FI60886B - FOERFARANDE FOER FRAMSTAELLNING AV PULVERFORMIGA TVAETT- OCH RENGOERINGSMEDEL SAMT MEDEL FOER GENOMFOERANDE AV FOERFARANDET - Google Patents

Description

R3F * 1 M p1) NOTICE, EXTERNAL.SU g O 8 86

Mg l J l 'UTLÄGGKIINGSSKRIFT

* (45) Patent granted on 13 April 1932

Patent a? Ödelnt ^ T ^ (51) Ky.lk.3 / lnt, CI.3 C 11 D 3/12 ENGLISH —Fl N LAN D (2.1) P * W «ittlM» mu · - PatuntaraSkning 752723 (22 ) Hskamlspiivt - Amekiilngtdag 29.09.75 (23) AlkupUvt — Giltlghvtvdag 29 * 09.75 (41) Interpreters slipped - Bllvlt offuntiig 11.OU. 76

Patent and Registration Office ... ...._____.... . . , _ 1 (44) Date of Nihciviksipanon (s moonLjulkalsun -

Patent- och registerstyreisen Anaökan utitgd och uti.skriftan puW, c * r »d 31.12.8l (32) (33) (31) Pyy ^« ty «tuolkuui —Bagird priority 10.10. 'Jk

Austria-Österrike (AT) 8l5lM, 19 · θ6.75 Federal Republic of Germany-Förbundsrepub-liken Tyskland (DE) P 2527388.5 (71) Henkel Kommanditgesellschaft auf Aktien, Henkelstrasse 67, ^ 000 Dus-seldorf, Federal Republic of Germany-Förbunds (72) Dieter Kuhling, Monheim Rhld., Josef Huppertz, Dusseldorf-Holthausen,

Dieter Jung, Hilden Rhld., Peter Krings, Krefeld, Herbert Reuter,

Hilden Rhld., Gunter Schenck, Neuss Rhld., Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (7¾) Oy Heinänen Ab (5 * 0 Method for the preparation of powdered detergents and an intermediate for the application of the method - Förfarande för fram-ställning av pul - och rengöringsmedel samt medel för genomförande av förfar andet

One of the major problems in the detergent industry is the desire to replace all or part of the calcium complexing phosphates previously used with other agents. An earlier patent (German patent application P 24 12 Θ37.Β-41) discloses methods for washing and cleaning solids, in particular textiles, and detergents for the application of this method, in which the functions of the phosphates which bind calcium complex completely or partially replaced by finely divided, water-insoluble aluminum silicates which have the ability to bind calcium and which generally contain bound water.

These substances are compounds of the general formula: (Kat-, 0) * A 1 .-, 0- (SiO-) (I) 2 / nxc J £ y where Kat represents a calcium-exchangeable cation with a valence of n, x is a number from 0.7 to 1.5 and y is a number from 0.8 to 6, preferably at least 1.3 to 4.

2 60886

Suitable cations are preferably sodium, but sodium can be replaced by lithium, potassium, ammonium or magnesium and cations of water-soluble organic bases, for example primary, secondary or tertiary amines or alkylamines having up to 2 C atoms per alkyl group and respectively atoms per alkylol group.

The compounds defined above which have the ability to bind calcium are hereinafter referred to as "aluminosilicates" for simplicity. These include particularly preferred sodium aluminum silicates. All functions assigned to the use of these in accordance with the invention, as well as all other functions related to their preparations and properties, apply mutatis mutandis to all of the compounds defined above.

Aluminosilicates which are particularly suitable for use in detergents have a calcium-binding capacity of preferably 50 to 200 mg CaO / g anhydrous aluminosilicate. When the term anhydrous aluminosilicate is used hereinafter, it means the state of the aluminosilicate which arises after drying for one hour at a temperature of 800 ° C. In this drying, the adhered and bound water is virtually completely removed.

In the preparation of detergents and cleaning agents which, in addition to the usual ingredients in such materials, contain aluminum silicates as defined above, aluminosilicates which are moist, for example moist after preparation, are preferably used as starting materials. In this case, the wet compounds are mixed with at least one part of the other ingredients of the product to be prepared and the mixture is transferred to the finished detergent or cleaning agent mixture, which is the final product, for example as a sprayable product.

According to the preparation method of the detergents described above, aluminosilicates are used, for example, as aqueous suspensions or wet filter cakes. In this case, certain improvements in the suspension properties, for example the depth and pumpability of the suspension, may be desirable properties for water-dispersed aluminosilicates.

i

According to the invention, it has been shown that certain compounds are particularly capable of stabilizing the calcium-binding aluminosilicates described above in such a way that they remain stable even at high solids concentrations for long periods of time and, if desired, even for a virtually indefinite period of time. after fully pumpable. It has been quite surprisingly found that there are certain compounds that have the ability to retain even moist Aluminum silicates with a water content of $ 70 or less, when pumped virtually regardless of the shelf life.

The object of the invention is to provide aqueous suspensions of water-insoluble silicates which have pumpable and improved stability and are suitable as storage suspensions and which have the ability to bind calcium, and are characterized in that they contain at least 20 Ί2 ^ finely divided, water-insoluble compounds, preferably those containing bound water and having the ability to bind calcium, having the general formula (Kat2 / rP ^ x ·. (SiO2) y (j) in which the symbols given have the same meaning as above, and B) it contains at least one dispersant belonging to the group comprising the following compounds: 1. an organic, macromolecular carboxylic and / or hydroxyl-containing polymeric compound, 2. a phosphonic acid containing at least one additional phosphonic acid and / or carboxyl group, 3. phosphonic acid alkyl ester emulsifier, with 3 to 20 carbon atoms in its alkyl chain 4. a non-ionic surfactant with a cloud point in aqueous butyl diglycol solution determined according to DIN 53917 -> - below 90 ° C, 5. surfactant sulphonate, 6. swellable insoluble in water silicate, which is a layered structure.

The water-soluble compounds can be used either as such or as water-soluble salts and, depending on the pK value and the pH of the suspension, are usually ionized in the suspension. The pH of the suspension is generally between about 7 and 12 and preferably between 8.5 and 11.5 and usually below 11.

4 60886

The compounds described above are the essential ingredients of the solid suspensions of the invention. However, they may also contain other ingredients, for example anti-foaming additives or so-called solubilizers, i.e. compounds which improve the solubility of the added dispersants in the aqueous phase. As the antifoaming agents, ordinary antifoaming agents can be used, for example, antifoaming soaps, silicone-based antifoams, antifoaming triazine derivatives, all of which are well known to those skilled in the art and are commercially available. The addition of such a substance is usually not necessary. However, in the case of foamable dispersions, it may be advantageous to use such an additive, especially when using larger amounts of alkylbenzenesulfonic acid.

The addition of solubilizers is also generally not necessary, but can be used if the suspension according to the invention contains a hydrophilic but sparingly water-soluble colloid, for example polyvinyl alcohol, as a stabilizing agent. Preferably, for example, a solubilizer is used, with dimethyl sulfoxide being very suitable if the concentration of the water-only Group 1 soluble water stabilizer is greater than about 1%. For example, the relative proportion of solubilizer in the total suspension may be of the same order of magnitude as the relative proportion of stabilizer. Other compounds suitable as solubilizers are generally known to those skilled in the art. Suitable hydrotropes are, for example, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid and their water-soluble salts or also octyl sulfate.

In the case of all omdnedsujs relating to "aluminum silicate concentration", "solid content" or "active substance content" (= AS), the amounts depend on the state of the aluminosilicate which is reached by drying it at 800 ° C for one hour. In this drying, the adhered and bound water is virtually completely removed.

All percentages are by weight.

v.r ...

The above components A and B are described in more detail below: 5 60886

The aluminosilicates used in component A can be amorphous or crystalline products, in which case, of course, mixtures of amorphous and crystalline products as well as partially crystalline products can also be used. Aluminosilicates can be obtained from nature! or synthetic products, with synthetic products being preferred. The preparation can be carried out, for example, by a reaction between water-soluble silicates and water-soluble aluminates in the presence of water. For this purpose, aqueous solutions of the starting material can be mixed together or the solid component can be reacted with another component, such as the water-soluble component Jfansnu. Also, by mixing both components together in a solid state, the desired aluminosilicates are obtained in the presence of water. Aluminum silylate can also be prepared from Al (OH) 2, Al 2 O 2 or SiO 2 by reacting them with alkali silicate or aluminate solutions. The preparation can also be carried out by other known methods. The invention is particularly directed to aluminosilicates which, in contrast to layered silicates, such as fractured morillonite, have a three-dimensional space lattice structure.

The preferred calcium binding capacity, which is mainly in the range of 100-200 mg CaO / g AS and usually about 100-180 mg CaO / g AS, is achieved above all by using compounds having the following composition: 0.7-1.1 Na 2 O. A1203. 1.3 - 3.3 SiO2 · This sum formula comprises two types with different crystal structures (as well as their non-crystalline precursors), which also differ due to the sum formulas. These substances are as follows: a) 0.7-1.1 Na 2 O. A1203. 1.3-2.4 SiO 2 B) 0.7-1.1 Na 2 O. A1203. 2.4 - 3.3 SiO 2.

