IE41866B1 - Stable suspensions of water-insoluble silicates capable of binding calcium ions, and their use in the production of washing and cleaning agents - Google Patents

Description

The present invention relates to stable suspensions of water-insoluble silicates capable of binding calcium ions, and their use in the production of washing and cleaning compositions.

One of the most immediate problems in the washing and cleaning agent industry is the partial or complete replacement by other substances of the calcium complex binding phosphates which to date are still used. In earlier patent applications (e.g.Patent Specification No. 40918) there is described, a process for washing and / or bleaching textiles by treatment with an aqueous liquor which contains in suspension a water-insoluble synthetically produced, finely-divided crystalline aluminium or boron silicate cation exchanger containing bound water having a calcium binding capacity (as hereinafter defined) of at least 50mg CaO/g of water-free active substance of the general formula 1 (Cat2/h0)x. Me203. (Si02)y (1) wherein Cat is a cation of valency exchangeable for calcium, x is a number from 0.7 to 1.5, Me represents boron or aluminium and y is a number from 0.8 to 6, preferably from 1.3 to 4.

Sodium is preferably used as the cation; it may, however, be replaced by lithium, potassium, ammonium or magnesium and also by the cations of water-soluble organic bases, e.g. by those of primary, secondary or tertiary alkyl amines having a maximum of 2 carbon atoms per alkyl group or alkanolamines having a maximum of 3 carbon atoms per alkanol group.

The above-defined compounds, which are capable of binding calcium, are hereinafter termed aluminium silicates for the sake of simplicity. In particular this also applies to the sodium aluminium silicates which are preferably used. All details relating to the use of sodium aluminium silicates in accordance with the invention and to their production and properties apply analogously to all the above-defined water-insoluble silicates.

The aluminium silicates which are particularly suitable for use in washing and cleaning agents have a calcium binding capacity preferably of 50 to 200mg CaO/g of the anhydrous aluminium silicate. Where anhydrous aluminium silicate is referred to hereinafter, it relates to that state - 2 41866 of the aluminium silicates achieved after drying for one hour at 800°C.

During this drying process the adherent and bound water is removed almost completely.

In the production of washing or cleaning agents, in which, in addition to the usual constituents of such agents, are found the above-defined aluminium silicates, processing is advantageously commenced using aluminium silicates which are moist, e.g. from their production. The moist compounds are mixed with at least some of the other constituents of the agent to be produced and the mixture is converted into the finished washing or cleaning agent as the final product, e.g. into a pourable product.

Within the framework of the above-outlined production process for washing or cleaning agents the aluminium silicates may for example be supplied or used in the form of aqueous suspensions or as wet filter cakes. In this case, certain improvements in the properties of the suspension, e.g. the stability of the suspension and the pumpability of the aluminium silicates dispersed in the aqueous phase, are desirable.

It has now been discovered that certain compounds have an exceptional capacity for stabilising suspensions of the above calcium binding aluminium silicates such that, even when they have a high solid matter content these silicates are stable for a long period and, indeed, if desired, for a practically unlimited period, and can still be pumped without any difficulty, even after standing for a long period of time. Surprisingly, it has become apparent that there are certain compounds which are able to maintain the pumpability, even of moist aluminium silicates having a water content of 70% and less, practically independently of their standing time; this was hitherto impossible.

The present invention provides a pumpable, aqueous suspension, whose stability is improved and which is suitable as a storage suspension, of a water-insoluble silicate capable of binding calcium, comprising A) at least 20, preferably 20 to 53, especially 20 to 42% by weight of a water-insoluble, synthetically produced, finely-divided aluminium - 3 41866 or boron silicate cation exchanger containing bound water having a calcium binding capacity (as hereinafter defined) of at least 50mg CaO/g of water-free active substance (= AS) of the general formula: ω wherein the symbols used have the above-mentioned meanings, B) 0.5 to 6% by weight of at least one dispersing agent selected from the following compounds: (i) organic, macromolecular polymers having carboxyl and / or hydroxyl groups, water-soluble salts and lactones thereof; (ii) phosphonic acids having at least one other phosphonic acid group and / or carboxyl group and water-soluble salts thereof; (iii) phosphoric acid alkyl ester emulsifiers having 3 to 20 carbon atoms ih the alkyl chain; (iv) a non-ionic surfactant having a turbidity point in aqueous butyldiglycol solution - determined in accordance with DIN 53917 - of less than 90°C; (v) surface-active sulphonates; (vi) water-insoluble silicates capable of swelling in water and having a stratified structure; and C) Water.

Acids may be used as such or as water-soluble salts and are generally ionised in the suspension in accordance with their pK value and the pH value of the suspension. The pH value of the suspension generally ranges from 7 to 12, preferably from 8.5 to 11.5, and generally is lower than 11.

The above-mentioned compounds are the essential constituents of the suspensions according to the invention. However, they may also contain other constituents e.g. foam-inhibiting additives or so-called dissolving intermediaries, i.e. compounds which improve the solubility of the added dispersing agent in the aqueous phase. The usual foam-inhibiting substances may be used as foam inhibiters, e.g. foam-inhibiting soap, silicone anti-foam agents, foam-inhibiting triazine derivatives, all of which are known and are common - 4 41866 in the technical world. As a rule an addition of this nature is not required; however, in the case of foam dispersing agents - particularly when larger amounts of alkylbenzene-sulphonic acid are used - it may be desirable.

Nor, as a rule, is an addition of dissolving intermediaries required, but may be advisable if the suspension according to the invention contains a colloid which is hydrophilic but scarcely soluble in water, such as polyvinyl-alcohol. For example, a dissolving intermediary - a very suitable substance for this purpose being dimethylsulphoxide - is advantageously used when the concentration which is used of an only slightly water-soluble stabilizer of the group 1 is greater than approximately 1%. The proportion of dissolving intermediary contained in the total suspension may, for example, be of the same order of magnitude as the proportion of stabilizer. Further compounds which are suitable as dissolving intermediaries are generally known in the technical world; hydrotropic agents, such as benzene-sulphonic acid, toluenesulphonic acid, xylene-sulphonic acid or their water-soluble salts or octylsulphate are suitable.

All particulars given relating to the concentration of the aluminium silicates to the solid matter content or to the content of active substance (= AS) have reference to that state of the aluminium silicate achieved after drying for one hour at 800°C. During this drying process the adhering and the bound water is almost completely removed.

All the percentages given are percentages by weight.

The above-mentioned components A and B will now be described in greater detail.

In the case of the aluminium silicates which are to be used, the component A may comprise amorphous or crystalline products; of course, mixtures of amorphous and crystalline products and also partially crystalline products may also be used. The aluminium silicates may be naturally occuring or synthetically produced products, the synthetically produced products being preferred. The production may for example be effected by reacting water-soluble silicates with water-soluble aluminates in the presence of water. To this end aqueous solutions of the starting materials may be mixed with one another - 5 41866 or a component in the solid state may be mixed with the other component which is in the form of an aqueous solution. The desired aluminium silicates may also be obtained by mixing both components when they are in the solid state in the presence of water. The aluminium silicates can also be produced from A1(0H)3, Al^O^ or SiOg by reaction with alkali metal silicate or aluminate solutions. Production may also be effected in accordance with other known processes. The invention relates particularly to aluminium silicates having a three-dimensional space lattice structure in contrast to the silicates having stratified structures such as montmorillonite.

The preferred calcium binding capacity, which lies in the region of approximately 100 to 200mg of CaO/g of AS but generally of 100 to 180 mg of CaO/g of AS is chiefly found in compounds having the following composition: 0.7 - 1.1 Na20. AT203. 1.3 - 3.3 SiOg.

This formula includes two different types of crystalline structures ( or their non-crystalline preliminary products), which also differ in their formulae which are as follows: a) 0.7 - 1.1 Na20. Al203- 1.3 1 2.4 SiOg b) 0.7 - 1.1 Na20 AlgOg. 2.4 - 3.3 SiOg The differing crystalline structures can be seen on the X-Ray diffraction diagram.

The amorphous or crystalline aluminium silicate present in the aqueous suspension can be separated by filtration from the remaining aqueous solution and dried, e.g. at temperatures of 50 to 400°C. The product contains a greater or lesser amount of bound water depending on the drying conditions.

Such high drying temperatures are generally not to be recommended; 200°C is advantageously not exceeded when the aluminium silicate is provided for use in washing and cleaning agents. However, subsequent to their production the aluminium silicates require no drying at all for the preparation of a suspension in accordance with the invention. Instead, it is possible for an aluminium silicate which is still moist from production to be used - a - 6 41866 feature which is particularly advantageous. However, aluminium silicates which have been dried at medium temperatures, e.g. of 80 to 200°C until the adhering liquid water has been removed, may also be used in the preparation of suspensions in accordance with the invention.

