DK154346B - PROCEDURE FOR THE PREPARATION OF POWDER-DETECTED DETERGENTS AND CLEANERS WITH A CONTENT OF WATER-SOLUBLE SILICATES ABLE TO BIND CALCIUM - Google Patents

Description

in

DK 154346 B

One of the most current problems facing the detergent and detergents industry is the partial or complete replacement of the previously used phosphates which bind calcium with other substances. Application No. 1384/74 discloses a method for washing and purifying solid materials, especially textiles, as well as detergents suitable for carrying out the process wherein the role of the phosphates which bind calcium is fully or partially taken over by water-insoluble boron or aluminum silicates capable of binding calcium, which are finely divided and generally contain bound water.

These are compounds of general formula I 15 (Kat2 / n0) x * Μβ2θ3. (S in 0 2) y (I) 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 1.3-4.

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

The compounds defined above which are suitable for the binding of calcium are hereinafter referred to, for simplicity, as 30 "aluminum silicates". This is especially true for the sodium aluminosilicates used mainly. All indications stated about their use according to the invention, and all indications regarding their preparation and properties, apply equally 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 all aluminum silicate. When in it 35

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2, when referring to anhydrous aluminum silicate, is meant 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.

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In the manufacture of detergents or detergents which contain, in addition to the usual constituents of such agents, the aluminum silicates defined above, are preferably based on aluminum silicates which are moist, for example 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 finished detergent as a final product, for example into a pourable product.

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Within the scope of the preparation method for detergents outlined above, the aluminum silicates are supplied or used, for example, as aqueous suspensions or as moist filter cakes. To this end, 20 certain improvements in the suspension properties are still desirable, for example, the suspension stability and pumpability of the aqueous phase dispersed aluminum silicates.

It has now been found that certain compounds have, in particular, the ability to stabilize suspensions of the above-mentioned calcium-binding aluminum silicates so that, even with high solids content, they are stable for a long time, possibly even practically unlimited, and also impeccably pumpable after long. time delay. Surprisingly, it has been found that there are certain compounds which are capable of holding even moistened aluminum silicates having a water content of 70 ° and smaller, pumpable and practically independent of their residence time, which was not heretofore possible.

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The present invention relates to a process of the kind set forth in the preamble of claim 1 which is characterized by the use of aqueous suspensions of aluminum silicates contained in

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A) at least 20, preferably 20-50 and especially 20-42% finely divided, water-soluble compounds suitable for binding calcium, and preferably containing bound water, having the general formula I (Cat 2 / n ° ) x · Μβ2θ3. (SiO 2) y (I) wherein the symbols used have the above meaning and 10 B) 0.5-6% by weight of at least one dispersant of the group of the following compounds: 1) an organic macromolecular polymer compound having carboxyl and / or hydroxyl groups, 2) a phosphonic acid having at least one additional phosphonic acid and / or carboxylic group, 3) a phosphoric acid alkyl ester emulsifier with 3-20 C atoms in the alkyl chain, 4) a nonionic surfactant having a cloud point in aqueous butyldiglyeol solution, determined according to DIN 53917, below 90 ° C, 5) a surfactant sulfonate, 6) a swellable, water-insoluble silicate with layer structure.

Acidic compounds can be used as such or as water-soluble salts and are consistent with their pK value and the pH of the 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 35, mostly below 11.

The above mentioned compounds are the essential components of the suspensions of the invention. However, there may be 4

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may also be a content of other ingredients, for example, antifoaming additives or so-called solvents, that is, compounds which improve the solubility of the added dispersants in the aqueous phase. As the antifoam 5, the usual antifoaming agents, for example, antifoam soap, silicone antifoam, antifoam triazine derivatives, all of which are well known to those skilled in the art can be used. 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.

Generally, addition of solvent-mediating agents is also not necessary, but may be convenient when the suspension of the invention as a stabilizing agent 15 contains a hydrophilic but slightly water-soluble colloid, such as polyvinyl alcohol. Preferably, for example, a solvent intermediate - very suitable is dimethyl sulfoxide - is used when the concentration of a water-soluble group 1 soluble stabilizer used in water is greater than about 1%. For example, the amount of solvent relative to the overall superposition may 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, for example, benzene sulphonic acid, toluene sulphonic acid, xylolsulphonic acid or their water-soluble salts or also octyl sulphate are suitable.

For all indications of "concentration of aluminum sieve neater", "content of solid" or content of "active substance" (= AS) 30, refer to the state of the aluminum silicates obtained after 1 hour drying at 800 ° C. In this drying, the adherent and bound water is removed virtually completely.

For all percentages, this is by weight%.

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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, which may be used.

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mixtures of amorphous and crystalline products and also partially crystalline products are reversed. The aluminum silicates may be naturally occurring products, but also synthetically produced products, with the synthetically produced products being preferred. The preparation can be made, for example, by reaction of water-soluble silicates with water-soluble aluminates in the presence of water. For this purpose, aqueous solutions of the starting materials may be mixed with each other, 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 all laminate 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 structural silicates, such as montmorillonite, have a three-dimensional space lattice structure.

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

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This sum formula includes two types of different crystal structures (their non-crystalline precursors, respectively), which also differ by their sum formulas. These are: a) 0.7-1.1 Na 2 O. A1203. 1.3-2.4 SiO2 b) 0.7-1.1 Na2O. A1203. 2.4-3.3 SiO2.

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

The aqueous, amorphous or crystalline aluminum silicate may be separated by filtration from the

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residual aqueous solution and dried at temperatures of, for example, 50-400 ° C. Depending on the drying conditions, the product contains more or less bound water.

Such high drying temperatures are generally not recommended. Conveniently, do not exceed 200 ° C if the aluminum screen is intended for use in detergents. However, all 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 can be used, and this is particularly advantageous. However, for the preparation of the suspensions of the invention, all aluminum screen may also be used in cater dried at medium temperatures, for example vec 80-200 ° C, until removal of the adherent liquid water. _

The particle size of the individual aluminum silicate particles may be different and, for example, may be in the range of 0.1 µ 20 to 0.1 mm. This disclosure relates to the primary particle size, that is, the size of the particles resulting from precipitation and, optionally, the subsequent crystallization. With particular advantage, aluminum silicates are used which, for at least 80 wt. V, consist of particles having a size of 10 to 0.01 µ, in particular of 8 to 0.1 µ. Preferably, these aluminum minium silicates contain no primary and secondary particles, respectively, with a diameter greater than 30 µm. As secondary particles, particles arising from agglomeration of the primary particles are referred to as larger aggregates. Most importantly, the range between about 1 and 30 is 10 µ.

