KR810000660B1 - Improved process for detergent composition - Google Patents

Abstract

An aqueous suspension having a pH of between 7 and 12 of water-insoluble, calciumbinding aluminosilicates with an improved stability against settling consisted of water-insoluble silicate compound having a calcium-binding power of at least 50mg CaO/mg of anhydrous active substance and a primary particle size of from 0.1 to 100 μ and having the formula, (M2O)x.Me2O3(SiO2)y (M = Na or K; X = 0.7-1.5; Me = Al or B; Y = 0.8-6) and organic dispersing agent selected from the group consisting of the free acids and alkali-metal salts.

Description

Improved manufacturing process of cleaning and cleaning agent compositions

The present invention relates to stable suspensions of insoluble silicates capable of binding to calcium ions and their use in the production of cleaners.

One of the most serious problems in the detergent industry is the problem of partial or total substitution by other materials of the phosphate-bound calcium complexes used to date. Previous patents (eg, patent application number 15797 / 74,2161 Korea) describe processes for cleaning solids, especially textiles, and describe detergents suitable for carrying out the process, where phosphate-linked calcium The role of the Compurex is replaced by insoluble boron or aluminum silicates, which are wholly or partially finely dispersed, which can bind calcium and generally contain bound water.

These silicates have the following general formula (1).

Where Cat is n and is a cation exchangeable with calcium, X is a number from 0.7-1.5, Me is boron or aluminum, Y is 0.8-6, generally 1.3-4.

Sodium is usually used as a cation, but can be replaced by lithium, potassium, ammonium or magnesium and also has a cation of soluble organic bases, eg a primary having up to two carbon atoms per alkyl group and three carbon atoms per alkanol group Or secondary or tertiary amines or alkanol amines.

Compounds that can bind to the calcium specified above are simply referred to as aluminum silicon acid salts. This applies in particular to the sodium aluminum silicon salts which are frequently used. All details relating to their use in accordance with the invention and also to their production and properties apply similarly to the compounds specified above.

Ammonium silicates, particularly those suitable for use as detergents, usually have a calcium binding capacity of 50-200 mg (mg) CaO per gram of anhydrous aluminum silicon salts (aluminum silicates). Referenced below to anhydrous aluminum silicate refers to the state of aluminum silicate obtained after drying at 800 ° C. for one hour. During this drying process the adherent water is almost completely removed.

In addition to the constituents of the formulation itself, in the production of cleaning agents, the above-mentioned aluminum silicates are produced, which is advantageous to start with the damp aluminum silicates produced. The moist compounds are mixed with other constituents of the material to be produced and the mixture is converted to a finished detergent which is porous as the final product. In the production process of the above-described cleaning agents, aluminum silicates are supplied or used, for example, in the form of an aqueous suspension or a wet filter cake. In this case, some improvement in the properties of the suspending agent is desired, for example the stability of the suspension and the pumping ability of the aluminum silicates dispersed in the water phase.

To date, some compounds have the special ability to stabilize suspensions of the aforementioned calcium-bonded aluminum silicates, so even if they have a high solids content, these silicates are stable for long periods of time and, if necessary, In fact, it can be stable for almost unlimited periods of time and can be pumped without any difficulty after a long period of time. Surprisingly, it is evident that even in the case of moist aluminum silicates having a water content of less than 70%, there are certain compounds that can maintain their pumping capacity regardless of their storage time, which has not been possible until now.

The present invention provides a pumpable, aqueous suspension of insoluble silicates capable of calcium binding, which has improved stability and is suitable as a storage suspension, which contains the following for the entire intangible of the aqueous suspension.

A) At least 20%, usually 20-53%, in particular 20-42%, finely dispersed insoluble compounds, capable of binding calcium, preferentially containing bound water and having the general formula:

The symbols used here have the meanings mentioned above.

(B) contains at least one dispersant selected from the following compounds.

i) organic, polymeric polymers with carboxyl and hydroxyl groups, ii) phosphates with at least one other phosphate group and / or carboxyl group, iii) phosphate alkylester emulsifiers with 3-20 carbon atoms in the alkyl chain. , IV) non-ionic surfactants having a turbidity point of 90 ° C. or lower, V) surfactant sulfonates, Vi) expandable and insoluble silicates, measured according to DIN 53917, in aqueous butyl dicyclyl solution Acid compounds are used as such or as insoluble salts and are generally ionized in the suspension according to their Pk value and the Ph value of the suspension. The pH value of the suspension is generally in the range of approximately 7-12, preferentially 8.5-11.5, and generally lower than 11. The above compounds are essential components of the suspensions according to the invention. But they also contain other components, such as so-called dissolution media or antifoam additives (antifoams) such as compounds which improve the solubility of the dispersant in the water phase.

Common foam inhibitors are used as foam inhibitors, such as foam inhibitor soaps, silicone antifoams, foam inhibitor triazine derivatives, all of which are well known and common in the art. Usually it is not necessary to add these, but it is preferred to use bubble dispersants, especially when large amounts of alkylbenzene sulfonic acid are used.

It is generally not necessary to add dissolution media, but it is preferred if the suspension according to the invention contains a hydrophilic but almost insoluble in water such as polyvinyl alcohol. For example, dissolution aids (medium), a very suitable material for this purpose is dimethyl sulfoxide, which is useful when the concentration of a Group 1 stabilizer is used that is only slightly soluble in water.

The proportion of dissolution aid contained in the total suspension is, for example, about the same as that of the stabilizer. Other compounds suitable as dissolution aids are generally known in the art. Hydrotropic agents or octyl sulfates such as benzene sulfonic acid, toluene sulfonic acid, xylenesulfonic acid or their water soluble salts are suitable. All details related to the concentration of aluminum silicates relative to the content of powdered substance or the content of "active substance (= A S)" refer to the aluminum silicates obtained after drying at 800 ° C. for 1 hour. During this drying process, the adhesive and bonded water are almost completely removed.

All percentages here are by weight. Let's take a closer look at the components A and B mentioned above.

In the case of the aluminum silicates to be used, component A is an amorphous or crystalline product. Of course, mixtures of amorphous and crystalline products and also partial crystalline products are used. Aluminum silicates are naturally occurring or synthetically produced products and are generally produced synthetically.

Production is effective, for example, when reacting water soluble silicates with water soluble aluminate salts in the presence of water.

For this purpose the aqueous solutions of the starting materials are mixed with one another or the solid component is mixed with other components in the form of an aqueous solution. Preferred aluminum silicates are also obtained by mixing the two in the presence of water when both components are solid. Aluminum silicates may also be obtained by reacting Al (OH) ₃ Al ₂ O ₃ or SiO ₂ with alkali silicate or alkali aluminate solutions. Production may be affected by known processes. The present invention relates in particular to aluminum silicates having a three-dimensional spatial lattice structure as opposed to silicates having a stratified structure such as montmorillonite.

In general, the calcium binding capacity is in the range of approximately 100-200 mgCaO per gram of AS (active substance), and generally 100-180 mg CaO per gram of AS, which is most commonly found in compounds having the following composition.

