DK156175B - CLEANER - Google Patents

Description

DK 156175 B

The present invention relates to a detergent according to claim 16 of Patent No. 151,231.

The main patent No. 151,231 relates to a process for cleaning, including washing, prewashing and bleaching of solid materials, in particular textiles, by treating these materials with an aqueous raft containing water-insoluble, finely divided aluminum silicate having an exterior effect. and at least one compound selected from synthetic surfactants and optionally a bleaching agent, the process of which is characterized by working with a float containing, as aluminum silicate and as a phosphate substitute in suspended form, a crystalline or pure genomorphic aluminum silicate containing bound water, is synthetically prepared and has a calcium binding capacity of at least 50 mg CaO / g of anhydrous active substance, in the manner specified in the specification, at 22 ° C, the aluminum silicate having the general forms 1 (Kat2Û) x, Al₂Ο3, (S in 0 2> y 20 where Kat is a calcium-exchangeable alkaline ion, x is a number of 0.7-1.5 and y is a number of 1.3-4.

Claim 16 of the main patent No. 151,231 relates to a detergent, including detergent, prewash detergent and bleach detergent for carrying out the aforementioned process, containing a water-insoluble, finely divided aluminum silicate as well as at least one compound of the group of surfactants, additives and bleaches and a substitute substance. or complete replacement of condensing phosphates, which is characterized in that it contains as a phosphate substitute a crystalline or X-ray-grafted aluminum silicate as set forth above.

The present invention relates to a detergent according to claim 35 16 of Patent No. 151,231, characterized in that it contains 0.1-30% by weight of surfactant components, 1-50, preferably 5-35% by weight, aluminum silicate of the formula:

, DK 156175B

2 0.7-1.1 Na 2 O, Al 2 O 3, 1.3-3.3 SiO 2 with a calcium binding capacity of 50-200 mg CaO / g of active substance and 0.5-50 wt% of usual liquid and paste constituents detergents and at least 20% by weight of free water.

The above defined ali nine samples also can be prepared synthetically in a simple manner, preferably by mixing aqueous silicate and aluminate solutions. During the precipitation, 10 intensive stirring is an advantage as in this way the formation of small particle sizes is promoted, thereby obtaining products which, after heating to 50-200 ° C, are transferred to crystalline state for at least 80 weight. % * s consist of particles with a size of 10 to 0.01 μ, especially from 8 to 0.1 μ, and practically no particle size above 40 μ.

The crystalline aluminum silicate can be separated by filtration from the remaining aqueous solution and, at 50-200 ° C, liberated from the externally adherent liquid water and converted into a powder which acts as a tort but contains more or less bound 20 water in amounts between and 35, wt.t% ... .Handless products are obtained when thawed at 800 ° C. Therefore, an active substance is understood as a precipitating product whose bound water has been removed at 1 hour heating to 800 ° C. In practice, at much lower drying temperatures, the humidified filtered aluminum silicates, e.g.

25 for 24 hours at 100 ° C, whereby an externally dry powder having a reproducible water content is obtained.

By adhering to certain conditions described in Application No. 5332/74, the crystallization process can be affected so that the aluminum silicates of the above composition appear as crystallites with rounded corners and edges and are present as particularly small particles with favorable particle size distribution residues.

Of the sodium aluminum silicates, aluminum silicates of other cations, e.g. of potassium, lithium, magnesium or water-soluble organic bases, is prepared simply by base exchange in aqueous 3

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suspension. The use of these compounds in place of the sodium = aluminum silicates may be appropriate if a particular effect is achieved by delivering said cations, e.g. affect the dissolution state of co-existing surfactants. As 5 water-soluble organic bases, there may primarily be primary, secondary or tertiary amines or alkylolamines having a maximum of 2 carbon atoms per alkyl residue or a maximum of 3 carbon atoms per alkylolrest.

In the liquid to paste cleansers according to the invention, the aluminum silicates still damp in the manufacturing process are advantageously used to avoid drying them and a subsequent rewetting. This measure not only allows the finely divided crystalline aluminum silicates to be directly converted, i.e. 15, without the use of cumbersome insulation and drying for the liquid compositions, but the use of even more moistened aluminum silicates also has the advantage that in this way the aluminum silicate particles retain substantially the degree of distribution determined by the manufacturing conditions, while baking together in an intermediate drying 20 for larger aggregates, so that further milling and sieving is necessary for further use.

Preferably, of the usual constituents of liquid to paste detergents, at least one of the following is present in the amounts indicated: 0.5-15% by weight of water-soluble inorganic and organic complexing agents or calcium ions precipitating agents, 10-50% by weight abrasives. , w 0 0.5-25 wt.% water-soluble or water-dispersible organic solvents, 0.5-15 wt.% hydrotropes, 0.5-15 wt.% dirt carriers,

O D

0.1-15 wt% acid additives, 0.01-20 wt% antimicrobials.

