation of the agent according to claims 16-20, which is characterized by the characterizing part of claim 21.

examples

Preparation of the finished aluminum silicates to be used is first described.

In a 15 liter container, a diluted aluminate = solution diluted with strong stirring was mixed with the silicate solution. Both solutions had room temperature. During exothermic reaction as primary precipitation product, an X-ray anhydrous sodium aluminum silicate was formed. After 10 minutes of vigorous stirring, the suspension of the precipitate product was transferred to a crystallization vessel where it remained for some time at elevated temperature for crystallization. After extraction of the liquor from the crystal crop and after washing with deionized water, until the running wash water had a pH of approx. 10, the filter residue was dried. Except as deviated from this general manufacturing regulation, this is expressly mentioned in the special section. Thus, e.g. in some cases for the applications of the application, the homogenized, non-crystallized suspension of the precipitate or crystal crop. The water content was determined by heating the product to 800 ° C for 1 hour.

In the preparation of microcrystalline aluminum silicates, which are characterized by the addition "mu, to the deionized water diluted aluminate solution, silicate solution was added and then treated with a fast-moving intensive stirrer (10,000 rpm," Ultraturrax "made by Eirma Janke & Kunkel IKA-Werk,

Staufen, Breisgau, Federal Republic of Germany). After 10 minutes of vigorous stirring, the suspension of the amorphous precipitate product was transferred to a crystallization vessel where the formation of large crystals was prevented by stirring the suspension. After suction of the liquor from the crystal crop and after washing with deionized water until the run-off wash water had a pH of ea. 10, the 40 filter residue was dried, then milled in a ball mill and separated into a centrifugal force sieve (Microplex Wind Sieve from Eirma Alpine, Augs. 151231 burg, Federal Republic of Germany) in two fractions, of which the fine contained no constituents above 10 µl. . The grain size distribution was determined using a sedimentation weight.

The degree of crystallization of an aluminum silicate can be determined from the intensity of the interference lines of an X-ray diffraction diagram for the product in question compared to the corresponding diagram of X-ray amorphous or fully crystallized products.

10 All percentages are weight percentages.

The calcium binding capacity of the aluminum silicates was determined as follows:

To 1 liter of an aqueous solution containing 0.594 g of CaCl2 (= 500 15 mg CaO / 1 = 30 ° dH) and adjusted to a pH of 10 with dilute NaOH is added 1 g of aluminum silicate (calculated on AS). The suspension is then stirred for 15 minutes at a temperature of 22 ° C (t 2 ° C). After filtration of the aluminum silicate, the residual hardness of the filtrate is determined x. Hence the calcium binding capacity in mg CaO / g AS of the formula is calculated: 20 (30 - x) · 10.

If the calcium binding capacity is determined at higher temperatures, e.g. at 60 ° C, generally better values are found than at 22 ° C. This circumstance distinguishes the aluminum silicates above most soluble complexing agents used in detergents so far and represents a particular technical advance in their use.

Preparation conditions for aluminum silicate I: 30 Precipitation: 2,985 kg of aluminate solution of the composition: 17.71 ° Ha 2 O, 15.8% Al 2 O 3, 66.6io HgO 0.15 kg of ethanol 9,420 kg of water 2,445 kg of one of the usual water glass and slightly alkaline soluble silicic acid freshly prepared, 25.8% sodium silicate solution of the composition 1 Na 2 O, 6.0 SiO 2

Crystallization: 24 hours at 80 ° C

Drying: 24 hours at 100 ° C

Composition: 0.9 Na 2 O, 1 Al <2 Qy 2.04 SiO 2, 4.3 H 2 O (= 21, 6 # H 2 O) Crystallization degree: fully crystalline

Calcium binding capacity: 150 mg CaO / g AS.

Drying the resulting product for 1 hour at 400 ° C gives an aluminum silicate Ia of the composition: 0.9 Na 2 O, 1 Al 2 O 5, 2.04 SiO 2, 2.0 H 2 O (= 11.4 # HgO) which also suitable for the purposes of the invention.

Cream setting conditions for aluminum silicate II: 15 Precipitation: 2,115 kg of aluminate solution of the composition: 17.7 # Na 2 O, 15.8 # Al 2 O 3, 66.5 # H 2 O 0.585 kg etching sodium 9.615 kg water 20 2.685 kg of a 25.8 # g sodium silicate solution. Composition of the composition 1 Ma 2 O, 6 SiO 2 (prepared as listed under I)

Crystallization: 24 hours at 80 ° C

O C

Drying: 24 hours at 100 ° C and 20 torr

Composition: 0.8 Na 2 O, 1 Al 2 O 3, 2.655 SiO 2, 5.3 H 2 O

Crystallization degree: fully crystalline

Calcium binding capacity: 120 mg CaO / g AS.

O Λ

Also, this product can be dehydrated by post-drying (1 hour at 400 ° C) until the composition: 0.8 la 2 O, 1 Al 2 O 5, 2.65 SiO 2, 0.2 H 2 O.