0.7-1.1 Na ₂ O Al ₂ O _3, 1.3-3.3 SiO ₂ ,

This compound includes two different crystalline structures (or their amorphous preproducts), which are also different in their formulas as follows.

a) 0.7-1.1 Na ₂ O, Al ₂ O _3. 1.3-2.4 SiO ₂

b) 0.7-1.1 Na ₂ O, Al ₂ O _3. 2.4-3.3 SiO ₂

The different crystalline structures can be seen from the X-ray diffractogram. The amorphous or crystalline aluminum silicate present in the aqueous suspension can be separated from the remaining aqueous solution by filtration and dried at a temperature of 50-400 ° C.

The product contains more or less bound water depending on the drying conditions. Too high a drying temperature is generally undesirable. When aluminum silicate is to be used as a cleaning agent, it is preferable not to exceed 200 ° C.

However, according to the invention, after their production, the aluminum silicates do not need to be dried for the preparation of the suspension. Instead, the still damp aluminum silicates produced can be used, which is particularly economical. However, aluminum silicates dried at 80-200 ° C. at moderate temperatures until the water attached is removed can also be used in the preparation of the suspensions according to the invention.

The size of the individual aluminum silicate particles varies widely, for example in the range of 0.1 μ-0.1 mm. This refers to the size of primary particles, ie particles that occur during precipitation or subsequent crystallization. It is particularly advantageous to use aluminum silicates which are at least 80% aqueous with particles ranging in size from 10-0.01μ, in particular 8-0.1μ.

These aluminum silicates preferentially do not contain primary or secondary particles larger than 30 microns in diameter. The term " secondary particles " here means that the primary particles formed larger particles by aggregation. The most important category is in the range of approximately 1-10 μ.

It has been found to be particularly suitable for the agglomeration of primary particles to form larger structures to use the aluminum silicates produced and still moist to make the suspension of the present invention, because using these still moist products, secondary particles It is clear that the formation of these fields is almost completely excluded. More details of the compounds used in accordance with the invention as component B will be mentioned below.

Suitable polymerizable polycarboxylic acids (i) are usually water soluble but are also insoluble polymerization products. The polymerizable polycarboxylic acids used are polymers of monomers which can be polymerized with carboxyl groups or polymers of polymerizable monomers which are only subsequently converted to polycarboxylic acids.

In addition to carboxyl groups, polycarboxyl groups also contain other functional groups, such as hydroxy groups, which are also etherified or esterified with small molecules, especially aliphatic groups. Polymerizable polycarboxylic acids of this type are copolymers of poly- (α-hydroxy acrylic acid) and acrylic acid, especially maleic acid, vinylmethyl ether or vinyl acetate. Since the vinyl acetate units in the polymer are fully or partially hydrolyzed, products are produced that are considered copolymers of unsaturated carboxylic acids with imaginary vinyl alcohols.

The carboxyl groups in the polymerizable polycarboxylic acids are not only partially substituted by mention of hydroxyl groups, for example by appropriate copolymerization with the appropriate monomers, but also all the carboxyl groups are substituted by hydroxy groups as mentioned. It is also clear that the present invention is appropriate. Thus, macromolecular polyhydroxy compounds are obtained. Polyvinyl alcohol is considered a sample of a suitable macromolecular polyhydroxy compound. Polyvinyl alcohol can be obtained by hydrolysis from polyvinyl acetate. Hydrolysis should never be complete, in order that polyhydroxy compounds can be used in accordance with the invention. Rather, products containing esterified hydroxy groups such as oxyacetyl groups in addition to hydroxy groups are suitable. The molecular weight of the polycarboxylic acids or polyhydroxy compounds used is wide. Particularly suitable are polymers having a molecular weight of at least about 1500, in particular at least 20,000. However, compounds with very large molecular weights are also very suitable, and preferred polycarboxylic acids are also water soluble. Low water solubility of the foregoing compounds requires the addition of dissolution aids as already mentioned. This applies essentially to polyhydroxyl compounds that do not contain carboxyl groups. The presence of the groups promotes water solubility and the solubility of the polymerizable polycarboxylic acids depends, therefore, on their carboxyl group content and is generally very good.

When the macromolecular compounds used according to the invention have ionic groups in aqueous solution, they are preferentially used in the form of water-soluble salts. Economically, alkali salts, in particular sodium salts, are included.

Polymers such as acrylic acid, hydroxy acrylic acid, maleic acid, itaconic acid, mesaconic acid, aconic acid, methylene malonic acid, citraconic acid, copolymers of carboxylic acids mentioned above, or compounds unsaturated with ethylene For example, with ethylene, furopropylene, isobutylene, vinyl alcohol, vinyl methyl ether, furane, acrolein, vinyl acetate, furan, acrolein, vinyl acetate, acrylamide, acrylonitrile, methacrylic acid, crotonic acid, etc. Suitable polymers are copolymers, such as 1: 1 copolymers of maleic anhydride with ethylene, furopropylene, or furan.

Poly acrylic acid and poly- (α-hydroxyacrylic acid) mentioned above are examples of particularly suitable compounds of group 1. The latter is used as the acid or in the form of internal lactones as well as in water-soluble salts. It is hydrolyzed in suspension.

Examples of products mentioned so far are generally straight chain polymers, ie those without side chains in their backbones.

In addition to the preferred synthetic polymers mentioned above, natural products are also used, for example alginates, carboxymethylcellulose, corn or potato starch or derivatives thereof. However, insoluble polymerizable three-dimensional cross-linked polyacrylic acids are also used. Their molecular weight range is very wide. In the case of poly- (α-hydroxy acrylic acid), the molecular weight of the commercial product is generally 20,000 or more, and in the case of the copolymer of vinyl methyl ether and maleic anhydride (monomer ratio 1: 1), the molecular weight of the commercial product is generally approximately 100,000 -2,500,000.

Another suitable group of stabilizers (ii) is phosphonic acids having at least one second phosphonic acid group or at least one carboxyl group. Alkane polyphosphonic acids, amino and hydroxyalkane polyphosphonic acids and phosphonic carboxylic acids are suitable acids, for example propane-1,2,3-triphosphonic acid, butane-1,2,3, 4-tetra phosphonic acid, polyvinyl phosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 1-amino-1-phenyl methane-1,1-diphosphonic acid, amino trimethylene triphosphonic acid, methylamino Or ethylene aminodimethylene diphosphonic acid, ethylene diamino tetramethylenetetraphosphonic acid, ethylenediamino tetra methylenetetraphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 2-phosphono-butane-1 And 2,4-tricarboxylic acid, 2-phosphonobutane-2,3,4-tricarboxylic acid, and copolymers of vinyl phosphonic acid and acrylic acid.

Emulsifiers in the form of partial esters of phosphoric acid are suitable for group (iii). These are esters having usually 1-2 moles of saturated alcohol, in particular 1.5 moles having 3-20 carbon atoms in the alkyl chain per mole of phosphoric acid. Esters of alcohols having 4 to about 10 carbon atoms, in particular those having 1.5 moles of butyl alcohol or dizooctyl alcohol, are suitable products.

