Stable Aqueous Suspension of Water-Insoluble, Calcium-Binding Aluminosilicates and Nonionic Suspending Agents

As known, the detergents used in the household, in commercial establishments and in industry, frequently contain large quantities of condensed phosphates, particularly tripolyphosphates. These are provided to sequester the hardness formers of tap water and are responsible to a great extent for increasing the cleaning power of the capillary-active washing substances. The phosphorus content of these agents has been criticized by the public in connection with questions of the protection of the environment. The view is frequently expressed that the phosphates, which arrive in the rivers and lakes after treatment of the sewage, have great influence on the eutrophication of the waters, and is said to lead to an increase of the growth of algae and of oxygen consumption. It has therefore been tried to eliminate phosphate from the washing and cleaning processes or from the agents used for this purpose, or at least to substantially reduce its proportion.

Copending, commonly-assigned U.S. patent application Ser. No. 458,306, filed Apr. 5, 1974, now abandoned, and its continuation application Ser. No. 800,308, filed May 25, 1977, now abandoned, and its continuation-in-part application Ser. No. 956,851, filed Nov. 2, 1978, discloses a process for the washing, bleaching or cleaning of solid materials, particularly textiles, by treating these materials with a liquor containing compounds able to bind the cations that make water hard. The process is characterized in that finely-dispersed, water-in-soluble silicate compounds having calcium-binding capacity of at least 50 mg CaO/gm of anhydrous active substance (AS) and having the formula I, combined water not shown

where M is a cation of the valence n, exchangeable with calcium, x is a number from 0.7 to 1.5, Me is aluminum or boron, and y is a number from 0.8 to 6, preferably from 1.3 to 4, are suspended in the aqueous treatment bath. The process of the patent makes possible the complete or partial replacement of phosphates that bind calcium ions by complexing and are still being used in the washing and cleaning process.

The calcium-binding capacity of the above-defined compounds may reach values of 200 mg CaO/gm AS and is preferably in the range of 100 to 200 mg CaO/gm AS. The above-defined compounds capable of binding calcium are referred to as "aluminosilicates" in the following text, for the sake of simplicity. This applies particularly to the sodium aluminosilicates that are to be used preferably. All data given for their preparation and processing apply accordingly to the totality of the above aluminosilicate compounds as defined in said earlier application.

The cation M employed is preferably sodium. However, the same can also be totally or partially replaced by other cations exchangeable with calcium, such as lithium, potassium, ammonium or magnesium, as well as by the cations of water-soluble organic bases, for example, by those of primary, secondary or tertiary alkylamines or alkylolamines with not more than 2 carbon atoms per alkyl radical, or not more than 3 carbon atoms per alkylol radical.

The anhydrous active substance (AS) of the aluminosilicates is that reached after one hour of drying at 800.degree. C., whenever reference to anhydrous aluminosilicate is made in the following text. The adhering water as well as the water of retention is removed partically completely by this drying.

Aluminosilicates that are still moist, for example, from their preparation, are used to advantage as starting compounds in the preparation of washing and cleansing agent compositions containing the above-defined aluminosilicates in addition to the conventional components. The moist compounds are at least mixed with a portion of the remaining components of the material to be prepared, and the mixture is incorporated into the finished washing and cleansing agent composition to give as the final product, a product that is a pourable powder.

The aluminosilicates are supplied or used, in the framework of the procedure for the preparation of washing and cleansing agent compositions outlined above, as aqueous suspensions or as moist filter cake. Certain improvements of the suspension characteristics, such as the stability of the suspension and the transferability of the aluminosilicates dispersed in the aqueous phase, by pumping, would be desirable.

An object of the present invention is the development of an aqueous suspension of water-insoluble, calcium-binding aluminosilicates with an improved stability against settling consisting essentially of (A) from 20% to 53% by weight on the anhydrous basis of at least one finely-divided, water-insoluble silicate compound having a calcium-binding power of at least 50 mg CaO/gm of anhydrous active substance and having the formula, combined water now shown

where M is an alkali metal, x is a number of from 0.7 to 1.5, Me is aluminum or boron, and y is a number from 0.8 to 6 and (B) from 0.5% to 6% by weight of at least one practically water-insoluble nonionic aliphatic surface-active compound having a turbidity point of a 1% solution in water of below room temperature, in water.

Another object of the invention is the development of a process for the preparation of washing and cleansing agent compositions employing the above suspensions.

These and other objects of the present invention will become more apparent as the description thereof proceeds.

We have now found that certain compounds possess to a special degree, the capability to stabilize suspensions of the above calcium-binding aluminosilicates so that these, even with a high solids content, remain stable for a long time, in fact for a practically unlimited time, and also can still be pumped without problems after long periods of standing. Surprisingly, it has been found that there are certain compounds which are capable of keeping suspensions of moist aluminosilicates which have a bound or adhering water content of 70% or less, pumpable practically, independent of their standing period, which was impossible until now.

The present invention therefore relates to aqueous suspensions of water-insoluble, calcium-binding aluminosilicates, suitable for use as stock suspensions and transferable by pump, with an improved stability, characterized by the fact that, based on the total weight of the aqueous suspension, they contain

(A) at least 20%, preferably 20% to 53% and especially 20% to 42% by weight on an anhydrous basis of finely-divided, water-insoluble compounds, capable of binding calcium, of the general formula, combined water not shown

in which the symbols have the meaning given above, and

(B) at least one dispersing agent, a practically water-insoluble nonionic aliphatic surface-ative compound having a turbidity point of a 1% solution in water of below room temperature.

