DK152484B - STABLE SUSPENSIONS OF VANDU-SOLUBLE SILICATES WHICH ARE ABLE TO BIND CALCIUMIONS. - Google Patents

Description

DK 152484 B

The invention relates to stable suspensions of the kind specified in the preamble of claim 1.

One of the most current problems in the detergent and detergent industry is the partial or complete replacement of the previously used phosphates which bind calcium with other substances. Application No. 138 ^ / 7 ^ discloses a process for washing and purifying solid materials, in particular textiles, and detergents suitable for carrying out the process in which the role of the phosphates which bind calcium is completely or partially assumed of water-insoluble boron or aluminum which are capable of bonding caleidium and which are finely divided and generally contain bound water.

These are compounds of general formula I

15 <Kat2 / n0) x · Me2 ° 3 · isl02> y (I)

2 DK 152484 B

where Kat is a calcium-exchangeable cation of valence n, x is a number of 0.7-1.5, Me is boron or aluminum and y is a number of 0.8-6, preferably 1.3-

As the cation, it is preferably sodium, but this can also be replaced with lithium, potassium, ammonium or magnium as well as with the cations of water-soluble organic bases, e.g. cations of primary, secondary or tertiary amines or alkylolamines having a maximum of 2 C atoms per alkyl residues, or a maximum of 3 C atoms, respectively. alkylolrest.

The compounds defined above which are suitable for binding calcium are hereinafter referred to as "aluminum silicates" for simplicity. This is especially true of the most commonly used sodium aluminum silicates. All indications stated about their use according to the invention and all indications of their preparation and properties apply correspondingly to all the compounds defined above.

The aluminum silicates particularly suitable for use in detergents and detergents have a calcium binding capacity of preferably 50-200 mg CaO / g of the anhydrous aluminum silicate. In the following, anhydrous 2Q aluminum silicate is referred to herein as the state of the aluminum silicate obtained after drying at 800 ° C for 1 hour. In this drying, the adhesive and the bound water are virtually completely removed.

In the manufacture of detergents or cleaning agents, in which, besides 25 usual constituents of such agents, the aluminum silicates defined above are preferably used, aluminum silicates which are moist, e.g. from their manufacture. The moist compounds are mixed at least with some of the other constituents of the agent to be prepared and the mixture is transferred into the final wash-2Q or detergent as the final product, e.g. in a pourable product.

Within the scope of the preparation method for detergents outlined above, the aluminum silicates are supplied or used e.g. as aqueous suspensions or as moist filter cakes.

For this purpose, certain improvements in suspension properties are still desirable, e.g. the suspension stability and pumpability of the aqueous phase dispersed aluminum silicates.

It has now been found that certain compounds have a very particular degree

3 DK 152484 B

the ability to stabilize suspensions of the aforementioned calcium-binding aluminum silicates such that, even with high solids content, they are stable for a long time, possibly even virtually unlimited, and are also impeccably pumpable after long standing. Surprisingly, it has been found that there are certain compounds capable of holding even moist aluminum silicates having a water content of $ 70 and less pumpable virtually independent of their residence time, which was not heretofore possible.

The present invention relates to pumpable, improved in their stability, suitable as storage suspensions, aqueous suspensions of water-insoluble silicates which are suitable for bonding calcium and which are not exclusive in that they, based on the total weight of the aqueous suspension contains at least 20, preferably 20-42% finely divided, water-insoluble compounds, which are suitable for binding calcium, and as a precursor.

stepwise containing bound water and having the general formula I

(Kat2 / n1 2 3 4 5 6 7 8 9 10 11 12 13 14X 'Me2 ° 3' <si02> y (D

wherein the symbols used have the above meaning and 0.5-6% of at least one dispersant of the group of the following compounds: 2 1) an organic, macromolecular polymeric compound having carb = 3 oxyl and / or hydroxyl groups, 4 2 ) a phosphonic acid having at least one additional phosphonic acid and / or carboxyl group, 5 3) a phosphoric acid alkyl ester emulsifier having 3-20 C atoms in the alkyl 6 chain, 7 30 8 +) a nonionic surfactant having a cloudiness point in aqueous buildup glycol solution, determined according to DIN 53917} below 90 ° C, 9 5) a surfactant sulfonate, 10 6) a swellable, water-insoluble silicate with layer structure.

11 35 12

Acidic compounds can be used as such or as water-soluble 13 salts and are consistent with their pK value and the pH of the 14 suspension mostly ionized in the suspension. The pH of the suspensions generally ranges from approx. 7 and 12, preferably between 8.5 and 11.5 and mostly below 11.

> ♦ DK 152484 B

The above mentioned compounds are the essential components of the suspensions of the invention. However, there may also be a content of other ingredients, e.g. antifoaming additives or so-called solvents, i.e. compounds which improve the solubility of the added dispersants in the aqueous phase. The usual antifoaming agents, e.g. antifoaming soap, silicone foam remover, antifoaming triazine derivatives, all of which are well known to those skilled in the art. Such an addition is generally not necessary, but with foaming dispersants it may be desirable, especially when large amounts of alkylbenzene sulfonic acid are used.

In general, addition of solvent-mediating agents is also not necessary, but may be appropriate when the suspension of the invention contains as a stabilizing agent a hydrophilic but slightly water-soluble colloid, such as e.g. polyvinyl alcohol. Preferably, e.g. a solvent - very suitable is di = methylsulfoxide - when the concentration of a water soluble stabilizing agent from group 1 is greater than approx. VFO. The amount of solvent intermediate relative to the total suspension 2q can be e.g. be of the same order of magnitude as the amount of the stabilizer. Other compounds suitable as solvents are well known in the art. Hydrotropic agents, such as benzolsulfonic acid, two = luolsulfonic acid, xylolsulfonic acid or their water-soluble salts or also octyl sulfate are suitable.

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For all indications of '' concentration of aluminum silicates '', 'solids content' or 'active substance' content (= AS), refer to the state of the aluminum silicates obtained after 1 hour drying at 800 ° C. the adhering and bonded water is virtually completely removed 3Q.

For all percentages, this is about $ weight.

The above components A and B are now further described:

The aluminum silicates used in component A may be amorphous or crystalline products, of course, mixtures of amorphous and crystalline products and also partially crystalline products may be used. The aluminum silicates may be naturally occurring products, 4Q but also synthetically manufactured products, being synthetically manufactured.

DK 152484 B

Leading products are preferred. The preparation can e.g. occur by reaction of water-soluble silicates with water-soluble aluminates in the presence of water. For this purpose, aqueous solutions of the starting materials can be mixed with one another or a solid component may be reacted with the other component present as an aqueous solution. Also, by mixing two solid state components, the desired aluminum silicates are obtained in the presence of water. Aluminum silicates can also be prepared from Al (OH) 3, Al2 O3 or SiO2 by reaction with alkali silicate solutions or alum = 10 minate solutions, respectively. The preparation can also be done according to other known methods. In particular, the invention relates to aluminum silicates which, unlike the layer structure silicates such as montmorillonite, have a three-dimensional space lattice structure.