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

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

As polymeric polycarboxylic acids (1), there may be in particular 5 water-soluble, but also water-insoluble polymerization products. The useful polymeric polycarboxylic acids can be both polymerizers of polymerizable 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, for example in particular the hydroxyl group, which may also be etherified or esterified with low molecular weight groups, especially aliphatic groups. Examples of such polymeric polycarboxylic acids are poly (α-hydroxylacrylic acid) as well as acrylic acid blending polymers or especially maleic acid with vinyl methyl ether or vinyl acetate, the vinyl acetate unit of the polymer being fully or partially hydrolyzed to produce products which may be construed as copolymerates of unsaturated carboxylic acids with the hypothetical vinyl alcohol.

It has been found that the carboxyl groups in the polymeric polycarboxylic acids can not only be replaced, as indicated, partially by hydroxyl groups, for example by suitable copolymerization with suitable monomers, but also by products in which all carboxyl groups are replaced by hydroxyl groups. suitable according to the invention. Thereby the macromolecular polyhydroxy compounds are obtained. As a prototype of suitable macromolecular polyhydroxy compounds, polyvinyl alcohol may be considered.

Polyvinyl alcohol can also be obtained from, for example, polyvinyl acetate by hydrolysis. Thus, the hydrolysis need not be complete in order for the polyhydroxyl compound to be useful in accordance with the invention, but on the contrary, products in which besides hydroxyl groups are esterified hydroxyl groups, for example oxyacetyl groups, are suitable.

The molecular weight of the polycarboxylic acids or polyhydroxyl compounds used may vary within wide limits. Especially 8

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suitable are polymerisates in the molecular weight range above about 1500, preferably about 20,000. Also very high molecular weight compounds are excellent, with preferred polycarboxylic acids still being water soluble. If the water solubility of said 5 compounds is poor, as mentioned, a solvent intermediary may be added. This is essentially true for polyhydroxyl 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 10 depends on their carboxyl group content and is generally excellent.

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

Suitable compounds are found among the polymerisates of acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, methylene malonic acid, citraconic acid and the like, the copolymers of the above carboxylic acids mutually and with ethylenically unsaturated compounds such as ethylene, propylene, tylene, vinyl alcohol, vinyl methyl ether, faran, acrolein, vinyl acetate, acrylamide, acrylonitrile, methacrylic acid, crotonic acid, and so on, for example, the 1: 1 mixture polymers of maleic anhydride and ethylene or propylene or furan.

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 products described so far 35 are substantially straight-chain, that is, in their polymeric backbone, unbranched polymerisates. In addition to the preferred synthetic polymers described above, natural products, such as alginates, carboxylic acid, may also be used.

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raethyl cellulose, corn or potato starch or their derivatives. However, the water-insoluble polymeric three-dimensional branching polyacrylic acids are also present.

The molecular weights can vary widely, and in the case of poly (α-hydroxyacrylic acid), the molecular weights of the commercial products are generally above 20,000, and for the copolymerates of vi1 methyl ether with maleic anhydride (monomer ratio 1: 1). For example, the molecular weight of the 10 commercially available products is usually around 100,000 to 2,500,000.

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 all kanpol phosphonic acids, amino and hydroxyalkane polyphosphonic acids or phosphonic carbonic acids. Examples are propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, 1- aminoethane-1,1-diphosphonic acid, 1-amino-1-phenyl methane-1, 1- 20 diphosphonic acid, aminotrimethylenetriphosphonic acid, methylamino or ethylaminodimethylenediphosphonic acid, ethylenediaminotetramethylenetetraphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 2-phosphonbutane-1,2,4-tricarboxylic acid, 2-phosphonobutanic acid 2,3,4- mixing polymers 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 the alkyl chain per mole of phosphoric acid.

Particularly suitable products are the esters of alcohols having from 4 to about 10 C atoms, especially, for example, esters having about 1.5 moles of butyl alcohol or isooctylal alcohol.

The nonionic surfactants (4) used according to the invention are in practice water-insoluble compounds. Their cloud point, determined according to DIN 53917 in aqueous butyl diglycol solution, is mostly at 90 ° C and below, preferably at 10 ° C.

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85 ° C and below. Similarly, the cloudiness points in water, determined on 1% solutions, for the suitable compounds are below about 55 ° C, preferably below 35 ° C. In particularly suitable products, the point of obscurity lies in water below room temperature.

5 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, with slight, possibly also strong shaking, and if necessary under temperature rise to above the melting point, that they cool to room temperature forms a milky, possibly gel-like, solidified dispersion. The cloud points determined by DIN 53917 are usually at least at 40 ° C, preferably at least 55 ° C.

The indications of the dispersibility in water and about the 15 cloud points respectively refer to the individual surfactant-like stabilizers in their technically pure form, for example as a statistical mixture of ethoxylation products, as obtained by the ethoxylation of fatty alcohol, fatty acid, fatty acid amide or fatty amine fraction.

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Suitable dispersing agents according to the invention are found especially among the non-ionic 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 mostly simply unsaturated, such as the particularly frequent oleic acid residue.

The hydrophilic group is mostly formed of 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 on C14-C18.

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η

An important group of suitable compounds are found among the carboxylic acid residues and carboxylic acid amides. Particularly suitable as dispersants of the invention are the mono- and di-ethanol amides of carbonic acids having 10-20, preferably 12-18 and especially 12-14 carbon atoms. The compounds are preferably derived from 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, monoethanolamine and di ethanol ami η may be in particular. However, a particularly suitable product is also the amide of a carboxylic acid as defined above and N- (hydroxyethyl) ethyl than iamine. The suitable amides can be seen as reaction products of carboxylic acid amides with ethylene oxide. The number of ethylene oxide units is usually at 1-6 and especially 1-4 is preferred.

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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 may 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 mole of carboxylic acid. Products with, for example, 4-10 ethylene oxide units can also be used.

However, as alcohol components, polyolcohols having more than 2 hydroxyl groups, for example glycerine, may also be present in the surfactant ester.

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Examples of amide or ester-type suspension stabilizers which are particularly suitable are the compounds: diethanolamides and amides derived from the same fatty acids derived from N- (hydroxyethyl) ethylenediamine. As ester-like stabilizers, the addition products of 1 and 2 must be mentioned

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mole of ethylene oxide to coconut fatty acid and of propylene glycol or glycerine to stearic or palmitic acid.