More particularly, the invention relates to an aqueous suspension of water-insoluble, calcium-binding alumino-silicates with an improved stability against settling consisting essentially of (A) from 20% to 53% by weight on the anhydrous basis of at least one finely-divided, water-insoluble silicate compound having a calcium-binding power of at least 50 mg CaO/gm of anhydrous active substance and having the formula, combined water not shown

where M is an alkali metal, x is a number of from 0.7 to 1.5, Me is aluminum or boron, and y is a number from 0.8 to 6, and (B) from 0.5% to 6% by weight of at least one practically water-insoluble nonionic aliphatic surface-active compound having a turbidity point of a 1% solution in water of below room temperature, in water.

Specifically the invention relates to an aqueous suspension having a pH of between 7 and 12 of water-insoluble, calcium-binding aluminosilicates with improved stability against settling consisting essentially of (A) from 20% to 42% by weight on the anhydrous basis of at least one crystalline, finely-divided, water-insoluble silicate compound having a calcium-binding power of from 100 to 200 mg CaO/gm when measured as described on pages 25 to 26 of the specification and a primary particle size of from 0.1.mu. to 50.mu. and having the formula, combined water not shown

where M is a member selected from the group consisting of sodium and potassium, x is a number from 0.7 to 1.5 and y is a number from 0.8 to 6, and (B) from 0.5% to 6% of a practically water-insoluble nonionic aliphatic surface-active compound having a turbidity point of a 1% solution in water of below room temperature, in water, said aqueous suspension being capable of being pumped after 24 hours of standing.

The pH of the suspensions is generally between about 7 and 12, preferably between 8.5 and 11.5, and usually below 11.

The above-mentioned compounds are the main components of the suspensions according to the invention. However, additional components may be contained, such as foam-reducing additives. The usual anti-foaming agents such as foam-reducing soap, silicones, triazine derivatives, which are all known to those skilled in the art, can be used as foam-reducing substances. Such an addition is not usually necessary. The anti-foaming agents are employed in amounts of from 0 to 0.5% by weight of the suspension.

The condition of the aluminosilicate reached after one hour of drying at 800.degree. C. in the basis on which all data of "concentration of the aluminosilicates", "solids content" or content of "active substance" (AS) are based. The adhering water and water of retention is removed practically completely by this drying procedure.

All data in percentages refer to percent by weight.

The above-mentioned components A and B are discussed in more detail below.

The aluminosilicates of component A to be used according to the invention may be X-ray amorphous or crystalline products, preferably crystalline products, with the use of mixtures of amorphous and crystalline products as well as partially crystallized products being permissible. The aluminosilicates may be naturally occurring or synthetically produced products, however, the synthetically prepared products are preferred. Their preparation can be carried out for example, by reacting water-soluble silicates with water-soluble aluminates in the presence of water. Preferably sodium silicates and sodium aluminates are employed. For this purpose, aqueous solutions of the starting materials can be mixed or one component in solid form can be reacted with the other component present in an aqueous solution. The desired aluminosilicates may also be obtained by mixing the two components in solid form, in the presence of water. Aluminosilicates are also produced by reacting Al(OH).sub.3, Al.sub.2 O.sub.3 or SiO.sub.2 with alkali metal silicate or alkali metal aluminate solutions, respectively. The preparation may be carried out according to other well-known processes, also. The invention refers, in particular, to aluminosilicates possessing, in contrast to the layered silicate structure of montmorillonite, a three-dimensional spatial lattice structure.

The preferred calcium-binding capacity, which is in the range of 100 to 200 mg CaO/gm AS and mainly about 100 to 180 mg CaO/gm AS, is found principally in compounds of the following composition:

This formula includes two different types of crystal structures (or their non-crystalline precurors) that differ also in their formulas.

The different crystal structures become apparent in the X-ray diffraction diagram.

The amorphous or crystalline aluminosilicate, present in an aqueous suspension can be separated from the remaining aqueous solution by filtration and drying at temperatures of 50.degree. to 400.degree. C. The product contains a larger or smaller amount of combined water, depending on the drying conditions.

The higher drying temperatures are not generally recommended. It is preferable that a temperature of 200.degree. C. is not exceeded in drying, when the aluminosilicate is to be used in washing and cleansing agent composition. However, the aluminosilicates do not have to be dried at all after their preparation, if they are used for the preparation a suspension according to the invention. On the contrary, and this is especially advantageous, an aluminosilicate that is still moist from its preparation may be used. Also suitable for the preparation of suspensions according to the invention are aluminosilicates that are dried at intermediate temperatures of 80.degree. to 200.degree. C., until the adhering liquid water is removed.

The particle size of the aluminosilicate particles may vary between 0.01.mu. and 0.1 mm. This is based on the primary particle size, i.e. to the size of the particles obtained by precipitation and, if desired, subsequent crystallization. Especially advantageous is the use of aluminosilicates consisting to at least 80% by weight of particles measuring 10 to 0.01.mu., particularly 8 to 0.1.mu.. It is preferably that these aluminosilicates do not contain any primary or secondary particles with a diameter above 30.mu.. Secondary particles are particles that are produced by the agglomeration of primary particles into larger forms. Most important is the range between ca. 1 and 10.mu..

The use of aluminosilicates still moist from their preparation, for the production of suspensions according to the invention, has been especially advantageous with respect to the agglomeration of primary particles into larger forms, since it was found that a formation of secondary particles is practically completely prevented by the use of these moist products.