The size of the individual aluminium silicate particles may vary and may for example range from O.lu to 0.1mm. This statement relates to the primary particle size, i.e. the size of the particles occuring during precipitation and possibly during subsequent crystallisation. The use of aluminium silicates at least 80% of which comprises particles which range from 10 to 0.01μ in size, in particular from 8 to 0.1μ is particularly advantageous. These aluminium silicates preferably no longer contain any primary or secondary particles which are larger than 30μ in diameter.

The term secondary particles denotes particles produced by agglomeration of the primary particles to form larger structures. The most important range is from 1 to 10y.

With respect to the agglomeration of the primary particles to form larger structures, the use of the aluminium silicates which are still moist from their production to produce the suspensions of the invention has proved particularly suitable since it has become apparent that when using these t products which are still moist, formation of secondary particles is almost completely precluded.

A more detailed description of the compounds which are to be used in accordance with the invention as component B is to be found hereinafter.

Suitable polymeric polycarboxylic acids (i) are in particular watersoluble but also water-insoluble polymerisation products. The polymeric polycarboxylic acids to be used may be either polymers of monomers which are capable of polymerisation and which contain carboxyl groups, or polymers of monomers which are capable of polymerisation and which are only subsequently converted into a polycarboxylic acid. In addition to carboxyl groups the polymeric polycarboxylic groups may also contain other functional groups such as,in particular, the hydroxyl group which may also be etherified or - 7 41866 esterified with lower molecular, especially aliphatic groups. Examples of polymeric polycarboxylic acids of this type are poly-(a-hydroxyacrylic acid), and also copolymers of acrylic acid or in particular maleic acid with vinylmethylether or vinylacetate: the vinylacetate unit in the polymer may be completely or partially hydrolysed, so that products result which may be considered to be copolymers of unsaturated carboxylic acids and the hypothetical vinylalcohol.

It has become apparent that the carboxylic groups in the polymeric polycarboxylic acids may not only, as stated, be partially replaced by hydroxyl groups, for example by suitable copolymerisation with suitable monomers, but that products wherein all the carboxyl groups are replaced by hydroxyl groups are also suitable in accordance with the invention.

Thus, the macromolecular polyhydroxy compounds are obtained; polyvinylalcohol may be regarded as the prototype of suitable macromolecular polydroxy compounds. Rolyvinylalcohol may be obtained, e.g. from polyvinylacetate, by hydrolysis; by no means does the hydrolysis have to be complete in order to render the polyhydroxyl compound utilisable in accordance with the invention; rather, those products are suitable which contain esterified hydroxyl groups, e.g. oxyacetyl group, in addition to hydroxyl groups.

The molecular weight of the polycarboxylic acids or polyhydroxyl compounds which are used may be varied within wide limits. Polymers in the molecular weight range of more than approximately 1500, preferably approximately 20,000, are particularly suitable. However, compounds having a far greater molecular weight are also extremely suitable, the preferred polycarboxylic acids still being water-soluble. As long as the water-solubility of the above-mentioned compounds is low, then, as has already been stated, a dissolving intermediary may be added. This basically applies to polyhydroxyl compounds containing no carboxyl groups. The presence of carboxyl groups promotes the water-solubility, and the solubility of the polymeric polycarboxylic acids is therefore dependent on their carboxyl group content and, in general, is excellent.

As long as the macromolecular compounds used in accordance with the Invention - 8 41866 have ionisable groups in an aqueous solution, they may also - and as a rule this is preferred - be used in the form of their water-soluble salts. On economic grounds it is generally the alkali metal salts, particularly sodium salts, which are involed.

Suitable compounds are to be found amongst the polymers of acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, methyl enema!onic acid, citraconic acid and the like, the copolymers of the above-mentioned carboxylic acids with one another or with ethylenically unsaturated compounds, such as ethylene, propylene, isobutylene, vinylalcohol, vinylmethylether, furane , acrolein, vinylacetate, acrylamide, acrylonitrile, methacrylic acid and crotonic acid, e.g. the 1:1 copolymers of maleic acid anhydride and ethylene or propylene or furano .

The above-mentioned polyacrylic acid and poly-(a-hydroxyacrylic acid) are examples of particularly suitable compounds of group 1. The lattermentioned may be used not only as free acid or water-soluble salt, but also in the form of its inner lactone; this is hydrolysed in the suspension.

Examples of the hitherto described products are substantially straight-chain polymers, i.e. those unbranched in their polymer spine. Besides the preferred, above described synthetic polymers, natural products may possibly also be used, e.g. alginates, carboxymethylcellulose, maize or potato starch or their derivatives. However, the water insoluble polymeric three-dimensionally crosslinked polyacrylic acids are also concerned.

The molecular weights may vary within wide limits. In the case of po1y-(n-hydroxyacrylic acid) the molecular weight of the commercial products is generally more than 20,000, whilst in the case of the copolymers of vinylmethylether with maleic acid anhydride (monomer ratio 1:1) the molecular weight of the commercial products is generally 100,000 to 2,500,000.

A further suitable group (ii) of stabilisers are phosphonic acids carrying at least one second phosphonic acid group and / or at least one carboxyl group. Alkanepolyphosphonic acids, amino- and hydroxyalkaneopolyphosphonic acids and phosphonocarboxylic acids etc. are suitable acids, examples thereof being propane1,2,3 - triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid,polyvinylphosphonic - 9 41866 acid, 1 - aminoethane - 1,1 - diphosphonic acid, 1 - amino - 1 - phenylmethane-1,1 - diphonphonic acid, aminotrimethylene - triphosphonic acid, methylamino - or ethylene aminodimethylenediphosphonic acid, ethylenediaminotetramethylenetetraphosphonic acid, 1 - hydroxyethane - 1,1 5 diphosphonic acid, 2-phosphone - butane - 1,2,4 - tricarboxylic acid, 2 phosphonobutane - 2,3,4 - tricarboxylic acid and copolymers of vinylphosphonic acid and acrylic acid.

Emulsifiers of the type of the phosphoric acid partial esters are also suitable.(iii) These are generally esters having 1 to 2 mols, particularly with approximately 1.5 mols of a preferably saturated alcohol having 3 to 20 carbon atoms in the alkyl chain per mol of phosphoric acid. Esters of alcohols havihg 4 to approximately 10 carbon atoms, particularly, for example, esters of approximately 1.5 mol of butyl alcohol or isooctyl alcohol, are particularly suitable products.

The nonionic surfactants (iv) to be used in accordance with the invention are practically water-insoluble compounds. Their turbidity point - determined in accordance with DIN 53917 in aqueous butyldiglycol solution - is less than 90°C, preferably 85°C or less. Accordingly, the turbidity point in water of the suitable compounds - to be determined in 1% solutions - is less -° than approximately 55°C, preferably less than 35°C. In the case of particularly suitable products the turbidity point in water is less than room temperature.

The most suitable products are to be characterised in that they can be dispersed in water (1 part of surfacant to 19 parts by weight of water) such that, when shaken gently or possibly more forcefully, and, if necessary, !5 subjected to an increase in temperature extending beyond the melting point of the surfactant, they form a milky dispersion, which possibly sets in the form of a gel, when cooled to room temperature. The turbidity points determined in accordance with DIN 53917 are generally at least 40°C, but are preferably at least 55°C. 0 The details concerning the dispersibility in water or concerning the turbidity points relate to the individual surfactant-like stahilisers in their pure technical form, e.g. as a statistical mixture of ethoxylation - 10 41866 products, as in the case with the ethoxylation of fatty alcohol, fatty acid, fatty acid amide or fatty amine fraction.

Examples of dispersing agents which are suitable according to the invention are, in particular, the non-ionic surfactants which comprise as the hydrophobic residue a long-chained alkyl or alkenyl residue mainly containing 10 - 20, preferably 12 - 18 C atoms. The alkyl or alkenyl residue is mostly straight-chained, but the compounds having branch-chained hydrophobic residues are also suitable products. Unsaturated hydrophobic residues are generally singly unsaturated like the oleic acid residue which occurs particularly frequently.

The hydrophilic group is mostly formed by polyalcohol residues such as ethylene glycol, propylene glycol, polyethylene glycol or glycerine residues which are connected to the hydrophobic residue by way of ester, amide, ether or amino groups. Ethylene oxide adducts are to be particularly emphasized.