Particularly suitable diethanolamides are lauric myristic acid diethanolamide, the diethanolamide 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 carbon atoms, with 1-8 moles of ethylene oxide per mole of alcohol. Preferably, these ethoxylation products are products of 2-7, in particular 2-6 moles of ethylene oxide per mole of alcohol. It is particularly appropriate within the scope of the invention to use derivatives of straight-chain alcoholic clays. However, derivatives of branched alcohols may also be used, especially alcohols produced by oxosynthesis. 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 14 C atoms can be used, since products with 1-5 moles of ethylene oxide, especially with 2-4 moles of ethylene oxide per mole of alcohol are particularly well suited.

The ethoxylation products used according to the invention are generally not chemically uniform compounds, but on the contrary 25 conventional mixtures in which addition products with different degrees of ethoxylation are present in statistical distribution side by side, including the ethoxylation degree G1, which is mostly present in only a small amount present in -ethoxylated starting material. The ethoxylation products used in accordance with the invention 30 are in practice water-insoluble compounds whose cloud point, determined according to DIN 53917 in aqueous butyldiglycol solution, is usually in the range of from about 55 to 85 ° C. Typical preferred products used are saturated fatty alcohol ethoxylation products derived from tallow fatty acids which have an ethoxylation degree of 2, 4, 5 or 7 moles of ethylene oxide per mole of fatty alcohol having cloud points of 58, 71, 77 or 83 ° C.

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Also, the alcohol component, for example Οχβ-ΐδ, is for the most part a technical mixture in which alcohols having more or fewer C atoms may also be present, mostly in minor amounts, for example up to 15%. For quantities exceeding 5, the following is applicable to any additional constituents present.

Instead of the aforementioned ethoxylation products of alcohols, the corresponding ethoxylation products of 10 fatty amines can also be used, in particular ethoxylation products of primary amines, which are preferably saturated and having 16-18 carbon atoms, with 1-8 moles of ethylene oxide per mole of amine. Suitable also have been found the non-ethoxylated amines which are surfactants in the sense of the invention. However, also suitable are products containing 2-5 to 15 moles of ethylene oxide per mole of amine.

Suitable all alkyl phenol products having a cloudiness peak below room temperature, respectively, below 85 ° C according to DIN 53917, are the water-insoluble nonylphenol-ethylene oxide addition products having 5-8 moles of ethylene oxide per mole of phenol. Addition products with 6-7 moles of ethylene oxide are preferred.

(5) As surfactants of the sulfonate type, alkyl benzene sulfonates (C--xg alkyl), olefin sulfonates, i.e., mixtures of alkene and hydroxyalkanesulfonates as well as disulfonates such as are obtained, for example, from C noolefins with terminal or internalized double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are the esters of α-sulfo fatty acids, for example, 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 in 4).

(6) Other dispersants suitable according to the invention are the water-insoluble but swellable silicates of the clay class which, in 14

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unlike the aluminum silicates to be suspended according to the invention, it has a layer structure instead of a three-dimensional space grille. The silicates with swellable layer structure are referred to as smectites. These are substances similar to the general formula

Al2 (Si2O5) 2 (OH) 2 and Mg3 (Si2Ο5) (OH) 2 ·

Examples are bentonite, montmori 1lonite, folchonskoit, nontronit, hectorite, saponite, sauconite and vermiculite. Depending on their origin, these swellable clays, as they are capable of ion exchange, still have cations, such as 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 about 50 µ, and particularly well suited are calcium-poor types capable of binding calcium.

In addition to the individual dispersants mentioned, mixtures may be used, since in various cases synergistic interaction is observed. For example, the addition of talgamine, carboxymethyl cellulose, cross-linked polyacrylate, alginic acid to surfactant stabilized suspensions, i.e., for example, the combination of Group 1 stabilizers with Group 5 stabilizers and especially 4, has proven advantageous. Another class of compounds which further improve the properties of suspensions stabilized according to the invention are the long chain fatty acids. Here, these are natural or synthetic, preferably saturated fatty acids with mostly 10-20 C atoms in the molecule, for example, tallow fatty acid.

Aqueous suspensions, particularly preferred within the scope of the invention, comprise substantially at least 20% of component A, the upper limit of the content of A being determined by the limit of flowability and mostly below 50, e.g. at about 42% by weight. Concentrations between 25 and 40 wt%, especially between about 28 and 38 wt%, are particularly preferred. In practice, the range from 30 to 38% by weight is the most important.

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The amount of component B to be used depends essentially on the desired degree of stabilization of the suspension.

In general, the concentration in the suspensions of the invention of component B is about 0.5-6, more frequently 0.8-6, 5% by weight, based on the total weight of the aqueous suspension. Preferably it is in the range of from about 1 to 4% by weight and in most cases conveniently at about 1.3-3% by weight. Since the viscosity of the suspension is influenced by the content of component B, the desired viscosity can optionally be adjusted by selecting 10 concentration of component B.

For more fine-grained aluminum silicates, lesser amounts of component B than for coarse-grained products must be used for stabilization. For example, aluminum silicatesus-15 pensions, where 90% or more of the particles have a particle size between 1 and 8 µ, can be stabilized as well already with a dispersant content of 0.5-1 wt% as products with an average particle size of 10-12 µ with a dispersant content of 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.

The viscosity of the suspension at 25pc is generally 25 to 500-30,000, preferably above 1,000 but below 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 about 0.5%, preferably at least about 0.8% of component B, and water.

Alongside the listed components, there are optionally 35 inorganic salts or hydroxides resulting from the precipitation or other preparation of the aluminum silicates. Thus, for example, low amounts of excess sodium hydroxide or sodium carbonate or bicarbonate may still be present.

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resulting from adsorption of carbon dioxide or, for example, sulphation may exist if aluminum sulphate was used in the manufacture of aluminum sulphate as an aluminum starting material.

In principle, the aqueous suspensions, in addition to the 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 small quantities. Of course, if further processing of the suspensions for detergents and detergents is intended, these additional available substances are, of course, suitable substances which are suitable as constituents of detergents. An indication of the stability of the suspensions provides a simple sample which produces an aluminum silicate suspension of the desired concentration, e.g., 31%, containing a dispersant of the invention and optionally other substances, for example detergent ingredients such as pentane sodium triphosphate. different quantities. The influence of the added substance 20 can then be observed visually at the deposition conditions of the suspension. After 24 hours of standing, a preferred suspension should generally have deposited at most so much that the clear or free solution of the above particles does not exceed 20%, preferably not more than 10 and 25, especially not more than 6% of the total. height. In general, the amount of the additives should be maintained such that the suspension after 12 hours, preferably after 24 hours and especially also after 48 hours of storage in storage containers and pipe and hose lines can still be impeccably pumped. The deposition conditions 30 for 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, even after 4 and especially after 8 days, is still within the range indicated. The 35 can also be easily pumped, even after 4 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 17

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According to the invention, as stock suspensions for longer storage in a reservoir from which they can be taken out with pumps as required, it may be convenient to keep the amount of such constituents, for example detergents, low or completely dispensed with.