This dewatering product 11a is also useful for the purposes of the invention.

Aluminum silicates I and II exhibit the following interference lines in the X-ray bending diagram: 22 151231 ά values recorded with Cu-K radiation in Å oc

I II

14.4 5 12.4 8.8 8.6 7.0 10 - 4.4 (+) 4.1 (+) 3.8 (+) 3.68 (+) 15, 3.38 (+) 3.26 (+) 2.96 (+) 2.88 (+) 2.79 (+) 2.73 (+) 2.66 (+) 2.60 (+)

It is also possible that in the X-ray bending diagram, not all of these interference lines appear, especially when the aluminum silicates are not fully crystallized. Therefore, the d values that are most important for characterizing these types are characterized by a "(+)".

Preparation conditions for aluminum silicate III: Precipitation: 2,985 kg of aluminate solution of the composition:,

35 11.1 fo Ήά20, $ 15.8 A1203, $ 66.5 HgO

0.150 kg of etching sodium, 9.420 kg of water 2.445 kg of a 25.8 $ sodium silicate solution of the composition 1 Ka 2 O, 6 SiO 2 (prepared as specified under I) 25 1 5 1 231

Crystallization: lapse Drying: 24 hours at 25 ° C and 20 torr

Composition: 0.9 Na 2 O, 1 Al 2 O 2, 2.04 SiO 2, 47 H 2 O Crystallization rate: X-ray amorphous

Calcium binding capacity: 160 mg CaO / g AS.

Cream setting conditions for aluminum silicate IY: 10 Precipitation: 2-, 985 kg of aluminate solution of the composition: $ 17.7 Wa20, $ 15.8 Al ^, $ 66.5 H Sodium Silicate Solution of Composition 1 Ifa20, 15 6 SiO2 (prepared as listed under I)

Crystallization: lapses

Drying: 24 hours at 100 ° C, then 1 hour at 400 ° C

Composition: 0.9 Ua20, 1 A120 ^, 2.04 SiO2, 0.1 H2O2Q Crystallization rate: X-ray amorphous

Calcium binding capacity: Through the extensive drying of the amorphous precipitate, the calcium binding capacity was reduced to 20 mg CaO / g AS. The product was practically useless for the purposes of the invention.

25

Preparation conditions for aluminum silicate V: Precipitation: 4 »17 kg of solid aluminate of the composition: 38 $ Ka20, 62 $ A120 ^ 2q 10.83 kg of a 34.9 $ sodium silicate solution of the composition: 1 Na2 O, 3.46 SiO

Crystallization: lapses

Drying: 24 hours at 100 ° C

Composition: 1.5 Na 2 O, 1 Al 2 O 3, 2 SiO 2, 3 H 2 O

Cross degree of number: X-ray amorphous

Calcium Tack; 140 mg CaO / g AS.

24 151231

Preparation conditions for aluminum silicate VI: Peel: 8.37 kg of aluminate solution of the composition: 20.0 $ Na 2 O, 10.2 $ Al 2, 69.8 $ H 2 (Aerosil ®) crystallization: lapses

Lo Drying: 24 hours at 100 ° C

Composition: 0.9 Ka 2 O, 1 Al 2 O 2, 2.04 SiO 2, 6.7 H 2 O

Crystallization rate: X-ray amorphous

Calcium binding capacity: 145 mg CaO / g AS.

Preparation conditions for aluminum silicate 711: Peel: 3,255 kg of aluminate solution of the composition: 17.7 $ Na2 O, 15.8 $ A1203, 66.5 $ Η £ 0. in sodium silicate solution of the composition: 1 Na 2 O, 3.46 SiO 2

Crystallization: lapses

Drying: 24 hours at 100 ° C

Composition: 1 Na 2 O, 1 Al 2 O 3, 2 SiO 2, 1 H 2 O (= 6 $ H 2 O)

Crystallization rate: X-ray amorphous

Calcium binding capacity: 150 mg CaO / g AS.

Preparation conditions for aluminum silicate VIII: Peel: 2,115 kg of aluminate solution of the composition: $ 17.7 Bia20, $ 15.8 AlgO Composition: 1 Na 2 O, 6 SiO 2

Crystallization: lapses 151231

Drying: 24 hours at 100 ° C

Composition: 0.8 Na 2 O, 1 Å 120 2, 2.65 SiO 2, 4 H2 O

Crystallization rate: X-ray amorphous

Calcium binding capacity: 60 mg OaO / g AS.

5

Preparation Conditions for Aluminum Silicate IX: Precipitation: 3.41 kg aluminate solution of the composition: 21.4 fo Na 2 O, 15.4 f kl20y 63.2 # H 2 O 10 10.46 kg water 1.13 kg of a 34.9 : 1 Na 2 O, 3.46 SiO 2

Crystallization: "lapses

Drying: 24 hours at 100 ° C

Composition: 1 TTa 2 O, 1 Al 2 O 2, 1 SiO 2, 1.4 H 2 O

Crystallization rate: X-ray amorphous

Calcium binding capacity: 120 mg CaO / g AS.