Different crystal structures can be seen from the X-ray diffraction pattern.

Amorphous or crystalline aluminosilicates in aqueous suspension can be separated from the remaining aqueous solution by filtration and dried at temperatures of, for example, 50 to 400 ° C. Depending on the drying conditions, the product contains more or less a large amount of bound water. However, such high drying temperatures are generally not recommended. Most preferably, the drying temperature is maintained at a maximum of 200 ° C if aluminosilicate is to be used in detergents. However, the alurainium silicates do not generally need to be dried after preparation in order to prepare the suspensions according to the invention. Instead, you can, and this is particularly advantageous, visit UT. continuously obtained, moist aluminosilicate obtained during manufacture. However, it is also possible to use aluminosilicates which have been dried at medium-high temperatures, for example 80-200 ° C, to remove adhering liquid water in the preparation of the suspensions according to the invention.

*

The particle size of private aluminosilicate particles can vary and be, for example, between 0.1 μιη and 0.1 mm. These values refer to the sizes of the primary particles, i.e. the size of the particles obtained in the precipitation and any crystallization associated with it. Preferably, aluminosilicates are used which contain at least 80% by weight of particles with a size of 10-0.01 μιη and in particular 8-0.1 μm, These aluminosilicates most preferably do not contain any primary and secondary particles with a diameter of more than 30 μιη, respectively. By secondary particles is meant particles obtained by agglomerating primary particles into larger particles. The most significant is the range of values between about 1 and 10pm.

In order to agglomerate the primer particles into larger pieces, the use of continuously moist aluminosilicate after preparation for the preparation of the suspensions according to the invention has proved to be very advantageous, as it has been shown that the formation of secondary particles is virtually completely prevented by this continuously moist product.

The following is a more detailed description of the compounds which can be used as components B according to the invention:

Suitable polymeric polycarboxylic acids (1) are, in particular, water-soluble but also water-insoluble polymerization products. Suitable polymeric polycarbonate extracts can be both polymers of polymerized carboxyl group-containing monomers and polymers of polymerizable monomers which are only subsequently converted to polycarboxylic acid. My polymeric dust? ' .

In addition to carboxyl groups, carboxylic acids may also contain other functional groups, for example, in particular hydroxyl groups, which can also be etherified or esterified with small-molecule groups, in particular aliphatic groups. Examples of such polymeric polycarboxylic acids are copolymers of poly (alpha-hydroxyacrylic acid) and acrylic acid, and in particular maleic acid, with vinyl methyl ether or vinyl acetate, whereby the carboxylate of the vinyl acetate unit in the polymer can be completely or partially hydrolyzed to give as copolymers with hypothetical vinyl alcohol.

i

It has also been found that carboxyl groups in polymeric polycarboxylic acids are not only partially substitutable for hydroxyl groups, as described above, for example by carrying out a preferred copolymerization with suitable monomers, but that products in which all carboxyl groups are replaced by hydroxyl groups are also suitable according to the invention. In this way, macromolecular polyhydroxy compounds are obtained. As the prototype suitable macromolecular polyhydroxy compounds, polyvinyl alcohol can be mentioned. Polyvinyl alcohol can be prepared, for example, from polyvinyl acetate by hydrolysis. The hydrolysis does not have to be complete in order for the polyhydroxy compound to be useful according to the invention, but also products in which, in addition to the hydroxyl groups, there are esterified hydroxyl groups, for example oxyacetyl groups, are suitable.

The molecular weights of the polycarboxylic acids and polyhydroxyl compounds used can vary within wide limits. Particularly suitable are polymers having molecular weights between about 1,500 and preferably about 20,000. However, compounds with much higher molecular weights are also particularly suitable, in which case the polycarboxylic acids are preferably water-soluble. If the water solubilities of the disclosed compounds are low, a solubilizer may be added as described above. This is especially true for polyhydroxyl compounds that do not contain any carboxyl groups. The presence of carboxyl groups promotes water solubility so that the solubility of polymeric polycarboxylic acids depends on their carboxyl group content, and is generally very good.

If the macromolecular compounds used according to the invention have ionizable groups when dissolved in water, they can also be used. · 8 60886 as their water-soluble salts, which are usually carried out. For economic reasons, alkali compounds and in particular sodium salts are generally used.

Suitable compounds include acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid, mesaconic acid ,. aconitic acid, methylmalonic acid, citraconic acid and the like, copolymers of the above-mentioned carboxylic acids with each other or ethylene-esters of unsaturated tower compounds, for example ethylene, propylene, acynyltrinene, vinyl alcohol, vinyl alcohol, vinylmethyl ether, vinylmethyl ether, vinylmethyl ether, such as maleic acid and a 1: 1 mixed dust merisate of ethylene or propylene or furan.

Examples of some particularly preferred Group 1 compounds are the above-mentioned polyacrylic acids and poly- (alpha-hydroxyacrylic acids). The latter can be used not only as the free acid or a water-soluble salt but also as an internal lacto-N. This compound is hydrolyzed in suspension. The products described above are mainly straight-chain, i. non-branched polymers with respect to the longitudinal direction of the polymer chain. However, in addition to the preferred synthetic polymers described above, natural products can also be used, for example alkinate, carboxymethylcellulose, corn or potato starch or derivatives thereof. However, water-insoluble polymeric, three-dimensionally crosslinked polyacrylic acids can also be used.

Molecular weights can vary widely, and in the case of poly (alpha-hydroxyacrylic acid), the molecular weight of a commercial product is generally greater than 20,000. In the case of a copolymer of vinyl methyl ether with maleic anhydride about 100,000 to 2,500,000.

Another preferred group (2) of stabilizers comprises phosphonic acids having at least one phosphonic acid group and / or one carboxyl group.

Suitable polyphosphonic acids, amino- and hydroxyalkane polyphosphonic acids and phosphonocarboxylic acids, among others, are suitable. Examples are propane-1,2,3-triphosphonic acid, butane-1,2,3,960886 4-tetraphosphonic acid, polyvinylphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 1-amino-1-phenylmethane-1,1- diphosphonic acid, amino-trimethylenetriphosphonic acid, methylamino or ethylaminodimethylene diphosphonic acid, ethylenediaminotetrameth, Lenetetrafosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 4-Tricarboxylic acid and a copolymer of vinylphosphonic acid and acrylic acid.

Also suitable are emulsifiers of the phosphoric acid partial esters type (3). In general, these are esters having 1 to 2 moles, and especially about 1.5 moles, preferably of a saturated alcohol having 3 to 20 carbon atoms in the alkyl chain per mole of phosphoric acid. Highly suitable products are alcohol esters having 4 to about 10 carbon atoms, especially esters with about 1.5 moles of butyl alcohol or isooctyl alcohol.

The nonionic surfactants (4) used in the invention are practically water-insoluble compounds. The cloud point of these substances, determined according to DIN 53917, in an aqueous solution of butyl diglycol is usually 90 ° C or less, preferably 85 ° C or even lower. Accordingly, the cloud point in water, determined from 10 solutions of suitable compounds, is less than about 55 ° C and preferably less than 35 ° C. The cloud point of very suitable products in water is lower than room temperature. The most preferred products are characterized in that they can be dispersed in water by using one part of a surfactant per 19 parts by weight of water while shaking gently and possibly also vigorously and, if necessary, raising the temperature above the melting point of the surfactant to form a milky mixture. possibly a gel-solidified dispersion. The cloud point determined according to DIN 53917 is usually at least 40 ° C and preferably at least 55 ° C.

The properties of water dispersibility and cloud point are related to the properties of stabilizers such as technically pure private surfactants, especially statistical mixtures of ethoxylation products obtained by ethoxylation of a fatty alcohol, fatty acid, fatty acid radical or fatty amine fraction.

According to the invention, suitable dispersants are present in particular in non-ionic surfactants which, as hydrophobic group, comprise a long-chain alkyl or alkenyl group which usually has 10 to 20 and preferably 12 to 18 carbon atoms. The alkyl and alkenyl groups, respectively, are usually straight-chain, but there are also suitable products in those compounds having branched hydrophobic groups. Unsaturated hydrophobic groups are usually simply unsaturated, such as the particularly common oleic acid group.

Hydrophilic groups are usually formed from polyalcohol groups, for example ethylene glycol-propylene glycol, polyethylene glycol or glycerol groups, which are joined to a hydrophobic group via ester, amide ether or amino groups. Ethylene oxide adducts are particularly preferred.

Of the ethylene oxide adducts having the same cloud point, those having a longer hydrophobic group, C 1 -C 6 g, are usually preferred. An important group of suitable compounds are among carboxylic acid esters and carboxylic acid amides. Particularly suitable dispersants according to the invention are the mono- and triethanolamides of carboxylic acids having from 10 to 20 and preferably from 12 to 18 and in particular from 12 to 14 carbon atoms. These compounds are preferably derived from saturated and straight-chain carboxylic acids. However, the products can also be derived from unsaturated carboxylic acids, in particular monounsaturated carboxylic acids. Suitable amine components from which the suitable amides according to the invention are derived are, in particular, monoethanolamine and diethanolamine. However, a very suitable product is also an amide derived from carbonic acid Posta as defined above and N- (hydroxyethyl) ethylenediamine. Suitable amides can be considered as reaction products of carboxylic acid amides with ethylene oxide. The number of ethylene oxide units is usually 1 to 6, and especially values 1 to 4 are recommended.