The preferred ethylene oxide adducts with the same turbidity point are usually those with the longer hydrophobic residue - C·^ - 0^θ.

One important group of suitable compounds is found in the carboxylic acid esters and carboxylic acid amides. Particularly suitable dispersing agents according to the invention are the mono and di ethanol amides of carboxylic acids having 10 - 20, preferably 12 - 18 and especially 12 - 14 carbon atoms. The compounds are preferably derived from saturated and straight-chained carboxylic acids. However, the products may also be derived from unsaturated, especially singly unsaturated carboxylic acids. Examples of amine components from which the amide which is suitable according to the invention is derived are in particular monoethanolamine and diethanolamine. However, one particularly suitable product is also the amide which is derived from a carboxylic acid, as defined above, and the N-(hydroxy-ethyl) ethylene diamine. The suitable amides may be considered, therefore, to be reaction products of carboxylic acid amides with ethylene oxide. The number of ethylene oxide units in the reaction product is preferably 1 to 6, especially 1 to 4. - 11 41866 The ester dispersing agents are derived from the same carboxylic acids as the amide dispersing agents, as in the case of the amides, the esters are derived from fatty acids or fatty acid mixtures, especially having the above-mentioned chain-length ranges, which may be of natural or synthetic origin. Suitable ester suspension stabilisers are the products which may be construed as addition products of carboxylic acids with ethylene oxide, such as, for example, the addition products of carboxylic acids with 1,2, or 3 mols of ethylene oxide per mol of carboxylic acid. Products with, for example, 4 to 10 ethylene oxide units also come into question, however: In the surface-active esters, however, poly-alcohols with more than 2 hydroxyl groups may also be the alcohol components, such as, for example, glycerin.

Examples of suspension stabilisers of the amide or ester type which are particularly suitable are the compounds: lauric acid monoethanol amide, coconut fatty acid monoethanol amide, myristic acid monoethanol amide, palmitic acid monoethanol amide, stearic acid monoethanol amide, oleic acid monoethanol amide, tallow fatty acid monoethanol amide and the diethanol amides derived from the same fatty acids and amides derived from N-(hydroxyethyl)-ethylene diamine. 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 may be mentioned as ester-like stabilisers.

Particularly suitable diethanol amides are lauric-myristic acid diethanol amide - the diethanol amide of a fatty acid mixture of lauric acid and myristic acid - and oleic acid diethanol amide.

A further very particularly suitable group of stabilisers is found in the ethoxylation products of alcohols, which are preferably saturated and have 10 to 20 carbon atoms, with 1 to 8 mols of ethylene oxide per mol of alcohol. These ethoxylation products are preferably products with 2 to 7, especially 2 to 6 mols of ethylene oxide per mol of alcohol; it is therefore particularly advantageous to use derivatives of straight-chained alcohols - 12 41866 within the framework of the invention. However, derivatives of branchchainedalcohols, especially alcohols produced by oxosynthesis, can also be used. The derivatives of preferably saturated and preferably straightchained alcohols having 16 to 18C atoms are preferred in particular. Ethoxylation products of alcohols having 12 and especially 14C atoms can also be used, however, products with 1 - 5 mols of EO, especially with 2-4 mols of EO per mol of alcohol, being then particularly suitable.

The ethoxylation products used according to the invention are generally not chemically uniform compounds, but are instead usually mixtures in which adducts with different degrees of ethoxylation co-exist in statistical distribution - including the degree of ethoxylation 0 which exists in the non-ethoxylated starting material which is mostly still present in small quantity. The ethoxylation products used according to the invention are practically water-insoluble compounds, their turbidity point - determined in accordance with DIN 53917 in aqueous butyldiglycol solution - usually lies in the region of 55 to 85°C. Typical products preferably used are saturated fatty alcohol ethoxylation products which are derived from tallow fatty acids and have turbidity points of 58, 71, 77 or 83°C with a degree of ethoxylation of 2,4,5 or 7 mols respectively or ethylene oxide per mol of fat alcohol.

The alcohol component - e.g. cig_-]g“ is mostly a technical mixture in which there may also be alcohols with more and / or fewer C atoms mainly in subordinate quantities of, for example up to 15%.

Instead of the ethoxylation products of alcohols which have been mentioned, the corresponding ethoxylation products of fatty amines can also be used, i.e. especially ethoxylation products of preferably saturated primary amines, having 16 - 18 carbon atoms, with 1 to 8 mols of ethylene oxide per mol of amine. The non-ethoxylated amines have also proved suitable here as the surfactants coming within the definition of the invention also. However, products with 2 to 5 mols of ethylene oxide per mol of amine are highly suitable. - 13 41866 Suitable alkylphenol products with a turbidity point below ambient temperature or below 85°C in accordance with DIN 53917 are the waterinsoluble nonylphenol ethylene oxide adducts with 5 to 8 mols of ethylene oxide per mol of phenol. Adducts with 6 to 7 mols of ethylene oxide are preferred.

Some examples to be considered as surfactants of the sulphonate type (v) are alkylbenzene sulphonates (Cg_15- alkyl), olefin sulphonates, i.e. mixtures of alkene and hydroxyalkane sulphonates and di sulphonates, such as are obtained for example from monoolefins with a terminal or internal double bond by sulphonation with gaseous sulphur trioxide and subsequent alkaline or acidic hydrolysis of the sulphonation products. In particular, the esters of α-sulpho fatty acids, e.g, the α-sulphonic acids from methyl or ethyl esters of hydrogenated coconut, palm-kernel or tallow fatty acids are also suitable.

Further dispersing agents (vi) which are suitable according to the invention are the water-insoluble silicates capable of swelling in water selected from the class of clays which, in contrast to the aluminium silicates to be suspended according to the invention, have a stratified structure instead of a three-dimensional space lattice. The silicates of a swellable stratified structure are called smectites. These are substances which correspond to the general formulae.

Al2(Si205)2(0H)2 and Mg3(Si205)(0H)2 Some examples thereof are bentonite, montmorillonite, volchonskoite, nontronite, hecorite, saponite, sauconite and vermiculite. Since they are capable of cation-exchange, these swell able clays still comprise, depending upon their origin, cations such as, for example, sodium, potassium or calcium. Naturally occuring and synthetically produced products are likewise suitable, the synthetic products frequently having the advantage of a higher degree of purity. The particle size of these stratified silicates is mostly below approximately 50y and types with a low calcium content which are capable of binding calcium are particularly suitable.

- T4 41866 Apart from the individual dispersing agents mentioned, mixtures can be used and in various cases synergistic co-operation is observed. For example, the addition of tallow amine, carboxymethyl cellulose, crosslinked polyacrylate or alginic acid to surfactant-stabilised suspensions e.g. the combination of stabilisers in group (i) with those in group (v) and in particular group (iv) has proved to be advantageous. The longchained fatty acids represent a further class of compounds which improves further the properties of suspensions stabilised according to the invention. These fatty acids are natural or synthetic, preferably saturated fatty acids with mostly 10-20 C atoms in the molecule, for example tallow fatty acid.

Within the framework of the invention, particularly preferred aqueous suspensions substantially comprise at least 20% of component A, the upper limit of the A content being governed by the flowability limit and being mostly at about 42% by weight. Concentrations between 25 and 40% by weight, preferably of 28 to 38% by weight, are particularly preferred. In practice, the range of 30 - 38% by weight, is the most important.

The quantity of component 8 to be used depends substantially upon the degree of stabilisation desired for the suspensions. In general, the concentration of component B in the suspensions of the invention is 0.5 to 6, and very often 0.8 to 6% by weight relative to the overall weight of the aqueous suspension. It is preferably in the region of I to 4% by wt. and in most cases is advantageously 1.3 to 3% by weight. Since the viscosity of the suspensions is affected by the content of component B, the desired viscosity can be taken into consideration, if need be, when selecting the concentration of component B.

With more finely-particled aluminium silicates, smaller quantities of component B are to be used for stabilisation than with coarse-particled products. Thus, for example, aluminium silicate suspensions whose particles have a particle size of between 1 and 8μ up to 90% and more, do in fact stabilise by a dispersing agent content of 0.5 to 1% by weight as satisfactorily as products with a mean particle size of 10-12u by a dispersing agent - 15 41866 content of 1 - 2%. These figures are merely approximate values; the suitable quantity of component I) to use can be determined individually to meet concrete needs. At 25°C, the viscosity of the suspension is generally 500 to 30,000, preferably above 1000, but below 15,000 cps. Particularly suitable are the suspensions having viscosities in the region of between 1,000 and 9,000.