2q Preparation conditions for aluminum silicate X: Precipitation: 2.835 kg of aluminate solution of the composition: 14.2 # Ka 2 O, 17.2 # Al 2 O 3, -68, 6 # H 2 O 6.93 kg water 25 5.25 kg of a 34.9 Composition: 1 Ma 2 O, 3.46 SiO 2

Crystallization: lapses

Drying: 24 hours at 100 ° C

Composition: 1 Na 2 O, 1 Al 2 O 2, 5 SiO 2, 2.8 H 2 O

Crystallization rate: X-ray amorphous

Calcium binding capacity: 100 mg CaO / g AS.

Preparation conditions for aluminum silicate XI: 35 Precipitation: 2.86 kg of aluminate solution of the composition: 13.8 # Na 2 O, 16.7 # A1 £ 03, 69.5 # H 2 O 6.01 kg water 6.13 kg of a 34.9 # Sodium Silicate Solution- ^ -P Ί "ΚΓλ C \ 26 151231

Crystallization: "lapses

Drying: 24 hours at 100 ° C

Composition: approx. 1 Ua ^ O, 1 AlgO ^, 6 Si02, 3 »2 B ^ O

Crystallization rate: X-ray amorphous Calcium binding capacity: 60 mg CaO / g AS.

Preparation conditions for aluminum silicate XII: Precipitation: 2.01 kg of aluminate solution of the composition:

$ 20.0 Ba20, $ 10.2 Al2203, $ 68.8 HgO

1,395 kg of etching sodium 9,405 kg of water 2.19 kg of a 25.8 µg sodium silicate solution of the composition: 1 Ha 2 O, 15 6 SiO 2 (prepared as listed under I)

Crystallization: 24 hours at 80 ° C

Drying: 24 hours at 100 ° C

Composition: 0.9 Na 2 O, 1 Al 2 O 3, 2 SiO 2, 3 H 2 O Crystallization degree: fully crystalline

Calcium binding capacity: 160 mg CaO / g AS.

Preparation Conditions for Aluminum Silicate XIII: 25 Precipitation: 2,985 kg of aluminate solution of the composition: 17 7 $ 1fa20, 15.8 $ Al20y 66.5 $ H20 0.150 kg etching sodium 9.420 kg water 2.445 kg of a 25.8 $ sodium silicate solution of composition: 1 Ka 2 O, 6 SiO 2 (prepared as listed under I)

Crystallization: 24 hours at 80 DEG C. To prepare the potassium aluminum silicate, the liquor was aspirated, the residue washed with water and slurried in an aqueous solution containing KOI. After 50 minutes of heating to 80-90 ° C, the filter was filtered off and washed.

27 151231

Drying: 24 hours at 100 ° C

Composition: 0.28 Ua 2 O, 0.62 K 2 O, 1 Al 2 O 2, 2.04 SiO 2, 4.3 H 2 O

Crystallization rate: fully crystalline 5 Calcium binding capacity: 170 mg CaO / g AS.

Preparation Conditions for Aluminum Silicate XIV: Precipitation: 8,450 kg of aluminate solution with compositions 10 11.3 $ Na 2 , 3.46 SiO 2

Crystallization: lapses 15 Drying: lapses

Composition: 1.5 "Na 2 O, 1 Å 120 2, 2 SiO 2, x H 2 O

Crystallization rate: X-ray amorphous

Calcium binding capacity: 120 mg CaO / g AS.

Preparation Conditions for Aluminum Silicate XV:

Precipitation: as for aluminum silicate XIV

Crystallization: 24 hours at 80 ° C

Drying: lapses Composition: 1.5 Na 2 O, 1 A 12 Q 2, 2 SiO 2, x H 2 O

Crystallization degree: fully crystalline

Calcium binding capacity: 170 mg CaO / g AS.

The primary particle size of the aluminum silicates described herein ranged from 10 to 45 µ. 30

Manufacturing conditions for aluminum silicate Im:

Precipitation: as for aluminum silicate I

Crystallization: 6 hours at 90 ° 0

Drying: 24 hours at 100 ° C

Composition: 0.9 Ka 2 O, 1 Al 2 O 3, 2.04 SiO 2, 4.3 H 2 O (= $ 21.6 H 2 O)

Crystallization degree: fully crystalline

Calcium binding capacity: 170 mg OaO / g AS.

28 151231

Manufacturing conditions for aluminum silicate IIm:

Precipitation: as for aluminum silicate II

Crystallization: 12 hours at 90 ° C

Drying: 24 hours at 100 ° C and 20 torr

Composition: 0.8 Na 2 O, 1 Al 2 O 2, 2.655 SiO 2, 5.2 H 2 O

Crystallization degree: fully crystalline

Calcium binding capacity: 145 mg CaO / g AS.

Preparation Conditions for Aluminum Silicate Xllm:

Precipitation: as for aluminum silicate XII

Crystallization: 6 hours at 90 ° C

Drying: 24 hours at 100 ° C

Composition: 0.9 Na 2 O, 1 Al 2 O 2, 2 SiO 2, 3 H 2 O

Crystallization degree: fully crystalline

Calcium binding capacity: 175 mg CaO / g AS.