Nonionic surfactants (iv) used according to the invention are largely insoluble compounds. Their turbidity, measured according to DIN 53917 in aqueous butyldiglycol solutions, is generally below 90 ° C and generally below 85 ° C. Accordingly, the clouding point (measured in 1% solution) of water of the appropriate compounds is about 55 ° C. or less, generally 35 ° C. or less. For particularly suitable products the cloud point in water is below room temperature.

The most suitable feature of the product is that they can be dispersed in water (one part of the surfactant for 19 parts of water), so when shaking slowly or with a slight force, if necessary, if the temperature is raised above the melting point of the surfactant, They form a milky dispersion and form a gel when cooled to room temperature.

The turbidity point measured according to DIN 53917 is generally at least 40 ° C but preferentially at least 55 ° C.

Details regarding the degree of dispersion in water or on the cloud point can be found in their pure technical form, e.g. in the case of ethoxylation of fatty alcohols, fatty acids, fatty acid amides or fatty amine moieties, statistical mixtures of ethoxylated products. As regards individual surfactant stabilizers.

Examples of suitable dispersants for the present invention are in particular nonionic surfactants, which have, as hydrophobic moieties, long-chain alkyl or alkenyl residues (usually having 10-20, preferentially having 12-18 carbon atoms).

Alkyl or alkenyl residues are mostly straight chains, but compounds with branched hydrophobic residues are also suitable. Unsaturated hydrophobic residues are generally unsaturated, one by one, such as oleic acid residues, and this is especially the case.

Hydrophilic groups are usually made up of polyalcohol residues such as ethylene glycol, propofylene glycol, polyethylene glycol, or glycerin residues, which are linked with hydrophobic groups in the form of ester, amide, ether or amino groups. Ethylene oxide adducts are particularly important. Preferred ethylene oxide precursors having the same cloud point usually have longer hydrophobic residues (C ₁₄ -c ₁₈ ).

Important groups in suitable compounds are carboxylic esters and carboxylic acid amides. In particular, dispersants suitable for the present invention are mono-di-ethanol amides of carboxylic acids having 10-20 carbon atoms, preferentially 12-18, in particular 12-14.

The compounds are generally saturated and derived from straight chain carboxylic acids. Examples of the amine compound from which the amides suitable for the present invention are derived are in particular mono ethanolamine and diethanol amine. However another particularly suitable product is an amide derived from carboxylic acid and N- (hydroxy-ethyl) ethylene diamine as specified above. Suitable amides are the reaction products of carboxylic acid amides with ethylene oxide. The number of ethylene oxide units in the reaction product is generally 1-6, in particular 1-4.

Ester type dispersants are derived from the same carboxylic acids as amide type dispersants. In the case of amides, the esters are derived from fatty acids or fatty acid mixtures, in particular natural or synthetic products having the aforementioned range of ring lengths. Suitable ester-type suspension stabilizers are adducts of carboxylic acids with ethylene oxide, for example products such as 1,2 or 3 moles of ethylene oxide adduct per mole of carboxylic acid and carboxylic acid. However, for example, it is doubtful whether products with 4-10 ethylene oxide units would be fine.

However, in the surfactant esters, polyalcohols having two or more hydroxy groups also exist as alcoholic components such as glycerin, for example. Examples of particularly suitable forms of amide or ester suspension stabilizers are as follows.

Lauric acid mono ethanol amide, palm fatty acid mono ethanol amide, myristic acid mono ethanol amide, palmitic acid monoethanol amide, stearic acid mono ethanol amide, oleic acid monoethanol amide, resin fatty acid monoethanol amide, and diethanol derived from the same fatty acids Amides and amides derived from N- (hydroxyethyl) -ethylenediamine.

Ester stabilizers can also be added to the addition of 1-2 moles of ethylene oxide to palm fatty acids and 1-2 moles of propylene glycol or glycerin to stearic acid or palmitic acid.

Particularly suitable diethanol amides are laurin-mistric acid diethanol amides (dietanol amides of fatty acid mixtures of lauric acid and myristic acid) and oleic acid diethanol amides.

Another particularly suitable stabilizer is the ethoxylated product of alcohols, which are generally saturated and have 10-20 carbon atoms and 1-8 moles of ethylene oxide per mole of alcohol. These ethoxylated products generally have 2-7, in particular 2-6 moles of ethylene oxide per mole of alcohol.

It is therefore particularly advantageous to use derivatives of straight chain alcohols within the scope of the present invention. However, branched alcohol derivatives, especially alcohols produced by oxo synthesis, can also be used. Particular preference is given to derivatives of straight-chain alcohols which are generally saturated and have 16-18 carbon atoms.

Ethoxylated products of alcohols having 12, in particular 14, carbon atoms can also be used, generally having 1-5 moles of ethylene oxide (EO) per mole of alcohol, in particular 2-4 moles of EO.

The ethoxylated products used according to the invention are generally not chemically homogeneous compounds, but are usually mixtures, in which the wholes with different degrees of ethoxylation coexist in statistical distribution. Most of the ethoxylations in the non-ethoxylated starting material, which are still present in small quantities, include ＂0＂. The ethoxylated products used according to the invention are actually insoluble compounds, and their cloud point as measured by DIN 53917 in butyl diclicol accommodation is usually in the range of 55-85 ° C. Representative products used preferentially are saturated fatty alcohol ethoxylated products derived from resin fatty acids, with a cloud point of 58,71,77, for a degree of ethoxylation of 2,4,5 or 7 moles of ethylene oxide per mole of fatty alcohol, respectively. Each having 83 ° C.

Alcohol components (e.g. C16-18) are mostly technical mixtures, which are alcohols with more or less carbon atoms, such as about 15% as the difference amounts.

Of the other components present, the following are other than% listed above.

Instead of the ethoxylated products of the alcohols mentioned above, the ethoxylated products of fatty amines may also be used, i.e., generally saturated primary amines with 16-18 carbon atoms and 1-8 moles of ethylene oxide per mole of amine. Ethoxylated products having Also within the scope of the present invention, nonethoxylated amines have proved to be suitable as surfactants. However, products with 2-5 moles of ethylene oxide per mole of amine are more suitable.

Suitable alkyl phenol products having a cloud point of atmospheric temperature or below 85 ° C. according to DIN 53917 are insoluble nonylphenolethylene oxide precursors having 5-8 moles of ethylene oxide per mole of phenol. Preferred is a whole with 6-7 moles of ethylene oxide.

(5) Examples considered as sulfonate-type surfactants include alkenes and hydroxys such as those obtained from alkyl benzene sulfonates (C9-15-alkyl), olefin sulfonates, ie, C12-C18 monoolefins. The C12-C18 monoolefins described above as a mixture of alkene sulfonates and disulfonates have double bonds at their ends or inside, which is achieved by SO ₃ gas sulfonation and alkali or acid hydrolysis of this sulfonate. .

Particularly suitable are also α-sulfo fatty acids, for example α-sulfonic acids from methyl or ethyl esters of hydrogenated palm, palm or resin fatty acids.

(6) Another dispersant suitable for the present invention is an insoluble, expandable silicate from a clay layer, which has a stratified structure instead of a three-dimensional space lattice in contrast to the aluminum silicates suspended by the invention. Silicates in the Pyeongchang stratified structure are called smectites. These are substances having the following general formula.