The suspensions may be prepared by simple mixing of their constituents, all of the aluminum silicates being used as such or optionally still moist from the preparation or in aqueous suspension. Particularly advantageous is the introduction of the still-moistened aluminum silicates, for example as filter cakes, into a dispersion of component B in water. Preferably, this dispersion of component B is somewhat heated, for example to 50-70 ° C.

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Of course, dried aluminum silicates, that is, aluminum silicates which are free from adherent water and which optionally contain bound water, can also be used.

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 solutions contain more alkali, i.e., more sodium hydroxide, than is necessary to form the final aluminum sieve 1 in cat, so that there is an excess of sodium hydroxide in the aluminum silyatsus pension which appears as an immediate precipitate product. This suspension is concentrated by filtration of a portion of the above mother liquor and then liberated with water for sodium hydroxide present to such an extent that the sodium hydroxide content of the solution is below about 5%, preferably below 3% or even below 2%. The residual sodium hydroxide is neutralized by the addition of an acid, especially aqueous sulfuric acid, so much so that the resulting suspension has a pH value in the range of about 5%. 7 and 12, especially between about 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.

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Herein, it is particularly convenient to perform the partial neutralization at least in part with an acid character dispersant, i.e., for example, with a macromolecular polycarboxylic acid or alkyl benzene sulfonic acid as defined above. Thus, various acidic dispersants can be used as acid for the neutralization and thus replace non-stabilizing acids, such as said sulfuric acid, in whole or in part.

The suspensions of the invention are distinguished by high stability and even more advantages. Their stabilizing effect is especially valuable for aluminum silicates with particle sizes of 5-30 μm. They are pumpable, enabling simple handling of moist aluminum silicates. Even after 15 long interruptions in the 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 20 are excellent as a form of delivery of aluminum silicates for delivery to, for example, detergent manufacturers.

The suspensions may be stored at room temperature or at higher temperatures and may be transported through pipelines, 25 pumps or otherwise. Mostly, the suspensions are handled at temperatures between room temperature, most preferably, at about 60 ° C.

Particularly suitable are the suspensions of the invention for further processing into pourable or rice-resistant products which look dry, ie for example in the preparation of powdery water-softening agents, for example by spray drying. Therefore, the suspensions are of great importance in the preparation 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.

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Because of their particular stability, the suspensions of the invention are already as such, that is, without further processing with or without other washing, bleaching and / or cleansing agents, useful, for example, as a water softener, detergent or detergent and especially as a liquid. abrasive with increased suspension stability.

A particularly important use of the suspension is the further processing for dry appearance, pourable or rice-resistant 10 detergents which contain, in addition to the suspension components, other compounds.

The suspensions according to the invention are especially suitable for preparing those in application no. 1384/74. and other earlier patent applications described detergents and detergents, and everything stated about their manufacture, their constituents, and the proportions of the constituents, applies here accordingly.

The invention therefore also relates to a process for the preparation of pourable, powdery products having a water-insoluble content, as defined above, to all aluminum silicates, whereby, based on an aqueous, liquid premix of the individual constituents of the agent, in the usual way produces a pourable product. The process is advantageous in that all the alaminates are used in the form of the suspensions according to the invention. The suspensions of the invention can be processed into the solid, pourable detergents and cleaners according to desired known methods.

In particular, in the preparation of powdery, rice-resistant detergents in the process of the invention, one proceeds in such a way as to mix a suspension according to the invention, for example from a storage container, with at least one washing, bleaching or purifying component of the agent. , And then the mixture is transferred to the powdered product according to any method. Preferably, a complexing agent is added, i.e. a compound capable of complexing those of the water 20

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hardness responsible alkaline earth metal ions, especially magnesium and calcium ions.

In preparing detergents by the process 5 of the invention, the suspension according to the invention is generally preferably combined with at least one water-soluble surfactant which does not belong to the possible components of component B.

10 Various variants are given in the production of detergents and detergents.

For example, the suspensions of the invention can be combined with substances capable of binding crystal water, conveniently by spraying the suspension onto the pre-arranged compounds capable of binding crystal water, so that at A final dry, dry looking product is obtained. Preferably, however, the suspensions of the invention are subjected to spray drying together with at least one further washing, bleaching or cleansing compound. Hereby, further surprising advantages are shown by the aluminum silicate suspensions of the invention. Namely, it has been found that by using the suspensions of the invention for spray drying very low dust products can be obtained. The products obtained by spray drying exhibit a high calcium binding capacity and are slightly wettable.

Detergents according to the invention, that is, detergents prepared using the above-described suspensions, can be composed in most diverse ways. Generally, they contain at least one water-soluble surfactant which does not belong to the dispersants used according to the invention, which are present in all nine millimeters in the suspension suspensions 35 of the invention. In general, the detergents of the invention, in terms of composition, may be similar to those described in the aforementioned older patent applications. They contain, in addition to at least one additional compound that acts 21

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washing, bleaching and purifying, and which is inorganic or organic, as the calcium-binding compound, as defined above, aluminum silicate. In addition, such agents may contain other usual adjuvants and additives which are mostly present in small quantities. For further details, see the earlier patent applications mentioned. The entries therein also apply here.

The aluminum silicate content of such agents may range from 10 to 5 to 95, preferably 15 to 60%.

The agents of the invention may further contain complexing agents or precipitating agents for calcium, the effect of which, depending on the chemical nature of the agent, can be preferably recognized at a content of 2-15%.

In the case of phosphorus-lowering agents, the amount of inorganic phosphates and / or organic phosphorus compounds must not be greater than a total P content in the mean of 20%, preferably 3%.

For example, other washing, bleaching or cleansing blemishes contained in the detergents may include surfactants which do not belong to those intended for the component B of the invention, surfactant or non-surfactant foam stabilizers or inhibitors, textile softeners, neutral or alkaline reacting builder substances, chemically acting bleaches and their stabilizers and / or activators. Other auxiliaries and additives which are present in small quantities, for example, are, for example, corrosion inhibitors, antimicrobials, dirt carriers, enzymes, detergents, colorants and fragrances, and so on.

The composition of typical textile detergents for use at temperatures in the range of 50 to 100 ° C is within the range of the following recipes: 22

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3-30% anionic and / or zwitterionic and / or nonionic surfactants, including surfactants according to the invention, preferably 5-30%; 5-70% aluminum silicates (calculated as AS), including layers of structural silicates used in the invention; 2-45% calcium complexers, including component B complexers; 10 0-50% washing alkali not suitable for complexation (s alkaline constituents); 0-50% bleach as well as other additives which are mostly present in small amounts in textile detergents.