A more detailed description of the compounds used as component B according to the invention follows.

The nonionic surface-active compounds or tensides used according to the invention are practically water-insoluble products. The turbidity point of a 1% solution in water of suitable products is below room temperature. The most suitable products are characterized by the fact that they can be dispersed in water in an amount of one part of tenside to 19 parts by weight of water, with light or more vigorous shaking if necessary, and with heating above the melting point of the tenside, if necessary, so that they form a milky or gel-like, solidified dispersion on cooling to room temperature.

The information concerning the dispersibility in water or the turbidity points refers to the individual, tenside-like dispersing agents in their technically pure form as a statistical mixture of ethoxylation products, such as is obtained by the ethoxylation of fractions of fatty alcohols, fatty acids, fatty acid amides or fatty amines.

The nonionic tenside dispersing agents suitable according to the invention are found expecially among the nonionic surface-active compounds containing a long-chain alkyl or alkenyl radical with mainly 10 to 20, preferably 12 to 18 carbon atoms, as the hydrophobic part of the molecule. The alkyl or alkenyl radical is primarily straight chained. However, suitable products are found also among the compounds with branched-chain hydrophobic radicals or even radicals derived from vicinal alkanediols. Unsaturated hydrophobic moieties are mainly mono-unsaturated, as the oleic acid or oleyl moiety found especially frequently.

The hydrophilic group is formed mainly by polyalcohol units such as ethylene glycol, propylene glycol, polyoxyethylene glycol or glycerine-units that are connected with the hydrophobic part through ester, amide, ether or amino groups. The ethylene oxide adducts are to be emphasized.

Among the ethylene oxide adducts with the same turbidity point, those with the longer hydrophobic moieties, preferably of from C.sub.14 to C.sub.18 are generally preferred.

An important group of suitable nonionic surface-active compounds is found among the aliphatic carboxylic acid esters and aliphatic carboxylic acid amides. These are higher fatty acid esters with alcohols having water-solubilizing group and higher fatty acid amides having water-solublizing groups. Particularly suitable as dispersing agents in the sense of the invention are the monoethanolamides and diethanolamides of carboxylic acids with 10 to 20, preferably 12 to 18 and especially 12 to 14 carbon atoms. The compounds are preferably derived from saturated and straight-chain carboxylic acids (alkanoic acids). However, the products may also be derived from unsaturated, particularly monounsaturated, carboxylic acids (alkenoic acids). Particularly monoethanolamine and diethanolamine are suitable as the amine component from which the amide suitable according to the invention is derived. Another particularly suitable product is also the amide derived from a carboxylic acid as defined above, and N-(hydroxyethyl)-ethylene diamine. The suitable amides can be considered to be the reaction products of carboxylic acid amides with ethylene oxide. The number of ethylene oxide units is usually 1 to 6, and especially preferred is 1 to 4.

The ester-like dispersing agents are derived from the same carboxylic acids as the amide-like dispersing agents. As in the case of the amides, the esters are derived from fatty acids or mixtures of fatty acids, particularly of the ranges of chain length given above, that may be of natural or synthetic origin. Suitable as ester-like suspension stabilizers are the products that may be considered addition products of the carboxylic acids with ethylene oxide. These are preferably the addition products of carboxylic acids with 1, 2 or 3 mols of ethylene oxide per mol of carboxylic acid. However, products with 4 to 10 ethylene oxide units are also suitable. Also suitable as alcohol components in the surface-active ester are polyalcohols with more than 2 hydroxyl groups, e.g. glycerin.

Examples of especially suitable dispersing agents or suspension stabilizers of the amide or ester type are the following compounds: monoethanolamide of lauric acid, monoethanolamide of coconut fatty acid, myristic acid monoethanolamide, palmitic acid monoethanolamide, stearic acid monoethanolamide, oleic acid monoethanolamide, tallow fatty acid monoethanolamide, and the diethanolamides derived from the same fatty acids and the amides derived from N-(hydroxyethyl)-ethylene diamine. Representatives of the ester-like stabilizers are the addition products of 1 and 2 mols of ethylene oxide to coconut fatty acid and of propylene glycol or glycerin to stearic acid or palmitic acid.

Especially suitable diethanolamides are lauric/myristic acid diethanolamide, the diethanolamide of a mixture of fatty acids of lauric acid and myristic acid, and oleic acid diethanolamide.

Another particularly good group of stabilizers is found among the ethoxylation products of preferably saturated aliphatic alcohols containing 10 to 20 carbon atoms with 1 to 8 mols of ethylene oxide per mol of the alcohol. Preferred products among these ethoxylation products are those with 2 to 7, particularly with 2 to 6, mols of ethylene oxide per mol of the alcohol. The use of derivatives of straight-chain alcohols is particularly advantageous within the framework of the invention. However, derivatives of branched-chain alcohols, especially of alcohols prepared by oxosynthesis, can also be used. Especially preferred are the derivatives of preferably saturated and preferably straight-chain alcohols containing 16 to 18 carbon atoms. The alcohols employed are preferably alkanols, alkenols and alkanediols having from 12 to 18 carbon atoms. Ethoxylation products of alcohols containing 12, and especially 14, carbon atoms can also be used, and products with 1 to 5 mols of ethylene oxide, especially with 2 to 4 mols of ethylene oxide, per mol of the alcohol are especially suitable.

The ethoxylation products used according to the invention are generally not chemically uniform compounds, but are rather common mixtures containing adducts of varying degrees of ethoxylation together in statistical distribution, including the ethoxylation degree "0". The non-ethoxylated starting material is usually present in small amounts in the final products. The ethoxylation products used according to the invention are practically water-insoluble compounds.