Manufacturing conditions for aluminum silicate XHIm: 20

Precipitation: as for aluminum silicate XIII

Crystallization: 6 hours at 90 ° 0

To prepare the potassium aluminum silicate, the liquor was aspirated, the residue washed with water and suspended in an aqueous solution containing KCl. After 50 minutes of heating to 80-90 ° C, the filter was filtered off and washed.

Drying: 24 hours at 100 ° C

Composition: 0.28 Na 2 O, 0.62 K 2 O, 1 AlgO 2, 2.04 SiO 2, 4.3 H 2 O

Crystallization degree: fully crystalline

Calcium binding capacity: 180 mg CaO / g AS.

Preparation conditions for aluminum silicate XVm:

Precipitation: as for aluminum silicate XIY

Crystallization: 24 hours at 80 ° C

29 151231 Drying: The filter cake was not dried but washed out

slurry suspended in water and used in this form for the application engineering studies. Composition: 0.9 Ka ^ O, 1 2 SiO 2, x H ^ O

5 Degree of crystallization: fully crystalline

Calcium binding capacity: 170 mg CaO / g AS.

Manufacturing conditions for aluminum silicate Xirillm:

10 Precipitation: as for aluminum silicate XIY

Crystallization: 6 hours at 90 ° C

Drying: 24 hours at 100 ° C

Composition: 0.9 Na 2 O, 1 Α 120 2, 2 SiO 2, 4.4 H 2 O

Crystallization degree: fully crystalline Calcium binding capacity: 172 mg CaO / g AS.

Preparation conditions for aluminum silicate XlXm: Precipitation: 2.96 kg of aluminate solution of the composition: 20 17.7 $ Na 2 O, 15.8 $ Al 2, 66 $ H 2 O 0.51 kg ether sodium 8.45 kg water 3.00 kg of one in the broth sodium silicate solution of the composition: 8.0 $ 25 Wa 2 O, 26.9 $ SiO 2, 65.1 $ H 2 O

Crystallization: 12 hours at 90 ° C

Drying: 12 hours at 100 ° C

Composition: 0.93 Na 2 O, 1 Al 2 O 5, 2.75 SiO 2, 5.5 H 2 O

Crystallisation degree: fully crystalline 30 /

Calcium binding capacity: 125 mg CaO / g AS.

Preparation conditions for aluminum silicate XXm: Precipitation: 0.76 kg of aluminate solution of the composition: 35 36.0 $ ffa20, 59.0 $ A1 £ 05, 5.0 $ H20 0.94 kg etching sodium 9.49 kg water 3.94 kg of a commercially available sodium silicon 30 1 5 1 231

Cat solution of the composition: 8.0 $ ITa20, 26.9 $ SiO2, 65.1 $ H2O Crystallization: 12 hours at 90 ° G

drying: 12 hours at 100 ° C

Composition: 0.9 Na 2 O, 1 ΑΙ, - Ο 3, 3.1 SiO 2, 5 H 2 O

Crystallization degree: fully crystalline

Calcium binding capacity: 110 mg CaO / g AS.

The grain size distribution determined by sedimentation analysis of the 10 microcrystalline products Im-XIIIm and XVIIIm-XXm described above was in the following range:> 40 µ = 0 $ Grain drying maximum = 3 - 6 µ <10 µ = 85 - 95 $ 15 ^ <8 µ = $ 50 - $ 95

The grain size distribution for the product XVm was in the following range:> 40 μ = 0 $ Grain size maximum = 1 - 3 μ 20 r r <10 μ = 100 $ <8 μ - 99 $

The saline constituents contained in the washing and washing aids in the Examples contained saline surfactants, other salts, other organic salts and inorganic salts as sodium salts, unless expressly stated otherwise. This also applies to the complexing agent or precipitating agent, which for simplicity is designated by the name of the corresponding acid. The terms or abbreviations used mean: "ABS" salted by a benzene condensation of straight chain olefins and sulfonation of the resulting alkylbenzene alkylbenzene = sulfonic acid having 10-15, preferably 11-13 carbon atoms in the alkyl chain, 35 "HPK sulfonate" one of hydrated palm kernel fatty acid methyl ester by sulfonation with SO 2 prepared sulfonate, "OA + x ÆO" or "TA + x ÆO" the ethylene oxide (EO) preparation products for technical oleyl alcohol (OA) or sebum fatty alcohol (IA) (iodine number = 0.5) , wherein the numerals for x characterize the molar amount of ethylene oxide, which is added to 1 mole of alcohol, the "ΜΊΑ" or "EDTA" salts of nitrilotriacetic acid or ethylenediamine = tert acetic acid, the "HEDP" salt of 1-hydroxyethane-1, 1- diphosphonic acid, "DMDP" salt of dimethylaminomethane diphosphonic acid,. The CMC salt of carboxymethyl cellulose.