Following is a discussion of substances suitable for use in the compositions of the invention.

The surfactants contain at least one hydrophobic, organic residue and one water-solubilizing, anionic, zwitterionic or nonionic group. The hydrophobic residue is mostly an aliphatic hydrocarbon residue of 8-26, preferably 10-22, and most preferably 12-18 C atoms or an alkylaromatic residue of 6-18, preferably 8-16 aliphatic C atoms.

As anionic surfactants, for example, soaps may be used of natural or synthetic, preferably saturated fatty acids, optionally also of resin acids or naphthenic acids. Suitable synthetic anionic surfactants are those of the sulfonate, sulfate or synthetic carboxylates type.

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

23

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In particular, as nonionic surfactants which may be present in addition to the ethoxylation products used in the invention, mention must be made of the 1 to 40 alloying products, preferably 9-20 moles of ethylene oxide to 1 mole of fatty alcohol.

5

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

The zwitterionic surfactants include substances of the type carboxy-betaine or sulfobetaine.

Suitable compounds include compounds capable of complexing calcium and compounds which do not possess this ability. The latter include, for example, bicarbonates, 15 carbonates, borates or silicates of alkali metals, alkali sulfates, and alkali salts of organic, non-capillary active sulfonic acids, carbonic acids and sulfocarboxylic acids containing 1-8 C atoms. Examples are the water-soluble salts of benzene sulfonic acid, toluene sulfonic acid or xylolsulfonic acid, as well as the water-soluble salts of sulfoacetic acid, sulfobenzoic acid or sulfodicarboxylic acids. Triphosphate, as well as a large number of known polycarboxylic acid organic complexes, which include polymeric carboxylic acids, amino carboxylic acids, phosphonic acids, phosphonic carbonic acids, hydroxycarboxylic acids, carboxylic alkyl ethers, and so on, are suitable as complexing agents.

As a bleaching agent, compounds which give off an aqueous solution of H2O2, such as perborate, or substances which give active chlorine, are suitable. Other additives that are mostly present in small quantities are, for example, foam stabilizers or inhibitors, textile softeners, stabilizers and / or activators for the bleach, corrosion inhibitors, antimicrobials, dirt carriers, enzymes, detergents, colorants and fragrances. etc.

The products of the invention can be used in numerous fields in the art and household of the 24

DK 154346 B

\ most diverse purification tasks. Examples of such applications are cleaning of utensils and containers of wood, plastics, metal, ceramics, glass and so on in industry or in commercial enterprises, cleaning of furniture, 5 walls, floors, ceramics, glass, metal, wood, plastics , cleaning of polished or varnished surfaces in the household and so on. A particularly important area of application is the washing of textiles of all kinds in the industry, in commercial laundries and in the household.

10

Preparation of the aluminum stylates

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 the aluminum silicates.

a) To the aluminum silicate solution, in a container of 20 15 liters was added with strong stirring the calculated amount of sodium in 1 icate solution (temperature of the solution: 20-80 ° C). Thereby, under exothermic reaction, as the primary precipitation product, an X-ray ammonium-sodium aluminum silicate formed. After 10 minutes of vigorous stirring, the suspension of the precipitate product was either further processed directly; that is, 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.

Β) 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 file (of al) and 62 (of a2, respectively).

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25 »γ) A microcrystalline aluminum silicate leaf made by adding to the diluted alorminate solution diluted with deionized water, stirring with a fast-moving, intensive stirrer (10,000 rpm, make: 5" Ultraturrax " from the firm Janke & Kunkel IKA-Werk, Stauf-fen / Breisgau / Federal Republic of Germany). After 10 minutes of vigorous stirring, the suspension of the amorphous precipitate product was transferred to a crystallization container, where formation of large crystals was prevented by stirring the suspension. After extraction of the liquor from the crystal crop and after washing with ionized water until the borite running wash water had a pH of about 10, the terrestrial residue was dried, then ground in a ball mill and we separated two fractions in a centrifugal force sieve. (Microplex windscreen from Al-15 pine, Augsburg, Federal Republic of Germany}), of which one fraction contained no constituents above 10 μ. Of the fine fraction was prepared a suspension in deionized water (yl). A similar suspension was prepared without the drying and splitting into two fractions. In other words, the EB still moist 20 filter remnants with different water content were introduced 1 water. Ban resulting suspension is referred to as y2. Instead of filtration, the separation of the silicates from most of the water present from the beginning was also performed by centrifugation.

25 The aluminum silicates produced had the approximate composition calculated on anhydrous products (= AS): 1 Na 2 O. 1 A1203. 2 SiO 2.

30

The calcium binding capacity of the precipitate product was found to be 150-175 mg Ca0 / g of active substance. It was ascertained as follows: To 1 liter of an aqueous solution containing 0.594 g of CaCl 2 (= 300 mg CaO / liter = 30 ° dH) and adjusted to a pH of 10 with dilute NaOH is added. 1 g aluminum silicate (calculated on AS). Then the suspension is stirred for 15 minutes at a temperature of 22 ° C (+ 2 ° C). After filtering off the aluminum sieve, the residual x content of the filter 26 is determined

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filtrate. Hence the calcium binding capacity in mg CaO / g AS is calculated by the formula: (30-x) · 10.

Preparation conditions for all aluminum sulfate in cat I: 5 Precipitation: 2,985 kg of alaminate solution of the composition: 17.7% Na 2 O, 15.8% Al 2 O 3, 66.6% H 2 O.

10 0.15 kg of ethanol 9,420 kg of water 2.445 kg of a commercially prepared water-15 glass and slightly alkali-soluble silicic acid, 25.8% in sodium sicate solution of the composition: 1 Na 2 O, 6.0 STO 2

Crystallization: 24 hours at 80 ° C

Drying: 24 hours at 100 ° C

Composition: 0.9 Na 2 O. 1 AI2O3. 2.04 SiO 2. 4.3 H₂O (= 21.6% H₂O)

Crystal grade 1: fully crystalline

Calcium binding capacity: 150 mg CaO / g AS

Drying the resulting product for 1 hour at 400 ° C gives an aluminum silicate 1a with the composition: 0.9 Na 2 O. 1 A1203. 2.04 SiO 2. 2.0 H 2 O (= 11.4% H 2 O) also suitable for the purposes of the invention.

27

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Preparation conditions for aluminum silica II: Precipitation: 2.115 kg of aluminate solution with the composition: 17.7% Na 2 O, 15.8% Al 2 O 3, 5 66.5% H 2 O 0.585 kg ether 9.615 kg water 10 2.685 kg of a 25, 8% sodium sodium in 1 ml solution with the composition: 1 Na 2 O.