Esteric dispersants are derived from the same carboxylic acids as amine-like dispersants. As well as amides are esters of fatty acids or mixtures of fatty acid, especially in the chain length range described above, from naturally occurring or synthetically prepared products. 1.2 or 3 moles of ethylene oxide per mole of carboxylic acid. However, products with, for example, 4-10 ethylene oxide units are also possible.

However, as the alcohol component, the surfactant ester may also contain polyalcohols having more than two hydroxyl groups, for example glycerol. For example, of the amide- or ester-type suspension stabilizers which are of the amide or ester type and which are very suitable * are the following compounds: derived diethanolamides and amides derived from N- (hydroxyethyl) ethylenediamine. Among the ester-like stabilizers, mention may be made of addition products containing 1 and 2 moles of ethylene oxide in coconut fatty acid and propylene glycol or glycerol in stearic acid or palmitic acid.

Particularly suitable diethanolamides are lauric myristic acid-diethanolamide, diethanolamide in a fatty acid mixture of lauric acid and myristic acid, and oleic acid diethanolamide.

In addition, a very suitable group of stabilizers comprises the ethoxylation products of alcohols having 1 to 20 carbon atoms and most preferably unsaturated with 1 to 8 moles of ethylene oxide per mole of alcohol. Preferably, these ethoxylation products are products with 2 to 7 and especially 2 to 6 moles of ethylene oxide per mole of alcohol. It is then very advantageous to use derivatives of straight-chain alcohols for the purposes of this invention. However, derivatives of branched-chain alcohols can also be used, especially alcohols prepared with oxosynthesis. Derivatives of alcohols having 16 to 18 carbon atoms and which are preferably saturated and preferably straight-chain alcohols are particularly preferred. However, it is also possible to use ethoxylation products of alcohols having 12 and especially 14 carbon atoms, the products having 1 to 5 moles of EO and in particular 2 to 4 moles of E0 (ethylene oxide) per mole of alcohol, with very good results.

The ethoxylation products used according to the invention are generally not any chemically homogeneous compounds but are usually ordinary 12 60886

Beoxy, which is rich in ethoxylated derivatives, also stably distributed with substances with a degree of ethoxylation of "O", which is a non-ethoxylated starting material usually present in fart. The ethoxylation products used according to the invention are practically water-insoluble compounds and the cloud point of these compounds, determined according to DIN 53917, in an aqueous solution of butyldi <lycol is usually in the range from about 55 to 85 ° C. Typical and preferred products are saturated fatty alcohol ethoxylation products derived from tallow fatty acids with a degree of ethoxylation of 2,4,5 and 7 moles of ethylene oxide per mole of fatty alcohol, respectively, with cloud points of 58.71.77 and 83 ° C, respectively.

The alcohol component, for example, is usually a technical mixture, which may also contain alcohols having a higher and / or lower number of C atoms, but in a smaller number, usually not more than 15. For higher concentrations, the following is suitable. other substances that may be present.

Instead of the ethoxylation products of alcohols described above, it is also possible to use corresponding ethoxylation products of fatty amines, i. especially ethoxylation products of saturated primary amines having 16 to 18 carbon atoms with 1 to 8 moles of ethylene oxide per mole of amine. Non-ethoxylated antibodies, which are surfactants as defined in this invention, have also been found to be suitable for this purpose. However, products with 2-5 moles of ethylene oxide per mole of amine are also very suitable.

Particularly suitable alkylphenol products with a cloud point lower than or corresponding to room temperature, respectively, according to DIN 53917, are water-insoluble nonylphenol-ethylene oxide adducts with 5-8 moles of ethylene oxide per mole of phenol. Adducts with 6-7 moles of ethylene oxide are preferred.

(5) Suitable sulfonate type surfactants are alkyl benzene sulfonates (C 1-4 alkyl), olefin sulfonates, i. mixtures of alkene and hydroxyalkane sulfonates and disulfonates, for example <t / V ·. ♦. ', 13 60886 are those obtained from C 1 -C 4 monoolefins which, by sulfonation at their ends or within them, are sulfonated with gaseous sulfur dioxide, the product obtained being subjected to alkaline or acid hydrolysis. Particularly suitable are esters of sulfonic fatty acids, for example methyl or ethyl esters of sulfonic acids obtained from hydrogenated coconut, palm kernel or tallow fatty acids.

However, the usually preferred stabilizing compounds within the scope of the invention are those e, i-ionic surfactants set forth in Section 4.

(6) Other dispersants suitable according to the invention are · water-insoluble but expandable clay-type silicates which, in contrast to the suspended aluminum silicates according to the invention, have a layered structure instead of a three-dimensional space lattice structure. Expandable layer structure Existing silicates are called smectites. These are substances with the general formula

Al 2 (Si 2 O 5) 2 (OH) 2 and Mg 3 (Si 2 O 2 OH) 2.

Examples are bentonite, montmorillonite, volkhonskoit, nontronite, hectorite, saponite, sauconite and vermiculite. Depending on the origin, these expandable clays, due to their cation exchange capacity, also contain cations, for example sodium, potassium or calcium. Naturally occurring and synthetically produced products are suitable, in which case synthetic products usually have the advantage of being cleaner. The particle size of these layered silicates is usually less than about 50, and calcium-poor types with the ability to bind calcium are particularly suitable.

In addition to the private dispersants described above, mixtures can be used in which a synergistic interaction can be observed in different cases. For example, it has been found that the addition of tallow amine, carboxymethylcellulose, crosslinked polyacrylate, alginic acid to surfactant-stabilized suspensions, for example combinations of Group 1 stabilizers with those belonging to Group 5 and especially Group 4, has advantages. An additional group of compounds that further enhances the properties of the stabilized suspensions according to the invention comprises long chain fatty acids. These are naturally occurring or synthetic and preferably saturated fatty acids, usually with 10 to 20 C-fat per molecule, for example tallow fatty acids.

14 6 0 8 8 6

According to the invention, a particularly preferred aqueous suspension mainly comprises at least 20% of component A, the upper limit of substance A being determined on the basis of the flow limit, and is usually less than $ 50, for example 42% by weight. Concentrations of 25-40% by weight and especially 28-38% by weight are preferred. In practice, the range of 30-38% by weight is presumably the most common.

The amounts of compound B used depend mainly on the desired degree of stabilization of the suspension. In general, the content of component B in the suspension according to the invention is about 0.5 to 6 and preferably 0.8 to 6% by weight, based on the total weight of the aqueous suspension. Preferably, the content is in the range of about 1 to 4% by weight and in most cases preferably about 1.3 to 3% by weight. Since the viscosity of the suspension is affected by the amount of component B, the desired viscosity can be varied, if necessary, by varying the concentration of component B.

When using fine aluminosilicates, small amounts of component B must be used for stabilization compared to the use of coarser products. Thus, for example, an aluminosilicate suspension in which 90 or more of the particles have a particle size of 1 to 8 can be stabilized by using already 0.5 to 1% by weight of dispersant, while products with an average particle size of 10 to 12 are stabilized with a dispersant content of 1 -2 ° / o. These values are for guidance only. Preferably, the available amounts of component B in individual cases must be decided taking into account the requirements to be set in each case. The viscosities of the suspensions at 25 ° C are 500-30,000 and preferably more than 1000 but less than 15,000 cps. Particularly preferred are suspensions having viscosities in the range of 1000 to 9000.

Highly preferred aqueous suspensions within the scope of the invention primarily comprise at least 20 [mu] l of component A, at least 0.5 [mu] l of component B, and preferably at least about 0.8 [mu] l of component B, and water.

In addition to the above-mentioned components, they also contain inorganic salts or hydroxides from precipitation or other preparation of aluminosilicates. Thus, for example, they may contain small amounts of excess sodium hydroxide or sodium carbonate or hydrogen carbonate resulting therefrom by the absorption of carbon dioxide, or they may also contain, for example, sulphate ions. 15 60886 aluminum sulphate has been used as an aluminum-containing starting material for the production of dirt.

In principle, aqueous suspensions may contain relatively small amounts of other ingredients in addition to the substances A and B mentioned above and, if appropriate, in addition to the substances which are continuously present in the preparation of these substances. If the suspensions are intended for further processing as detergents and cleaners, the additives contained therein are, of course, preferably substances which are suitable as detergent and detergent ingredients. One solidification point associated with the stability of the suspensions is given by a simple experiment according to which a desired concentration of snow of 11%, e.g. 31%, is prepared containing the dispersant according to the invention and possibly also other substances, e.g. detergent ingredients such as detergents. pentasodium triphosphate, which may contain different amounts of additives. The effect of the added substances can then be visually examined for the settling properties of the suspension. After storage of the suspension for 24 hours, the suspension should generally have settled at most to the extent that the clear, i.e. silicate-free, solution at the top is not more than 20% and preferably not more than 10%, especially not more than 6% of the total height of the layer. In general, the amounts of additives should be chosen in such a way that after the suspension has been stored for 20 hours and preferably for 24 hours and in particular for 4 hours, it must be possible to recycle it in the storage tank up to the pipes or hoses again without difficulty. The settling properties of suspensions which may contain other ingredients are tested at room temperature using a total suspension height of 10 cm. Particularly preferred suspensions have a height of the clear solution on top continuously at 4 and especially after Θ days at values in the above range.