The calcium binding capacity, which is preferably in the range of 100 to 200 mg CaO / g AS, mostly at ca. 100-180 mg CaO / g AS, is found especially in compounds of the composition: 0.7-1.1 Wa 2 O. A1203. 1.3-3.3 SiO2 · 20

This sum formula includes two types of different crystal structures (their non-crystalline precursors, respectively) that also differ by their sum formulas. These are: a) 0.7-1.1 Na 2 O. A1203. 1.3-2, ½ Si02

25 J

b) 0.7-1.1 Na 2 O. A1203. 2.1 ± -3.3 SiO2 ·

The various crystal structures are shown in the X-ray bending diagram

The aqueous, amorphous or crystalline aluminum silicate in filtration can be separated by filtration from the residual aqueous solution and dried at temperatures of e.g. 50- ^ 00 ° 0th Depending on the drying conditions, the product contains more or less bound water.

Such high drying temperatures are generally not recommended.

35 o o

Conveniently, it does not exceed 200 C if the aluminum silicate is intended for use in detergents. However, the aluminum silicates need not be dried at all after their preparation in order to prepare a suspension according to the invention. On the contrary, an aluminum silicate which is still moist after manufacture is used, and this is particularly advantageous. For the preparation of suspensic

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However, in accordance with the invention, aluminum silicates dried at medium temperatures, e.g. at 80-200 ° C until removal of the adherent liquid water.

The particle size of the individual aluminum silicate particles may be different and e.g. lie in the range between 0.1 µ and 0.1 mm. This indication relates to the primary particle size, i.e. the size of the particles resulting from precipitation and possibly the subsequent crystallization. With particular advantage, aluminum silicates are used which, for at least 80 wt.%, Consist of particles having a size of 10-0.01 µ, in particular of 8-0.1 µ. Preferably, these aluminum = silicates contain no primary or secondary particles, respectively, with a diameter greater than 30 µ. As secondary particles are referred to as particles formed by agglomeration of the primary particles into larger aggregates. Most importantly, the area is between approx. 1 and 10 µ.

In view of the agglomeration of the primary particles into larger aggregates, the use of the still-humid aluminum silicates from their preparation has proved particularly suitable for the preparation of the suspensions of the invention, since it has been found that formation of secondary particles is practically completely prevented. using this yet moisturizing product.

A more detailed description of the compounds which can be used as component B is now given:

As polymeric polycarboxylic acids (1), water soluble, but also water insoluble polymerisation products may be in particular. The useful polymeric polycarboxylic acids can be both polymerizers of polymerisable carboxyl group-containing monomers and polymerisates of polymerizable monomers which are only later converted to a polycarboxylic acid. The polymeric polycarboxylic acids may, in addition to carboxyl groups, carry other functional groups, e.g. especially the hydroxyl group, which may also be etherified or esterified by low molecular weight groups, especially aliphatic groups. Examples of such polymeric polycarboxylic acids are poly (α-hydroxyacrylic acid) as well as acrylic acid or especially maleic blend polymers with vinyl methyl ether or vinyl acetate, the vinyl acetate unit of the polymer being fully or partially hydrolyzed to produce products which can be perceived as copolymerizers 40 of unsaturated carboxylic acids with the hypothetical vinyl alcohol.

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It has been found that the carboxyl groups in the polymeric polycarboxylic acids can not only, as stated, be partially replaced by hydroxyl groups, namely e.g. by suitable copolymerization with suitable monomers, but also that products in which all carboxyl groups are replaced by hydroxyl = 5 groups are suitable according to the invention. Thereby the macro-molecular polyhydroxy compounds are obtained. As a prototype of suitable macromolecular polyhydroxy compounds, polyvinyl alcohol may be considered. Polyvinyl alcohol may also be obtained from e.g. polyvinyl acetate by hydrolysis. Thus, the hydrolysis need not be complete in order for the poly = 10 hydroxyl compound to be useful in accordance with the invention, but on the contrary are products in which, in addition to hydroxyl groups, there are esterified hydroxyl groups, e.g. oxyacetyl groups, suitable.

The molecular weight of the polycarboxylic acids or polyhydroxyl compounds used may vary within wide limits. Particularly suitable are polymericates in the molecular weight range above ca. 1500, preferably of approx. 20,000. Also very high molecular weight compounds are excellent, with preferred polycarboxylic acids still being water soluble. If the water solubility of said compounds is poor, a solvent intermediary may be added as already mentioned. This is essentially true for polyhydroxy compounds which do not contain any carboxyl groups. The presence of carboxyl groups promotes water solubility, so that the solubility of the polymeric polycarboxylic acids depends on their carboxyl group content and is generally excellent.

25

Insofar as the macromolecular compounds of this invention exhibit ionizable groups in aqueous solution, they may also, and generally preferred, be used in the form of their water-soluble salts. For economic reasons, these are generally the al = 30 potassium salts, especially the sodium salts.

Suitable compounds are found among the polymers of acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, methylene malonic acid, citraconic acid and the like, the copolymericates of the above carboxylic acids mutually and with ethylenically unsaturated compounds such as ethylene, propylene, , vinyl methyl ether, furan, acrolein, vinyl acetate, acrylamide, acrylonitrile, methacrylic acid, crotonic acid, etc., e.g. The 1: 1 mixture polymers of maleic acid = anhydride and ethylene or propylene or furan.

8 DK 152484 B

Examples of particularly suitable compounds of group 1 are the above-mentioned polyacrylic acid and poly (α-hydroxyacrylic acid). The latter can be used not only as free acid or water-soluble salt, but also in the form of its inner lactone. In suspension, this is hydrolyzed. The 5 products described so far are substantially straight-chain, i.e. in their polymeric backbone unbranched polymerisates. In addition to the preferred synthetic polymers described above, natural products such as e.g. alginates, carboxymethyl cellulose, corn or potato starch or their derivatives. However, the water-insoluble 1 ° polymeric, three-dimensional branched polyacrylic acids are also considered.

The molecular weights can vary widely, and in the case of poly (oc-hydroxyacrylic acid), the molecular weights of the commercial products are generally above 20,000, and for the copolymerisates of vinyl methyl ether with maleic anhydride (monomer ratio 1: 1 ), the molecular weight of the commercially available products is usually at approx. From 100000 to 2500000.