6 SiO 2 (prepared as listed under I) 15

Crystallization: 24 hours at 80 ° C

Drying: 24 hours at 100 ° C and 20 hours dry Composition: JO, 8 Na2 O. 1 Al2 O3. 2,655 SiO 2. 5.2 H2 O

Crystallization degree: fully crystalline Calcium binding capacity: 120 mg CaO / g AS.

This product can also be dewatered by post-drying (1 hour at 400 ° C) to the composition: 0.8 Na 2 O. 1 A1203. 2.65 SiO 2. 0.2 H2 O

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

35 Aluminum screens 1 and II in the X-ray bending diagram show the following interference lines:

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28

d values recorded with Cu-Ka currents in A I II

5 - 14.4 12.4 8.8 8.6 7.0 10 - 4.4 (+) 4.1 (+) 3.8 (+) 3.68 (+) 3.38 (+) 3.26 ( +) 2.96 (+) - 2.88 (+) 2.79 (+) 2.73 (+) 20 - 2.66 (+) 2.60 (+)

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 crystal1 in the sera. Therefore, for the characterization of these types of main d-values, they are characterized by a "(+)".

Preparation condition for aluminum silicate VIII: 30 Precipitation: 2.115 kg of aluminate solution of the composition: 17.7% Na 2 O, 15.8% Al 2 O 3, 66.5% H 2 O.

0.585 kg etching sodium 9.615 kg water 35 29

DK 154346 B

2.685 kg of a 25.8% in sodium sulfate solution containing the composition: 1 Na2 O, 6.0 S10 O2 Crystallization: Above age

Drying: 24 hours at 100 ° C

Composition: ©, 8 Na20. 1 A1203. 2.65 SfiOO2. 4 H2O 10

Crystal Degree of Degree: r / x-ray amorphous

Calciumbindeevne-. <S (0 mg CaO / g AS 15

Preparation conditions for aluminum sieve 1 icat IPX: Precipitation: 3 "41 kg of aluminate solution with the composition: 21.4% NajpD ,, 15.4% AI2O3,

63.2% H 2 O

m., 46 kg of water of 13 kg of a 34.9% in sodium sieve 1 icat solution of the composition: 1 Na30.

3.46 SiO3

Crystallization: [lapses

Drying: 24 hours at 100 ° C

Composition: 1 Na 2 O. 1 AI2O3. 1 Si02. 11.4 H 2 O

Crystal 1 in satiation degree: X-ray amorphous

Calcium binding capacity: 120 mg CaO / g AS

30

DK 154346 B

Preparation conditions for aluminum silicate XXm: Precipitation: 0.76 kg alumina solution of the composition: 36.0% Na 2 O, 59.0% Al 2 O 3, 5.0% 5 H 2 O 0.94 kg ether sodium 9.49 kg water 10 3.94 kg of a commercially available sodium sulphate solution containing the composition: 8.0% Na 2 O, 26.9% SiO 2, 65.1% H 2 O

Crystallization: 12 hours at 90 ° C

Drying: 12 hours at 100 ° C

Composition: 0.9 Na 2 O. 1 A1203. 3.1 SiO 2. 5 H2 O

Crystal grade 1: fully crystalline

Calcium binding capacity: 110 mg CaO / g AS

examples

The abbreviations used below mean; "TA + x E0" means a ten alloying product of x moles of E0 per mole of a substantially saturated fatty alcohol produced by the reduction of sebum fatty acid, consisting of a mixture of alcohols having different numbers of carbon atoms, approximately in the following formulation. division: C12: 0-2% C14: 4-7% 31

DK 154346 B

C16: 25-35%

CO 2: 60-67% C 2q: 0-2% 5 "Coconut-Cig-18 + 6 EO": an ethoxylation product of 6 moles of ethylene oxide per mole of a substantially saturated, by reduction of coconut fatty acid and subsequent distillation prepared fatty alcohol reaction, which consists of equivalents of Cøø alcohol and C88 alcohol and containing less than 2% C1414 and C ^ ø alcohol.

"Oxo + 5 EO": is the ethoxylation product of tendon obtained by oxosynthesis alcohol mixture having the following composition:

The branch chain Branched 15 C 15: 1.5% 0.9% 0.6% C 16: 29.7% 10.5% 119.2% C 17: 41.5% 12.4% 229.1% C 18 : 21.4% 8.2% 113.2% 20 C 19: 5.2% 0.6% 4.6% 32.6% 666.7% which alcohol blend is reacted with 5 moles of ethylene oxide per mole of alcohol.

25 "0A + 10 E0": a tertiary product of ethylene oxide for technical oleyl alcohol in the molar ratio of 10: 1.

"EDTA" means the salt of ethylene diamine tetraacetic acid.

"CMC": the salt of carboxymethyl cellulose.

"ABS" means the salt of a benzene which is condensed by condensing straight-chain olefins and sulfonating the resulting alkylbenzene-alkylbenzene sulfonic acid having about 11-1 carbon atoms in the alkyl chain.

"Water glass" means a sodium sieve 1 in cat (Na 2 O: Sitfc2, accounting)

DK 154346 B

32 "Perborate" means a technical product having the approximate composition: NaBO2, H2O2 / 3 H2O.

All saline compounds were used as sodium salt.

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

"Cop 1": lauric acid monoethanolamide.

"Cop 2": ant isoic acid monoethanolamide.

"Cop 3": lauric myristic acid monoethanolamide.

"Cop 4": coconut fatty acid monoethanolamide.

"Cop 5": lauric myristic acid diethanolamide.

"Cop 6": oleic acid diethanolamide.

"PVA" means polyvinylal carbon (molecular weight> 1500).

Suspensions of the Invention 25

Example 1

The suspensions according to the invention are illustrated with the microcrystalline aluminum silicate 30 prepared according to γ2 as an example, since this is preferred for preparation according to the invention of detergents. Similarly, suspensions according to the invention can also be prepared with the suspensions / 31, / 32 and yl, respectively, with corresponding aluminum silicates isolated as solids.

155-195 g of humid aluminum silicate (method y2; the amount of moist aluminum silicate used was adjusted to the water content so that in each case 35

DK 154346B

33 introduced the same AS) was introduced into a mixture of as many parts of water and dispersant as the resulting mixture exhibited an aluminum silicate content as active substance in the range of 30 to 38% by weight. The amount of ethoxylation product added was 1, 3, 3% by weight. Work was done at room temperature. The dispersant used was the dispersant listed in Table I, for which also the point of clarity is indicated. Some suspensions and the components from which they were formed are listed in Table 2.