Within the framework of the invention, particularly preferred aqueous suspensions comprise at least 20% of component A, at least 0.5%, preferably at least approximately 0.8% of component B and water.

Besides the components mentioned, there may be present inorganic salts or hydroxides possibly from the precipitation or other production processes of the aluminium silicates; thus, for example, small quantities of excess sodium hydroxide or sodium carbonate or sodium bicarbonate, produced therefrom by the adsorption of carbon dioxide, may be present, or,· for example, the sulphate ion may be present if aluminium sulphate has been used as the aluminium-containing starting material when producing aluminium silicate.

Apart from the components A and B which have been mentioned and apart from substances which possibly still remain from starting materials for the production of these components, the aqueous suspensions can also contain further components in comparatively small quantities. If provision is made for the suspensions to be further treated to form washing and cleaning agents, then the additionally present substances are of course advantageously substances which are suitable as components of washing and cleaning agents. A criterion for the stability of the suspensions is provided by a simple test whereby an aluminium silicate suspension of the desired concentration - e.g. 31% - is produced which contains a dispersing agent according to the invention and possibly further substances, for example, washing agent components such as pentasodium triphosphate, in various quantities. The effect of the substance added can then be observed visually in the settling behaviour of the suspension. After standing for - 16 41866 hours, a preferred suspension should generally have settled at most to such an extent that the supernatant solution, which is clear or free of silicate particles, does not account for more than 20% , preferably not more than 10, especially no more than 6% of the total depth. The quantity of additional substances should generally be such that the suspension can still be pumped round again satisfactorily after standing in the storage container and pipelines or hosepipes for 12 hours, preferably for 24 hours and especially for 48 hours. The settling behaviour of the suspensions, which may still contain further components, is tested at ambient temperature - with a total depth for the suspension of 10 cm. With particularly preferred suspensions, the depth of the supernatant clear solution is still within the range mentioned even after 4 and especially after 8 days; they are also pumpable and pumpprimable to a satisfactory degree after 4 or 8 days respectively.

Using the suspensions of the invention as stock suspensions for a relatively long storage time in a storage tank, from which they can be drawn off by means of pumps as required, it may be advantageous to keep the portion of other components, for example, of washing and cleaning agents small or to dispense with these components altogether.

The suspensions may be produced by simply mixing their components, the aluminium silicates being able to be used, e.g. as such or - possibly originating from preparation - when wet or when present in aqueous suspension. It is particularly advantageous to introduce the aluminium silicates which are still wet from their preparation, e.g. as filter cakes, into a dispersion of component B in water. This dispersion of component B is preferably slightly warm, for example at 50 to 70°C.

However, aluminium silicates may of course also be used which are dry, i.e. they are devoid of any adhering water, and possibly still contain bound water.

One particularly suitable method of producing the suspensions of the invention is as follows: the aluminium silicate is precipitated by - 17 41866 mixing sodium aluminate and sodium silicate solution. These solutions have more alkalinity, i.e. more sodium hydroxide than is necessary to form the finished aluminium silicate, so that there is excess sodium hydroxide in the aluminium silicate suspension which occurs as the direct precipitation product. This suspension is made more concentrated by filtering off part of the mother liquor. Subsequently the aluminium silicate is washed with water to such an extent that the sodium hydroxide content in the solution is below approximately 5%, preferably below 3 or even below 2%. The remaining sodium hydroxide is neutralised by the addition of an acid, especially aqueous sulphuric acid, to such an extent that the suspension obtained assumes a pH value in the region between 7 and 12, especially between 8.5 and 11.5. The quantity of dispersing agent required to obtain the desired degree of stabilisation is added to this suspension, the addition being able to be effected before, during and after partial neutralisation.

It is thus particularly advantageous to effect partial neutralisation at least partially with a dispersing agent having an acid nature, i.e. e.g. with a macromolecular polycarboxulic acid or alkylbenzene sulphonic acid - as defined above. These acid-1ike dispersing agents can therefore be used as acid for the neutralisation and can thus replace non-stabilising acids, such as, for example, the sulphuric acid mentioned, wholly or partially.

The suspensions of the invention are noted for their high stability and other advantages, Their stabilising effect is particularly valuable especially with aluminium silicates having particle sizes of 5-30μ. They are pumpable so that they render it possible to handle wet aluminium silicates in a simple manner. Even after relatively long interruptions in the pumping process, the suspensions can be pumped round again satisfactorily. Because of their high stability, the suspensions can also be transported in conventional tankers and tank trucks without there being any danger of useless or troublesome residues forming. The suspensions are thus suitable - 18 41866 principally as a delivery form for delivery to washing composition manufacturers, for example.

The suspensions can be preserved at ambient temperature or even at higher temperatures, and can be transported by pipelines, pumps or otherwise. The suspensions are mainly handled at temperatures between ambient temperature - mostly preferred - and approximately 60°C.

The suspensions of the invention are particularly suitable for further treatment to form products which appear dry and are pourable or sprayable, i.e. they are suitable for producing, for example, powdery watersoftening agents, e.g. by way of spray-drying. Thus, the suspensions are of considerable importance in the production of powdery aluminium silicates. No troublesome residues appear when conveying the aqueous suspension to the drying apparatus. Moreover, it has been proved that the suspensions of the invention render treatment possible for producing extremely dustfree products.

Because of their particular stability, the suspensions of the invention can in fact be used as such, i.e. without further treatment with or without further washing, bleaching and / or cleaning additives, for example as water-softening agents, washing or cleaning agents and especially as liquid scouring agents with high suspension stability.

One particularly important use of the suspension is the further treatment to form washing and cleaning agents which appear dry, are pourable or sprayable and contain further compounds as well as the suspension components.

The suspensions of the invention are especially suitable for producing the washing and cleaning compositions described in patent specification Nos. 40918, 40642 and ^/77^ and all the information given for their production, for their contents and for the quantities of the contents apply to the present invention. - 19 41866 The invention therefore also provides a method of producing a solid, pourable washing and cleaning composition containing a water-insoluble aluminium silicate as defined above comprising mixing an aqueous suspension of the present invention with at least one washing or cleaning further constituent of the composition to be produced and subsequently converting the mixture into a solid pourable composition. The suspensions of the invention can be treated to form solid, pourable washing and cleaning compositions, according to known methods.

In the production of powdery sprayable washing and cleaning agents according to the method of the invention the operation is carried out so that a suspension of the invention - for example from a storage container is mixed with at least one washing, bleaching or cleaning component of the composition to be produced and the mixture is subsequently converted into the powdery product in accordance with a known method. A complexformer is advantageously added, i.e. a compound which can bind the alkalineearth metal ions responsible for water hardness, especially magnesium and calcium ions, in a complex manner.

In the production of washing and cleaning agents according to the process of the invention, the suspension of the invention is generally combined preferably with at least one, water-soluble surfactant which is not one of the possible constituents of component B.

There are different ways of producing washing and cleaning compositions.

The suspensions of the invention may, for example, be combined with substances capable of binding water of crystallisation, by advantageously spraying the suspension onto the compounds which have been previously placed in a mixer and are capable of binding water of crystallisation, so that ah eventually solid product which appears dry is obtained with constant intermixing. However, the suspensions of the invention are preferably mixed as slurry and subjected to spray drying with at least one further washing, bleaching or cleaning compound. Further surprising advantages of the claimed aluminium silicate suspensions are thus apparent. It has in fact been proved that products which have very little dust can be obtained by using - 20 41866 suspensions of the invention in spray drying. The products obtained by spray drying have a high calcium binding power and can be wetted satisfactorily.

Washing compositions of the invention, i.e. washing compositions which have been produced using the above-described suspensions, can be mixed in the most varied ways. They generally contain at least one watersoluble surfactant which is not one of the dispersing agents which are used according to the invention and which are present in the aluminium silicate suspensions; the washing and cleaning compositions of the invention can be in general agreement with the overall formulations of the abovementioned patent.applications. Besides at least one further compound which has a washing, bleaching or cleaning effect and is inorganic or organic, they contain as the calcium binding compound an aluminium silicate as defined above. Moreover, other conventional adjuvants and additives which are mostly present in relatively small quantity may be present in such compositions. For further details, reference is made to the patent applications mentioned.

The aluminium silicate content of such compositions may be in the region of 5-95 preferably 15-60%.

Furthermore, the compositions of the invention may contain complex formers or precipitants for calcium whose effect, depending upon the chemical nature of the composition, can be seen preferably in contents of 2-15%.

In low-phosphorus compositions, the portion of inorganic phosphates and / or organic phosphorus compounds should not be greater than that which corresponds to a total P content in the composition of 6%, preferably 3%.