Another suitable group (2) stabilizers are phosphonic acids which carry at least one other phosphonic acid group and / or at least one carboxyl group. These may be alkane polyphosphonic acids, amino and hydroxy = alkane polyphosphonic acids or phosphonic arboric acids. Examples are propane-1,2,3-triphosphonic acid, butane-1,2,3,1-tetraphosphonic acid, polyvinylphos = phonic acid, 1-aminoethane-1,1-diphosphonic acid, 1-amino-1-phenylmethane-1,1 -diphosphonic acid, aminotrimethylenetriphosphonic acid, methylamino or ethylaminodimethylenediphosphonic acid, ethylenediaminotetramethylenetetra = phosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-1,2,3 * + - tricarboxylic acid, 2-phosphonobutane-2,3 -30 Risates of Vinyl Phosphonic Acid and Acrylic Acid.

Also suitable are phosphoric acid partial ester emulsifiers.

(3) In general, these are esters of 1-2 moles, especially of ca. 1.5 moles of a preferably saturated alcohol having 3-20 C atoms in alkyl = 35 chain per mole of phosphoric acid. Particularly suitable products are the esters of alcohols with! + To approx. 10 C atoms, especially e.g. esters with approx. 1.5 moles of butyl alcohol or isooctyl alcohol.

The non-ionic surfactants (β -) used in the invention are in practice 40 water-insoluble compounds. Their point of obscurity, determined according to DIN

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53917 in aqueous butyl diglycol solution is mostly at 90 ° C and below, preferably at 85 ° C and below. Similarly, the obscurity points in water, determined on equal solutions, for the suitable compounds are below ca. 55 ° C, preferably below 35 ° C. In particular products, the point of obscurity lies in water below room temperature. The most suitable products are characterized in that they can be dispersed in water - 1 part surfactant to 19 parts by weight of water - in such a way under light, possibly also vigorous shaking and, if necessary, under temperature rise to above the melting point, that they cooling to room temperature forms a milky, possibly gel-like, solidified dispersion. The cloudiness points determined by DIN 53917 are usually at least at * + 0 ° C, preferably at least 55 ° C.

The indications of the dispersibility in water or of the cloud points respectively refer to the individual surfactant-like stabilizers in their technically pure form, e.g. as a statistical mixture of ethoxylation products as they appear in the ethoxylation of fatty acid = carbonic, fatty acid, fatty acid amide or fatty amine fraction.

Suitable dispersing agents according to the invention are found especially among the nonionic surfactants which have as a hydrophobic residue a long chain alkyl or alkenyl residue which usually contains 10-20, preferably 12-18 C atoms. The alkyl or alkenyl residue is mostly straight-chain, but suitable products are also found among the compounds with branched hydrophobic residue. Unsaturated hydrophobic residues are usually simply unsaturated, such as the particularly frequent oleic acid residue.

The hydrophilic group is mostly formed from polyalcohol residues, such as ethylene glycol, propylene glycol, polyethylene glycol or glycerine residues, which are linked to the hydrophobic residue via ester groups, amide groups, ether groups or amino groups. Particular attention should be paid to the ethylene oxide addition products.

Of the ethylene oxide addition products with the same cloud point, those with longer hydrophobic residues are usually preferred at C ^-C ^g.

An important group of suitable compounds are found among the carboxylic acid esters and carboxylic acid amides. Particularly suitable as dispersants according to the invention are the mono- and diethanolamides of carboxylic acids of 10-20, preferably 12-18 and especially 12-1 * + carbon atoms. The compounds are derived

DK 152484 B

stepwise of saturated and straight chain carboxylic acids. However, the products can also be derived from unsaturated, especially single unsaturated carboxylic acids. As amine components from which the amide suitable according to the invention is derived can be "in particular monoethanolamine and diethanolamine. However, a particularly suitable product is also the amide of a carboxylic acid as defined above and E- (hydroxyethyl) ethylenediamine. amides can be seen as reaction products of carboxylic acid amides with ethylene oxide, the number of ethylene oxide units being mostly at 1-6 and especially 1-½ preferred.

The ester-like dispersants are derived from the same carboxylic acids as the amide-like dispersants. As for the amides, the esters are derived from fatty acids or fatty acid mixtures, especially within the chain length range listed above, which may be of natural or synthetic origin. Suitable as ester-like suspension stabilizers are those products which can be perceived as addition products of carboxylic acids with ethylene oxide, for example the addition products of carboxylic acids with 1, 2 or 3 moles of ethylene = oxide per liter. moles of carboxylic acid. Products with e.g. H-10 ethylene oxide units.

However, as alcohol components, polyolcohols having more than 2 hydroxyl groups, e.g. glycerin.

Examples of amide or ester type suspension stabilizers which are particularly suitable are the compounds: lauric acid monoethanolamide, coconut fatty acid monoethanolamide, myristic acid monoethanolamide, palmitic acid monoamide, ethanolamide, stearic acid monoethanolamide, oleic acid monoethanolamide, oleic acid monoethanolamide N- (hydroxyethyl) ethylenediamine. As ester-like stabilizers are to be mentioned the addition products of 1 and 2 moles of ethylene oxide to coconut fatty acid and of propylene glycol or glycerine to stearic or palmitic acid.

Particularly suitable diethanolamides are the lauric myristic acid diethanolamide, the di = 35 ethanolamide of a fatty acid mixture of lauric acid and myristic acid, and oleic acid diethanolamide.

Another particularly suitable group of stabilizers is found among the ethoxylation products of preferably saturated alcohols of 10-20 40 carbon atoms, with 1-8 moles of ethylene oxide per liter. moles of alcohol. Preferably,

11 DK 152484 B

you are aware of these ethoxylation products about products with 2-7, especially with 2-6 moles of ethylene oxide per liter. moles of alcohol. It is particularly convenient within the scope of the invention to use derivatives of straight-chain alcohols. However, derivatives of branched alcohols, especially alcohols produced by oxosynthesis, can also be used. Particularly preferred are the derivatives of preferably saturated and preferably straight chain alcohols having 16-18 C atoms. But also ethoxylation products of alcohols with 12 and especially 1 C atoms can be used, as products 10 with 1-5 moles of ethylene oxide, especially with 2-k moles of ethylene oxide per liter. moles of alcohol are particularly suitable.

The ethoxylation products used according to the invention are generally not chemically uniform compounds, but, on the contrary, conventional mixtures in which addition products with different degrees of ethoxylation are present in statistical distribution side by side, including the degree of ethoxylation 0, which is mostly still only in small amounts in non-ethoxylated starting material present. The ethoxylation products used according to the invention are in practice water-insoluble compounds whose cloud point, determined according to DIN 53917 in aqueous butyldiglycol solution. usually ranges from approx. 55 to 85 ° C. Typical preferably used products are saturated fatty alcohol ethoxylation products derived from tallow fatty acids, which have an ethoxylation rate of 2, +, 5 or 7 moles of ethylene oxide per liter. moles of fatty alcohol have 25 cloudiness points of 58, 71? 77 or 83 ° C.