These suspensions can be pumped and removed continuously by pumping after 4 or Θ days. Also, these properties, which apply to the suspension s tabii1 is new, are only indicative. The suspension stability to be adjusted for the mixture in each case is decided on a case-by-case basis. When using the suspensions according to the invention as basic suspensions for long-term storage in a container from which the suspension must be able to be pumped out if necessary, it may be advantageous to keep the relative amounts of common ingredients small or completely avoidable, for example in detergents.

Suspensions can be prepared by simply mixing the ingredients together, in which case, for example, the aluminosilicates can be used either as such or possibly continuously wet after preparation or as aqueous suspensions. It is particularly advantageous to continuously add moist aluminosilicate from the manufacture, for example as a filter cake, to a dispersion of component B in water. Preferably, the dispersion of this component B is slightly heated, for example 50-70 ° C.

Of course, already dried can also be used, i.e. aluminosilicates released from adhering water and which may also contain bound water.

One very suitable process for preparing the suspensions according to the invention is as follows: The aluminosilicate is precipitated by mixing together sodium aluminate and sodium silicate solutions.

These solutions are alkaline, i.e. they contain more sodium hydroxide than is required to obtain the finished aluminosilicate, resulting in an excess of sodium hydroxide in the aluminosilicate pencil obtained as a direct precipitation product. This suspension is concentrated by filtering off a portion of the supernatant and then releasing water from the sodium hydroxide continuously in it to such an extent that the sodium hydroxide content of the solution becomes less than about $ 5, and preferably less than $ 3, and possibly less than $ 2. The remaining sodium hydroxide is neutralized by adding an acid, especially an aqueous solution of sulfuric acid, to such an extent that the pH of the resulting suspension is in the range of 7-12 and especially in the range of about 8.5-11.5. The amount of dispersant required to achieve the desired degree of stabilization is added to this suspension, so that the addition can be performed before, during, or after partial neutralization.

In this case, it has proved very advantageous to carry out the partial neutralization at least in part using an acidic dispersant, i. for example macromolecular polycarboxylic acid or alkylbenzenesulfonic acid as defined above. These acidic dispersants can thus be used as an acid for neutralization and, as a result, to replace the stabilizing acids, for example the abovementioned sulfuric acid, in whole or in part.

uVV '17 60 8 8 6

The suspensions according to the invention are very stable and also have other advantages. The stabilizing effect is especially valuable in the case of urns with a particle size of 5-30 μm. These can be pumped in such a way that simple handling of damp snowdrops becomes possible. Even after a prolonged interruption of the pumping effect, the suspensions can be pumped again without difficulty due to their large s tab i 1 i and the suspensions can therefore also be transported in ordinary tank and tank wagons without the risk of any unserviceable or unserviceable birth. Suspensions are therefore a very suitable form of delivery of aluminum pigs for supply to, for example, detergent manufacturers.

Suspensions can be stored at room temperature or higher, pumped down pipelines, or otherwise transported. The treatment of the suspensions is usually carried out at temperatures between room temperature, which is considered particularly preferred, and about 60 ° C.

Particularly suitable are the suspensions according to the invention for further processing into droplets or sprinklers which are dry in appearance, for example to be prepared as a powdered water softener, for example by spray-drying. Suspensions are therefore valuable in the preparation of powdered aluminiums i 1 i kaa tte and. In this case, no interfering residues are generated when the aqueous suspensions are introduced into the drying equipment. It has further been found that the suspensions according to the invention make it possible to prepare highly dust-free products from them.

Due to the good stability of the suspensions according to the invention per se, i.e. without further treatment and with or without the use of detergents, bleaching and / or detergents, they are suitable, for example, as water softeners, detergents or cleaning agents and in particular as liquid scrubbers with good suspension stability.

A very important use of suspensions is the further processing into scatterable or pourable detergents and cleaners which are dry in appearance and which, in addition to the ingredients of the suspension, contain other compounds.

18 60886 '

The suspensions according to the invention are quite suitable for preparing the detergents and cleaning agents described in the previous patents (German patent applications P 24 12 837.8-41, P 2412 836.7-15 and P 24 12 839.0) and all aspects relating to their preparation, including the substances contained therein. and the proportions between the materials used disclosed in these older patents also apply to the present invention.

Also within the scope of the invention is a process for preparing spreadable or pourable powdered products having water-soluble aluminosilicates as defined above, and using an aqueous, liquid mixture of the various ingredients of the substance as starting material for preparing pourable or spreadable detergents.

In particular, in the preparation of powder spreadable detergents and cleaners by the process of the present invention, at least one substance having detergent, bleaching or cleaning properties for the substance to be prepared is mixed into the suspension according to the invention, for example · when taken from a storage tank, in any way in powder form. It is preferred to add a complexing agent, i.e. a compound having the ability to complex bind those alkaline earth ions, especially magnesium and calcium ions, which provide water hardness.

In general, when preparing a detergent and a cleaning agent by the process according to the invention, it is generally advantageous to combine in the suspension at least one water-soluble surfactant which is not one of the possible ingredients of component B.

Various variations can be used in the preparation of detergent and cleaning agent.

For example, substances having the ability to bind water of crystallization can be combined with the suspensions of the invention, preferably by spraying the suspension with compounds of water having the ability to bind water of crystallization placed in a mixing device so that continuous mixing produces a solid final product. Preferably, however, the suspensions according to the invention, which have been mixed into a "slurry", together with at least one further compound having washing, cleaning or bleaching properties, are passed to a powder drying device (spray drying device). In this case, the aluminosilicate suspensions according to the invention have also proved to have other surprising advantages. Namely, it has been found that the use of the suspensions according to the invention in spray-drying devices gives very dust-free products. The products obtained from spray dryers are rich in calcium binding and very moist.

Detergents according to the invention, i.e. Detergents prepared using the suspensions described above can be formulated in a variety of ways. In general, they contain at least one water-soluble surfactant which is not one of the dispersants used according to the invention in the aluminosilicate suspensions according to the invention. In general, the cleaning agent according to the invention can correspond to its composition in the above-mentioned older patents. These substances contain, in addition to at least one additional compound which has washing, bleaching or cleaning properties and which is inorganic or organic, as a calcium-binding compound, aluminosilicate as defined above. In addition, such substances may contain the usual excipients and additives, most often in penile concentrations. For other details, reference is made to the earlier patents mentioned above. The aspects set forth therein also apply to the present invention. The aluminosilicate content of these materials can be in the range of 5-95 and preferably $ 15-60.

The substances according to the invention may further contain substances which form complexes with calcium or calcium-doping substances, the effect of which, depending on the chemical nature of the substances, is generally achieved in concentrations of 2 to 15%.

In the case of phosphorus-poor substances, the content of inorganic phosphates and / or organic phosphate compounds must not exceed that corresponding to a total content of 6% in the substance, and preferably 3

Other washing, bleaching or cleaning compounds which are present in detergents or cleaning agents are, for example, surfactants which do not fall within the definition of component B according to the invention, surfactants such as surfactants or non-surfactants such as foam stabilizers or antifoaming agents, , chemically active bleaching agents and their stabilizers and / or activators. Other excipients and additives that are usually present in small amounts include, for example, corrosion inhibitors, antimicrobials, soil release agents, enzymes, bleaches, dyes and fragrances, etc. Some typical textile detergents useful in the temperature range of 50-100 ° C are included in the following recipe. : 3-30% of anionic and / or zwitterionic and / or nonionic surfactants, including the surfactants used according to the invention, and most preferably 5-30% of 5-70% aluminosilicates (calculated as AS), comprising layered silicates for use in accordance with the invention, 2-45 ° calcium complexing agents, including complexing agents containing component B, 0-50 and non-complexing washing alkalis (= alkaline supports), 0-50 bleaching agents and other substances normally used in small amounts in textile detergents additives.

The following is a calculation of the materials suitable for use in the products of the invention.

Surfactants contain at least one hydrophobic organic group and a water-soluble anionic, zwitterionic or nonionic group in the molecules. The hydrophobic group is usually an aliphatic hydrocarbon group having 8 to 26, preferably 10 to 22 and especially 12 to 18 C atoms, or an alkyl aromatic group having 6 to 18 and preferably 8 to 16 aliphatic C atoms.

As anionic surfactants, for example, soaps based on naturally occurring or synthetic, preferably saturated fatty acids and optionally resin-naphthenic acids can be used. Suitable synthetic anionic surfactants are those of the sulfonates, sulfonates and synthetic carboxylates type. Suitable sulphate type surfactants include sulfuric acid monoesters of primary alcohols (for example coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and the corresponding compounds of secondary alcohols. Also suitable for use are sulfoted Raeva acid alkanolamides, nitric acid glycerides or reaction products, 21 60886 obtained from 1-4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols.

As nonionic surfactants which may be present in addition to the ethoxylation products used according to the invention, it is possible in particular to use reaction products in which 9 to 40 and preferably 9 to 20 moles of ethylene oxide are attached to one mole of fatty alcohol. Amine oxide-type or sulfoxy-type nonionic surfactants are also useful.