Examples of further washing, bleaching or cleaning compounds contained in the washing or cleaning compositions are the surfactants not provided for according to the invention for component B, surfactant-like or non-surfactant-like foam stabilisers or inhibitors, textile softeners, neutral or alkaline-reacting builder substances, chemically-acting bleaching agents - 21 41866 and stabilisers and / or activators therefor. Other adjuvants and additives mostly present in relatively small quantity are, for example, corrosion inhibitors, anti-microbial substances, dirt-carriers, enzymes, brightners, colouring and odorants.

The composition of typical textile washing agents to be used at temperatures within the range of 50-100°C is within the range of the following recipe: - 30% anionic and / or amphoteric and / or non-ionic surfactants, including the non-ionic surfactants used as dispersing agents in accordance with the invention, preferably 5 - 30%, - 70% aluminium silicates (relative to AS), including stratified structure silicates used according to the invention, - 45% complex formers for calcium, including the complex forming compounds of B(i) and (ii). - 50% washing alkalis not capable of complex formation (= alkaline builder substances), - 50% bleaching agqnts and other additives mostly present in relatively small quantity in textile washing agents.

There now follows a list of substances suitable for use in the composition of the invention.

The surfactants contain in the molecule at least one hydrophobic organic residue and one anionic, hybrid ionic or non-ionic water-soluble-rendering group.

The hydrophobic residue is mostly an aliphatic hydrocarbon residue having 8 - 26, preferably 10 - 22 and especially 12 - 18 C atoms, or an alkylaromatic residue having 6 - 18, preferably 8-16 aliphatic C atoms.

Soaps made from natural or synthetic, preferably saturated fatty acids, possibly made also from resin or naphthene acids, may be used, for example, as anionic surfactants. Suitable synthetic anionic surfactants arc those of the sulphonate (other than those of B (v)), sulphate and synthetic carboxylate type.

Suitable surfactants of the sulphate type are the sulphuric acid - 22 41866 monoesters of primary alcohols (e.g. from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and those of secondary alcohols. Moreover, sulphated fatty acid alkanol amides, fatty acid monoglycerides or reaction products of 1 - 4 mols of ethylene oxide with primary or secondary fatty alcohols or alkyl phenols are suitable.

Examples of non-ionic surfactants (other than those of B (iv) which may be present besides the ethoxylation products used according to the invention are in particular the addition products of 9 - 40, preferably 9-20 mols of ethylene oxide of 1 mol of fatty alcohol.

Non-ionic surfactants of the amine oxide or sulphoxide type can also be used.

Belonging to the amphoteric surfactants are substances of the carboxybetaine or sulphobetaine type.

Suitable builder substances are both compounds, which are able to bind calcium in a complex manner and those which do not possess this ability. Belonging to the latter, for example, are the bi carbonates, carbonates, borates or silicates of alkali metal, the alkali metal sulphates and alkali metal salts of organic non-surface-active sulphonic acids, carboxylic acids and sulphocarboxylic acids containing 1 - 8 C atoms. Some examples are the water-soluble salts of benzene, toluene or xylene sulphonic acid and the water-soluble salts of sulphoacetic acid, sulphobenzoic acid or sulphodicarboxylic acids. Suitable complex-forming builder substances other than those of 8 (i) and (ii) are sodium triphosphate and a large number of known organic complex formers of the polycarboxylic type, including here also polymer carboxylic acids, of the aminocarboxylic acid, phosphonic acid, phosphonocarboxylic acid, hydroxycarboxylic acid and carboxyl alkyl ether type.

Suitable bleaching agents are compounds which release H202 in aqueous solution, such as, for example, sodium perborate, or substances supplying active chlorine. Other additives which are mostly present in relatively small quantity are, for example, foam stabilisers or inhibitors, textile softeners, stabilisers and / or activators for the bleaching agents, - 23 41866 corrosion inhibitors, anti-microbial substances, dirt-carriers, enzymes, brighteners, colouring and odorants.

The products produced according to the invention can be used in numerous technical and domestic fields for the most varied cleaning jobs. Examples of such fields of application are the cleaning of appliances, vessels made of wood, plastics material, metal, ceramics, glass etc. in industry or in commercial concerns, the cleaning of furniture walls, floors,articles made of ceramics, glass, metal, wood, plastics material, the cleaning of polished or varnished surfaces in the home. One particularly important field of application is the washing of all types of textiles in industry, in commerical laundries and in the home.

PRODUCTION OF ALUMINIUM SILICATES The synthesis of aluminium silicates as usedin suspensions according to the invention is firstly described. Moreover, the description is illustrative; other known methods of producing the aluminium silicates may also be used. n) The aluminium silicate solution was mixed and vigorously stirred in a 15 1 vessel with the calculated quantity of sodium silicate solution (temperature of the solutions: 20 - 8Q°C), An X-ray amorphous sodium aluminium silicate was thus formed as the primary precipitation product with an exothermic reaction· After vigorous stirring for 10 mins., the suspension of the precipitation product was either 1. treated further directly, i.e. without crystallisation, or 2. left for 3-5 hours at 80°C for crystallisation purposes, purely crystalline products having been obtained according to X-ray structure analysis. β) The mother liquor was filtered off from the suspension. The remaining filter cake was rinsed with deionised water and then mixed with deionised' water, forming the suspension pi (from al) or s2 (from a2). γ) A microcrystalline aluminium silicate was produced by mixing the aluminate solution, diluted with deionised water, with the silicate solution, - 24 41866 stirring being effected with a high-speed intensive stirrer (10,000 rev/min; Ultraturrax (Registered Trade Mark) product made by Janke & Kunkel IKA Werk, Stauffen / Briesgau, Federal Republic of Germany). After vigorous stirring for 10 mins the suspension of the amorphous precipitation product was transferred to a crystallisation tank where the formation of large crystals was prevented by stirring the suspension: After drawing off the liquor from the crystal slurry by suction and subsequently washing with deionised water until the discharging washing water had a pH value of approx. 10, the filter residue was dried, then ground in a ball mill and divided into two parts in a centrifugal separator (Microplex air separator made by Alpine. Augsburg, Federal Republic of Germany), the finer part containing no portions above 10μ. A suspension was produced in deionised water from the finer part (γΐ). An appropriate suspension was produced without the drying process and the division into two parts; the filter residue, still moist, having a variable water content, was therefore, introduced into water; the suspension obtained is referred to as γ2. 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 aluminium silicates obtained had the approximate composition calculated on the basis of anhydrous products (=AS): Na20.1Al203.2 Si02 The calcium binding power of the precipitation products was 150-175 mg CaO/g of active substance. The expression “calcium binding capacity is to be understood as being the value obtained by the following test: 1 litre of an aqueous solution, containing 0.594 g CaCl2 (=300mg CaO/1) and adjusted to a pH value of 10 with dilute NaOH, is mixed with lg of aluminium silicate (relative to AS). Then the suspension is vigorously stirred for 15 minutes at a temperature of 22°C (±2°C). After the aluminium silicate has been filtered off, the residual hardness x in mg CaO/litre of the filtrate is determined. The calcium binding power is then determined from the formula;:- 25 41866 Calcium binding capacity = 300-x Production conditions for aluminium silicate 1: Precipitation: 2.985 kg. aluminate solution of the composition 17.7% Na.,0, 15.8% Al203, 66.6% H20 0.15 kg. caustic soda 9.420 kg. water 2.445 kg. of a 25.8% sodium silicate solution of the composition 1 Na20.6.0 Si02, freshly produced from commercial water glass and silicic acid which is easily alkali-soluble Crystallisation: 24 hours at 80°C Drying: 24 hours at 100°C Composition: 0.9 Na20.1 Al203.2.04 SiOg. 4.3 HjO (= 21.6% H20) Degree of crystallisation: fully crystalline Calcium binding power: 150mg CaO/As If the product thus obtained is subsequently dried for 1 hour at 400°C, then an aluminium silicate la of the composition: 0.9 Na20.1 Al203. 2.04 SiOg. 2.0 H20 (= 11.4% H20) is obtained which is likewise suitable for the purposes of the invention. Production conditions for aluminium silicate 11: Precipitation: 2.115 kg. aluminate solution of the composition: 17.7% Na20, 15.8% AlgOg, 66.5% H20 0.585 kg. caustic soda 9.615 kg. water - 26 41866 2.685 kg. of a 25.8% sodium silicate solution of the composition 1 Na20.6 SiOg (produced in the manner given in 1) Crystallisation: 24 hours at 80°C Drying: 24 hours at 100°C and 20 torr Composition: 0.8 Na20.1 Al203.2.655 SiOg.5.2 HgO Degree of crystallisation: fully crystalline Calcium binding power: 120mg CaO/g AS This product can also be dehydrated by subsequent drying (1 hour at 400°C) as far as the composition: 0.8 Na20.1 Al203.2.65 SiOg.0.2 HgO; this dehydration product Ila may likewise be used for the purpose of the invention.