The alcohol component such as the tallow fatty alcohols of the C.sub.16 to C.sub.18 range, is usually a technical mixture where alcohols with more and/or less carbon atoms may be present, mainly in small amounts of up to 15%. What is said below about the additional substances that may be present, if desired, also applies for amounts exceeding the above.

The respective ethoxylation products of fatty amines can be used instead of the mentioned ethoxylation products of alcohols, especially ethoxylation products of preferably saturated primary amines or fatty amines with 16 to 18 carbon atoms and 1 to 8 mols of ethylene oxide per mol of amine. Also suitable are the non-ethoxylated amines which are tensides in the sense of the definition of the invention, as well as products with 2 to 5 mols of ethylene oxide per mol of amine.

Mixtures can be used in addition to the single nonionic dispersing agents, where a synergistic interaction is observed in several cases. For example, the addition of tallow fatty amine, to suspensions stabilized with a nonionic tenside, has been found to be advantageous. An additional class of compounds which further improve suspensions stabilized according to the invention are the long-chain fatty acids. These are natural or synthetic, preferably saturated fatty acids, usually with 10 to 20 carbon atoms in the molecule, such as tallow fatty acid. When employed, the fatty acid or fatty amines are present in an amount of from 0 to 6% by weight in the suspension.

Aqueous suspensions especially preferred in the invention consist mainly of at least 20% of component A. The upper limit of the content of the aluminosilicate component A is determined by the limit of the flow characteristics, which lies generally at under 53%, for example about 42% by weight. Concentrations between 25% and 40% by weight, especially between about 28% and 38% by weight, are preferred. The range of 30% to 38% by weight is the most important for practical application.

The amount of component B to be used depends mainly on the desired degree of stabilization of the suspensions. In general, the concentration of component B of the suspensions according to the invention lies between about 0.5% to 6%, more often from 0.8% to 6% by weight, calculated on the total weight of the aqueous suspension. It is preferably in the range of about 1% to 4% by weight and in most cases about 1.3% to 3% by weight, as a matter of practicality. The desired viscosity can be taken into consideration in the selection of the concentration of component B, if necessary, since the viscosity of the suspensions is influenced by the content of component B.

Smaller amounts of component B are used for the stabilization of the finer aluminosilicates than of coarser products. For example, aluminosilicate suspensions containing 90% or more of particles measuring between 1 and 8.mu. can be stabilized equally well by a content of from 0.5% to 1% by weight of dispersing agent, as products with intermediate size particles of 10 to 12.mu. which are stabilized by 1% to 2% of dispersing agent. These data are only guidelines. The suitable amount of component B must be determined for the definite requirements of the individual case.

The viscosity of the suspension at 25.degree. C. should in general be between 500 to 30,000, preferably above 1000 but under 15,000 cps. Particularly suitable are suspensions with a viscosity in the range of between 1000 and 9000 cps.

Especially preferred aqueous suspensions in the invention consist mainly of at least 20% of component A, at least about 0.5%, preferably at least about 0.8% of component B and water.

Inorganic salts or hydroxides from the precipitation or other processes for the preparation of the aluminosilicates are present in addition to the mentioned components. That is, small amounts of excess sodium hydroxide, or sodium carbonate or bicarbonate formed from it by absorption of carbon dioxide may be present, or the sulfate ion, if aluminum sulfate was used as the aluminum-containing starting material for the preparation of aluminosilicate.

Basically, the aqueous suspensions also may contain additional substances in relatively small amounts besides the mentioned components A and B and, if necessary, substances remaining from the starting materials for the preparation of these components. Where the suspensions for washing agents and detergents are to be processed further, the additionally present substances are preferably substances suitable as components of washing and cleansing agent compositions.

An indication of the stability of the suspensions is provided by a simple test, in which an aluminosilicate suspension is prepared of the desired concentration, such as 31%, and containing a dispersing agent according to the invention as well as optionally other substances, and/or detergent components such as pentasodium tripolyphosphate, in varying amounts. The influence of the added substances can be observed visually by the precipitation characteristics of the suspension. A preferred suspension generally should not have settled beyond the point where the clear supernatant liquid, the solution free from silicate particles, amounts to more than 20%, preferably more than 10%, especially more than 6%, of the total height, after standing for 24 hours. In general, the amount of additives should be adjusted so that the suspension can be readily transferred again by pumping after standing for 12 hours, preferably 24 hours and especially also after 48 hours of standing in the storage tank and pipes or tubes. The settling characteristics of the suspensions containing further components, if desired, is tested at room temperature, at an overall height of 10 cm for the suspension. If the height of the clear supernatant liquid of especially preferred suspensions stays within the given range, even after 4 and especially after 8 days, they can be pumped without any problem after 4 and after 8 days. These data concerning the stability of the suspension again are guidelines. The desirable stability for the suspension must be determined for each individual case. When using the suspensions according to the invention as stock suspensions for extended storage in a tank; from which it can be removed by pumping, it may be advantageous to keep the portion of other components of washing and cleansing agent compositions, low or to eliminate them completely.

The suspensions can be prepared by the simple mixing of their components, in which process the aluminosilicates may be used, as is or moist, optionally from their preparation, or in aqueous suspension. Especially advantageous is the addition of aluminosilicates that are still moist, as filter cakes, to a dispersion of component B in water. This dispersion of component B is preferably warmed, to 50.degree. to 70.degree. C.