Zwitterionic surfactants are substances of the type carboxy-betaines or sulfobetaines. ,

Suitable carriers are both compounds which have the ability to bind calcium in a complex manner and those which do not. The latter include, for example, bicarbonates, carbonates, borates or silicates with alkalis, alkali sulfates and alkali salts of organic non-capillary active sulfonic acids, carboxylic acids and sulfocarboxylic acids having 1 to 8 carbon atoms. Examples which may be mentioned are the water-soluble salts of benzene, toluene or caliper sulfonic acid and the water-soluble salts of sulfonic acetic acid, sulfobenzoic acid or sulfodicarboxylic acids. Suitable complexing agents are triphosphates and a large number of known organic complexing agents of the type polycarboxylic acids, in this case also polymeric carboxylic acids, aminocarboxylic acids, phosphonic acids, phosphonocarboxylic acids, hydroxycarboxylic acids, carboxyalkyl ethers, etc.

Suitable bleaching agents are those which donate HgOg from their aqueous solutions, for example perborates, or active chlorine. Other additives which are usually present in small amounts are, for example, foam stabilizers or antifoams, fabric softeners, bleach stabilizers and / or activators, corrosion inhibitors, antimicrobials, soil release agents, enzymes, bleaching agents, colorants.

The products made according to the invention can be used in many fields of technology and household for most cleaning purposes. Examples of such applications are the cleaning of equipment and utensils of wood, plastic, metal, chemistry, glass, etc. 22 6 0 8 8 6 in industry or in the practice of matting, furniture, walls, floor coverings and ceramic, glass, metal, wood, plastic or polished objects, polished cleaning of lacquered surfaces in the household, etc. One particularly important area of application is the washing of all kinds of textiles in industry, commercial laundries and households.

Manufacture of aluminosilicates

First, the synthesis of aluminosilicates suitable for use in the suspensions of the invention, which do not require protection in this context, will be described. This description comprises a pure example. Other known methods for preparing aluminosilicates can also be used.

oi) The aluminosilicate solution was placed in a 15 liter vessel and vigorously stirred with the calculated amount of sodium silicate solution (solution temperature 20-80 ° C.) An exothermic reaction gave an X-ray amorphous sodium aluminosilicate as the primary precipitate. After vigorous stirring for 10 minutes, the suspension of precipitated product was treated as follows: 1. The product was subjected directly to further work-up, i.e. without crystallization, or 2. the suspension was allowed to crystallize by maintaining it at 80 ° C for 3-6 hours to give a completely crystalline product by X-ray structure analysis.

/ 3) The mother liquor was removed by filtration from the suspension. The remaining filter cake was washed with deionized water and then mixed with deionized water to form a suspension of β 1 (of substance Λ1) and β 2 (of substance c6 2), respectively.

The microcrystalline aluminosilicate was prepared by adding a silicate solution to the aluminate solution diluted with deionized water and precipitating with a rapidly rotating intensive mixing apparatus (10,000 rpm, Ultratur-Rax, Janke & Kunkel ΙΚΑ-Werk). / Breisgau, Germany) After vigorous stirring for 10 hours, the suspension of the amorphous precipitate was transferred to a crystallization vessel, 23 6 0 8 8 6 where the formation of large crystals was prevented by stirring the suspension. the wash water had a pH of about 10, was dried in a filter cake and then ground in a ball mill and divided by a blower (Mikroplex-V / indsichter, manufactured by Alpine, Augsburg, Germany) into two fractions, the finer of which did not contain ingredients that were more than ΊΟ μπι. A suspension of the finer fraction was prepared in deionized water (1/1). The corresponding suspension was prepared without drying treatment and divided into two fractions. To this was then added a continuously moist filter residue of varying water content. The resulting suspension was labeled 12. After filtration, the largest amount of water in the silicates was removed by partial centrifugation.

The aluminosilicates obtained had the following calculated approximate composition of 1 Na 2 O based on the anhydrous product (= AS). 1 Al 20 ^, 2 SiO 2 *

The calcium binding property of the precipitated product proved to be 150-175 mg CaO / g active substance. This was determined as follows: 1 liter of an aqueous solution containing 0.594 g of CaCl 2 (= 300 m "CaO / liter = 30 ° dH) adjusted to pH 10 with dilute NaOII was mixed with one gram of aluminosilicate (calculated as AS). The suspension was stirred vigorously for 15 minutes at 22 [deg.] C. (Ϊ2 [deg.] C.) After filtration of the aluminosilicate, the residual hardness · x of the filtrate was determined, and the calcium binding property was then calculated as high in mg CaO / g AS from the following formula: (30 - x).

Conditions for the preparation of aluminosilicate I.

Precipitation: 2.985 kg of aluminate solution, composition: 17.7 1 ° Na 2 O, 15.8 klfly 66.6 fo H 2 O 0.15 kg sodium hydroxide 9.420 kg water 2.445 kg of commercial grade water glass and slightly alkali-soluble silicon faucet 25.8 - '^ 24 60886 sodium silicate solution with a composition of 1 Na 2 O. 6.0 SiOg

Crystallization: 80 ° C for 24 hours

Drying: 24 hours at 100 ° C

Composition: 0.9 Na 2 O. 1 A1203. 2.04 SiO 2 · 4.3 HgO

(= 21,6foH20)

Crystallization rate: fully crystalline Calcium binding capacity: 150 mg CaO / g AS

If the product thus obtained is dried for one hour at 400 ° C, aluminum silicate Ia having the following composition is obtained: 1 0.9 NägO. 1 A1203. 2.04 SiO 2. · 2.0, Η20 (= $ 11.4 H 2 O) which is also suitable for use according to the invention.

Conditions for the production of aluminosilicate II:

Precipitation: 2.115 kg of aluminate solution with the composition: 17.7 / 0 Na 2 O, 15.8 f * Al 2 O 3, 66.5 fo H 2 O 0.585 kg of sodium hydroxide 9.615 kg of water 2.685 kg of 25.8- $ sodium silicate solution with the composition of 1 Na 2 O. 6 SiO2 (prepared as described in I)

Crystallization: 24 hours at 80 ° C

Drying: 24 hours at 100 ° C and 20 Torr

Composition: 0.8 Na 2 O. 1 A1203. 2,655 SiO 2. 5 »2 H 2 O.

Crystallization rate: fully crystalline

Calcium binding capacity: 120 mg CaO / g AS

This product can also be post-dried (one hour at 400 ° C) to the composition:

0.8 Na 2 O. 1 A1203. 2.65 SiO 2. 0.2 HgO

This anhydrous product Ha is also useful for use in accordance with the invention.

According to the X-ray diffraction pattern, the aluminosilicates χ and H have the following interference lines: 60886 25 d-values obtained with Cu-K ^ f radiation, in A units

I II

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

It is entirely possible that not all of these interference lines appear in the X-ray diffraction pattern, especially if the aluminum silicates are not completely crystallized. To this end, the notation "(+)" has been used to characterize the most important d-values of this type.

Conditions for the preparation of aluminosilicate VIII:

Precipitation: 2.115 kg of aluminate solution with composition: 17.7 * Na 2 O, 15.8 # Al 2 O 3, $ 66.5 H 2 O 0 * 585 kg of sodium hydroxide 9.615 kg of water 2.685 kg of 25.8 - $ sodium silicate solution with composition i Nä20. 6 SiO2 Crystallization: omitted

Drying: 24 hours at 100 ° C

Composition: 0.8 Na 2 O. 1 ΛΙ ,, Ο ^. 2.65 SiO 2. 4 H 2 O.

Crystallization rate: X-ray amorphous Ka: calcium binding capacity: 60 mg CaO / g AS

26 60886

Conditions for the preparation of aluminosilicate IX;

Precipitation: 3.41 kg of aluminate solution Composition: 21.4 # Na 2 O, 15.4 Al 2 O, 63.2 "fo H 2 O 10.46 kg water, 1.13 kg of 34.9 $ sodium silicate solution with composition 1 Na 2 O 3.46 SiO 2

Crystallization: not performed

Drying: 24 hours at 100 ° C

Composition: 1 Na 2 O. 1 AlgO ^. 1 SiO 2 1, 4 H 2 O.

The degree of crystallinity: röngenamorfinen

Calcium binding capacity: 120 mg CaO / g AS

Conditions for the production of ALUMINUM SILICATE XXm:

Precipitation: 0.76 kg of aluminate solution with a composition of: 36.0 f Na 2 O, 59.0 l »Al 2 O 3, 5.0 l H 2 O 0.94 kg sodium hydroxide 9.49 kg water 3.94 kg commercial grade sodium silicate solution, which composition: 8.0 in Na 2 O, $ 26.9 SiO 2, $ 65.1> H 2 O.

Crystallization: 12 hours at 90 ° C

Drying: 12 hours at 100 ° C

Composition: 0.9 Na 2 O. · 1 Al 2 O 3. 3.1 SiO 2. 5 H 2 O.