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

Examples thereof include bentonite, montmorillonite bolonscote, nontronite, hectorite, saponite, soconite and vermiculite.

Because they are capable of cation exchange, these expansive studies have cations such as sodium, potassium or calcium depending on their source.

Both naturally occurring and synthetically produced products are suitable and the advantage is that the synthetics usually have a higher purity. Most of the particle size of such stratified silicates is about 50 μm or less, and those having a low calcium content capable of binding with calcium are particularly suitable.

In addition to the individual dispersants mentioned above, mixtures may be used, in which case synergistic cooperation has been observed. For example, adding a resinous amine, carboxymethyl cellulose, crosslinked polyacrylate or alkyne acid to a surfactant stabilized suspension, e.g., stabilizers of group (i) and those of group (V), In particular, combinations with those of the group (iV) have proven beneficial. Long chain fatty acids form another class of compounds which further improve the properties of the stabilized suspensions according to the invention.

These fatty acids are generally saturated fatty acids, natural or synthetic, having, in general, 10-20 carbon atoms in the molecule, such as resin fatty acids.

Particularly preferred aqueous suspensions within the scope of the present invention generally have at least 20% of component A with an upper limit of component A being defined by the fluidity limit, in the range of 25-40% by weight for concentrations of approximately 42% by weight, A limit of approximately 28-38% by weight is particularly preferred. In practice, the range of 30-38% by weight is most important. The amount of component B used depends largely on the degree of stabilization desired for the suspension.

Generally, the concentration of component B in the suspension of the invention is approximately 0.5-6, in particular 0.8-6% by weight, based on the total weight of the aqueous suspension. Preferred is 1-4% by weight, in most cases 1.3-3% by weight. Since the viscosity of the emulsion is influenced by the content of component B, the desired viscosity must be taken into account and, if necessary, the viscosity can be taken into account when selecting the concentration of component B.

In the case of finer granulated aluminum silicates, a smaller amount of component B is used for its stabilization. So, for example, an aluminum silicate suspension with a particle size of 1-8 μm or more is satisfactorily satisfied with 0.5-1% by weight of dispersant, just as with 1-2% dispersant when the average particle size is 10-12 μm. It can be stabilized.

These values are approximate only.

The appropriate amount of component B to be used can then be determined by firm necessity. The viscosity of the suspension at 25 ° C. is generally 500-30,000 CPS, usually 1000 or more and 15,0000 CPS.

Especially suitable are suspensions having a viscosity in the range of 1000-9000.

In the scope of the present invention, particularly preferred aqueous suspensions generally consist of at least 20% of component A, at least approximately 0.5% of preferentially at least 0.8% of component B and water.

In addition to the components mentioned above, there are inorganic salts or hydroxides from precipitation or other production processes involving aluminum silicates. So if, for example, excess sodium hydroxide, sodium carbonate or sodium bicarbonate produced by the absorption of carbon dioxide gas from it is still present, or if, for example, aluminum sulfate is used as an aluminum-containing initial material in the production of aluminum silicate, Sulfate ions are also present.

In addition to the components A and B mentioned above, in addition to the substances still remaining from the initial material in the production of these components, the aqueous suspensions contain essentially a relatively small amount of other products. If the suspension is ready to be further processed for detergent formation, those additionally present materials are of course useful materials suitable as detergent components.

Standards for the stability of the suspensions are set by simple tests, whereby an aluminum silicate suspension of the desired concentration (eg 31%) is produced, which contains a dispersant according to the invention or a cleaning component such as pentasodium triphosphate. It contains substances in various amounts. The effect of the added substances can be observed visually during the preparation of the suspension.

After 24 hours, the preferred suspension generally subsides most of the time. To that extent, the supernatant free of silicate particles should be less than 20% of the total depth, preferentially 10%, in particular less than 6%. The amount of additional material is generally adjusted so that the suspension can be pumped satisfactorily after standing for 12 hours in the reservoir and the pipeline or hose line, preferably 24 hours, in particular 48 hours. The standing action of the suspension still containing other components is tested at room temperature as the suspension's total length of 10 cm. Particularly preferred suspensions include homologous clear liquids which are within the above-mentioned range even after 4 days, in particular 8 days. They are satisfactorily pumpable after 4 or 8 days, respectively.

This information relating to suspension stability only provides a reference and in each case defines the stability of the suspension. When a suspension of the invention stored in a storage tank for a relatively long time as a storage suspension can be withdrawn from it by a pump when necessary, for example, keeping other portions of the cleaner in small amounts or without all of these components is possible. It is advantageous.

Suspensions are produced by simply mixing the components, and the altium silicates can be used either as moist or aqueous suspensions from the production. It is particularly advantageous to introduce the produced and still moist aluminum silicates into the dispersed phase of component B in water. This dispersed phase of component B is generally slightly warmer, for example 50-70 ° C.

However, aluminum silicate is also used in the already dried state, that is, a dry body in which the adhesive water is removed and the bound water remains intact.

One particularly suitable method of producing the suspension of the present invention is as follows. Aluminum silicate is precipitated by mixing sodium aluminate and sodium silicate solution. These solutions have a higher alkalinity and because calculations require more sodium hydroxide to form aluminum silicates, there is more excess sodium hydroxide in the aluminum silicate suspension, which occurs as a direct precipitation product.

This suspension is further concentrated as a boiling point by filtration of the upper mother liquor, followed by the use of water to relieve the remaining sodium hydroxide, with the sodium hydroxide content in the solution of approximately 5% or less, preferentially 3% or 2 It should be less than%. The remaining sodium hydroxide is neutralized by the addition of acid, in particular the pH value of the suspension obtained by the addition of aqueous sulfuric acid is approximately 7-12, preferentially between 8.5-11.5. The amount of dispersant required to achieve the desired degree of stability is added to this suspension, which addition can be made before, during or after partial neutralization.

Thus, it is particularly beneficial to at least partially neutralize dispersants having acidity, such as macromolecular polycarboxylic acids or alkyl benzene sulfonic acids, as specified above. These acidic dispersants can be used as acids for neutralization and thus can completely or partially replace unstable acids, such as the sulfonic acids mentioned. Note the high stability and other advantages of the suspensions of the present invention. Their stabilizing effect is particularly valuable in aluminum silicates having a particle size of 5-30 mu. They are pumpable, allowing them to handle wet aluminum silicates in a simple way. After a relatively long pause in the pumping process, the suspensions can again be satisfactorily pumped. Because of their high stability, the suspensions can be transported to conventional tankers or tank trucks without any unnecessary or problematic risk of residue formation. In this way the suspensions are inherently suitable as a form of delivery to the detergent manufacturer.

Suspensions can be stored at ambient or higher temperatures and can also be delivered by pipeline, pump or other means.

Suspensions are mainly handled between ambient temperatures-mostly between 60 ° C.

The suspensions of the present invention are also particularly suitable for forming dried or flowable or sprayable products, ie they are suitable for producing powdered water softening formulations, for example by spray drying. Such suspensions are therefore also of great importance for the production of powdered aluminum silicates. Even when transporting the aqueous suspension to the drier, there are no problematic residues. Furthermore, to the best of our knowledge, the suspensions of the present invention allow for treatment to produce extremely powderless products.