Dried aluminosilicates, for example, substances from which the adhering water has been removed, but that contain bound water, can also be used in the preparation of stable suspensions.

In an especially suitable process for the preparation of the suspensions according to the invention, aluminosilicate is precipitated by mixing sodium aluminate and sodium silicate solutions. These solutions are more alkaline, thus containing more theoretical sodium hydroxide than is necessary for the formation of the final aluminosilicate, so that an excess of sodium hydroxide is present in the aluminosilicate suspension, the immediate product of precipitation. This suspension is concentrated by filtering off part of the supernatant mother liquor, and subsequently freed from a sufficient amount of the excess sodium hydroxide present by rinsing with water, so that the sodium hydroxide content of the suspension is below about 5%, preferably below 3% or even below 2% by weight. The remaining sodium hydroxide is neutralized by the addition of an acid, particularly aqueous sulfuric acid, to such a degree that the obtained suspension has a pH between about 7 and 12, particularly between about 8.5 and 11.5. The amount of dispersing agent necessary to achieve the desired degree of stabilization is added to the suspension. This addition may be made before, during or after the partial neutralization step.

The suspensions according to the invention are characterized by high stability and other advantages. Their stabilizing effect is particularly valuable for aluminosilicates with a particle size of 5 to 30.mu.. They can be pumped, permitting the easy handling of moist aluminosilicates. The suspensions can be moved without any problem by pumping, even after longer interruptions in the pumping process. Due to their high stability, the suspensions can be transported in regular tank trucks and drum trucks without formation of useless or interfering residues. The suspensions are therefore exceptionally suitable as a form in which aluminosilicates can be delivered to detergent manufacturers, for example.

The suspensions can be stored at room temperature or higher temperatures, and transported through pipe lines, pumps or other means. The suspensions are usually handled between room temperature, most preferably and about 60.degree. C.

Particularly suitable are the suspensions according to the invention for the processing of flowing or trickleable products with a dry appearance, and for the preparation of powdery water softeners, through spray-drying. Thus, the suspensions have considerable value for the preparation of powdery aluminosilicates. No troublesome residues are found during the feeding of the aqueous suspension into the drying equipment. It was also observed that the suspensions of the invention can be processed into extremely dust-free products.

Because of their special stability, the suspensions according to the invention can be used as they are, without further compounding and with or without further additives possessing a cleansing bleaching and/or washing effect, for example as water softeners, washing or cleansing agents and particularly as liquid scouring products with increased suspension stability.

An especially important use of the suspension is in the further conversion into pourable or trickleable washing and cleansing agents and containing other compounds in addition to the components of the suspension.

The suspensions according to the invention are especially suitable for the preparation of washing and cleansing agent compositions described in the U.S. patent application Ser. Nos. 458,306; 458,333 and 458,326, all filed Apr. 5, 1974, now abandoned, U.S. Pat. No. 4,071,377 and abandoned, respectively, and all data for their preparation, their composition components and for the proportions of the components are applicable correspondingly.

Thus the invention also concerns a process for the preparation of pourable powdery products with a content of water-insoluble aluminosilicates, as defined above, in which a pourable product is produced in the usual manner by starting with an aqueous, flowing solution of a premix of individual components of the products. The process is characterized by the fact that the aluminosilicates are used in the form of the suspensions according to the invention. The suspensions according to the invention can be converted into the solid, pourable washing and cleansing agent compositions by well-known processes.

Powdered, trickleable washing and cleansing agent compositions according to the invention are prepared in such a manner that a suspension according to the invention, from a storage tank, is mixed with at least one washing, bleaching or cleaning component of the product to be prepared, and that the mixture is subsequently converted into a powdered product by a customary process. A sequestering agent, a compound capable of binding the alkaline earth metal ions that make the water hard, particularly the magnesium and calcium ions, is added to advantage.

In general, the suspension according to the invention is combined preferably with at least one water-soluble surface-active compound tenside for the preparation of washing and cleansing agent compositions according to the invention, which is not one of the nonionic substances of component B.

There are several variations of the preparation of washing and cleansing agent compositions. For example, the suspensions according to the invention can be combined with substances capable of adding water of crystallization, preferably by spraying the suspension onto the anhydrous or partially anhydrous compounds capable of adding water of crystallization, placed in a mixer, so that with constant mixing, a finally solid product of dry appearance is obtained. However, the suspensions according to the invention are preferably mixed into a slurry, and spray-dried with at least one additional washing, bleaching or cleansing substance. Additional, surprising advantages of the claimed aluminosilicate suspensions are observed herein. It has been found that highly dust-free products can be obtained through the use of the suspensions according to the invention for spray-drying. The products of spray-drying have a high capacity for binding calcium and are readily wettable.

Washing agent compositions according to the invention, that is washing agent compositions that can be prepared with the use of the suspensions described above, may have various compositions. Generally, they contain at least one water-soluble tenside that does not belong to the dispersing agents used according to the invention and present in the claimed aluminosilicate suspensions. The washing and cleansing agent compositions of the invention can be in general agreement with the overall formulations of the above-mentioned, prior patent applications. They contain an aluminosilicate, defined as above, as a calcium-binding compound, in addition to at least one other inorganic or organic compound that has a washing, bleaching or cleansing effect. Furthermore, such products may contain other conventional additives and adjuncts found mainly in smaller quantities. The above-mentioned, prior patent applications should be consulted for further details. The data also apply to these cases.

The content of aluminosilicates of such products may be from 5% to 95%, preferably from 15% to 60% by weight.