Crystallization rate: fully crystalline

Calcium binding capacity: 110 mg CaO / g AS

Execution example r

The abbreviations used below have the following meanings: "Ta + x EO" means a reaction product in which x moles of EO are associated with one mole of a predominantly saturated fatty alcohol prepared by reduction of tallow fatty acids containing a mixture of alcohols with varying amounts of carbon atoms, mainly as follows: 60886 27 σ12: 0-2 io

Cu: 4-7 * 016: · 25 -35 i 018: 60 -67 # C20: 0 - 2 fo 'Coconut-C ^ g ^^ g + 6 EO "means an ethoxylation product in which 6 moles of ethylene oxide are associated with one mole primarily saturated coconut waxic acid and a fatty alcohol fraction obtained by reduction and subsequent distillation, containing equal parts of C 1-4 alcohol and C 1-4 alcohol and proving to be less than 2 μg and C 1-4 alcohol.

"Oxo + 5 EO" means the ethoxylation product of an alcohol mixture obtained by oxosynthesis, having the following composition:

Straight-bodied Haarova C 15: 1.5 f 0.9 fo 0.6% C 16: 29.7 i 10.5 0 19.2 i C 17: 41.5 # 12.4 i 29.1 i C 18 : 21.4 i 8.2 i 13.2 ic 19: 5.2 0.6 already 4.6 already 32.6 i 66.7 i whereby this alcohol mixture was reacted with 5 moles of ethylene oxide per mole of alcohol.

"OA + 10 EO" means the reaction product of ethylene oxide with technical oleyl alcohol in a molar ratio of 10: 1.

"EDTA" means a salt of ethylenediaminetetraacetic acid.

"CMC" means a salt of carboxymethylcellulose.

"ABS" means a salt of an alkylbenzenesulfonic acid having 11 to 13 carbon atoms in the alkyl chain prepared by condensing straight-chain olefins with bericene and sulfonating the alkylbenzene thus obtained.

"Water glass" means sodium silicate (Na 2 O: SiO 2 »calculated 1: 3.35).

"Perborate" means a technical product having an approximate composition of NaBO 2. H 2 O 2 · 3 H 2 O.

All saline compounds were used as sodium salts.

"AC" means continuously water-soluble polyacrylic acid or its sodium salt (molecular weight of polyacrylic acid greater than 1500).

"Cop 1" means lauric acid monoethanolamide.

"Cop 2" means myristic acid monoethanolamide.

"Cop 3" means lauric-myristic acid monoethanolamide.

"Cop 4" means coconut fatty acid monoethanolamide.

"Cop 5" means lauric myristic diacid diethanolamide.

"Cop 6" means oleic acid diethanolamide.

"PYA" means polyvinylalkylene (molecular weight 1500)

Suspensions according to the invention.

Example 1

The suspensions according to the invention are illustrated in the example as microcrystalline aluminosilicate prepared according to s1.2, since this is advantageous in the preparation of the detergent and cleaning agent according to the invention. The suspensions according to the invention can also be prepared in a similar manner from suspensions jB 1, p 2, and 1 and in the same manner as aluminosilicates isolated as solids.

155-195 g of wet aluminosilicates (method 2; the amounts of wet aluminosilicates used were adjusted to the water content in such a way that in each case the same amount of AS was mixed with so many aliquots of water and dispersant that the concentration of aluminosilicate relative to the active substance was 30 to 38% by weight The amounts of ethoxylation product added were 1.3 to 3% by weight Worked at room temperature The ethoxylation products shown in Table I were used as dispersants and the cloudy points are also shown for this purpose A few suspensions and the components from which they are prepared are shown in the table. II.

29 60 8 8 6

Table I

Ethoxylation product used Melting point ° C

According to DIN 53917 1. TA + 2 EO 58 2. TA + 4 EO 71 3. TA + 5 EO 77 4. TA + 7 EO 83 5. Mixture of TA + 2 EO and TA + 7 EO (1: 1) (77 ) 6. Mixture of TA + 0 Ξ0 (non-ethoxylated tallow alcohol) and TA + 7 EO (1: 1 ') (76) 7. Mixture of TA + 2 EO and TA + 12 EO (1st) (76-77) 8. Mixture of TA + 5 EO and TA + 12 EO (1: 1) (83) 9. Coconut-C -ji Q + 6 EO (80) Quantity ratios refer to weight ratios

Table Ta

In addition, used stabilization- cloud point ° C

substances (DIN 53917)

Myristic acid monoethanolamide 59

Lauric acid monoethanolamide 59

Lauric acid-myristic acid monoethanolamide 6T, 5 01 / diethyldiethanolamide 77.5

Lauric acid-myristic acid diethanolamide 87

Stearic acid poroethanolamide 64

Thalamine + 5 EO (ethylene oxide) 83.5

Thalliamine 40

Unsaturated tallow alcohol with 5 EO 72

Coconut fatty acid monoethanolamide + 2 EO 79

C 12 -C 14 fatty acid + 4 EO n.68

Cocosamine + 2 EO

Nonyl phenol with 6.5 EO 72

Nonylphenol with 7 EO 73 30 6 0 8 8 6 ✓ — N ^ ^ ro rv rs ^ —s * -, \

'«(M N CVI C \ l (\ l (\ 1 O

^ '"” ”'” "" BO OOOOOOOlTcOOOOOOOOOOO

W OCMi-CMCMOOCJOCMCMCMCMCMCMCMCMCMO

o

B

M CM

+. ^ ~ «* * G

E-c · '"' · iniAiAiniACMOCAt ^ f'Ti-inininiAiriiniA

„* LT \ v £) -— +

O

X

o ω £

ΙΛ CG • H

11 O 'Τ' p000000iA00000mirNir \ ^ - cr> irv ω cMbo b-co ^ oo ^ ffiac ^ oooococo ^ oiMir '

CC rOrOrOCMC \ | T-r- T— T- (MC \ IC \ JCMC \) CMC \ JC \ IC \ lro UO

+ M ° M o § .s 3 3 E ^ • H Ti- Ö ‘g P Cti ω O rOrnOrrrrrr ^ rl ^^ Oh-CO ^ r, —j 03 CO CO rororororororororororororororororororor m

Eh CO O jj sk l

§ fi S

Q) -H sL

Λ cO, CO Pi +> P 2 CO rs .p bO O * -T-CM00OOOOOOCT> OOOOOOO nj ro CO - * O ro ro rot— »- t— t-γ- t— θ'— 1Λ CO h- CO t— * - J>

«T! rOrOrorOCMrOrOrorororomrOrorororororO M

O

Real

C/O

• M 03 • 0: cii fn .p 'Τ' ΟΟΟΟΟΟΟΟΟΟΟΟΟίΓΝίΓν - ^ - νοτ-ιη cm: cd bo OiAininococooococococooom'-ooo * - σ \ -μ> E --- MDMD'vO C— C— cr ^ - C - C— C— C ^ - CNJ t "- MD C— t— kO LA aj •> <- o 2 o §» • HV ^ OI + +> o

B

p «« -t ro CO OO 00 00 00 OO OO 00 ro e <

IccS ·> «s CO P, OOO ^ frCT'iO'NO'iCTlCT'vCriCrNCTi o in CM CM r- * · <--- lOUOLTivCrorOrorOrorororO LA m ΙΛ ΙΛ * - 60886 31

Table II shows:

Column 1: "AS content" means the active ingredient content of the wet aluminosilicate used.

Columns 3 and 4: "AS in suspension" means the concentration of active substance in the suspension formed, in grams or% by weight.

Column 2: amounts of moist aluminosilicate for suspension preparation.

f

Column 5: amounts of water added to moist aluminosilicate.

Plastics 6 and 7: the ethoxylation product used 'and the amount used in grams or percentage.

All suspensions were largely stable and could be continuously pumped out of the tank after one day or longer without difficulty using a standard tubing pump (AGE P 20, AGE Werk, Staufen / Breisgau, Federal Republic of Germany).

Example 2

A suspension of 31% by weight of pure microcrystalline aluminosilicate prepared according to 12 was prepared in water. As dispersants according to the invention, dispersant 9 in Table I was used in an amount of 1.8% by weight, based on the total weight of the suspension. The stability of the suspension was further improved by the addition of very small amounts of tallow ("tallow" means a primary amine corresponding to tallow as defined above) and tallow fatty acid. The suspension prepared in this way could be kept stable for months.

Example 3

A powdered, spreadable detergent having a composition corresponding to Table 3 was prepared as follows: a basic suspension prepared by adding wet aluminosilicate prepared according to step 2 to a dispersant dispersion heated to 70 ° C and containing 36% by weight of aluminosilicate and 2% by weight in all cases TA + 5% based on the total weight of the suspension, was pumped from the storage tank to the tank, to which the other components and such a large amount of water were then added successively with stirring to obtain a detergent charge (slurry), 32 6 0 8 8 6 with a water content of about 45% by weight.

This was transferred by pumping through a mist placed at the top of the spray drying tower and converted into a fine powder by spray drying and directing hot air countercurrent to it (ca. 260 ° C).