The washing effects obtained with aluminum silicates according to the invention were demonstrated by washing experiments with pieces of non-impregnated or iron-free (wrinkle-free) impregnated cotton or on polyester and impregnated cotton blend fabrics with a test soiling of soot, iron oxide, kaolin and grease-made ( Krefeld L5).

The tests were carried out with tap water of 16 ° dH partly in the Launderometer and partly in a commercially available 4 · kg drum washing machine (25 liters of liquor).

In the Launderorneter, each container was filled with two test pieces of> 0 each 2.1 g and two non-soiled pieces of the same material, also weighing 2.1 g each. The drum washer was filled with six test pieces, each 20 x 20 cm in size, and 3> 8 kg of non-soiled fabric of the same kind.

The aluminum silicate concentrations in the treatment liquids are, like the aluminum silicate content of the detergent recipe, calculated on the anhydrous component of the product (determined at 1 hour dewatering at 800 ° C). This also applies to the use of suspensions of the X-ray amorphous precipitate or the crystal crop.

0

The wash times specified for each experiment relate to the duration of treatment at said temperature including the heating time.

Cold tap water was used for rinsing.

After washing the clothes in the Launderorneteret, a four times follow

ISLAND

flushing with tap water, each of 30 seconds duration. In the tests carried out in the commercial washing machines, the drainage from washing and rinsing was determined by the washing program's automaticity, as was foreseen for each washed textile material. After drying and ironing the fabrics, their remission value was measured in a Zeiss light photometric "Elrepho" photometer under filter 6 (throughput maximum at 461 nm). The test pieces used in the tests had a remission value of approx. 43rd

Example 1

This example demonstrates the washing action of various aluminum silicates to be added according to the invention without the addition of additional detergent active ingredients.

10

Working conditions:

Non-impregnated cotton 10 g / l aluminum silicate „Elot ratio: 1:12

Q

30 minutes at 90 ° C in launderets.

In parallel experiments, the dirt removal was detected with water without any other addition or with the addition of 10 g / l tripolyphosphate.

2Q The "water values" or "tripolyphosphate values" thus established as well as the other values are shown in the following statement:

Addition Remission

No addition 42.4 25 Ha5P3 ° 10 76.8

Aluminum Silicate I 68.0 "II 66.0» III 67.5 30 "IV 50.5» VIII 62.0 "XIII 69.3" XIVx 66.0 35 »XVx) 69.4 x) These Aluminum Silicates were used such as precipitate or crystal porridge, but after 33 151231

Example 2

To demonstrate the enhancement of the washing action of an aluminum silicate-containing detergent prepared by mixing the dry aluminum silicate with perborate, a calcium-binding or precipitating agent and a hot-spray detergent powder which does not contain the above-mentioned components, by the addition of complexing agents or calcium precipitants, detergents of the following composition were used: 5.3 $ ABS 2.596 Na 2 O, 3.3 SiO 2

2.0 $ TA + 14 Æ0 1.296 CMC

2.8 $ Soap C12-C22 1,796 MgSiO ^ 15 or 4.2 $ Complex Former or 2.1 $ Ha2S0 ^ precipitant for g q calcium ^ 45.0 $ Al-silicate la 22.1 $ Perborate 20

Working conditions:

Impregnated cotton 25 9 g / in detergent

Great Ratio: 1:12 30 minutes at 90 ° C in Launderometer.

The results can be seen from the following set: 30

Complex or precipitant Remission for calcium (like Ha salts)

No addition 64.0 35 Oxalic acid 68.0

Tartaric acid 66.0

Citric Acid 68.5 34 O-Carboxymethyl-Tartronic Acid 74.8 O-Carboxymethyl-Methyl-Tartronic Acid 75.7

Na5P3 ° 10 71, °

Alanine 68.9 G-lutamic acid 72.0

Nitrilotriacetic acid 71.0 Ethylenediaminetetraacetic acid 67.5 Ν, ΪΤ-dimethylamino-methanediphosphonic acid 71.0

Polyacrylic acid 69.5

Polyhydroxy-polycarboxylic acid 1 71.7

Polyhydroxy Polycarboxylic Acid II 72.0 15) These two substance samples had been prepared by polymerizing acrolein and treating the polymerizate of Cannizzaro in the presence of form aldehyde.

With a detergent according to the above recipe, in which the complexing agent or precipitating agent for calcium and the aluminum silicate is completely replaced with sodium tripolyphosphate, the above washing conditions are obtained, a remission value of 72.5 is obtained.

Example 5

This example demonstrates the effect of the stepwise replacement of the triphosphate containing aluminum silicate in a detergent. The composition of the detergent was within the scope of the following recipe: 30

5, 3 $ ABS 22.1 $ liaB02, H202, 3 HgO

2.0 $ IA + 14 ÆO 2.5 $ ffa20, 3.3 Si02

$ 2.8 Soap C12-C22 $ 1.2 CMC

$ 4.2-33.4 $ ffa5P3010 1.7 $ MgSiO ^ 45 - 0.0 $ Aluminum Silicate la 2.1 $ Ja2S0 ^

Best H20 35 151231

Test conditions:

Impregnated cotton 9 g / l detergent 5 Nice ratio: 1:12 30 minutes at 90 ° C in Launderometer.