The aluminium silicates 1 and 11 exhibit the following interference lines in the X-ray diffraction diagram: d values, plotted with Cu-K, radiation in A 1 11 14.4 12.4 _ 8.8 8.6 _ 7.0 _ 4.4 (+) 4.1(+) 3.68(+) 3.38(+) 3.26(+) 2.96(+) 3.8(+) 2,88(+) - 27 41866 η 2.79 (+) 2.73(+) 2.65(+) 2.60(+) It is quite possible that not all these interference lines appear in the X-ray diffraction diagram, especially when the aluminium silicates are not fully crystallised. The d values which are not the most important for characterising these types have therefore been marked with a (+).

Production conditions for aluminium silicate Vll1: Precipitation: 2.115 kg. aluminate solution of the composition: 1.7% NagO, 15.8% Al203,66.5% HgO 0.585 kg. caustic soda 9.615 kg. water 2.685 kg. of a 25.8% sodium silicate solution of the composition: Na20.6 Si02 Crystallisation: omitted Drying: 24 hours at 100°C Composition: 0.8 Na20. 1 Al203, 2.65 Si02. 4Η£0 Degree of crystallisation: X-ray amorphous Calcium binding power: 60mg CaO/g AS Production conditions for aluminium Silicate IX: Precipitation: 3.41 kg. aluminate solution of the composition: 21.4% Ha20, 15.4% AlgOg. 63.2% HgO 10.46 kg. water 1.13 kg. of a 34.9% sodium silicate solution of the composition: Na20. 3.46 SiOg Crystallisation: Omitted Drying: 24 hours at 100°C Composition: - 28 41866 NagO.l Α1203. 1 SiOg. 1.4 HgO Degree of crystallisation: X-ray amorphous Calcium binding power: 120mg CaO/g AS Production conditions for aluminium silicate XXm: Precipitation: 0.76kg aluminate solution of the composition: 36.0% NagO, 59.0% A1203, 5.0% HgO 0.94 kg. caustic soda 9.49 kg. water 3.94 kg. of a commerical sodium silicate solution of the composition: 8.0% Na20, 26.9% SiOg, 65.1% HgO Crystallisation: 12 hours at 90°C Drying: 12 hours at 100°C Composition: 0.9Na20. 1 AlgOg. 3.1 SiOg. 5 HgO Degree of crystallisation: fully crystalline Calcium binding power: llOmg CaO/g AS The present invention will now be further described by means of the following Examples.

The abbreviations used hereinafter have the following meanings: TA+ EO is an addition product of x mols of EO per mol of a substantially saturated fatty alcohol which is produced by reducing tallow fatty acid and comprises a mixture of alcohols with various numbers of carbon atoms, in substantially the following distribution: C]2: 0-2%C14: 4-7%C16: 25-35%C18: 60-67%C20: 0-2% Coconut-Cig_-|g+ 6 EO is an ethoxylation product from 6 mols of ethylene oxide per mol of a fatty alcohol fraction, which is produced by reduction - 29 41866 coconut fatty acid and subsequent distillation, comprises equal parts of C-jg alcohol and C-jg alcohol and contained a portion of C·^ and C2g alcohol of below 2% in each case. 0xo+5 EO is the ethoxylation product of an alcohol mixture, obtained by oxosynthesis, of the following composition: Branched Straight-chained C15: 1.5% 0.9% 0.6% C16: 29.7% 10.5% 19.2% C1?: 41.5% 12.4% 29.1% C18: 21.4% 8.2% 13.2% Cig: 5.2% 0.6% 4.6% 32.6% 66.7% this alcohol mixture being reacted with 5 mols of ethylene oxide per mol of alcohol. 0A+10 EO is an addition product of ethylene oxide to technical oleyiaicohol in the molar ratio of 10:1.

EDTA is the salt of ethylene diamine tetraacetic acid.

CMC is the salt of carboxymethyl cellulose.

ABS is the salt of an alkylbenzene sulphonic acid obtained by condensing straight chained olefins with benzene and sulphonating the alkylbenzene thus produced and having approximately 11-13 carbom atoms in the alkyl chain. · Water glass is a sodium silicate (Na20: Si02, 1:3.35).

Perborate is a technical product having the appropriate composition NaB02.H202. 3H20 All the salts compounds are sodium salts.

“AC is a water-soluble polyacrylic acid or its sodium salt (molecular weight of polyacrylic acid > 1500).

Cop 1 is lauric acid monoethanol amide.

Cop 2 is myristic acid monoethanol amide.

Cop 3 is lauric myristic acid monoethanol amide.

Cop 4 is coconut fatty acid monoethylanol amide.

Cop 5 is lauric myristic acid diethanol amide.

Cop 6 is oleic acid diethanol amide PVA is polyvinyl alcohol (molecular weight > 1500). sunnw:;ions of nm rimwrroN EXAMPLE 1 The suspensions of the invention are illustrated in the example of the microcrystalline aluminium silicates produced according to γ2, since these are preferred for producing washing and cleaning agents according to the invention. Suspensions of the invention can also be produced with the suspensions ¢1,g2 and γΐ or with appropriate aluminium silicates which are isolated as solid bodies. 155*195g of moist aluminium silicates (method γ2; the quantity of moist aluminium silicates used was adapted or adjusted to the moisture content so that the same quantity on an anhydrous basis (AS) was added in each case) were introduced into a mixture of so many parts of water and dispersing agent that the mixtures obtained contained aluminium silicate active substance in the range of 30 to 38% by wt. The quantity of ethoxylation product added amounted to 1.3 to 3% by wt. The operation was effected at ambient temperature.

The compounds which are listed in Tables 1 and la and for which the turbidity point is also given in each case were used as dispersing agents.

Some suspensions and the components from which they were formed are listed in Table 2. - 31 41866 TABLE 1 Ethoxylation product used Turbidity point in°C acc. 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+7E0 (1:1) (77) 6. Mixture of TA+0 EO(Non-ethoxylated tallow alcohol) (76) and TA+7 EO (1:1) 7. Mixture of TA+2 EO and TA+12 E0(l:1) (76-77) 8. Mixture of TA+5 EO and TA+12 EO (1:1) (83) 9. Coconut-C^g_-|g+6 EO (80) The ratios given relate to the weight TABLE IA Further stabilisers used Turbidity point in°C (DIN 53917) Myristic acid monoethanolamide 59 Lauric acid monoethanolamide 59 Lauric acid/myristic acid monoethanolamide 61.5 Oleic acid diethanolamide 77.5 Lauric acid/myristic acid diethanolamide 87 Stearic acid monoethanolamide 64 Tallow amine+5 EO (ethyleneoxide) 83.5 Tallow amine 40 Unsat. tallow alcohol with 5 EO 72 Coconut fatty acid monoethanolamide+2 EO 79 Ci2~ C^4 fatty acid+4 EO approx. 68 Coconut amine+2 EO 1 Nonylphenol with 6.5 EO 72 Nonylphenol with 7 EO 73 - 32 41866 TABLE 2 1 AS content (% by wt) 2 amount (g) 3 AS (g) 4 in suspension (% by wt) 5 H20 add -ition (9) 6 TA+„E0 (X) 7 (g) 50 600 300 30 370 5 30 50 650 331 33 330 5 20 50 650 331 33 340 5 10 44.3 750 332 33 230 5 20 39.8 700 278 30 200 5 20 39.8 780 310 31 190 2+12 30 39.8 780 310 31 190 0+7 30 39.8 780 310 31 195 5 24 39.8 780 310 31 190 7 30 39.8 780 310 31 200 7 20 39.8 780 310 31 200 4 20 39.8 1,280 509 34 200 5 20(1.3) 780 310 31 200 5 20(2) 50.4 695 350 35 285 5 20(2) 715 360 36 265 5 20(2) 734 370 37 245 5 20(2) 55.3 686 380 38 294 5 20(2) 52 711 370 37 269 5 20(2) 52 595 310 31 375 0X0+5 EO (1) 30(3) /) TA+5 EO is here replaced by OXO+5 EO. - 33 - 41866 The following explanations are given for Table 2: Column 1: AS content is the active substance content in the moist aluminium silicate used.

Columns 3 and 4: AS in suspension” is the active substance content in the suspension formed in grams or % by wt.