Also the alcohol component, e.g. C - ^^ g g is mostly a technical mixture in which alcohols having more or fewer C atoms may also be present, mostly in minor amounts, e.g. up to $ 15.

30 In addition, the quantities listed below apply to any additional components present.

Instead of the aforementioned ethoxylation products of alcohols, the corresponding ethoxylation products of fatty amines can also be used, ie especially ethoxylation products of primary amines, which are preferably saturated and having 16-18 carbon atoms, with 1-8 moles of ethylene oxide per liter. mol amine. Suitable also have been found the non-ethoxylated amines which are surfactants in the sense of the invention. However, suitable products with 2-5 moles of ethylene oxide per liter are also suitable. mol amine.

40

Suitable alkylphenol products having a cloud point below room temp.

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temperature below 85 ° C respectively according to DIN 53917? Mention should be made of the water-insoluble nonylphenol-ethylene oxide addition products with 5-8 moles of ethylene = oxide per liter. mole of phenol. Addition products with 6-7 moles of ethylene oxide are preferred.

5 (5) As sulfonate-type surfactants, alkylbenzene sulfonates (c <2 _] 5-alkyl), olefin sulfonates, i.e. mixtures of alkene and hydroxyalkanesulfonates as well as disulfonates as obtained e.g. of C 1 -Cis monoquefins with terminal or internalized double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline electricity - LQ clays acidic hydrolysis of the sulfonation products. Also suitable are the esters of α-sulfo fatty acids, e.g. the α-sulfonic acids of methyl or ethyl esters of hydrated coconut, palm kernel or tallow fatty acids.

However, the most preferred stabilizing compounds of the invention are the nonionic surfactants as defined under * +).

(6) Other dispersants suitable according to the invention are the water-insoluble but swellable silica-class silicates which, unlike the aluminum silicates to be suspended according to the invention, have a 20-layer structure instead of a three-dimensional space grating. The silicates with swellable layer structure are referred to as smectites. These are substances similar to the general formula ... Al2 (Si2O5) 2 (QH) 2 and Mg-3 (Si2O5) (OH) 2.

25

Examples are bentonite, montmorillonite, folchonskoit, nontronite, hecto = rite, saponite, sauconite and vermiculite. Depending on their origin, these swellable clays, since they are capable of ion exchange, still have cations such as e.g. sodium, potassium or calcium. Naturally occurring and synthetically produced products are equally suitable, as the synthetic products often have the advantage of greater purity. The particle size of these layer silicates is usually less than ca. 50 μ, and particularly suitable are calcium-poor types capable of binding calcium.

35

In addition to the aforementioned individual dispersing agents, mixtures may be used, in various cases a synergistic interaction is observed. For example, addition of talgamine, carboxymethyl cellulose, cross-linked polyacrylate, alginic acid to surfactant-stabilized suspensions, i.e., e.g. 1

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the combination of Group 1 stabilizers with Group 5 stabilizers, and especially + +, proved advantageous. Another class of compounds which further improve the properties of suspensions stabilized in accordance with the invention are the long chain fatty acids. These are natural or synthetic, preferably saturated fatty acids with mostly 10-20 C atoms in the molecule, e.g. tallow.

Aqueous suspensions, which are particularly preferred within the scope of the invention, consist essentially of at least $ 20 of component A, the upper limit of the content of A being determined by the limit of flowability and being less than about 10%. 42 weight% ·. Cup centers: between 25 and 40% by weight, especially between ca. 28 and '38 wt%, are particularly preferred. In practice, the area is seeds. 30 'to 38% by weight d-one v-major. *.

æ5 The amount of component B to be used depends essentially on the desired degree of stabilization of the suspension. The concentration in the suspensions according to the invention of component B is 0.5-6, more frequently 0.8-6 wt% ·· ', calculated on the total weight of the aqueous suspension. Preferably, it is in the range of ca. 1 to 2Q b weight $ and in most cases conveniently at approx. 1.3-3 weight $.

Since the viscosity of the suspension is influenced by the content of component B, the desired viscosity can optionally be adjusted by selecting the concentration of component B.

25 For more fine-grained aluminum silicates, lesser amounts of component B than for coarse-grained products must be used for stabilization. Thus, e.g. aluminum silicate suspensions, where $ 90 or more of the particles have a particle size between 1 and 8 µ, are as well stabilized already with a dispersant content of 0.5-1 wt $ as products with an average particle size of 10-12 µ with a content of dispersant at 1-2 $. These indications are only indicative values, as the appropriate amount of component B to be used in each case is determined by the specific needs.

g ,. The viscosity of the suspension is generally at 25 ° C of 500-30,000, preferably above 1,000 but less than 15,000 cp. Particularly suitable are suspensions having viscosities in the range of 1,000 to 9 · 000.

Aqueous suspensions, particularly preferred within the scope of the invention, consist essentially of at least $ 20 of Component A, at least approx.

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$ 0.5, preferably at least approx. 0.8% of component B and water.

In addition to the listed components, there are optionally inorganic salts or hydroxides resulting from the precipitation or other preparation of the aluminum silicates. Thus, e.g. there are still small amounts of excess sodium hydroxide or sodium = carbonate or bicarbonate resulting from the adsorption of carbon dioxide, or e.g. sulphation is present if aluminum sulphate was used in the manufacture of aluminum silicate as an aluminum-containing starting material.

In principle, the aqueous suspensions, in addition to said components A and B, and in addition to substances which may have been left over from starting materials for the preparation of these components, may contain other ingredients in relatively low quantities. Of course, if further processing of the suspensions for detergents and detergents is intended, these additional available substances are, of course, convenient substances which are suitable as constituents of detergents. An indication of the stability of the suspensions provides a simple sample in which an aluminum silicate suspension of the desired concentration is prepared, e.g. 31 $ containing a dispersant of the invention and optionally other substances, e.g. detergent ingredients, such as pentane sodium triphosphate, in various amounts. The influence of the added substance can then be observed visually at the deposition conditions of the suspension. After 2 hours of standing, a preferred suspension in

9 C

have at most deposited so much that the above clear or silicate-free solution does not amount to more than $ 20, preferably not more than 10, and in particular not more than $ 6 of the total height. In general, the amount of the added substances should be kept such that the suspension after 12 hours, preferably after 2k hours and especially also after qn +8 hours of storage in storage containers and pipe and hose lines can still be impeccably pumped. The deposition conditions of the suspensions, which may contain additional constituents, are tested at room temperature with a total height of the suspension of 10 cm. For particularly preferred suspensions, the height of the above clear solution, n per even after * + and especially after 8 days, is still within the range indicated. They can also be easily pumped, even after * + or 8 days. Also, these indications of suspension stability only provide clues. The suspension stability to be adjusted depends on the individual case.