Washing result: 10 Detergent percentage of

Na ^ PjO- ^ Q Aluminum Silicate% Remission 4.2 45.0 72 8.3 39.4 72 15 12.5 35.8 73 16.7 28.1 73 20.8 22.5 73 25.0 16.9 73 20 29.2 11, 3 73 33.4 0 72 25 Examples 4 and 5

Some examples show the washing effect of two detergents according to the invention against different fabrics in comparison to detergents in which the aluminum silicate is replaced by Nar-P 2 O. The detergents had the following composition, the detergent according to the invention being characterized by the addition " e "and the comparative detergent of the addition" v ".

Component of Weight $ ingredient in detergent detergent 4v 4e 5v 5e 35 ABS 8.0 8.0 TA + 14 ÆO 3.0 3.0 OA + 10 ÆO - - 15.0 15.0

η n -z c -z c r? Λ ^ D

36 33.4 2.5 10.0 3.0

Aluminum silicate Ia - 45.0 - 27.0

HaB02, H2 O2, 3 H2 O 22.1 22.1 24.0 24.0

Na 2 O, 3.3 SiO 2 2.5 2.5 10.0 10.0 5 CMC 1.2 1.2 - -

MgSiO ^ 1.7 1.7

Ua2SO4 19.0 2.1 10.0 10.0 H2G 5.6 8.4 8.0 8.0 10

Washing conditions: Natural and impregnated cotton, blend fabric of cotton and polyester

Detergent 4v and 4e: 9 g / l Detergent 5v and 5e: 7.5 g / l.

Elot ratio: 1: 5

Drum washing machine with washing program for cooking washing Maximum temperature 95 ° C

20 Wash result: see table

Detergent Remission of the washed fabric in $ according to Natural Impregnated Cotton Sample Cotton Cotton Polyester 25 4v 83 74 70 4e 82 73 74 5v 82 74 74 5e 82 73 74 30

If you want to achieve the same washing results as with tripolyphosphate, it is advisable to select the aluminum silicate concentration in the wash float somewhat higher than the triphosphate concentration in the comparison float.

Example 6

For use in industrial laundries, detergents of the following prescriptions 6a and 6b are suitable: 37 1 5 1 231

Content in% of detergent Component 6a 6b ABS 1.4 1.4 OA + 10 Æ 7.6 7.6

Na2CO3 18.5 18.3 5 lfa2S103 5.4 5.4

Aluminum Silicate V 18.3 33.4 lia5P3010 16.7 5.8 CMC 0.8 0.8

Detergent, Na2 SO4 10.0 10.0 H2 O 21.5 17.3

In the detergent 6a, the H₂P₂O Q can be replaced by a calcium-free organic complexing agent for calcium and in detergent 6b with HEDP or another phosphonate which binds calcium, by a phosphorus-free complexing agent for calcium or by a non-complexing calcium precipitant ( e.g. oxalic acid, adipic acid or sebacic acid in the form of their water-soluble salts).

20 Using each of these detergents, normally soiled household laundry was washed under the following condition!

Machine type: Centrifuge washing machine with a capacity of 90 kg, filled with 75 kg of laundry 25 o

Water: tap water cured to 5 dH

1. Brush washing: 25 g of detergent per kg of dry laundry

Plot Ratio: 1: 4

30 minutes at 60 ° C

2. Second wash: 20 g of detergent per 0.5 g of active oxygen (as H2O2) per kg of dry laundry kg of dry laundry

Plot Ratio: 1: 4

12 minutes at 90 ° C

^ A -v-i ν »· r \ (TOTI γγΛ τηΩ / 1 o -Pincs 4 * τγον» A r \ re 4 ~ r \ rrQYi rrO mo / 1 38 151231 In both cases the washing result was perfectly satisfactory.

Example 7

A detergent for washing heavily soiled workwear has the following composition: 18.0% OA + 10 10O 5.5% O-carboxymethyl-tartronic acid 60.0 $ Ha2003 (Ha salt)

$ 12.0 Aluminum Silicate Y - ^> 3 $ OMO

0.3% Clarifier 2.9% H2 O

Example 8 15

Bleaching washing aids, of which the product a is suitable for addition to washing floats in industrial laundries and the product b as a cold additive for rinsing water, has the following composition: 20% by weight of the composition according to ex component 8a 8b l <ra2B02, H202 , 3 Η £ 0 36.0 18.0

Tetraacetyl glycoluril - 18.0

MgSiOj 3.6 3.6

Aluminum silicate V 31.5 31.5

Na citrate 7.2 7.2 Ua 2 CO 3 15.0 15.0

Clarifying agent 0.3 0.3 H2 O 6.4 6.4 The following is the prescription of some additional aluminum silicate = 35 detergents containing.

Detergent- Weight% component of detergent according to Ex.