Column 2: the quantity of moist aluminium silicate used to produce the suspension.

Column 5: the quantity of water added to the moist aluminium silicate. Columns 6 and 7: the ethoxylation product used and its quantity in grams or percent.

All the suspensions were outstandingly stable and could still be pumped out of a storage tank satisfactorily by means of a conventional hose pump (mark IKA P 20, IKA-llerk, Staufen/BreiSgau, Fed. Rep. of Germany) after periods of 1 day and more.

EXAMPLE 2 A suspension of 31% by wt. of pure microcrystalline aluminium silicate, produced according to γ2, in water, was produced. Dispersing agent 9 in Table 1 was used as the dispersing agent of the invention in a quantity of 1.8% by wt. relative to the total suspension. The stability of the suspension was improved even further by the addition of traces of tallow amine (what is meant by tallow amine is the primary amine corresponding to the above-defined tallow alcohol) and tallow fatty acid. Suspensions thus produced can be stable for months.

EXAMPLE 3 Powdery sprayable washing compositions given in Table 3 were produced as follows: a stock suspension, which had been produced by introducing a moist aluminium silicate, produced according to Example 2, into a dispersion of the dispersing agent heated to 70°C, and contained 36% by wt. of aluminium silicate and 2% by wt. of TA+5 EO - relative to the total weight of the suspension in each case - was pumped from a storage vessel into a container where the remaining components and so much water were then intro- 34 41866 -duced one after the other with stirring that a washing composition slurry containing substantially 45% by wt. of water was formed.

This slurry was supplied by pumps to the atomizing nozzles located at the upper end of an atomizing tower and converted into a fine powder by means of atomization and counter flow of hot air (approx. 260°C).

TABLE 3 A B ABS 1.4% TA+10 EO 7.0% 0A+10 EO 8.0% TA+5 EO (2) 2.0% Sodium triphosphate 7.8% Sodium triphosphate 20.0% Water glass 5.4% Sodium carbonate 5.0% CMC 0.8% Water glass 3.0% Aluminium silicate (^ )(AS) 36.0% CMC 1.8% TA+5 EO (1) 2.0% Aluminium silicate (^)(AS) 18.0% Remainder: water and TA+5 EO (1) 1.0% NagSO^ EDTA MgSiO3 3 Perborate ( ) Soap Remainder: water and NagSO^ 0.5% 2.5% 28.0% 2.5% o ( ) TA+5 EO added with the other components (1) introduced with stock suspension ( ) added after atomization When producing a washing agent corresponding to B, suspensions which contain, for example polyacrylate AC (see above) and are likewise very stable but also highly pumpable can be used instead of a suspension stabil- 35 41866 ised with TA+ 5 EO. Since polyacrylate is a complex-former for calcium, the proportion of sodium triphosphate can be substantially reduced accordingly. When producing washing agents containing ABS, however, a suspension containing ABS can also be used according to the invention, an ABS having 11-13 C atoms in the alkyl residue being used in the concrete case. In this case stabilisation is rather lower.

' EXAMPLE 4 PUMPING AND STANDING TESTS WITH ALUMINIUM SILICATE SUSPENSIONS 594 - 780g of sodium aluminium silicate having various water contents were introduced, with stirring, into the emulsions, heated to 65-70°C, of 190360g of water and 10-30g of dispersing agent and homogenised. The quantity was so proportioned that the AS content was 31 - 34%. With continued stirring, the homogenous suspensions were pumped round with the aid of a hose pump (ΪΚΑΡ20 type) for one hour at ambient temperature. Afterwards, the pumping and stirring processes were interruped for one hour. Subsequently, the stirring and pumping processes were continued. In the comparative test prepared without any dispersing adjuvant - no further stirring and pumping could be effected.

After pumping and stirring for a further 4-6 hours, the suspensions were left overnight and the settling behaviour was tested visually subsequently and after several days’ standing at ambient temperature. The statement: sediment=100% thus signifies that the suspension is completely (up to 100%) homogenous and stable (see Table, last column).

In connection with determining the settling behaviour, the suspensions were again.tested for their pumpability. All the substances mentioned proved thereby to be useful dispersing adjuvants since the suspensions produced therewith could be stirred effortlessly and pumped both off and round.

The individual slurries are given in the following list in table form.

An aluminium silicate of the approximate composition Na20,Al203.2Si02, produced according to β2, was used which was introduced in the form still wet from preparation. The particle size was predominantly between 5 and 15μ. - 36 41866 Observations (^) to (8) are listed separately on the following page. σι © σι ai > © ro σι ro ai 3M στ ro JM co JM s-i > © »-x ro © o 00 Si © ro © o 00 si > © ro I 39.8% | AS content of the silicate στ 2 στ σι σι to P* σι to JM tn © JM tn © JM © JM o © JM © © JM o © JM © © © © o © o vj co o xj © O vj CO O amount used (9) UJ Jm O © s © o UJ o UJ © UJ O UJ © UJ © UJ -J o UJ o UJ J o ω —j o © o © J o © o © O © > © _4 o ω jm UJ «J UJ UJ UJ UJ UJ •—j UJ UJ UJ _□ © UJ © © © © o Si ro Si w © 1 UJ FM σι v. ΓΟ © UJ στ •v. JM O trt PO to © v^ 00 vj **© UJ © JM *V. A © σ UJ © JM X ro ro σ UJ ω © UJ UJ © UJ JM o UJ UJ o UJ © o © © o © vj O © O ro o o ho ro o cu 0. Ο. X © ro rf O o 3 © o © o to o vl o -o < > tn o σ < > W o © © JM UJ ro o o σ > o (X > o © 3> O © 1 σ © ->· t/ι •a ro “5 ω -j. o ho o ΡΌ ro © l\5 ro o ro ro © PO PO o ro © o UJ UJ © UJ PO o UJ © UJ UJ o UJ UJ o © ro o ro © o © ro o ro 1 3 © > © ro Si 3 rf + + + + + + •f + + + + + + + + Pumpabi af 1 hr. + + + + + + + 4- + + + + + + + o 3 -j. rf rf ro o. rf —1 ro «j» ro -< rf JM << 3* *-* -$ JM iz> v-* ω co <·>» to JM 00 o vj Χ-Χ» CO tn 5 CO o /“s cn *4 tn © 00 © o o © © «J o o © © © © 3 cr © VJ © co © o Sediment % (days) *o c *o ex OJ =5 o. rf ro w rf •n -s o Q.

E Π rf o’ o Π CU rf ro Ό ro 418 6 6 Observations concerning the Table: Production of aluminium silicate suspensions (1) The aqueous aluminium silicate suspension had settled with up to 50% solid. (2) The moist aluminium silicate was produced in the Loedige mixer from spray-dried material having an AS content of 79% with the addition of water. (3) The acid polyacrylic acid solution was adjusted to pH 10 before the addition of sodium aluminium silicate with caustic soda solution. Poly (α-hydroxyacrylic acid) was also used alternatively. (4) Pumpability after x hours; the following signs mean: - = no longer able to be pumped round + = can be pumped off and round (5) The polyvinyl alcohols used are difficulty soluble in water and consequently variable portions of dimethyl sulphoxide (20-87g) acting as the dissolving intermediary were added to the costs of the quantity of water.

With the introduction of 1% PVA 90, the addition of dimethyl sulphoxide could be eliminated.

The polyvinyl alcohols used are commercial products (Mowiol Registered Trade Mark) belonging to EarbwerkeHoechst) and the most suitable proved to be Mowiol 76/98.

EXAMPLE 5 Suspensions of the invention are produced by introducing the products Ι,Π,ΧΠΙ,ΙΧ and XX m respectively into a dispersion of TA+5 E0 in water, which had been previously heated to 60-70°C, thus forming silicate suspensions having a 33% AS content and a 2% content of TA+5 E0.

The suspensions are cooled down to ambient temperature and observed at this temperature. The same operation was therefore carried out as in Example Tat ambient temperature. The suspensions are outstandingly stable.

EXAMPLE 6 A moist aluminium silicate of the approximate composition Nag.AlgOg.ZSiC^ - 38 41866 with a water content of 50%, produced according to Example 2 and adjusted to a pH value of approximately 10.5, is introduced into an aqueous solution of a) 1,3-hydroxyethane-l,1-diphosphonic acid b) dimetbylaminonetbane diphosphonic acid, suspensions with a solid content (AS content) of 31% and a dispersing agent content of 2% being formed The phosphonic acids are used 1. as tetrasodium salts 2. as disodium salts, and 3. as free acids.