Using the suspensions of the invention as stock suspension 40 W DK 152484B! For longer storage in a reservoir from which they can be extracted with pumps as needed, it may be convenient to keep the amount of such components, e.g. detergents, low or completely renounce it.

The suspensions may be prepared by simple mixing of their constituents, the aluminum silicates being used as such or optionally still moist from manufacture or in aqueous suspension. It is particularly advantageous to introduce the still-moistened aluminum silicates from their manufacture, e.g. as filter cakes, in a dispersion of the component B in water. Preferably, this dispersion of component B is somewhat heated, e.g. to 50-70 ° C.

Of course, dried aluminum silicates, i.e. aluminum silicates which are liberated from adherent water and possibly contain bound water.

A particularly suitable process for preparing the suspensions of the invention is as follows: The aluminum silicate is precipitated by mixing sodium aluminate solution and sodium silicate solution. These op-2Q solutions contain more alkalinity, ie more sodium =. hydroxide than necessary to form the final aluminum silicate so that there is a sodium hydroxide excess in the aluminum silicate suspension which appears as an immediate precipitate product. This suspension is concentrated by filtration of part of the above __ mother liquor and then liberated with water for the sodium present = 25 µm hydroxide to such an extent that the sodium hydroxide content of the solution is less than ca. 5 $ 5 preferably below 3 $ or even below 2 <fo.

The residual sodium hydroxide is neutralized by the addition of an acid, especially aqueous sulfuric acid, to such an extent that the resulting suspension has a pH of between 7 and 12, especially between ca. 8.5 and 11.5.

To this suspension is added the amount of dispersant needed to achieve the desired degree of stabilization, the addition being possible before, during or after the partial neutralization.

Below, it is particularly appropriate to perform the partial neutralization.

ISLAND ISLAND

sation at least in part with an acidic dispersant, i.e. e.g. with a macromolecular polycarboxylic acid or alkylbenzolsulfonic acid as defined above. Thus, these acidic dispersants can be used as acid for the neutralization and thus replace

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non-stabilizing acids, such as said sulfuric acid, in whole or in part.

The suspensions of the invention are characterized by high stability and additional advantages. Their stabilizing effect is particularly valuable for aluminum alic having particle sizes of 5-30 P - They are pumpable to allow simple handling of moist aluminosilicates. Even after prolonged interruption of pumping, the suspensions can still be impeccably pumped. Due to their high stability, the suspensions are also transportable in conventional tank and boiler wagons, without the need to fear the formation of useless or disruptive residues. Therefore, the suspensions are excellent as a form of delivery for aluminum silicates for delivery to e.g. detergent manufacturers.

The suspensions may be stored at room temperature or at higher temperatures and may be transported through pipelines, pumps or otherwise. For the most part, the suspensions are handled at temperatures between room temperature, most preferably, and approx. 60 ° C.

Particularly suitable are the suspensions of the invention for further processing into pourable or rice-resistant products that look dry, ie e.g. for the preparation of powdery water-softening agents, for example by spray drying. Therefore, the suspensions are of great importance for the production of powdered aluminum silicates. There are no annoying residues in the application of the aqueous suspension to the drying apparatus. Furthermore, it has been found that the suspensions according to the invention enable processing into extremely dust-free products.

Due to their particular stability, the suspensions according to the invention are already as such, i.e. without further processing with or without other washing, bleaching and / or cleansing agents, usable, for example, as a water softener, detergent or cleaning agent and especially as a liquid scouring agent with increased suspension stability.

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DK 152484B

17

Preparation of the aluminum silicates

First described is the synthesis of aluminum silicates used in the suspensions of the invention for which protection is not required in the present application. The description is otherwise purely illustrative. Other known methods can be used to prepare aluminum alloys.

α) To the aluminum silicate solution, the calculated amount of sodium silicate solution (temperature of the solution: 20-80 ° C) was added in a 15 liter container with strong stirring. Thereby, under exothermic reaction, as the primary precipitation product, an X-ray morphine sodium = aluminum silicate formed. After 10 minutes of vigorous stirring, the suspension of the precipitate product was either 1) further processed directly, i.e. without crystallization, or 2) for crystallization recommended for 3-6 hours at 80 ° C, thus yielding fully crystalline products according to X-ray structure analysis.

20) The mother liquor was filtered from the suspensions. The remaining filter cake was washed with deionized water and then mixed with deionized water to form suspension βΐ (α1) and β2 (α2, respectively).

25 γ) A microcrystalline aluminum silicate was prepared by adding the silicate solution diluted with the deionized water solution, stirring with a fast-moving, intensive stirrer (10,000 rpm, make: "Ultraturrax" from Janke & Kun -30 kel IKA-Werk, Stauffen / Breisgau / Federal Republic of Germany). After 10 minutes of vigorous stirring, the suspension of the amorphous precipitate was transferred to a crystallization vessel, where formation of large crystals was prevented by stirring the suspension. After leaving 35

18 DK 152484 B

suction of the liquor from the crystal crop and after washing with deionized water until the running wash water had a pH of approx. 10, the filter residue was dried, then milled in a ball mill and separated into two fractions in a centrifugal force sieve (Microplex windscreen from Company 5 Alpine, Augsburg, Federal Republic of Germany), one of which contained no constituents above 10 u. fraction was prepared in suspension in deionized water (γΐ). A similar suspension was prepared without the drying and splitting into two fractions. In other words, the still moist filter remnants with different water contents were introduced into water. The resulting suspension is designated γ2. Instead of filtration, the separation of the silicates from most of the water present from the beginning was also performed by centrifugation.

The aluminum silicates produced had the approximate composition calculated on anhydrous products (= AS): 1 Na 2 O. 1 A120 ^ '. 2 SiO 2 · 2Q The calcium binding capacity of the precipitate product was found to be 150-175 mg CaO / g of active substance. It was found as follows: To 1 liter of an aqueous solution containing 0.59 µg CaCl 2 (= 300 mg CaO / liter = 30 ° dH) and adjusted to a pH of 10 with dilute NaOH was added 1 g of aluminum silicate (calculated on AS). Then the suspension is stirred for 15 minutes at a temperature of 22 ° C (- 2 ° C). After filtration of the aluminum silicate, the residual hardness x of the filtrate is determined. Hence the calcium binding capacity in mg CaO / g AS is calculated by the formula: (30 - x) · 10.