Because of their particular stability, the suspensions of the present invention can be used as softeners, washing or cleaning agents of water, especially liquid laundry detergents having a high suspension stability, without further washing, bleaching, or further treatment with cleaning additives.

One particularly important use of this suspension is further processing to make detergents containing dry ingredients, as well as cleaning and cleaning agents which are dry or ductile or sprayable.

The suspensions according to the invention are particularly suitable for the production of the detergents described in patent applications 15797/74, 15798/74, 15800) 74 and all the information from their production, ie their components and their contents, is applicable as is. Do.

The present invention therefore also relates to a process for producing a flowable powdered product as described above containing insoluble aluminum silicates, while the effluent product is produced from an aqueous flowable premix of the individual components of the material in a general manner. .

A feature of the method is that aluminum silicates are used in the form of suspensions according to the invention. Suspensions of the invention can be treated to form solid spill type detergents by any known method.

In the production of powdered nebulizable detergents according to the method according to the invention, the work is carried out in particular, invented suspensions (e.g. in storage containers) for washing, bleaching, cleaning components of at least one of the resulting formulations. And the mixture is then converted to a powdered product by any method. Complex formers are usefully added, ie alkaline earth metal ions, especially those related to magnesium and calcium ions, which are related to water hardness can be added.

In producing the detergents according to the process according to the invention, the suspension is generally preferentially associated with at least one water soluble surfactant, which refers to a surfactant which does not belong to any component of component (B).

There are different variants for producing cleaners.

The suspensions of the present invention are combined with substances capable of binding crystalline water and usefully spraying the suspension with compounds that are pre-loaded into the mixer, and are thus combined with substances capable of binding crystalline water, resulting in a constant interaction between solid products that appear to be dry. Obtained in mixed state.

However, the suspensions of the present invention are preferentially mixed into a mortar and sprayed and dried with at least one other washing, bleaching or cleaning compound. In doing so, further surprising advantages of the removed aluminum silicate suspension are evident. In practice it has been shown that products with virtually no residue can be obtained using the spray suspension invention suspension. The products obtained by spray drying have a high calcium binding strength and can be wetted satisfactorily. The detergents according to the invention, ie the detergents produced using the suspensions mentioned above, can be combined in a wide variety of ways. They generally contain at least one water soluble surfactant which does not belong to the dispersant used according to the invention and they are present in the claimed aluminum silicate suspensions. The cleaning agents of the present invention may generally be compatible with the scope of previous patent applications described in their preparation and prescription. In addition to at least one other compound which has a washing, bleaching, or cleaning effect and is inorganic or organic, they contain aluminum silicates described as calcium binding compounds.

Moreover, other previous auxiliaries and additives, which are mostly present in relatively small amounts, may also be present in such formulations. For details, reference may be made to the previous patent application mentioned and the information is also applicable to the present invention.

The aluminum silicate content of such formulations is in the 5-95%, preferentially 15-60% category.

The formulations of the invention also contain complexing agents or precipitants for calcium whose effects depend on the chemistry of the formulation and preferentially appear in 2-15% content.

For agents with low phosphoric acid content, the inorganic phosphates or organophosphate compound portions should not be greater than the total phosphorus (P) content in the formulation corresponding to 6%, preferentially 3%.

Examples of other cleaning, bleaching or cleaning compounds contained in the cleaning or cleaning agents are surfactants which are not provided by the present invention for component (B), surfactant or non-surfactant foam stabilizers or inhibitors, fabric softeners. , Neutral- or alkali-reactive moldings, chemically reactive bleaches and stabilizers or accelerators thereof. Other auxiliaries or additives, which are mostly present in relatively small amounts, are, for example, corrosion inhibitors, antibiotics, dirt media, enzymes, luminaries, colorants and fragrances.

Representative fabric cleaners used within the temperature range of 50-100 ° C. are in the following plaque categories:

Surfactants used according to the invention as 3-30% anionic, mixed or nonionic surfactants, preferentially 5-30%, 5-70% aluminum silicates (for AS), Including silicates of stratified structure used according to the invention. Contains complex forming agent for component (B) as complex forming agent for 2-45% calcium.

Washing alkali (= alkaline moldings) capable of forming 0-50% complex.

0-50% bleach and other additives usually present in relatively small amounts in fabric cleaners.

The following is a list of materials suitable for use in the present formulations.

Surfactants contain at least one hydrophobic organic residue and one anionic, mixed or nonionic water-soluble group in the molecule. Hydrophobic residues are usually alkylaromatics having aliphatic hydrocarbon residues having 8-26 carbon atoms, preferentially 10-22, in particular 12-18, and aliphatic carbon atoms 6-18, preferentially 8-16. Residues.

As examples of the anionic surfactants, naturally or synthetically saturated fatty acids or soaps are used. Suitable synthetic anionic surfactants are those in the form of sulfonates, sulfates, and synthetic carboxylates.

Suitable surfactants in the form of sulphates are sulfuric acid monoesters of primary alcohols (e.g. coco, fatty alcohols, resin fatty alcohols or oleyl alcohols) and sulfuric acid monoesters of secondary alcohols. Also suitable are reaction products of sulfated fatty acid alkanol amides, fatty acid monoglycerides or 1-4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols.

Examples of nonionic surfactants present in addition to the ethoxylated products used by the present invention are, in particular, 1 mole of fatty alcohols, ethylene oxide 9-40, preferentially 9-20 moles of adducts.

Amine oxide or sulfoxide type nonionic surfactants may also be used. Examples of the substance belonging to the cationic surfactant include carboxybetaine and sulfobetain type.

Suitable molding materials include all those capable of binding calcium by the complex method or not having this ability. Examples of the latter include alkali bicarbonates, alkali carbonates, alkali borates or alkali siliconates, alkali sulfates and alkali salts of organic non-surfactant sulfonic acids, carboxylic acids and sulfocarboxylic acids containing 1-8 carbon atoms. And so on.

Some examples include water-soluble salts of benzene, toluene, or xylene sulfonic acid, water-soluble salts of sulfoacetic acid, sulfobenzoic acid or sulfodicarboxylic acids. Suitable complex forming materials are triphosphates and polycarboxylates (including polymer carboxylic acids), which are numerous known organic complex formers such as aminocarboxylic acids, phosphonic acids, phosphonic carboxylic acids, hydroxycarboxylic acids and carboxyalkyl ethers.

Examples of suitable bleaches are compounds which liberate H ₂ O ₂ in aqueous solution, for example substances which feed perborate or active chlorine. Other additives, most of which are present in relatively small amounts, are for example foam stabilizers or inhibitors, fabric softeners, stabilizers or promoters for bleaches, inhibitors, antibiotics, soil media, enzymes, luminaries , Generating and fragrant substances.

The products produced by the present invention can be used in numerous technical and domestic areas for a wide variety of cleaning operations. Examples of such application areas include cleaning of furniture, containers made of machinery, wood, plastic materials, metals, ceramics, glass, etc. in industrial or commercial companies, furniture, walls, floors, ceramics, glass, metal, wood, plastics For example, cleaning of household wiped or threaded surfaces.