Table III

A B

ABS 1.4 1 * TA + 10 EO $ 7.0> OA + 10 EO 8.0 i * TA + 5 EO2 ^ $ 2.0>

Sodium triphosphate7.8 l Sodium triphosphate 20.0 i

Water glass 5.4 9 ^ Sodium carbonate 5.0 # CMC 0.8 i Water glass 3.0 i

Aluminum silicate ^ 'Λv (AS) 36.0 i Aluminum silicate1' (AS) 18.0 i Residual water TA + 5 EO1 ^ 1.0 i and Na2SO4 EDTA 0.5 ^

MgSiO 3 2.5 9 ^

Perborate3) 28.0 #

Soap 2.5 ^ Residual water and Na 2 SO 4 ^ added to the basic suspension 2 ^ TA + $ EO added to the other components 3V added after spraying.

In combination with TA + 5 EO, instead of a stabilized suspension, it is also possible to work with product B using preparations which contain, for example, polyacrylate and are also very stable but also easy to pump. Since the polyacrylate is a calcium complexing agent, the sodium triphosphate content can be reduced to a correspondingly small amount. However, in the preparation of ABS-containing detergents, an ABS-containing suspension can be used according to the invention, in which case, in a concrete case, an ABS having 11 to 13 C atoms in the alkyl group is used. The stabilization then becomes a little worse.

Λ '' 2 ► 33 60886

Example 4

Pumping, 1a storage experiments with aluminosilicate suspension Emulsions heated to 65-70 ° C with 190-360 g of water and 10-30 g of dispersant were mixed by shaking 594-780 g of sodium aluminosilicate with different water concentrations, after which the mixture was homogenized. The amounts were dosed in such a way that the AS content was 31-34. The homogeneous suspensions were circulated by stirring continuously with a hose pump (preparation AGE P 20) for one hour at room temperature. In this case, pumping and mixing were stopped for one hour. Stirring and pumping were then continued. In this case, in a comparative experiment carried out without a dispersing aid, no further mixing and pumping could be performed.

After continued pumping and stirring for 4-6 hours, the suspension was allowed to stand overnight and then examined visually as well as after several days at room temperature for its precipitation. In this case, the numerical values mean the following: base amount = $ 100> that the suspension is completely ($ 100>) homogeneous and stable (see table, last column). With respect to the precipitation ratio assay, the suspension was retested for its pumpability. In this case, it turned out that all the substances presented were useful as dispersants, because the suspensions prepared so-called could be mixed without difficulty with both pumping and circulating pumping.

The compositions of the private mixtures will be apparent from the following tabular presentation. Aluminosilicate prepared according to B 2 with an approximate composition of Na 2 O was used. Al 2 O 2 SiO 2, which, unless otherwise stated, was used in the manufacturing and continuously wet form. The particle size was between 5 and 15 μιη.

34 60886 ......... fr! ........ ΓΊ ..... Γ "'I Γ fn! I u:, P! I I ^ r * i"' 'I * - * j'-N, j Ijfl jP 1 j * -; * -} »- r— r— t— ^ r— j MU VO t— I r— t— red CÖ jt ~ 1! :, ° I i! : cd Aii O 'co> r-; . in in o ia! o; ia mo mo -3- co S I o m; σν en (p m m o w; 0 co e— ao oo co cn po «'P;, I I I | -

• hs: o i:! j I

0 ^ 1: i i; i j

* ~ i ί: i. : I I

; _! j,! I f I J! si 3 1; j I; 1 I - f ............... ~ 1 p ϊ o I, 1

P ΙΛ: ft; , J I

3 (+1+ +: 1 + 1 +, + +, + 1+ + + + + + +

- + H - +: aj j! I! 'll I

1 p, cm: cö; i; '. ! I i! p 1 'n,' i l a P; :: 'ϊ I! § &? S ........: r; -i j! "1 -------------------- f .....

.H ft -p cö! Ä: ϊ! ! 1 ϊ I i E ^ I '++ (+ 1 + + 1 + +' + j + j______ + + +: +. + .. + __ cö P 1 / -nt — J ^ -s I cvj ϊ oj c \ j | cvi cni, i—> o! cm m nj: mi m, mwm: mj —- --- · —— jw P p; i!, iw,! I ooo 'ο ο | o ra cö 1 1 o (oio οοιοοοο cv »cvj cmi cm cm * -

Td CÖ ^ | CM l fO CM ro ro ro CM ro; ro> I I 1 - cö

• H hfl \ ........ r- · - -f - I i [OI O o, O O jo H

o k | 60,: r: w ro ^ -imiifl ro; mi o-, en ση is H

HP CU '· ^ K Ή, j; i 3 ra <u P, 1: ro ro ro Ph ’il <i <ö> p ra! ra I I! o O! O S o::: ϊ i:> s ε! s> s -h ra Ai ί -h i i <i! -aj i <J o | : Ph | Ph ra

P. O i P: lii I i) I

ra Ai i i; | iti! rt

ra!> j: n r I 1 j i H- r * -. r ~ 'rH

• hp I t ϊ m m m m p p> 3 ra, i I,]; lojoo-joo i> pH> »i i; I '. > c \ j -tf oo! ^ cm | cö Cö Ή I: cö ί; ί! \ V \ j \ \ \ cö

cö: cö ora, «50 o o; o, o o! o o1 o o o ί j H1 m, m vo P

Ai ra (M -H C \ l 1 O. OV t ~ - VO VO roj - + | ro, rO | ra io cni Ιΰ ^ r I- 3

• H W H OJ! OJ i T-1 ro i ro ro rO | ro ro ro i m O nj m ro'ro CU

h cö 'I iii; i, ra • H P., 1. I ..... 1; <! ! ί I ί m 1 i ': · · f-> ---- p § III j 1' ί ί I ra p tO * “· r“ <f · t * · t— jr r-1 τ — 1 ^ - r— * φ

• H 3 I ro ro ro, ro ro, ro! ro1 ro 1 ro ro ro c * 1 ro! ro ro ro W

P 3 O 1 I I 1; ,! I Ai • H Pt P; i I il I -r * E Ph p! ‘R; ! ! · - p

3 a cö I I; ; I I CU

H3 1PP! W) Oi OOIO; O · O'o o o o oooooo ^ j 3! ro 1 ro 'ro! ro1 roi ro! ro1 ro! ro1 ro ro ro ro ro ro | .........-! _______ 4 .....-...... f- ~ i .....! ·! ί! - - I _ g

i I i I il; (CU

W I II 43

ί >> ^ I ί I -H

p I; : ra | P: cd I O OOO OlOOOOO ^ H} ^ Ur m <} o>

: cdP I co co co ι-i h—! h— rj- -j · i 1 tn σ m m r- S

; m: cd i r- r— c ^ -voi ra ra ra rarai ra m in ire m ra co ^ • h: P: j ^ m

i J B i ί j I g I

i '! and I

I! : I i R p i e! ; EP p I i j 1 * - · ra! P I lev j cm cm i cm m l-Hra! co co co co i co o Ai! p 3 I <i C m 3 'cö 3 e ^ ^ i i cö ra ^ 3

Ai -H 1 I D- cö

• HO CO 00 (00 · ^ - H- M- H

i — lp ·· · * '· ^ · ΗΪ · h O

; H -H en O j O CO CM 3

I co Pi ro mjmo m Γρ EP

j. i '. I

Jf 35 60886

Notes to the table:

Upon completion of the aluminosilicate suspensions (1) The aqueous HAB suspension of the mixture was precipitated up to $ 50 (2) The wet aluminosilicate was prepared in a "Lödigemischer" type apparatus using a spray-dried substance having an AS content of 79 by adding water as a starting material.

(3) The acidic polyacrylic acid solution was adjusted to a silicon value of 10 with sodium hydroxide before the addition of sodium aluminum silicate. Alternatively, poly (tert-hydroxyacrylic acid) was used.

(4) Pumpability after x hours, where the markings mean: - = no longer circulating + = pumpable and circulating (5) the polyvinyl alcohols used are sparingly soluble in water and then varying amounts of dimethyl sulphoxide (20-87 g) were added to dissolve at the expense of water.

Using 1 i of PVA 90, the addition of dime style sulfoxide could be omitted.

The polyvinyl alcohols used are commercial products ("Mowiol, manufactured by Farbwerke Hoechst"), with "Mowiol 76/98" proving to be the most suitable.

Example 5

Suspensions were prepared according to the invention by mixing products I, II, VIII, IX and XXm in a preheated dispersion TA + 5 EO in water at 60-70 ° C to give a silicate suspension with 33 afi AS content and 2 $ TA + 5 EO.

The suspensions were cooled to room temperature and monitored at this temperature. In this case, work was carried out as in Example 1 at room temperature. The suspensions were very stable.

Example 6

A wet aluminosilicate prepared according to Example 2 and washed to a pH of about 10.5 with an approximate composition of NagO. 2 SiO 2, water content 50 was mixed with an aqueous solution containing.

a) 1,3-hydroxyethane-1,1-diphosphonic acid b) dimethylaminomethanediphosphonic acid to prepare suspensions with a solid having an AS content of 36 60886 31 i ° dispersant concentration 2 Phosphonic acids were used as the 1. tetrasodium salt 2. and the disodium salt acid

After mixing the surfactants and possibly other detergent ingredients, the suspensions could be prepared as a detergent, for example by spray-drying it.

Example 7 ·

According to Example 6, suspensions were prepared from $ 31 sodium aluminum silicate and $ 4 phosphonic acid butyl ester or phosphoric acid isooctyl ester (pH used was 10). Phosphoric acid esters were products with about 1.5 moles of alcohol per mole of phosphoric acid.