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As surfactants of the sulfonate type, there may be many alkylbenzene sulfonates (CQ-C- alkyl), olefin sulfonates, i.e. mixtures of alkene-γ-j-b and hydroxyalkanesulfonates as well as disulfonates such as those, e.g. is obtained with terminal or internally double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which can be obtained from C 1 -C 4 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins and esters 10 of oc-sulfonic fatty acids, e.g. α-sulfonic acids of methyl or ethyl = esters of hydrated coconut acids, palm nucleic acids or sebaceous fatty acids.

Suitable surfactant surfactants are sulfuric acid monoesters of primary aliphatic C 1 -C 4 alcohols (e.g., of coconut fatty alcohols, tallow = 15 fatty alcohols or oleyl alcohol) and of secondary, aliphatic ^ 10 In addition, sulfated fatty acid alkanolamides, fatty acid monoglycerides with C 1 -C 6 Cg fatty acids, and sulfates of the 1-6 moles of ethylene oxide reacted with primary or secondary aliphatic C 1 -C 2 Q 4 alcohols are also suitable.

20

In the case of the soaps, these are the water-soluble salts, especially alkali salts of the natural or synthetic sources, preferably saturated C C-CC-fatty acids.

The surfactants with anionic groups can be in the form of their sodium, potassium and ammonium salts as well as soluble salts of organic bases such as mono-, di- or triethanolamine.

Suitable nonionic surfactants are, first of all, the practically water-soluble adjuvant products of 7-20 moles of ethylene oxide to 1 mole of an aliphatic C1-C2Q alcohol or an alkylphenol, fatty amine or a fatty acid. Particularly important are the ethoxylation products of the aliphatic alcohols, especially the coconut or tallow fatty alcohols, oleyl alcohol, C10-C2O oxoalcohols, and the secondary = 35 aliphatic alcohols having substantially 12-18 carbon atoms.

In addition to these water-soluble non-ionic substances, the corresponding non-water-soluble or not fully water

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soluble ethoxylation products having 2-6 ethylene glycol ether residues in the molecule of interest when used with the water-soluble ethoxylation products. Suitable nonionic substances are also the fat = acid alkanolamides, such as the compounds coconut or tallow = 5 fatty acid ethanolamide and diethanolamide, oleic acid diethanolamide, etc.

Also useful are nonionic surfactants, the surface-active amino oxides, which are mostly derived from tertiary amines with a hydrophobic C CQ- ^ alkyl group and two shorter alkyl and / or alkylol = 10 groups each containing up to 4 carbon atoms. Typical representatives are e.g. compound N-dodecyl-N, N-dimethylamine oxide, N-tetradecyl-N, N-dihydroxyethylamine oxide, N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) amine oxide.

The usable non-cationic surfactants contain at least one hydrophobic and at least one basic optionally water-soluble group. In the case of the hydrophobic group, it is an aliphatic or cycloaliphatic hydrocarbon group having preferably 10-22 carbon atoms or an alkylaromatic or cycloalkylaromatic group having preferably 8-16 aliphatic carbon atoms. As basic groups, there may be firstly basic hydrogen atoms, of which there may also be more in a surfactant molecule. Preferably, these are quaternary ammonium compounds.

25

As cationic surfactants, e.g. mention is made of: N-dodecyl-N, N, N-trimethyl = ammonium methosulfate, N-hexadecyl or N-octadecyl-N, N, N-trimethyl = ammonium chloride, W, N-dicocosalkyl-N, N-dimethylammonium chloride, N-dodecyl -N, N-dimethyl-N-benzylammonium bromide, the reaction product 30 of 1 mole of tallow alkylamine with 10 moles of ethylene oxide, N-dodecyl-N, N ', N'-trimethyl-1,3-diaminopropane, N-hexadecylpyridinium chloride.

Said nitrogen compounds may be replaced by corresponding compounds with quaternary phosphorus atoms or with tertiary sulfur = 35 atoms.

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Suitable zvitterionic surfactants contain in the molecule, in addition to a hydrophobic mostly aliphatic group, both hydrophilic acid groups such as e.g. carboxylic, sulfo, sulfuric acid half-ester, phosphonic or phosphoric acid ester groups and basic groups such as e.g.