Preparation Conditions for Aluminum Silicate I: 30 Precipitation: 2,985 kg of aluminate solution of the composition: 17,796 Na 2 O, 15.89 b Al 2 O 2, 66,696 H 2 O 0.15 kg of ether sodium 9, 20 kg of water 2, M + 5 kg of a commercially available water glass and slightly alkali-soluble silicic acid freshly prepared, 25.8 µg sodium silicate solution of the composition: 1 Na 2 O, 6.0 S

Crystallization: 2k hours at 80 ° C

Drying: 2k hours at 100 ° C * 40

DK 152484 B

19

Composition: 0.9 Na 2 O. 1 Al ^ O ^ · 2.01 * Si02. +, 3 H2 O (= 21, efo H2 O)

Crystallization degree: fully crystalline

Calcium binding capacity: 150 mg CaO / g AS

Drying the product thus obtained for 1 hour at + OQ ° C gives an aluminum silicate 1a with the composition: 0.9 Na 2 O. 1 A1203. 2, Ok SiO 2. 2.0 H 2 O (= 11.1 $ H 2 O) also suitable for the purposes of the invention.

10

Preparation Conditions for Aluminum Silicate II: Precipitation: 2.115 kg of aluminate solution with the composition: 17.7 # Na 2 O, 15.896 Al 2 O 3, 66.576 H 2 O 0.585 kg etching sodium 9.615 kg water 2.855 kg of a 25.87¾ sodium silicate solution having the composition: 1 Na20. 6 SiO 2 (prepared as listed under I)

Crystallization: 2k hours at 80 ° C

20 Drying: 2k hours at 100 ° C and 20 torr

Composition: 0.8 Wa20. 1 A1203. 2,655 SiO 2. 5) 2 H2 O

Crystallization degree: fully crystalline

Calcium binding capacity: 120 mg CaO / g AS

25

Also, this product can be dewatered by post-drying (1 hour at M) Q0C) for the s

0.8 Na 2 O. 1 A1203. 2.65 SiO 2. 0.2 H₂O

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

The aluminum silicates I and II show in the X-ray bending diagram the following interference lines: 35

DK 152484 B

d values recorded with Cu-Ka radiation in A

I II

i1 *, ** 12, J + 5 - 8.8 8.6 7.0 (+) k, l (+) 10 - 3.8 (+) 3.68 (+) 3.38 (+) 3, 26 (+) 2.96 (+) 15 2.88 (+) 2.79 (+) 2.73 (+) 2.66 (+) 2.60 (+) 20

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

25

Preparation conditions for aluminum silicate VIII: Precipitation: 2.115 kg of aluminate solution with the composition:

17.7 # Na 2 O, 15.8 # Al 2 O 3, 66.5 # HgO

0.585 kg etching sodium 9.615 kg water 2.685 kg of a 25.8 µg sodium silicate solution of the composition: 1Ta20. 6 SiO2

Crystallization: lapses 35. λ

Drying: 2k hours at 100 C

Composition: 0.8 Wa20. 1 A1203. 2.65 SiO 2. k H2 O

Crystallization rate: X-ray polymorph

Calcium binding capacity: 60 mg. CaO / g AS

40

21 DK 152484B

Preparation Conditions for Aluminum Silicate IX: Precipitation: 3, 1 kg of aluminate solution of composition * 21, * + $ Na 2 O, 15, * $ Al 2, 63.2 $ H2 O 10, * + 6 kg of water 5 1.13 kg of a 3 Sodium silicate solution with composition: 1 Na 2 O. 3, * + 6 SiO 2

Crystallization: lapses

Drying: 2k hours at 100 ° C

Composition: 1 Na 2 O. 1 AlgO ^. 1 Si02. 1.1+ H2 O

Crystallization rate: X-ray amorphous

Calcium binding capacity: 120 mg CaO / g AS

Preparation conditions for aluminum silicate XXm: 15 Precipitation: G> 76 kg aluminate solution with composition

$ 36.0 Na 2 O, 59.0 $ Al 2, $ 5.0 HgO

0.9 µg + kg of ether sodium 9, * + 9 kg of water 20 3.9 * + kg of a commercially available sodium sill cat solution with the composition: 8.0 $ Wa 2 O, 26.9 $ SiO 2, 65.1 $ H 2 O

Crystallization: 12 hours at 90 ° C

Drying: 12 hours at 100 ° C

Composition: 0.9 Na2Q. 1 Å120 ^. 3.1 SiO 2. 5 H2 O

Crystallization degree: fully crystalline

Calcium binding capacity * 110 mg CaO / g AS

Examples 30

The abbreviations used below mean: "TA + x E0": an preparation product of x moles of EO per liter. moles of a substantially reduced saturated fatty alcohol produced by the reduction of saturated fatty acid = 35 hollow, consisting of a mixture of alcohols having different numbers of carbon atoms, approximately in the following distribution:

22- DK 152484 B

C12: O - $ 2

ClL (.: K -%

Cl6: 25 - $ 35

Clg: 60 - 67 $ 5 C2Q: O - 2 $ "Coconut-C1 + 6 EO": an ethoxylation product of 6 moles of ethylene oxide per liter. mole of a substantially saturated, by reduction of coconut fatty acid and subsequent distillation, produced fatty alcohol fraction, which consists of 10 parts of C ^ g alcohol and C ^ alkohol alcohol and containing less than 2 C and C₂20 alcohol.

"Qxo + 5 E0n: is the ethoxylation product of an alcohol mixture obtained by oxosynthesis of the following composition:

Straight-chain Branched G 15: 1,596 0.9 $ 0.6 $ C 16: 29.796 10.5 $ 19.2 $ C 17: * + 1.5 $ 12, * + $ 29.1 $ 20 G 18: 21, 1 + $ 8.2 $ 13.2 $ C 19: 5.2 $ 0.6 $ ^ +, 6 $ 32.6 $ 66.7 $ 25 which alcohol mixture is reacted with 5 moles of ethylene oxide per liter. moles of alcohol.

"OA + 10 EO" means an ethylene oxide product for technical oleyl = alcohol in the molar ratio of 10: 1.

"EDTA" means the salt of ethylenediaminetetraacetic acid.

"CMC" means the salt of carboxymethyl cellulose.

"ABS" means the salt of a benzene 35 by condensing straight-chain defines and sulfonation of the resulting alkylbenzene, alkylbenzene sulphonic acid produced by ca. 11-13 carbon atoms in the alkyl chain.

"Water glass": a sodium silicate (Na 2 O: SiO25, 1: 3.35) · 40 "Perborate": a technical product of the approximate composition:

NaB02, H2O2, 3H2O.

-23 DK 152484 B

All saline compounds were used as sodium salts.

"AC" means a still water-soluble polyacrylic acid or its sodium salt (molecular weight of the pplyacrylic acid> 1500).

"Cop 1": lauric acid monoethanolamide.