The compositions according to the invention may also contain sequestering or precipitating agents for calcium, preferably with contents of 2% to 15% by weight, depending on the chemical nature of the agents.

The substantially phosphorus-free washing agent compositions should have a content of inorganic phosphates and/or organic phosphorus compounds not exceeding a total content of 6% P, preferably of 3% P.

The additional components with a washing, bleaching or cleansing effect contained in the washing and cleansing agent compositions are surface-active compounds, surface-active or non-surface-active foam stabilizers or inhibitors, textile softeners, neutral or alkaline builders, chemically active bleaches as well as stabilizers and/or activators, that are different from component B. Other additives and adjuncts are usually present in smaller amounts, such as corrosion, inhibitors, antimicrobial agents, soil suspension agents, enzymes, optical brighteners, dyes and perfumes.

The composition of typical washing agent compositions to be used at temperatures between 50.degree. and 100.degree. C. is in the range of the following formation.

3% to 30%, preferably 5% to 30%, of anionic and/or amphoteric and/or nonionic surface-active compounds, including the nonionic surface-active compounds used according to the invention;

5% to 70% of aluminosilicates (calculated for AS);

2% to 45% of sequestering agents for calcium;

0 to 50% of wash alkalis not capable of forming complexes (alkaline builders);

0 to 50% of bleaching agent components as well as other adjuncts mainly found in smaller amounts in textile washing agent composition,

Following is an enumeration of compounds suitable for use in the products according to the invention.

The surface-active compounds or tensides contain in the molecular at least one hydrophobic organic moiety and one water-solubilizing, anionic, nonionic or amphoteric group. The hydrophobic moiety is mostly an aliphatic hydrocarbon radical with 8 to 26, preferably 10 to 22 and particularly 12 to 18 carbon atoms or an alkyl aromatic radical, such as alkylphenyl, with 6 to 18, preferably 8 to 16 aliphatic carbon atoms.

Among the anionic surface-active compounds are, for example, soaps of natural or synthetic, preferably saturated, fatty acids, optionally, also, soaps of resinic or naphthenic acids. Suitable synthetic anionic tensides are those of the type of the sulfonates, sulfates and synthetic carboxylates.

Suitable tensides of the sulfate type are the sulfuric acid monoesters of primary alcohols (e.g. from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and those of secondary alcohols. Also suitable are sulfated fatty acid alkanolamides, sulfated fatty acid monoglycerides or sulfated reaction products of 1 to 4 mols of ethylene oxide with primary or secondary fatty alcohols or alkylphenols.

Nonionic tensides that may be present in addition to the ethoxylation products used according to the invention are mainly the addition products of 9 to 4, preferably 9 to 20 moles of ethylene oxide onto 1 mol of a fatty alcohol.

Nonionic tensides of the type of the aminoxides and/or sulfoxides are also suitable.

The amphoteric surface-active compounds or tensides are of the type of the carboxybetaines or sulfobetaines.

Compounds capable of binding calcium as a complex, as well as those that do not possess this property, are suitable as builders. The alkali metal bicarbonates, carbonates, borates or silicates, or wash alkalis, the alkali metal sulfates as well as the alkali metal salts of organic sulfonic acids, carboxylic acids and sulfocarboxylic acids that do not possess any surface activity and contain 1 to 9 carbon atoms are exmples of the non-complexing builders. Specific examples are the water-soluble salts of benzene, toluene or xylenesulfonic acid as well as the water-soluble salts of sulfoacetic acid, sulfobenzoic acid or of sulfodicarboxylic acids. The complexing builders are the alkali metal tripolyphosphates, as well as a large number of the known organic complexing agents of the type of the polycarboxylic acids, also including polymeric carboxylic acids, of the aminocarboxylic acids, phosphonic acids, phosphonocarboxylic acids, hydroxycarboxylic acids, carboxylalkyl ethers, etc.

Suitable bleaching agents are compounds that release H.sub.2 O.sub.2 in aqueous solution, such as alkali metal perborates, or substances releasing active chlorine. Other additives, present mainly in small amounts, are foam stabilizers or inhibitors, textile softeners, stabilizers and/or activators for bleaching agents, corrosion inhibitors, antimicrobial compounds, soil suspension agents, enzymes, optical brighteners, dyes and perfumes.

The products prepared according to the invention can be use for the various cleaning tasks in numerous technical areas and in the household. Examples of such areas of application are the cleaning of tools, vessels of wood, plastics, metal, earthenware, glass, etc. in the industry or in commercial establishments, the cleaning of furniture, walls, floors, objects of earthenware, glass, metal, wood, plastics, the cleaning of polished or shellacked surfaces in the household, etc. An especially important area of application is the washing of textiles of all types in the industry, in commercial cleaning establishments and in the household.

The following specific embodiments all illustrative of the invention without being limitative in any respect.

First, the synthesis of aluminosilicates used in the suspenions according to the invention is described for which no invention is claimed. The description is purely illustrative; other well-known processes for the preparation of aluminosilicates can be used as described in the U.S. patent application Ser. Nos. 458,306, 458,333 and 458,326, all filed Apr. 5, 1974.

(.alpha.) The sodium aluminate solution was reacted with the calculated amount of sodium silicate solution under vigorous agitation in a 15 liter vessel (temperature of the solutions 20.degree. to 80.degree. C.). A sodium aluminosilicate that was X-ray amporphous was produced as primary precipitation product in an exothermic reaction. After ten minutes of vigorous agitation the suspension of the precipitation product was either

1. processed further directly, i.e. without crystallization, or

2. heated at 80.degree. C. for 3 to 6 hours for crystallization, or aging, after which products were obtained completely crystalline according to X-ray.