Table 1

Cloudiness point ° C

Ethoxylation product used. DIN 53917 15 ._ 1. TA + 2 EO 58 2. TA + 4 EO 71 3. TA + 5 EO 77 20 4. TA + 7 EO 83 5. Mixture of TA * 2 EO and TA + 7 EO (1: 1) (77) 6. Mixture of TA 40 EO (unethoxylated tallow (76) alcohol) and TA * 7 EO (1: 1) 7. Mixture of TA - * 2 EO and TA + 12 EO (1 : 1) (76-77) 25 8. Mixture of TA * 5 EO and TA + 12 EO (1: 1) (83) 9. Coconut -Cie-18 * 6 EO (80)

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

30 35 in 34

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Table 1a

Cloudy point ° C

Other stabilizers used in f1 g. DIN 53917. 5 _

Myristinic acid monoethanolamide 59

Lauric acid monoethanolamide 59

Lauric Acid Ant Acetic Acid Monoethanolam Id 61.5 10 Acetic Acid Diethanolamide 77.5

Lauri nsyremyristi nsyrediethanolamide 87

Stearic acid monoethanolamide 64

Talgamine + 5 E0 (ethylene oxide) 83.5

Talgamin 40 15 Unsaturated tallow alcohol + 5 EO 72

Coconut fatty acid monoethanolamide + 2E0 79

C2-C14 ~ fatty acid + 4 EO approx. 68

Cocosamine + 2 EO

Nonylphenol with 6.5 EO 72 20 Nonylphenol with 7 EO 73 25 30 35 35

DK 154346 B

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Table 2 lists:

Column 1: "AS content", the active substance content of the humid aluminum silicate used.

5

Column 3 and 4: "AS in suspension", the active substance content of the suspension formed in grams, wt%, respectively.

Column 2: The amount of humidified aluminum alloy silicate 10 used.

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

Column 6 and 7: The ethoxylation product used and the amount thereof used in grams, respectively,%.

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

Example 2 A suspension of 31 wt% pure, microcrystalline aluminum silicate, prepared according to γ 2, 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" means the primary amine corresponding to the above-defined tallow alcohol) and tallow fatty acid. Suspensions made in this way can be stable for months.

35

Example 3

Powdered rice-resistant detergents of the composition listed in Table 3 were prepared as follows: 37

DK 154346 B

A stock suspension prepared from introducing a humid aluminum silicate made according to γ2 into a dispersion of the dispersant heated to 70 ° C and having a content of 36% by weight of aluminum and 2% by weight of TA + 5 EO, calculated on the total weight of the suspension, from a storage container was pumped into a container in which, with stirring one after the other, the other components and so much water were introduced so that a detergent slurry containing about 45% by weight of water was formed.

10

This was supplied with pumps to the atomizer nozzles at the upper end of a nebulizer tower and veil nebulization and guidance of warm larvae (about 260 ° C) in counterstain converted into a fine powder.

15

Table 3

A B

ABS 1.4% TA + 10 EO 7.0% OA + 10 E0 8.0% TA + 5 Εθ2) 2.0%

Sodium triphosphate 7.8% Sodium triphosphate 20.0%

Water glass 5.4% Soda 5.0% 25 CMC 0.8% Water glass 3.0%

Aluminum sieve icatD) (AS) 36.0% CMC 1.8% .TA + 5 E0 2.0% Aluminum sieve 1 iocatl)

Residue: water and Na2 & D4 (AS) 18.0% TA + 5 EOU 1.0% 30 EDTA 0.5%

MgSiO3 2.5%

Perborate3) 28.0% Soap 2.5%

Residue: water and ff ^ SO * 35 _ 2) TA + 5 E0 added together with the other components.

1) Introduced with the stem suspension.

3 i Τί 1 eaf aff an ne 4 * m \ t n i nn An

DK 154346 B

38 Instead of a suspension stabilized with TA + 5 EO, a detergent corresponding to B can also be used with suspensions containing, for example, polyacrylate, which are also very stable and also well pumpable. Since polyacrylate is a complexing agent for calcium, the amount of sodium triphosphate can be reduced accordingly. However, in the manufacture of ABS-containing detergent, an ABS-containing suspension according to the invention can also be used, in which case an ABS with 11-13 C-10 atoms is used in the alkyl residue. Stabilization is thus somewhat inferior.

Example 4 I5 Pump and stand-off experiments with all aluminum silicate suspensions In the heated to 65-70 ° C emulsions of 190-360 g of water and 10-30 g of dispersant, with stirring, 594-780 g of sodium aluminosilicate with different water contents were introduced and homogenized. . The amount was dosed such that the AS content ranged from 31-34%. The homogeneous suspensions were pumped around with continued stirring by means of a hose pump (brand IKA P 20) for 1 hour at room temperature. Then the pumping and stirring stopped for 1 hour. Thereafter, stirring and re-pumping were continued. In a comparison experiment without the use of dispersant, no more could be stirred and pumped.

After a further 4-6 hours of re-pumping and stirring, the suspension was allowed to stand overnight and the deposition conditions at room temperature were visually tested afterwards, or after several days standing. The indication: "precipitate = 100%" means that the suspension is completely (100%) 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 listed substances appeared to be useful dispersants

DK 154346 B

39 auxiliary aids as they thus produced Oxygenated suspensions could easily © stirred and pumped.

The individual materials can be seen by the following tabular 5 composition. An aluminum silicate of the approximate composition Na 2 O, Al 2 O 3, 2 SiO 2, which was used in the still moist form of the manufacture, was used, according to | 82. The particle size was predominantly between 5 and 15 µ.

10 15 20 25 3α 35 40

DK 154346 B

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DK 154346B

41

Notes for the table:

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

(2) The moist aluminum silicate was quenched 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 the addition of the sodium aluminum silicate Ltii 1 pH 10 with sodium hydroxide solution. Alternatively, poly (a-hydroxyacrylic acid) was also used.

(4) Pump capacity after x means: - = no longer pumpable.

+ = pump in g.

(5) The polyvinyl alcohols used are heavily soluble in water; therefore, at the expense of the amount of water, alternating amounts of dimethylsul foxide (20-87 g) were added as solvent. With the use of 1% PVA 900, the addition of dimethyl sulfoxide could be waived.

The polyvinyl alcohols used are commercial products (Mowiol from Farbwerke Hoachst) and, as most well-known, have been found "Mowiol 76/98".

30

Example 5

Suspensions according to the invention are prepared by introducing products I, II, 3KIII, IX and XXm respectively into a preheated dispersion of TA + 5 ED in water to form silicate suspensions with 33% / GS content and 2% content of TA + 5 E0.