Example 8. According to Example 6, a suspension of $ 31 of sodium aluminum silicate at an AS content of 4 alkyl benzenesulfonate (ABS) was prepared. ABS was used as the partially free salt and the partially free acid. It was also possible to use the methyl ester of hardened tallow fatty acid by sulfonating the sulfonate obtained with SO 2 or the olefin sulfonate obtained by sulfonating straight-chain olefins having internal double bonds and 12 to 18 carbon atoms, and by hydrolyzing the product obtained by sulfonation. Strong foaming of the suspension could be overcome without difficulty by adding small amounts of a commercially available silicone-based defoamer. The suspensions were particularly suitable for the preparation of sludges in the preparation of aluminosilicate-containing detergents. However, they could also be spray-dried either as such and thus converted into powdered water softeners or detergent auxiliaries.

Example 9

Aluminum silicate suspensions with an AS content of 31 ° C and the following concentrations of dispersants ($ AS® dispersant) were prepared as described in Example 4 a) stearic acid monoglyceride (31/2) b) stearic acid propylene glycol ester (31/2) (c) reaction product of the reaction between tallow and N-hydroxyethyl-ethylenediamine (31/2) · (d) thallamine (long-chain i., · · 37 amine obtained by reduction of tallow fatty acids) (31/2) 608 8 6 e. moles of ethylene oxide per mole of thallamine (31/2) f. oleyl alcohol with 5 moles of ethylene oxide per mole of alcohol (31/2) g · a mixture of saturated C12 ($ 70- $ 75) and C14 ($ 25-30) alcohols, ethoxylated with 3-4 moles of ethylene oxide (31/2) h. corn starch (31/2) or carboxymethylcellulose i. poly- (d-hydroxyacrylic acid) (31/2) k. poly- (t-hydroxyacrylic acid) polylactone (31 / 2)

Stabilized suspensions are suitable, inter alia, for the preparation of aqueous charges (fines; slurries) from detergent ingredients, which are then spray-dried. They can also be processed directly into granules by adding salts which bind water to crystalline water (e.g. pentasodium triphosphate).

Example 10

The aqueous suspension prepared according to Example 1, containing about $ 30 aluminosilicate and $ 2 TA + 5 EO, was spray dried in a stream of hot air and then dried, i. was released from the infected water. The spray-dried product was substantially more dust-free than the similarly prepared product, however, the combination TA + 5 E0 was omitted. The obtained powdered aluminum silicate was very suitable as a water softener and detergent. Example 11

To the suspensions of bentonite in water was added a silicate wet at about room temperature containing $ 50 of water and a composition of Na 2 O. A120 ^. 2 SiOg. The stabilized suspension had an AS content of $ 33 and a concrete content of $ 2 or $ 4. The bentonite used was a commercially available product under the trade name "active-vi-bentonite" and supplied by Erbslöh, Sa.ksan, Federal Republic. Analytical composition:

SiO 2 56.8 Al 2 O 3 20.1

Pe20 ^ 4.8

CaO 1.8 M /? 0 4.0 K 2 O 0.7

Na2Q 3.1 Λ 38 60886

Annealing loss 8.7 Bentonite type "Montigel F" obtained from Sudchemie AG, Federal Republic of Germany was also used.

Products derived from or made from natural products usually contain persistent iron-containing impurities as well as silicate impurities. In addition to the above, commercial products include "active bentonite" (Erbslöh, Federal Republic of Germany), "Volclay" (Bentonite International), "Eurogel" (Araberger Kaolinwerke, Federal Republic of Germany); Synthetic products can be obtained, inter alia, from Lange & Co., Bremen.

Detergents of the type described in German application 24 12 Θ3Θ. can be prepared as described therein using aluminosilicate suspensions which, however, are stabilized with bentonite or a synthetic expandable silicate of the smectite type by combining the stabilized suspension with other ingredients of the substance to be prepared to form a slurry which may, for example, contain 50% by weight. water, after which it is dried in a stream of hot air. For example, a product can be prepared having the following composition: TA + 10 EO 3.0% TA + 5 E0 2.0%

Sodium triphosphate 20.0%

Sodium carbonate 5.0%

Water glass 3.0 5 ^ CMC 1.8%

Aluminum silicate (AS) 18.0%

Bentonite 1.1% EDTA 0.5%

MgSi03 2.5%

Perborate 28.0%

Soap 2.5% Residual water and Na 2 SO 4 by mixing a suspension containing 2% bentonite with other detergent ingredients except perborate to a slurry which is normally dried in a stream of hot air by spray drying, after which the resulting powder is mixed with perborate.

39 6 0 8 8 6

All suspensions described in the examples had clearly improved stability and flowability.

In this case, the non-ionic surfactants belonging to compound class 4 have, quite surprisingly, proved to be clearly superior.

Claims (7)

A process for the preparation of powdered detergents, characterized in that, in the manufacture, a pumpable, such as stock suspension, is stored and / or transported a water suspension with improved stability of a water-insoluble silicate capable of binding calcium, whereby the suspension, calculated , contains A) as aluminum silicate suitable for bonding calcium, at least 20% by weight and preferably 20-53% by weight of a finely divided, synthetically prepared, water-insoluble crystalline aluminum silicate containing bound water, of the general formula (Kat2 / n °> x Ä12 ° 3 'SiO2> y (I> in which Kat represents a calcium-exchangeable cation with the valence n, x is a tai of 0.7-1.5 and y a tai of 0.8-6, preferably 1.3 -4, wherein the aluminum silicate has a calcium binding capacity of 50-200 mg CaO / g of anhydrous active substance, as measured by determining the reduction in hardness of 1 liter of water at 30 ° dH and 2 2 ° C after 15 minutes of action of 1 g of anhydrous active substance of this silicate, and B) as a dispersant 0.5-6% by weight of at least one of the following compounds: 1. organic, macromolecular polymeric compound containing carboxyl groups and / or hydroxyl groups with a molecule weight exceeding 1500, 2. phosphonic acid from the group of alkane polyphosphonic acids, amino or hydroxyalkyl polyphosphonic acids or phosphonocarboxylic acids; a non-ionic surfactant having a cloud point 44 60886 in aqueous butyldiglycol solution below 90 ° C, determined according to DIN 53 917, 5. a surfactant sulfonate from the group of alkylbenzenesulfonates containing 9-15 C atoms in the alkyl group, sulfonates of monoolefins having 12-18 C atoms saint esters of α-sulfo fatty acids, 6. a swellable water-insoluble silicate of layer structure and the general form A12 <S12 ° 5> 2 <0H> 2 or Mg3 (Si2 O5) 2 (O H) 2 Process according to claim 1, characterized in that a suspension having a pH value between 7 and 12 is provided. Method according to claim 1 or 2, characterized in that a suspension is used in which component A has the composition 0.7-1.1 Na 2 O · Al 2 O 3 · 1.3-3.3 SiO 2. Method according to any one of claims 1-3, characterized in that a suspension is used in which component A in X-ray diffraction diagrams has the following interference lines (d values recorded with Cu-Ka radiation in 10 µm): 4, 1; 3.68; 3.38; 3.26; 2.96; 2.73; 2.60; or 4.4; 3.8; 2.88; 2.79; 2.66. 5. A means for carrying out the process according to any one of claims 1-4, characterized in that the agent consists of a suspension consisting essentially of: A) at least 20% by weight, preferably 20-53% by weight of a finely divided, synthetically prepared, water-insoluble crystalline aluminum silicate. containing bound water, having the general form V 60 60886 (Kat2 / n0) x 'A12 ° 3' (SiO2> y (I) in which Kat represents a calcium-exchangeable cation with the valence n, x is a tai of 0.7 -1.5 and γ a tai of 0.8-6, preferably 1.3-4, wherein the aluminum silicate exhibits a calcium-binding capacity of 50-200 mg Ca0 / g of anhydrous active substance, as measured by determining the reduction in the hardness of 1 liter water of 30 ° dH and 22 ° C after 15 minutes of action of 1 g of anhydrous active substance of this silicate, B) 0.5-6% by weight of at least one of the following compounds:. (a) a phosphonic acid from the group of alkane polyphosphonic acids, amino or hydroxyalkyl polyphosphonic acids or phosphonocarboxylic acids, (b) a phosphoric acid alkyl ester containing 1-2 moles of a saturated alcohol having 3-20 C atoms in the alkyl chain, ( c) a practically water-insoluble, nonionic surfactant having a cloud point in a 1% aqueous solution below room temperature; (d) a swellable, water-insoluble silicate having layer structure of the general formula A12 (S12 ° 5> 2 < OH 2 or Mg 3 (Si 2 O 5) 2 (OH) 2 and NC) water. 6. Agent according to claim 5, characterized in that the suspension, as component B (c), contains the ethoxylation product of a saturated alcohol containing 16-18 C atoms with 1-8 moles of ethylene oxide per mole of alcohol. An agent according to claim 5 or 6, characterized in that the suspension, as component B (c), contains the ethoxylation product of a saturated tallow fatty alcohol with 2-7 moles of ethylene oxide per mole of alcohol.