(.beta.) The mother liquor was filtered off from the suspensions obtained above. The remaining filter cake was washed with deionized water and then mixed with deionized water to form the suspension .alpha.1 (from .alpha.1) or .beta.2 (from .beta.2).

(.gamma.) A microcrystalline aluminosilicate was prepared by reacting the aluminate solution, diluted with deionized water, with the silicate solution, with vigorous agitation with a high-speed agitator (10,000 rpm; "Ultraturrax" made by Janke & Kunkel IKA-Werk, Stauffen/Breisgau, Federal Republic of Germany). After ten minutes of vigorous agitation, the suspension of the amorphous precipitation product was transferred to a crystallization vessel, where the formation of large crystals was prevented by agitating the suspension. After the removal of the liquor from the crystal mass by suction and washing with deionized water until the collected wash water had a pH of about 10, the filter residue was dried, then pulverized in a ball mill and separated into two fractions by a centrifugal sifter ("Microplex" air sifter by Alpine, Augsburg, ederal Republic of Germany). The finer fraction did not contain any particles above 10.mu.. From the finer fraction, a suspension in deionized water (.gamma.1) was prepared. A corresponding suspension was also prepared without the drying process and the separation into two fractions. The moist filter cake of variable moisture content was added to water. The suspension obtained is called .gamma.2. The separation of the silicates from the larger portion of the originally present water was carried out by centrifuging instead of filtration in some cases.

The aluminosilicates obtained had the approximate composition calculated for anhydrous products (AS):

The calcium binding power of the precipitation products was 150 to 175 mg CaO/gm active substance. The calcium binding power was determined as follows. One liter of an aqueous solution containing 0.594 gm CaCl.sub.2 (300 mg CaO/1=30.degree. dH) and adjusted to pH 10 with dilute NaOH was reacted with 1 gm of the aluminosilicate (on the anhydrous basis, AS). Then, the suspension was agitated vigorously for 15 minutes at a temperature of 22.degree. C.+2.degree. C. After filtering the aluminosilicate, the residual hardness x of the filtrate was determined. The calcium binding power was calculated from this in mg CaO/gm AS, using the formula

For short hand purposes this test procedure will be referred to as the Calcium Binding Power Test Method.

If the product obtained was dried for 1 hour at 400.degree. C., an aluminum silicate Ia was obtained of the composition:

which is likewise suitable for the purposes of the invention.

This product too can be dehydrated by drying (for 1 hour at 400.degree. C.) to the composition:

This dehydration product IIa is likewise suitable for the purposes of the invention.

The aluminosilicates I and II show in the X-ray diffraction diagram the following interference lines.

It is quite possible that not all these intereference lines will appear in the X-ray diffraction diagram, particularly if the aluminosilicates are not fully crystallized. For this reason, the d-values which are the most important for the characterization of these types are identified by a "(+)".

The abbreviations used in the following text mean:

TA+EO an addition product of x mols ethylene oxide (EO) per mol of a mainly saturated fatty alcohol mixture with varying carbon atoms, prepared by the reduction of a tallow fatty acid. The fatty alcohol mixture has the following approximate distribution:

C.sub.12 : 0-2%

C.sub.14 : 4-7%

C.sub.16 : 25-35%

C.sub.18 : 60-67%

C.sub.20 ; 0-2%

CA+6EO an ethoxylation product of 6 mols of ethylene oxide per mol of a mainly saturated fatty alcohol fraction consisting of equal parts of a C.sub.16 alcohol and a C.sub.18 alcohol and having 2% each of C.sub.14 and C.sub.20 alcohol, prepared by reduction of coconut oil fatty acid and subsequent distillation.

OXO+5EO the ethoxylation product of 5 mols of ethylene oxide per mol of an alcohol mixture obtained by oxosynthesis and having the following composition:

OA+10EO an addition product of 10 mols of ethylene oxide per mol of a technical grade oleyl alcohol.

EDTA the salt of ethylenediaminetetraacetic acid;

CMC the salt of carboxymethyl cellulose;

ABS the salt of an alkylbenzene sulfonic acid with about 11 to 13 carbon atoms in the alkyl chain, obtained by condensation of straight-chain olefins with benzene and sulfonation of the alkylbenzene produced in this manner.

Sodium silicate a sodium silicate (Na.sub.2 O:SiO.sub.2, theoretically 1:3.35

Perborate a technical grade product of the approximate composition

All salt-like compounds were employed in the form of the sodium salts.

The suspensions according to the invention are illustrated with the microcrystalline aluminosilicates prepared according to .gamma.2, since these are preferred for the preparation of washing and cleansing agent compositions. The suspensions according to the invention can also correspondingly be prepared from the suspensions of .beta.1, .beta.2 and .gamma.1 or from corresponding aluminosilicates isolated as solids.

155 to 195 gm of moist aluminosilicates (.gamma.2 process) were employed. The amount of moist aluminosilicate used was adjusted to the moisture content so that the same amount on an anhydrous basis (AS) was added. The moist aluminosilicates were added to a mixture of so many parts of water and dispersing agent that the mixtures obtained had a content of as active substance (AS) of aluminosilicate in the range of 30% to 38% by weight. The amount of the added nonionic dispersing agent was 1.3% to 3% by weight. The process was carried out at room temperature. The dispersing agents were the nonionic surfactive compounds given in Table I. The turbidity points are also given. Several suspensions and the components from which they were prepared are given in Table II.