42

DK 154346 B

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.

5

Example 6

A humid aluminum silicate made according to 2, leached to a pH of about 10.5 and having the approximate composition Na 2 O, Ο β, 2 SiO 2, having a water content of 50%, is introduced into an aqueous solution of a ) 1,3-hydroxyethane-1,1-diphosphonic acid 15 b) dimethylaminomethane diphosphonic acid, forming suspensions with a solids content (AS content) of 31% and a dispersant content of 2%.

20

The phosphonic acids are used as 1) tetrasodium salt 2) di sodium salts and 3) free acids.

The suspensions can be processed into detergents by incorporating surfactants and optionally other detergent ingredients, for example by subsequent spray drying.

Example 7

In accordance with Example 6, suspensions of 35% sodium aluminum silicate and 4% phosphoric acid butyl ester or phosphoric acid ooctyl ester (adjusted to pH 10) are prepared.

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Phosphoric acid terms are products with about 3. 5 mol of alcohol per mol of phosphoric acid.

Example 8 5

In accordance with Example 6, a suspension of sodium aluminum urns in 1 in cat with 31% AS content and an alkyl benzene sulfonate (ABS) content of 4% was obtained. AB3S was used partly as salt and partly as free acid. Also used is a sulfonate obtained from the methyl ester of ferrous cured fatty acid by sulphoning with SO3 or a rolef insulphonate, which is obtained by sulphonation of 1 chain, internalized definers, with 12-18 C atoms and hydrolysis of the sulphonation product. The strong foaming agent suspension 15 could be removed without difficulty by inserting small quantities of a commercially available silicone foaming agent. The suspensions are particularly suitable for suspending slurries for the production of aluminum-containing detergents. However, they can also be spray-dried as such and converted into powdered water softeners or detergent builder fabrics.

Example 9 25 Similar to Example 4, aluminum silicate suspensions with 31% AS content and a content of the following dispersants (% AS,% dispersant) were prepared: a) stearic acid monoglyceride (31/2) 30 b) stearic acid propylene glycol ester (31/2) c) reaction product from the reaction of tallow and N-hydroxyethylethylenediamine (31/2) 35 d) tallow amine (long chain amine derived from tallow fatty acid by reduction) (31/2) 44

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e) addition product with 5 moles of ethylene oxide per mole of talgamine (31/2) f) oleyl alcohol with 5 moles of ethylene oxide per mole of alcohol 5 (31/2) g) mixture of saturated O₂ (70-75%) - and C14 (25-30) %) - Alcohols ethoxylated with 3-4 moles of ethylene oxide (31/3) 10 h) Corn starch (31/1) or carboxymethyl cellulose i) Poly (α-hydroxyacrylic acid) (31/2) k) Polylactone of poly ( α-hydroxyacrylic acid) (31/2).

15

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 (for example, pentane sodium triphosphate) directly to granules.

Example 10

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

Example 11 35 In suspensions of bentonite in water, at about room temperature, a moist silicate containing 50% water was introduced and of the formula Na 2 O, Al 2 O 3 »2 SiO 2. The stabilized suspensions exhibited an AS content of 33% and a bentonite content 45

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teams of 2 and 4% respectively. The iteentonite used was a commercial product which was on the market under the name "Aktiv-Bentonite" from the firm Erbsloh, Federal Republic of Germany.

5

Analytical composition: S1O2 56.8 Al2 O3 20.1 10 Fe2 O3 4.8

CaO 1.8

MgO 4.0 K2O 0.7

Na20 3.1 15 Glow loss 5.7

Also bentonite "Montigel F" from SUdchemie ΑΏ "Federal Republic of Germany, just used.

20 The naturally-occurring or naturally-produced products have generally iron-deficient contaminants as well as silicate contaminants. Commercial products are, in addition to the "Active-Bentoni t" (Erbsloh, Federal Republic of Germany), "Volclay" (Bentonite International), 25 "Eurogel" (Amberger Kaolinwerke, Foitbund Republic not Germany). Synthetic products are available, among others. from Lange & Co., Bremen.

Detergents can be prepared with aluminum silicate suspensions, however stabilized with bentonite or a synthetic, smectite-type silicate, combining the stabilized suspension with the other ingredients to form the agent to be prepared, slurry containing about 50% by weight of water and then drying it in a hot air stream.

For example, a product similar to the following recipe may be prepared:

Claims (4)

5 Water Glass 3.0% CMC 1.8% Aluminum Si 1 in Cat (AS) 18.0% Bentonite 1.1% EDTA 0.5% 10 MgSiO3 2.5% Perborate 28.0% Soap 2.5% Residue: water and Na 2 SO 4, mixing the suspension containing 2% bentonite with the other detergent ingredients, except the perborate, to a slurry which is spray-dried in a customary manner in a hot air stream, and then mixing the resulting powder with the perborate. All of the suspensions described in the Examples were clearly improved in terms of stability and flowability. Surprisingly, the non-ionic surfactants of the compound class 4 have proved to be the best. 25 Patent claims. A process for the preparation of powdered detergents and detergents containing a water-insoluble silicate capable of binding calcium, by which, starting from an aqueous, liquid premix of individual constituents of the agent, in a conventional manner, produces a pourable product, characterized in that aqueous suspensions of aluminum silicates containing A) employ at least 20 finely divided, water-insoluble compounds suitable for the binding of calcium, and preferably containing water, and which has the general formula I (Kat2 / n0) x · Μβ2θ3. (SiO 2) y (I) 5 where Kat is a calcium-exchangeable catnoon with the 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 1.3-4, and B) 0.5-6% by weight of at least one di-barrier in the imidimide moiety of group 10 of the following compounds: 1. an organic macromolecular polymer compound having carboxyl and / or hydroxyl groups 2) a phosphonic acid having at least one additional phosphonic acid and / or carboxyl group, 3. a phosphoric acid alkyl ester emulsifier with 33-20 C atoms in the alkyl chain, 4. a nonionic surfactant having a cloudy peak in water butyl diglycolo; solution, determined according to DIN 53917, below 90 ° C; 5) a surfactant sulfonate; 6. a swellable, water-insoluble silicate coating structure. Process according to claim 1, characterized in that the suspension is mixed with at least one washing, bleaching or purifying additional component of the agent to be prepared and then converted in a manner known per se to the powder into a powdered product. . Process according to claim 2, characterized in that the suspension is combined with a further water-soluble surfactant which does not belong to component B, and optionally additional components of the agent, to be produced. Process according to claims 1-3, characterized in that the suspension, optionally after addition of other components of the agent to be prepared, is converted into a powdered product by spray drying. 10 15 20 25 30 35