In particular, the main field of application is the cleaning of all types of fabrics in industrial, laundry and home.

Production of Aluminum Silicates:

The synthesis of the aluminum silicates used in the suspensions according to the invention is first mentioned, where no protective measures are necessary. The description is also purely illustrative: other known methods of aluminum silicate production are also used.

α) The aluminum silicate solution was mixed with the calculated amount of sodium silicate solution in a 15 liter vessel and stirred vigorously. (Temperature of solutions: 20-80 ° C.), X-ray amorphous sodium aluminum silicate was thus formed as a primary precipitate product with exothermic reaction. After vigorous stirring for 10 minutes, the suspension of precipitate product

1. direct treatment to a subsequent step, i.e. without crystallization,

2. The product was obtained by X-ray structural analysis when the product was left for 3-6 hours at 80 ° C. for crystallization.

β) The mother liquor was filtered out of the suspension. The remaining filtration is washed with deionized water and mixed with deionized water to form a suspension β ₁ (from α 1) or β ₂ (from α ₂ ).

γ) Alumina solution diluted with deionized water was mixed with a silicate solution to produce a fine crystalline aluminum silicate, which was stirred at a high speed vigorous stirrer (10,000 revolutions per minute, made by Janke kunkel IKA-Werk, Stavffen / Breisgan, Federal Republic of Germany). Product, "ultraturrax". After vigorous stirring for 10 minutes, the suspension of amorphous precipitate product is transferred to a crystal tank where it is stirred to prevent the formation of large crystals. The liquid is removed from the crystal slurry by suction filtration and washed with deionized water until the pH of the wash water discarded is about 10 and then the filtration residue is dried.

It is then milled and divided into two parts in a centrifuge (micropine air separator made by Alpine, Augsburg Germany). The suspension is produced in deionized water from the micropart γ ₁ . Suitable suspensions are produced without the drying process and are divided into two parts.

Still wet and various water content filtration residues are introduced into the water. The suspension obtained is impregnated with γ ₂ . Instead of filtration, the silicates are also separated from most of the water initially present, in part by water extraction.

The obtained aluminum silicates have the following composition calculated on the basis of anhydride (= AS); Calcium binding capacity of 1Na ₂ O · 1Al ₂ O ₃ · 2SiO ₂ precipitated products was 150-175 mg of CaO per gram of active ingredient. This is determined as follows; One liter of an aqueous solution containing 0.594 g CaCl ₂ (= 300 mg CaO / L = 30 ° German hardness) and adjusted to pH 10 with NaOH is mixed with one gram of aluminum silicate (corresponding to AS). The suspension is then vigorously stirred at 22 ° C. (± 2 ° C.) for 15 minutes. After the aluminum silicate is filtered, the residual hardness X of the filtrate is determined. Calcium binding capacity is determined in mg of CaO per gram of AS according to Eq. (30-X) 10.

Production conditions for aluminum silicate I;

Precipitation: composition 17.7% Na ₂ O; 15.8% Al ₂ O ₃ ,

Aluminate solution of 66.6% H ₂ O 2.985

0.15kg caustic soda

9.420kg water

2.445 kg of 25.8% sodium silicate solution (composition 1Na ₂ O. 6.0 SiO ₂ , produced from commercial water-soluble glass and alkali soluble silicic acid).

Crystallization: 24 hours at 80 ℃

Drying: 24 hours at 100 ℃

Composition: 0.9Na ₂ O, 1Al ₂ O ₃ 2.04 SiO ₂ 4.3 H ₂ O (= 21.6% H ₂ O)

Crystallinity: Full Crystallinity

Calcium binding force: 150mg CaO / g-AS

If the product thus obtained is dried at 400 ° C. for 1 hour, the composition of aluminum silicate Ia 0.9Na ₂ O, 1Al ₂ O ₃ 2.04 SiO ₂ , 2.0 H ₂ O (= 11.4% H ₂ O) is obtained. It is suitable for the purpose of the invention.

Production conditions of aluminum silicate II.

Precipitation: Aluminate solution 2.115 kg (17.7% Na ₂ O, 15.8% Al ₂ O ₃ , 66.5% H ₂ O)

Caustic Soda 0.585kg

9.615kg of water

2.685 kg 25.8% sodium silicate solution (produced in the same manner as in I) with a composition of 1Na ₂ O 6 SiO ₂ .

Crystallization: 24 hours at 80 ℃

Drying: 24 hours at 100 ° C and 20 torr

Composition: 0.8Na ₂ o · 1Al ₂ O ₃ · 2.655 SiO ₂ · 5.2 H ₂ O.

Crystallinity: Complete Crystal

Calcium binding force: 120mg CaO / g AS

This product may also be dehydrated by subsequent drying at 400 ° C. for 1 hour, the composition being 0.8Na ₂ O, 1Al ₂ O ₃ , 2.65 SiO ₂ 0.2 H ₂ O.

This dehydration product IIa is used for the purpose of the present invention.

Aluminum silicates I and II show the following interference lines in the X-ray diffraction plot.

D-value plotted with Cu-Kα radiation, Å

Not all of these interference lines appear in the X-ray diffraction plot, especially when the aluminum silicates are not all crystallized.

The most important d value for characterizing this type is therefore marked with (+).

Production conditions for aluminum silicate VIII.

Precipitation: 2.115 kg aluminum acid solution (composition of 1.7% Na ₂ O, 15.8% Al ₂ O ₃ , 66.5% H ₂ O)

Caustic Soda 0.585kg

9.615kg of water

2.685 kg 26.8% sodium silicate solution having a composition of 1Na ₂ O. 6SiO ₂ .

Crystallization: Omitted

Drying: 24 hours at 100 ° C.

Composition: 0.8 Na ₂ O. 1Al ₂ O ₃ . 2.65 SiO ₂ . 4H ₂ O.

Crystallinity: X-ray amorphous

Calcium binding capacity: 60mg CaO / g AS.

Production conditions for aluminum silicate IX;

Precipitation: Alumina acid solution (composition 21.4% Na ₂ O, 15.4% Al ₂ O ₃ , 63.2% H ₂ O) 3.41 kg.

10.46 kg of water.

1.13 kg 34.9% sodium silicate solution with composition of 1Na ₂ O. 3.46 SiO ₂

Crystallization: Omitted

Drying: 24 hours at 100 ℃

Composition: 1 Na ₂ O. 1 Al ₂ O ₃ . 1 SiO ₂ . 1.4 H ₂ O

Crystallinity: X-ray amorphous

Calcium binding capacity: 120mg CaO / g AS.

Production conditions for aluminum silicate XXm;

Precipitation: 0.76 kg aluminum acid solution (36.0% Na ₂ O, 59.0% Al ₂ O ₃ , 5.0% H ₂ O).

Caustic Soda 9.94㎏

9.94 kg of water.

3.94 kg of sodium silicate solution on the market whose composition is 8.0% Na ₂ O, 26.9% SiO ₂ 65.1% H ₂ O

Crystallization: 12 hours at 90 ℃

Drying: 12 hours at 100 ℃

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

Crystallinity: Complete Crystal

Calcium binding force: 110mg CaO / g AS

The invention will be described in more detail by means of the following examples.