The substances are characterized by their turbidity points determined according to DIN 53917. The substances being practically water-insoluble at room temperature, i.e. having turbidity points below 20.degree. C., the determination of their turbidity points was carried out in aqueous butoxyethoxyethanol solution according to a variation of DIN 53917.

All suspensions were very stable and culd be transferred without any problems by pumping from a storage tank with the aid of a commercial peristaltic pump (model IKA P 20, IKA-Werk, Stauffen/Breisgau, F.R. of Germany), even after periods of one day and more.

A suspension of 31% by weight (AS) of pure microcrystalline aluminosilicate (.gamma.2) was prepared in water. Dispersing agent 9 of Table 1 (CA+6EO) was used as dispersing agent according to the invention in an amount of 1.8% by weight, based on the total suspension. The stability of the suspension was further improved by the addition of traces (about 0.01% by weight) of tallow fatty amine (tallow fatty amine is the primary amine corresponding to the above-defined tallow fatty alcohol) and tallow fatty acid. Suspensions prepared in this manner were stable for months.

Powdery, trickleable washing agents of the compositions A and B given in Table 3 were prepared as follows: A stock suspension, previously prepared by the addition of a moist aluminosilicate (prepared according to .gamma.2) to a dispersion of the dispersing agent, heated to 70.degree. C., and which had a content of 36% by weight of aluminosilicate and 2% by weight of TA+5EO, based on the total weight of the suspension, was pumped from a storage tank into a vessel to which were added, one at a time and with agitation the remaining components and sufficient water to form a detergent slurry containing approx. 45% by weight of water.

This slurry was pumped through spray jets at the upper end of a spray-drying tower and converted into a fine powder by atomizing the slurry into a stream of hot air (about 260.degree. C.).

The suspensions according to the invention were prepared by the addition of aluminosilicates I, II, XIII, IX or XXm to a dispersion of TA+5EO in water, which was warmed to 60.degree. to 70.degree. C. with the formation of silicate suspensions with a content of 33% AS and 2% TA+5EO.

The suspensions were cooled to room temperature and observed at that temperature. Thus, the evaluation was carried out at room temperature, as in Example 1. The suspensions are very stable.

Sodium aluminosilicates in the amount of 594 to 780 gm and having various moisture contents, were added to the emulsions heated to 65.degree. to 70.degree. C., of 190 to 360 gm of water and 10 to 30 gm of dispersing agent, and homogenized. The amount was calculated in such a manner that the AS content of the aluminosilicate in the suspensions was about 31%. The homogeneous suspensions were circulated by a peristaltic pump (model IKA P 20) for one hour at room temperature and with continued agitation. Then, the circulating and agitation were stopped for one hour. Subsequently, agitation and circulating were continued. At this point, the suspension of the comparison test, prepared without dispersing agents, could not longer be agitated and circulated.

After further agitating and circulating for 4 to 6 hours, the suspensions of the invention were allowed to stand overnight and the settling characteristics at room temperature were determined visually, the next day and after several days of standing.

In the following Table 4, the column headings have the following meanings: sediment=100% means that the suspension was completely (100%) homogeneous and stable (last column).

The suspensions were again tested for their pumping characteristics after the determination of the settling characteristics. All recorded substances were found to be suitable dispersing agents, since the suspensions prepared with them could be agitated and circulated or pumped out without problems, after standing.

The individual batches can be found in Table 4 in tabular form. An aluminosilicate prepared according to .beta.2 and of the approximate composition Na.sub.2 O.Al.sub.2 O.sub.3.2SiO.sub.2 was used. Unless stated other wise, it was added while still moist from the preparation. The particle size was mainly between 5 and 15.mu..

Aluminosilicate suspensions were prepared according to Example 5, with a 31% AS content and a content of the following dispersing agents (% AS; % dispersing agent):

a. stearic acid monoglyceride (31/2)

b. stearic acid propylene glycol ester (31/2)

c. reaction product of the reaction of tallow fatty acid and N-hydroxyethyl ethylene diamine (31/2)

d. tallow fatty amine (long-chain amine derived from tallow fatty acid by reduction) (31/2)

e. adduct of 5 mols of ethylene oxide per mol of tallow fatty amine (31/2)

f. oleyl alcohol adducted with 5 mols of ethylene oxide per mol of the alcohol (31/2)

g. mixture of saturated C.sub.12 (70 to 75%)- and C.sub.14 (25 to 30%)-alcohols ethoxylated with 3 to 4 mols of ethylene oxide (31/3).

The suspensions are very stable. The stabilized suspensions are suitable for the preparation of aqueous slurries of washing agent composition components that are then spray-dried. The stabilized suspensions can also be converted directly into granulates by the addition of compounds which bind water in the form of water of crystallization (for example, pentasodium tripolyphosphate).

An aqueous suspension, prepared according to Example 1 and containing about 30% aluminosilicate (AS) and 2% TA+5EO, was sprayed into a stream of hot air and thereby dried, i.e., the adhering water was removed. The spray-dried product contained considerably less dust than a corresponding product prepared without the TA+5EO. The powdery aluminosilicate obtained is especially suitable as a water softener and as a builder in washing agent compositions.

All of the suspensions described in the above examples were clearly improved with respect to their stability and flow properties.

The preceeding specific embodiments are illustrative of the practice of the invention. It is to be understood however, that other expedients known to those skilled in the art or disclosed herein, may be employed without departing from the spirit of the invention or the scope of the appended claims.