The suspensions can be treated by incorporating surfactants and possibly further washing composition components, e.g. by subsequent atomizing drying, into washing compositions.

EXAMPLE 7 In accordance with Example 6, suspensions of 31% sodium aluminium silicate and 4% phosphonic acid butyl esters or phosphoric acid isooctyl esters (adjusted to pH 10) are produced. The phosphoric acid esters are products having approximately 1.5 mol of alcohol per mol of phosphoric acid.

EXAMPLE 8 In accordance with Example 6, a suspension of 31% sodium aluminium silicate AS content and an alkyl benzene sulphonate (ABS) content of 4% was produced. The ABS was once used as a salt and once as a free acid. A sulphonate obtained from the methyl ester of a hardened tallow fatty acid by sulphonation with SOj, or an olefin sulphonate obtained by sulphonating straight-chained internal olefins having 12-18C atoms and hydrolysing the sulphonation product can also be used. The strong foaming of the suspensions could be removed easily by adding slight quantities of a commercial silicone anti-foam agents. The suspensions are suitable for the production of washing compositions containing aluminium silicate especially to produce slurries. However, they can also be atomizing-dried as such and converted into powdery water softening composition or washing composition - 39 41866 builder substances.

EXAMPLE 9 In accordance with Example 4, aluminium silicate suspensions with a 31% AS content and a content of the following dispersing agents (AS per cent; dispersing agent per cent). a. stearic acid monoglyceride (31/2) b. stearic acid propylene glycol ester (31/2) c. reaction product from the reaction of tallow and N-hydroxy-ethyl-ethylene diamine (31/2) d. tallow amine (long-chained amine derived from tallow fatty acid by way of reduction) (31/2) e. adduct with 5 mols of ethylene oxide per mol of tallow amine (31/2) f. oleyl alcohol with 5 mols of ethylene oxide per mol of alcohol (31/2) g. mixture of saturated C12(70-75%) and C14(25-30%) alcohols ethoxylated with 3 to 4 mols of ethylene oxide (31/3) h. maize starch (31/1) or carboxymethyl cellulose i. poly(a-hydroxyacrylic acid) (31/2) k. polylactone of poly(a-hydroxyacrylic acid) (31/2) were produced.

The stabilised suspensions are suitable, inter alia, for the production of aqueous slurries of washing composition components which are then spraydried. They can also be treated directly as water of crystallisation binding salts (e.g. pentasodium triphosphate) to form granules by the addition of water.

EXAMPLE 10 An aqueous suspension produced according to Example 1 and containing approximately 30% of aluminium silicate and 2% of TA+5 EO was atomized in a hot-air stream and thus dried, i.e. relieved of adhering water. The spraydried product contained considerably less dust than a product which was produced accordingly, but with the absence of TA+5 EO. The powdery aluminium silicate obtained is predominantly suitable as a water softening - 40 41866 agent and as a washing composition builder substance.

EXAMPLE 11 A moist silicate of the formula Na20. AlgOg. 2Si02 containing 50% water was introduced at substantially ambient temperature into suspensions of bentonite in water. The stabilised suspensions had an AS content of 33% and a bentonite content of 2 or 4%. The bentonite used was a commercial product which has been put on the market by Erbsloh, Fed. Rep. Germany, under the name of Aktiv-Bentonit (Active Bentonite).

Analytical composition: Si02 56.8 ai203 20.1Fe2°3 4.8 CaO 1.8 MgO 4.0 k2o 0.7 Na20 3.1 Loss on ignition 8.7 Bentonite Montigel F ll belonging to Sudchemie AG, Fed. Rep. Germany, was also used.

The products which occur naturally or are prepared from natural products generally contained impurities still containing iron, and also silicate impurities.

Commercial products besides the one mentioned, Aktivbentonit (Erbsloh, Fed.Rep. Germany) are Volclay (Bentonite International),Eurogel (Amberger Kaolinwerke, Ger.Fed.Rep.). Synthetic products can be obtained, inter alia, from Lange & Co., Bremen.

Washing compositions can be produced by using aluminium silicate suspensions stabilized with bentonite or a synthetic swellable silicate of the smectite type, in a manner that comprises combining the stabilised - 41 41866 suspension with the remaining components of the washing composition to be made thus forming a slurry which still contains, for example, approximately 50% by weight, and by this slurry then being dried in a hot air current.

For example, a product may be produced which corresponds to the following recipe: TA+10E0 3.0% TA+5E0 2.0% Sodium triphosphate 20.0% Soda 3.0% CMC 1.8% Aluminium silicate (AS) 18.0% Bentonite 1.1% EDTA 0.5% MgSiO3 2.5% Perborate 28.0% Soap 2.5% remainders water and Na,S0. by the suspension, containing 2% bentonite being mixed with the remaining washing composition components - with the exception of the perborate - to form a slurry which is Spray-dried in a conventional manner in a hot air current and the powder obtained is then mixed with the perborate.

All the suspensions described in the examples were clearly improved from the point of view of stability and flowability; thus the non-ionic surfactants of the compound class (iv) proved to be decidedly outstanding in a surprising manner.

Claims (14)

1. A pumpable aqueous suspension comprising, A) at least 20% by weight of a water-insoluble, synthetically produced, finely-divided, aluminium or boron silicate cation exchanger containing bound water having a calcium binding capacity (as hereinbefore defined) of at least 50mg CaO/g of water free active substances (=AS) of the general formula: (Cat 2 / n O) x . Me 2 0 3 .(Si0 2 ) y wherein Cat represents a cation having a valency n exchangeable with calcium, x is a number from 0.7 to 1.5, Me represents boron or aluminium and y is a number from 0.8 to 6, 8) 0.5 to 6% by weight of at least one dispersing agent selected from: (i) organic, macromolecular polymers having carboxyl and / or hydroxyl groups, water soluble salts and lactones thereof, (ii) phosphonic acids which have at least one other phosphonic acid group and / or carboxyl group and water soluble salts thereof, (iii) phosphoric acid alkyl ester emulsifiers having 3 to 20 carbon atoms in the alkyl chain, (iv) non-ionic surfactants having a turbidity point in aqueous butyldiglycol solution determined in accordance with DIN 53917 of below 90°C, (v) surface active sulphonates, and (vi) water-insoluble silicates capable of swelling in water having a stratified structure; and C) water.

2. A suspension as claimed in claim 1 in which y in the general formula (1) is a number from 1.3 to 4.

3. A suspension as claimed in claim 1 or 2 having a pH value between 7 and 12.

4. A suspension as claimed in any one of claims 1 to 3 in which the amount of component A is from 20 to 42% by weight of the total weight of the suspension.

5. A suspension as claimed in any one of claims 1 to 4, in which the - 43 418 66 water-insoluble silicate of component A is crystalline.

6. A suspension as claimed in any one of claims 1 to 5, in which the water-insoluble silicate of component A shows the following interference lines in the X-ray diffraction diagram (d values plotted with Cu-fL radiaa tion in A); 4.1; 3.68; 3.38; 3.26; 2.96; 2.73; 2.60 or 4.6; 3.8; 2.88; 2.79; 2.66.

7. A suspension as claimed in any one of claims 1 to 6, in which the water-insoluble silicate of component A has a calcium binding capacity of from 50 to 200mg CaO/g, of the anhydrous component A.

8. A suspension as claimed in claim 7 in which the water-insoluble silicate of component A has a calcium binding capacity of 100 to 200mg (CaO/g of the anhydrous component A).

9. A suspension as claimed in any one of claims 1 to 8, wherein component B is the ethoxylation product of a saturated alcohol having 16 to 18 carbon atoms with 1 to 8 mols of ethylene oxide per mol of alcohol.

10. A suspension as claimed in claim 1 substantially as hereinbefore described with reference to any one of Examples 5 to 11.

11. A method of producing a solid, pourable washing and cleaning composition containing a water-insoluble silicate as defined in claim 1, comprising mixing an aqueous suspension as defined in any one of claims 1 to 10 with at least one washing or cleaning further constituent of the composition to be produced and subsequently converting the mixture into a solid, pourable composition.

12. A method as claimed in claim 11, wherein the suspension as defined in any one of claims 1 to 10 is mixed with a further water-soluble surfactant, other than that of Component B, and further constituents, if any, of the compositions to be produced, and then converted into a powdery product.

13. A method as claimed in any one of claims 11 to 12 wherein the suspen- 44 41866 sion as defined in any one of claims 1 to 10 is converted into a powdery product by spray drying after the addition of further constituents, if any, of the composition to be produced.

14. A powdery washing and cleaning agent whenever produced by a method 5 as claimed in any one of claims 11, 12 or 13.