Ingredient 9 10 11 12 39 151231 ΤΑ + 14 ÆO 7.0 10.3 10.7 6.8

Aluminum silicate YII 52.1 47.2 51.2 64.2

Na + P = 010 - 5.1 3.2 6.2

Sodium citrate 7.3 - 2.1 EDTA 0.2 0.2 0.1 0.3

Na 2 O, 3.3 SiO 2 1.7 6.3 3.1 3.5

NaBO2, H2O2, 3H2O 24.9 24.9 20.3 10 CMC 0.8 1.6 1.1 2.0

Na2 SO4 + H2 O 6.0 4.4 8.2 17.0

Detergent- Weight component of detergent according to Ex.

Component 13 14 15 16 15 HPK Sulfonate 1.0 2.6 - 1.6 ABS 4.5 4.7 7.1 TA + 14 ÆO 2.3 1.9 - 6.4 2q OA + 10 ÆO - - - 4.1 Soap 2.0 1.6 3.2

Aluminum Silicate VII 45.0 47.3 48.1 49.3 3 a 5 3 3 10 5.0 6.3 8.0 7.2 EDTA 0.2 0.9 0.2 0.2

Na 2 O, 3.3 SiO 2 6.5 3.7 2.6 3.4

NaBO 2, H 2 O 2, 3 H 2 O 25.1 26.3 22.3 22.1 CMC 1.3 0.9 1.5 1.6 30

Na2 SO4 + H2 O 7.1 3.8 7.0 4.1

As will be seen from the examples, in particular of the experiments described therein, the aluminum silicates of cation exchange 35 used in the invention are capable of improving the washing performance of the detergent and of the detergent and of replacing tripolyphosphate in the water and in the soiled calcium. . As far as the recipes in the examples contain triphosphate, this can be replaced with phosphorus-free complexing agents if necessary. Useful complexing agents are found under the compounds of ta-Ήοΐ 1 em in PlrHpnmpl 9 inlral aurp per iTrlrfi a ΤτητητΠ extender. mfin a trap ή - 40 151231

Although the aluminum silicates are water-insoluble, they can be easily flushed out of the washed textile materials and neither the washing machine nor the drainage pipes deposits.

The experiments and agents described in Examples 1-16 were prepared using microcrystalline aluminum silicates. This showed a better effect of the microcrystalline aluminum silicates, at least when the products to be compared with each other had the same composition. In detail, the following microcrystalline aluminum silicates were tested or used to prepare detergent or washing aids: In Example 1: Aluminum Silicate Im, Adhesive In Example 2: Aluminum Silicate XIIm In Example 3: Aluminum Silicate Im In Example 4: Aluminum Silicate XHIm In Example 5: Aluminum In Example 6: Aluminum Silicate XVIIIm. Ha 5P3 ° 10 can be replaced in the detergent 6a with a phosphorus-free organic complexing agent for calcium, in detergent 6b with HSDP or another phosphate-binding calcium, with a phosphate-free calcium binding agent or with a non-complexing calcium = precipitating agent. (e.g. oxalic acid, adipic acid or sebacic acid in the form of their water-soluble salts) In Example 7: aluminum silicate glue 30 In Example 8: aluminum silicate Im

In Examples 9-12: Aluminum Silicate XII

In Examples 13-16: Aluminum Silicate XVIIIm.

35 Using the aluminum silicates -χχχ · and xx j-, iev detergents of the following examples prepared:

Detergent- Weight component of detergent according to Ex.

Ingredient 17 18 19 20 TA + 14 ÆO 7.0 10.3 10.7 6.8

Aluminum Silicate XlXm 50.1 45.2 49.2 62.2 Na5P3010 - 5.1 5.2 6.2

Sodium citrate 7.3 - 2.1 EDTA 0.2 0.2 0.1 0.3

Na 2 O, 3.3 SiO 2 1.7 6.3 3.1 '3.5 10 NaBO 2, H 2 O 2, 3 H 2 O 24.9 24.9 20.3 CMC 0.8 1.6 1.1 2.0

Na2 SO4 + H2 O 8.0 6.4 10.2 19.0 Detergent Weight $ ingredient in detergent according to Ex.

Component 21 22 23 24 HPK Sulfonate 1.0 2.6 - 1.6 ABS 4.5 4.7 '7.1 20 TA + 14 ÆO 2.3 1.9 - 6.4 OA + 10 ÆO - - - 4.1 Soap 2.0 1.6 3.2

Aluminum Silicate XXm 43.0 45.3 46.1 45.3 Na5P3010 5.0 6.3 8.0 7.2 EDTA 0.2 0.9 0.2 0.2

Na 2 O, 3.3 SiO 2 6.5 3.7 2.6 3.4

NaBO2, H2 O2, 3 H2 O 25.1 26.3 22.3 22.1 CMC 1.3 0.9 .1.5 1.6

Fa2 SO4 + H2 O 9.1 5.8 9.0 8.1

A better washability of the microcrystalline aluminum silicates used according to the invention is particularly evident at edges and corners a. Bedspread and pillowcases and by shirt collars and cuffs:

Claims (22)

151231 A process for cleaning, including washing, prewashing and bleaching, of solid materials, especially textiles, by treating these materials with an aqueous raft containing water-insoluble, finely divided aluminum silicate having a builder effect, and at least one compound selected from '' synthetic surfactants '' and, optionally, a bleaching agent, characterized in that it works with a raft which, as aluminum silicate and as suspended phosphate substitute, contains a crystalline or X-ray-grafted aluminum silicate containing bound water, is synthetically prepared and has one in it. 10, at least 50 mg CaO / g of anhydrous active substance, said aluminum silicate having the general formula (Cat 2 O) x, Al 2 O 3, (SiO 2) y, wherein cat is a calcium exchangeable alkali, x is a number of 0.7 to 1.5, and y is a number of 1.3-4. Process according to claim 1, characterized in that the 20 suspended water-insoluble aluminum silicate according to claim 1 has a calcium binding capacity of up to 200 mg CaO / g anhydrous active substance and preferably at least 100 mg CaO / g anhydrous active substance. Process according to claims 1 and 2, characterized in that the water-insoluble aluminum silicate has the composition 0.7-1.1 (Cat20), Al2 O3, 1.3-3.3 SiO2 and preferably the composition 30-1-1. 1 (Cat20), Al2O3, 1.3-2.4 SiO2 · Process according to claims 1-3, characterized in that the water-insoluble aluminum silicate of the formula according to claim 1 is a sodium aluminum silicate. 15123f ' Process according to claims 1-4, characterized in that the aluminum silicate is crystalline. Process according to claims 1-5, characterized in that the water-insoluble aluminum silicate in the X-ray bending diagram 5 has the following d-values (in Å): 12.4 8.6 7.0 4.1 3.68 3.38 3.26 2.96 2.73 2.60 10 or 14.4 8.8 4.4 3.8 2.88 2.79 2.66. Process according to claims 1-5, characterized in that the suspended water-insoluble aluminum silicate has a primary particle size between dust fineness and 100 µ. 15 Process according to claims 1-7, characterized in that the particle size of the water-insoluble aluminum silicate is in the range 50 - 1 µ. Process according to claims 1-7, characterized in that the primary particle size of the water-insoluble aluminum silicate can also be less than 10 µ. Process according to claims 1-9, characterized in that the suspended water-insoluble aluminum silicate for at least 80% by weight consists of particles having a size of 10-0.01 µ, preferably 8 - 0.1 µ. Process according to claims 1-10, characterized in that the suspended aluminum silicate does not comprise any particles above 40 µ. Process according to claims 1-11, characterized in that the treatment float further contains compounds which can complex and / or precipitate calcium, and which are in particular of the following types: 44 1 5 1 23T Pyrophosphate, triphosphate, higher polyphosphates and metaphosphates , poly = carbonic acids, hydrocarbon acids, amino carbonic acids, carboxyalkyl ethers, polyanionic polymeric carbonic acids, phosphonic acids, polyphosphonic acids, preferably as water-soluble salts. 5 Process according to claims 1-12, characterized in that the complexing agents or precipitating agents for calcium are used at concentrations of 0.05 to 2 g / l. Method according to claims 1-13, characterized in that the treatment float contains at least one surfactant of the group of surfactants of the sulfate or sulfonate type, zwitterionic surfactants, nonionic surfactants. Process according to claims 1-14, characterized in that phosphorus compounds are found at most in such quantities that the phosphorus content of the treatment float does not exceed 0.6 g / l, preferably 0.3 g / l. A detergent, including detergent, prewash detergent and bleach detergent, for carrying out the process according to claims 1-15, containing a water-insoluble, finely divided aluminum silicate as well as at least one compound of the group of surfactants, builders and bleaches and a partial or complete substitute replacement of condensed phosphates, characterized in that it contains as a phosphate substitute a crystalline or x-ray-morphed aluminum silicate as claimed in claim 1. Agent according to claim 16, characterized in that it contains the aluminum silicates in amounts of 5 - 95, preferably 15 - 60% by weight. Agent according to claims 16 and 17, characterized in that it further contains complexing agents or precipitating agents for calcium in amounts of 2 to 15% by weight. 35 Agent according to claims 16-18, characterized by a content of organic and / or inorganic phosphorus compounds in such amounts that the total P content of the agent does not exceed 6% by weight, preferably 3% by weight. 15f2Tt An agent according to claims 16-19, characterized in that it has a powdery to grainy nature. Process for preparing agents according to claims 16-20, 5. characterized in that the powdered water-insoluble aluminum silicate according to claims 1-10 is mixed with the other components of the agent, preferably it is incorporated in an aqueous mixture of the water-stable agent and heat-stable constituents, drying it in a manner known per se and optionally mixing the dried product with heat-2 sensitive or moisture-sensitive constituents of the agent. Method according to claim 21, characterized in that oily or paste-shaped components of the detergent, especially the non-ionic surfactants, are sprayed onto the powder.