The brevity used below is based on the following means.

＂TA + XEO＂ is usually a molar addition product per mole of saturated fatty alcohol, which is produced by reducing the resin fatty acid and consists of an alcohol mixture with various carbon atoms.

＂Coconit C _16-18 + 6EO＂ is an ethoxylated product from 6 moles of ethylene oxide per mole of fatty alcohol moiety, which is reduced from coco fatty acids, produced by distillation, and constitutes the equivalent of C ₁₆ alcohol and C ₁₈ alcohol In each case up to 2% of C ₁₄ and C ₂₀ alcohol moieties.

"OXO + 5EO" is an ethoxylated product of the alcohol mixture obtained by oxo synthesis and has the following composition.

This alcohol mixture is reacted with 5 moles of ethylene oxide per mole of alcohol. “OA + 10EO” is an ethylene oxide addition product for industrial oleyl alcohol in a ratio of 10: 1 molecular weight.

"EDTA" is ethylenediaminetetraacetate.

“CMC” is carboxymethyl cellulose.

"ABS" is an alkyl benzene sulfonate which condensed benzene to linear olefins and sulfonated the alkylbenzene thus obtained, and has approximately 11 to 13 carbon atoms in the alkyl chain.

Water glass is sodium silicate (Na ₂ O: SiO ₂ = 1: 3.35)

＂Perborate＂ composition NaBO ₂ . H ₂ O ₂ . It is an industrial product with 3H ₂ O.

All salt type compounds are used as sodium salts.

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

“Cop 1” is lauric acid monoethanol amide

“Cop 2” is myristic acid monoethanol amide

＂Cop 3＂ is a lauric myristic acid monoethanol amide

＂Cop 4＂ is palm fatty acid monoethanol amide

＂Cop 5＂ is a lauric myristic acid ethanol imide

＂Cop 6＂ is an oleic acid diethanol amide

＂PVA＂ is polyvinyl alcohol (molecular weight ＞ 1900)

Suspension of the Invention

Example 1

The suspensions of the present invention are shown in the examples of microcrystalline aluminum silicates produced according to γ ₂ because these are preferred for the production of detergents according to the invention.

The suspensions of the invention can also be produced as suitable aluminum silicates separated into suspensions β ₁ , β ₂ and γ ₁ or solids.

155-195 g of moist aluminum silicate (method γ ₂ : the same amount of AS is then put in because the amount of water-containing aluminum silicate used is applied to the water content) is then put into a mixture of a large amount of water and a dispersant so that the resulting mixture Silver contains an aluminum silicate active ingredient in the range of 30-38% by weight.

The amount of ethoxylated product added corresponds to 1.3-3% by weight.

The action is carried out at ambient temperature.

The ethoxylated products listed in Table 1 and given cloud point in each case were used as dispersants. Many suspending agents and their components are listed in Table 2.

TABLE 1

Ratio is about weight.

TABLE 1a

TABLE 2

1) TA + 5EO is replaced by 0 × 0 + 5EO here.

The following description is for Table 2.

Row 1; AS content is the active substance content in the hydrous aluminum silicate used.

Row 3 and 4; ＂AS＂ in the suspension is gram or weight percent of the active ingredient in the suspension formed.

2 rows; The amount of hydrous aluminum silicate used to produce the suspension.

Row 5; The amount of water applied to the hydrous aluminum silicate

Row 6 and 7; The used ethoxylated products in grams and% and their amounts of addition All suspensions were very limited and would be satisfactory even after one or more days of storage by the usual hose pulp (mark IKA P 20, IKA-Werk Staufen / Breisgan, Fed. Rep. Of Germang). Could be pumped from the storage tank.

Example 2

A 31 wt% suspension of pure microcrystalline aluminum silicate produced according to 2 was produced.

Dispersant 9 in Table 1 was used at 1.8% by weight (total weight) as the dispersant of the present invention. The stability of the suspension was further improved by the addition of small amounts of resin fatty acid and resin amine (wherein the “resin amine” is a 21st class amine corresponding to the resin alcohol mentioned above). The suspension so produced was stable for several months.

Example 3

The powdered sprayable cleaning agents of the compositions in Table 3 were produced as follows.

The storage suspension produced in the dispersion of the dispersant heated to 70 ° C. containing hydrous aluminum silicate produced according to Example 2 containing 36% by weight of aluminum silicate and its weight percentage of TA + 5EO by weight of the suspension in each case It was pumped from the resistance vessel into the other vessel, where a large amount of water and the remaining components were added sequentially with stirring to form a detergent slurry containing approximately 45% by weight of water.

This slurry was fed to a spray nozzle located at the top of the spray tower by a pump and finely powdered by the backflow of spray and heat (about 260 ° C.).

TABLE 3

2) TA + 5EO added with other ingredients

1) introduced with storage suspension.

3) added after spraying.

In the production of the cleaning agents corresponding to B, suspensions, for example polyacrylates containing very stable and pumpable suspensions can be used in place of suspensions stabilized with TA + 5EO.

Since polyacrylates are complex formers for calcium, the sodium triphosphate moiety can be reduced in general. However, in the production of cleaning agents containing ABS, suspensions containing ABS can also be used according to the invention, in which ABS having 11 to 13 carbon atoms in the alkyl moiety is used in the case of solids. In this case, the stability is lower.

Example 4

Pumping and standing test of aluminum silicate suspension

594-780 g of sodium aluminum silicate with varying moisture content consisted of 190-360 g of water and 10-30 g of dispersant, heated to 65-70 ° C. with stirring, and added to a homogenized emylzone. The amount was a ratio of 31-34% AS content.

With continued stirring, the homogenized suspensions were pumped for one hour at ambient temperature with a hose pump (IKAP Type 20). After that, the pump and agitation were stopped for an hour.

Then stirring and pumping continued.

In the comparative test-no further stirring and pumping with those made without the dispersion aid could be carried out.

After an additional 4-6 hours of pumping and stirring, the suspensions were left overnight and left to stand at ambient temperature for several days and then visually inspected for precipitation.

The sedimentation = 100% refers to setting the precipitation state that the suspension is completely homogeneous and stable (close to 100%) (see the last column in the table) and the suspensions are again tested for their pumping capacity. All the materials mentioned proved to be useful as dispersion aids, because the suspensions produced as they could be stirred effortlessly, pumped off and continued.

Individual slurries can be found in the list in the following table.

The approximate composition produced according to β ₂ is Na ₂ O. Al ₂ O ₃ . Aluminum silicate, 2SiO ₂ , was used, which was introduced in the form of moisture produced. The particle size was generally between 5-15μ.

1) -5) are mentioned on the following pages respectively.

Production of Aluminum Silicate Suspension

1) The aqueous HAB suspension was adjusted to 50% solids.

2) The hydrous aluminum silicate was produced in a Roeju mixer from spray dried material having a 79% AS content by adding water.

3) The acid polyaporinic acid solution was adjusted to pH 10 with caustic soda solution before sodium aluminum silicate was added.

Poly- (α-hydroxyacrylic acid) could also be used.