"Cop 2": myristic acid monoethanolamide.

"Cop 3" · lauric myristic acid monoethanolamide.

"Cop k": Coconut fatty acid monoethanolamide.

"Cop 5" · lauric myristic acid diethanolamide.

"Cop 6": oleic acid diethanolamide.

"PVA" means polyvinyl alcohol (molecular weight> 1500).

Suspensions of the Invention 20

Example 1

The suspensions according to the invention are illustrated with the microcrystalline aluminum silicate prepared according to γ2 as this example is withdrawn for preparation according to the invention of detergent and detergents. Suspensions according to the invention can similarly be prepared with the suspensions β1, β2 and γΐ, respectively, with corresponding aluminum silicates isolated as solids.

155-195 g of humid aluminum silicate (process γ2; the humid aluminum silicate used was adjusted to the water content so that in each case the same amount of AS was introduced) was introduced into a mixture of so many parts of water and dispersant that it The resulting mixture exhibited an aluminum silicate content as active ingredient 35 ranging from 30 to 38% by weight. The amount of ethoxylation product added amounted to 1.3-3 wt. Work was done at room temperature.

As the dispersant, the ethoxylation 40 listed in Table I was used

24: DK 152484 B

products for which the point of obscurity is also indicated. Some suspensions and the components from which they were formed are listed in Table 2.

Table 1

5 Cloud point ° C

Ethoxylation product used according to DIN 53917 1. TA + 2 EO 58 2. TA + k EO 71 3. TA + 5 EO 77 10 k. TA +7 EO 83 5. Mixture of TA. + 2 EO and TA + 7 EO (1: 1) (77) 6. Mixture of TA + 0 EO (unethoxylated tallow = alcohol) and TA + 7 EO (1: 1) (76) 7. Mixture of TA + 2 EO and TA + 12 EO (1: 1) (76-77) 15 8. Mixture of TA + 5 EO and TA + 12 EO (1: 1) (83) 9. Coconut + 6 EO (80)

The indication of the quantity ratios is based on the weight.

20

Table 1a

Point of cloud ° c

Other stabilizers used according to DIN 53917 25 ~

Myristinic acid monoethanolamide 59

Lauric acid monoethanolamide 59

Lauric acid myristic acid monoethanolamide 61.5

Oleic Acid Diethanolamide 77.5 Lauric Acid Mystic Acid Diethanolamide 87

Stearic acid monoethanolamide 6 ^

Talgamine + 5 EO (ethylene oxide) 83.5

Talgamin 1 + 0

Unsaturated tallow alcohol + 5 EO 72 25 Coconut fatty acid monoethanolamide + 2 EO 79 C 68

Cocosamine + 2 EO

Nonylphenol with 6.5 EO 72

Nonylphenol with 7 EO 73 40 --—-—-

DK 152484 B

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26 DK 152484 B

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Column 3 and ^: "AS in suspension", the active substance content of the suspension formed in grams, respectively, by weight $.

Column 2: The amount of humid aluminum silicate used to make the suspension.

Column 5: The amount of water added to the moist aluminum silicate.

Columns 6 and 7: The ethoxylation product used and the amount thereof used in grams, respectively 10

All suspensions were extremely stable and could be pumped impeccably after 1 day or more using a conventional hose pump (brand IKA P 20, IKA-Werk, Staufen / Breisgau, Federal Republic)

Germany) from a reservoir.

15

Example 2

A suspension of 31 wt.% Pure microcrystalline aluminum silicate prepared according to γ2 was prepared in water. As the dispersant of the invention, dispersant 9 from Table 1 was used in an amount of 1.8% by weight based on the total suspension. The stability of the suspension was further enhanced by the addition of traces of tallow amine ("tallow amine" is understood to be the primary amine of the above defined tallow alcohol) and sebum fatty acid. Suspensions prepared n c ° in this way can be stable for months.

Example 3

Ρητητιρ and stand trial with aluminum silicate suspensions O U

Into the 65 to 70 ° C heated emulsions of 190-360 g of water and 10-30 g of dispersant were introduced with stirring 59) + - 780 g of sodium aluminum silicate with different water content and homogenized. In the dose, the dose was adjusted so that the AS content was 31-3hfi. The homogeneous suspensions were pumped around with continued stirring by means of a hose pump (brand TO P 20) for 1 hour at room temperature. Then the pumping and stirring was stopped for 1 hour. Thereafter, stirring and re-pumping were continued. In a comparison experiment without the use of dispersant, it was then no longer possible to stir and repump.

27 DK 152484 B

........... After a further * + - 6 hours of repacking and stirring, the suspension was allowed to stand overnight and the deposition conditions at room temperature were visually tested, after several days, respectively. The statement: "precipitate = 100o" means that the suspension is completely (100 $) 5 homogeneous and stable (see table, last column).

In connection with the determination of the outlet ratio, the pumpability of the suspensions was again examined. Hereby, all the substances listed appeared to be useful dispersing aids, since the thus prepared suspensions could be easily stirred and pumped.

The individual materials can be seen by the following tabular composition. An aluminum silicate prepared from β2 of the approximate composition Na 2 O, A 2 O 2, 2 SiC 2 was used. which, where nothing else is stated, was used in the still moist form of manufacture. The particle size was predominantly between 5 and 15 μ.

DK 152484 B

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DK 152484 B

29

Notes for the table:

Preparation of Aluminum Silicate Suspensions (1) The aqueous HAB suspension had settled to an extent of 5 50 *.

(2) The moist aluminum silicate was prepared in a Lodig mixer, starting from spray-dried material having an AS content of 79 ° while adding water.

(3) The acidic polyacrylic acid solution was adjusted to pH 10 with sodium hydroxide prior to the addition of the sodium = 10 aluminum silicate. Alternatively, poly (α-hydroxyacrylic acid) was also used.

(* +) Pump capacity after x hours means: - = no longer pumpable.

15 + =? pumpable.

(5) The polyvinyl alcohols used are heavily soluble in water; therefore, at the expense of the amount of water, alternating amounts of dimethyl sulfoxide (20-87 g) were added as solvent.

Using. Vfo PVA 90 could be waived for the addition of dimethyl sulfoxide 20.

The polyvinyl alcohols used are commercial products (Mowiol from Farb-werke Hoechst), and as most conveniently found "Mowiol 76/98".

Example 4

Suspensions according to the invention are prepared by introducing products I, II, XIII, IX and XXm respectively into a preheated dispersion of TA + 5 E0 in water to form silicate suspensions having 339 of TA + 5 E0.

The suspensions are cooled to room temperature and observed at this temperature. Thus, as in Example 1, work was done at room temperature. The suspensions are excellent stable.