4) Pump capacity after X hours, the following symbol means

-= No more pumping.

+-Can be pumped.

5) The polyvinyl alcohols used were insoluble in water, so dimethyl sulfoxide (20-87 g) was added to the amount of water as a dissolution aid.

By adding 1% PVA 90, the addition of dimethyl sulfoxide

The polyvinyl alkoxy used was commercially available (Mowioi Farbwerk Hoechst disinfection) and the “Mowioi 76/98” proved to be the most appropriate.

Example 5

The suspension of the present invention was produced by addition of products I, II, X III, XI and XXm into the dispersion of TA + 5EO in water. It was previously heated to 60-70 ° C. and the silicate suspension thus formed had a 33% AS content and a 2% TA + 5EO content.

The suspension was cooled to ambient temperature and observed at this temperature.

The same operation as in Example 1 was carried out at ambient temperature. The suspension was very stable.

Example 6

The approximate Na ₂ O. Al ₂ O ₃ , 2SiO ₂ , with a water content of 50%, produced by Example 2 and having a pH of about 10.5, hydrous aluminum silicate is introduced into the next aqueous solution.

a) 1,3-hydroxyethyl-1,1-diphosphonic acid.

b) dimethylamino methane diphosphonic acid, 31%

Suspension phosphonic acids formed with a solids content (AS content) and a 2% dispersant content are used as follows.

1.Tetrasodium salts,

2. As disodium salts,

3. As the mountain itself,

Suspensions can be treated with surfactants or detergent components, for example by subsequent spray drying, into detergents.

Example 7

In accordance with Example 6 suspensions of 31% sodium aluminum silicate 4% phosphoric acid butylesters or sorbic acid di-octylesters (pH10) are produced. Phosphoric acid esters are those containing about 1.5 moles of alcohol per mole of phosphoric acid.

Example 8

According to Example 6 a suspension containing 31% sodium aluminum silicate AS content and 4% alkylbenzene sulfonate (ABS) was produced. ABS was once used as a salt and once as a litter. Sulfonates obtained by sulfonation with SO ₃ from methyl esters of cured resin fatty acids, or olefin sulfonates obtained by sulfonating linear internal olefins having 12 to 18 carbon atoms and hydrolyzing the sulfonated products are also used. Can be.

Strong bubble phenomena of the suspension could be easily removed by adding a small amount of commercial silicone antifoam. The suspensions are suitable for producing cleaning materials containing aluminum silicates, in particular slurries. However, they can also be spray dried and converted into powdered water softeners or detergent forming materials.

Example 9

In accordance with Example 4 aluminum silicate suspensions were produced containing 31% AS content and the following dispersant (AS%:% dispersant).

a. Stearic Acid Monoglycerides (31/2)

b. Stearic acid furopropylene glycol ester (31/2)

c. Reaction Products from Resin-Hydroxyethyl-ethylenediamine Reactions (31/2)

d. Long-chain amines derived from resin amine fatty acids by reduction (31/2)

e. Prodrugs with 5 moles of ethylene oxide per mole of resin amines (31/2)

f. Oleyl alcohols with 5 moles of ethylene oxide per mole of alcohol (31/2)

g. A mixture of saturated (70a-75%) C ₁₂ and C ₁₄ (25-30%) alcohols ethoxylated with 3-4 moles of ethylene oxide.

h. Corn Starch (31/1) or CMC

i. Poly (α-hydroxy acrylic acid) (31/2)

k. Polyacetone of poly (-hydroxyacrylic acid) (31/2)

Stabilized suspensions are particularly suitable for use by spray drying in the production of an aqueous slurry of detergent components. They may also be treated directly to form granules by adding water as crystalline water bound salts (eg pentasodium triphosphate).

Example 10

The aqueous suspension, produced according to example 1 and containing about 30% aluminum silicate and 2% TA + 5EO, was spray dried in bases to remove adhered water. The spray dried product contained much less debris than would be produced without TA + 5EO. The powdered aluminum silicate obtained was very suitable as a bearding agent and a cleaning agent molding material.

Example 11

Moisture 50%, formula Na ₂ O. Al ₂ O ₃ . The hydrous silicate of 2SiO ₂ was placed in bentonite water suspension at ambient temperature. Stabilized suspensions contain 23% AS and 2 or 4% bentite content. The bent knight used was commercially available from Erbslon (German Federal Republic) under the trade name Aktiv-Bentonit.

Analytical composition

"Montigel F" pentonato, according to Sudchemic AG (Germany), is also used.

Products that occur naturally or are produced from natural products generally contain iron and silicate impurities.

Other commercially available Aktivbentonit products include VolClay (Bentonite International) and Eurogel (Amberger Kaolinwerke, Federal Republic of Germany).

Synthetic products can be obtained in particular from Lange CO., Bremen. Cleaners, such as those described in US patent application 458303, are stabilized with synthetic expandable silicates of bentonite or smectite type with aluminum silicate suspensions as described therein. The pre-stabilization suspension forms a slurry in combination with the remaining components of the formulation to be produced, which contains 50% by weight and the slurry is dried in bases.

For example, a product with the following composition is produced.

The suspension containing the remaining water and Na ₂ SO ₄ 2% bentonato is mixed with the rest of the detergent ingredients-with the exception of perborate-to form a slurry, which is spray dried in hot air in a known manner and the powder obtained is perboron Mixed with acid salts.

All suspensions depicted in the examples are clearly improved in terms of stability and flowability.

Thus, the nonionic surfactants of the (iV) group compounds have proved surprisingly excellent.

Claims (1)

In the manufacturing process of the cleaning and cleaning agent composition comprising spray drying the liquid slurry of the individual components of the cleaning and cleaning agent containing the binder and the surfactant to recover the flowable cleaning and cleaning agent composition of the powder Aqueous suspensions insoluble in water, having calcium binding ability and stable to coagulation, using an aqueous suspension with a pH of 7-12 have improved the process. The aqueous suspension has 22 ° C according to the method for testing calcium binding capacity. When measured at, it has a CaO binding capacity of at least 50 mg per 1 mg of inert material, and the particle size is 0.1μ-100μ and the finely dispersed crystalline water having the same structure as I (but not shown) At least one silicate compound that is insoluble comprises from 20-50% by weight based on anhydride (M ₂ O) x. Me ₂ O ₃ . (SiO ₂ ) y In addition, organic polymers having carboxyl and hydroxyl groups, organophosphoric acids having at least one acid group selected from the group consisting of phosphoric acid and carboxyl, alkyl acid phosphate emulsifiers having 3 to 20 carbon atoms of alkyl, DIN 53917 Selected from the group consisting of nonionic surfactants, alkali metal salts of anionic surfactant sulfonates and free acids with a turbidity point below 90 ° C. in aqueous butoxyethoxy ethanol and a haze point below room temperature in 1% aqueous solution. An improved process for producing a cleaning and cleaning composition comprising at least 0.5-6% by weight of at least one organic dispersant, up to 100% of which consists of water and wherein said aqueous suspension can be pumped after 24 hours. In Formula I, M is selected from the group consisting of sodium and potassium, X is a number between 0.7-1.5, M is aluminum or boron, and y is a number between 0.8-6.