35

Example 5

A damp aluminum silicate prepared according to 2, washed out to a pH of approx. 10.5 and with the approximate composition Na 2 O, A 2 O 5

ao DK 152484 B

2 SiC 2, having a water content of $ 50, is introduced into an aqueous solution of a) 1,3-hydroxyethane-1,1-diphosphonic acid b) dimethylaminomethane diphosphonic acid 5, forming solids-containing suspensions (AS content) ) of $ 31 and a dispersal content of $ 2.

The phosphonic acids are used as 1) tetrasodium salts 2) disodium salts and 3) free acids.

The suspensions may be processed into detergents by incorporating surfactants and optionally other detergent ingredients, e.g. by subsequent spray drying.

Example 6

Similar to Example 5, suspensions of 31 $ sodium aluminum silicate and * + $ phosphoric acid butyl ester or phosphoric acid ooctyl ester (adjusted to pH 10) are prepared.

The phosphoric acid esters are products with approx. 1.5 moles of alcohol per mol phos = 25 phoric acid.

Example 7

In accordance with Example 5, a suspension of sodium = 30 aluminum silicate having 31 $ AS content and an alkylbenzene sulfo = night (ABS) content of k $ was prepared. ABS was used partly as salt and partly as free acid. Also, a sulfonate obtained from the methyl ester of a cured tallow fatty acid can be used by sulfonation with SO 2 or an olefin sulfonate which is obtained by the sulfonation of straight chain, indentified olefins having 12-18 C atoms and hydrolyzing the sulfonation product. The strong foaming of the suspension could be removed without difficulty by adding small amounts of a commercially available silicone antifoam. The suspensions are particularly suitable for the preparation of slurries for the production of aluminum silicate-containing detergents. However, they can also be spray-dried as such and converted into powdery ones

31 DK 152484 B

water softeners or detergent builders.

Example 8

In accordance with Example 3, aluminum silicate suspensions with 31 $ AS content and a content of the following dispersants 5 ($ AS, $ dispersant) were prepared: a) stearic acid monoglyceride (31/2) b) stearic acid propylene glycol ester (31/2) c) reaction product from the reaction of tallow and N-hydroxyethylethylene = -'- O diamine (31/2) d) tallowamine (long chain amine derived from tallow fatty acid by reduction) (31/2) f) oleyl alcohol with 5 moles of ethylene oxide per mole of tallow amine (31/2) mole of alcohol (31/2) 15 g) mixture of saturated 0 ^ (70-75 ^) and C ^ (25-30 $) - alcohols ethoxylated with 3 - * + mole of ethylene oxide (31/3) h) corn starch (31/1) or carboxymethyl cellulose i) poly (α-hydroxyacrylic acid) (31/2) k) poly (oc-hydroxyacrylic acid) polylactone (31/2).

20

The stabilized suspensions are suitable, inter alia, for the preparation of aqueous slurries of detergent ingredients which are then spray dried. They can also be processed by adding water as crystal-forming salts (e.g. pentane sodium triphosphate) directly to granules. 25

Example 9

An aqueous suspension prepared according to Example 1 containing approx. 30 $ aluminum silicate and 2 $ TA + 5 EQ were atomized in a hot air stream and thereby dried, i.e. freed from adherent water. The spray-dried product was significantly more dust-poor than a similar product made in the absence of TA f 5 E0. The resulting powdered aluminum silicate is excellent as a water softener and as a detergent builder.

35

Example 10 In suspensions of bentonite in water, at ca. room temperature introduced a moist silicate containing 50 $ water and of the formula Ha ^ O, Α1ΛΧ.

Claims (6)

32 DK 152484 B 1. Pumpable and stability-enhanced and storage suspensions suitable for the preparation of detergents, aqueous suspensions of water-insoluble silicates suitable for binding calcium, characterized in that they, based on the total weight of the aqueous suspension, contain , At least 20%, preferably 20-42%, finely divided, water-insoluble compounds suitable for the binding of calcium and preferably containing bound water having the general formula 5 (Kat2 / n0) x · Me2 ° 3 · (SiO 2> y (I) where Kat is a calcium-exchangeable cation with the valence n, x is 0.7-1.5, Me is boron or aluminum, and y is 0.8 -6, preferably 1.3-4, and B) 0.5-6% of at least one dispersant of the group of the following compounds: 1) an organic, macromolecular polymer compound having carboxyl and / or hydroxyl groups; phosphonic acid having at least one additional phosphonic acid group and / or carboxylic group, 3. a phosphoric acid alkyl a non-ionic surfactant having a cloud point in aqueous butyldiglycol solution, determined according to DIN 53917, below 90 ° C, 5. a surfactant sulfonate, 6. a swellable, water-insoluble silicate with layer structure. 30 Suspensions according to claim 1, characterized in that they have a pH value between approx. 7 and 12. 2 SiOg. The stabilized suspensions exhibited an AS content of 33 $ and a bentonite content of 2 and * + $, respectively. The bentonite used was a commercial product which was on the market under the name "Aktiv-Bentonite" from the firm Erbsloh, Federal Republic of Germany. Suspensions according to claims 1 and 2, characterized in that component A is crystalline. 35 40 DK 152484B Suspensions according to claims 1-3, characterized in that component A in the X-ray bending diagram shows the following interference lines (d values recorded with Cu-K radiation in Angstrom): 3. 4.1; 3.68; 3.38; 3.26; 2.96; 2.73; 2.60 or 4.4; 3.8; 2.88; 2.79; 2.66 Suspensions according to claims 1-4, characterized in that component A has a calcium binding capacity in the range of 50 to 200 mg CaO / g, preferably 100-200 mg CaO / g of the anhydrous component A. Analytical composition: SiO 2 56.8 Al 2 O 2 20.1 Fe 2 O 3 U, 8 CaO 1.8 10 MgO 2, 0 K 2 O 0.7 Na 2 O 3.1 Iron loss 8.7 15 Also bentonite "Montigel F" from Sudchemie AG, Federal Republic of Tysli country, was used. The naturally occurring or naturally produced products' generally have ferrous contaminants as well as silicate contaminants on commercial products, alongside the 'Active-Bentonite' (Erbsloh, Federal Republic of Germany), 'Volclay' (Bentonite International), 'Eurogel' (Amberger Kaolinwerke , Federal Republic of Germany). Synthetic products are available from, among others, Lange & Co., Bremen. p c All of the suspensions described in the Examples were clearly improved in stability and flowability. Surprisingly, the non-ionic surfactants of the compound class ^ have proved to be the best. 30 Patent claims Suspensions according to claims 1-5, characterized in that, as component 10, they contain the ethoxylation product of a saturated alcohol having 16-18 carbon atoms having 1-8 moles of ethylene oxide per liter. moles of alcohol. 15 20