5 amino, imino or ammonium groups. Zvitterionic compounds having a four-fold substituted, i.e. quaternary ammonium group belongs to the betaine type if they also have a covalently bound acid group in the molecule and the positive and negative charge is intramole = culturally equalized. In a further sense, the betaine class also includes the 1 ° correspondingly substituted quaternary phosphonium and tertiary sulfonium compounds. Due to their good cleaning properties and their compatibility with other surfactants, carboxy, sulfonate and sulfabethanes of nitrogen have a particularly practical importance. Typical representatives of zvitterionic surfactants are e.g. compounds 3- (N-hexadecyl-N, N-dimethylammonium) propanesulfonate, 3- (N-hexadecyl-N, N-bis (2-hydroxyethyl) ammonium) -2-hydroxypropyl sulfate, 3- (N-cocoalkyl) -N, N-bis- (2,3-dihydroxypropyl) -ammonium) propanesulfonate, N-tetradecyl-N, N-dimethylammonium acetate.

Λ Λ

Liquid for paste-based cleaners according to the invention, especially intended for textile washing, advantageously contain within the range of the above-mentioned quantity range of 0.5-15% by weight of water-soluble inorganic or organic complexing agents or precipitating agents for calcium ions. It has been found that in their presence, the contaminants can be removed substantially faster or more completely. In order to stabilize the compositions of the invention against decomposition reactions catalyzed by heavy metal ions, it is also appropriate to add such water-soluble complexing agents which, in addition to the complex action against 30 calcium ions, also have a pronounced complexing ability against heavy metal ions. For the masking of heavy metal ions, which are mostly present only in traces in the compositions of the invention, small amounts of these heavy metal complexes of the order of 0.1-0.3% by weight are sufficient.

35

Optionally, it is appropriate to use these complexing agents or precipitants which are mostly water-soluble neutral to alkaline reacting salts of compounds with carboxylic acid groups.

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phosphonic acid groups, sulfo groups or phosphoric acid groups in the form of their free acids, since by this measure it is possible to reduce the pH of the composition in the desired manner and thereby avoid the addition of an acidifying agent which itself has no washing technical properties.

The water-soluble, inorganic or organic complexing agents or precipitating agents for calcium ions and for heavy metal ions precipitants suitable for detergents according to the invention are described in more detail below. It is noteworthy that for complexing or precipitating calcium ions within the scope of the invention, such substances are also suitable which have so little complexing ability that they have not hitherto been considered as typical complexers for calcium, but such compounds often have the ability to · The desired acceleration of dirt removal by textile washing is achieved within the range of 0.5-15% by weight, for the most part already with small amounts added. Especially when using complexing agents or precipitating agents containing inorganic or organically bound phosphorus, it is sufficient to add such small amounts that the phosphorus load in the wastewater is clearly inferior to that of the presently usual preparations on the basis of condensed phosphates. For the complexing agents or the precipitating agents, those of inorganic character such as e.g. pyrophosphate, triphosphate, higher polyphosphates and metaphosphates.

Organic compounds which are suitable as complexing agents or calcium precipitating agents are the water-soluble salts of 30 aminopolycarboxylic acid, such as e.g. hitrilotriacetic acid, ethylenedia = mintetraacetic acid, hydroxycarboxylic acids, e.g. citric acid, gluconic acid, carboxymethyl ether carboxylic acids, e.g. carboxymethyl = oxyacetic acid, carboxymethyl tartaronic acid, ethylene dioxide acetic acid, oxydiethylene dioxide acetic acid, the water-soluble salts of polymeric carboxylic acids with molecular weights above 350 and at least one carboxyl group calculated on a molecular weight unit of 175, such as polyacrylic acid, poly-α-hydroxyacrylic acid, polycarboxylic acids of blend polymerisates 8

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of maleic anhydride with ethylene, propylene, vinyl methyl ether, etc., as well as the polyhydroxycarboxylic acids obtained from acrolein and acrylic acid with and subsequent Cannizzaro reaction.

Particularly of the type of organic phosphonic acids are the water-soluble salts of the compounds of the group of phosphonic alkane polycarboxylic acids and amino- and hydroxy-substituted alkane polyphosphonic acids, such as e.g. the salts of aminotrimethylenetriphosphonic acid, dimethylaminomethane = phosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid.

As the hydrotropic substances, the salts of sulfonic acids, carbonic acids and sulfocarboxylic acids containing 2-10 carbon atoms, such as e.g. alkali = the salts of benzolic, toluene, xylol or cumolsulfonic acids, C1Q-15 olefin sulfonic acid, suphobenzoic acid, sulfophthalic acid, soloric acid, and salts of acetic or lactic acid. Also, acid amides, such as urea and acetamide, are suitable as hydrotropes.

Like the complexing agents and the precipitating agents, the 20 saline hydrotropes may optionally be added as free acids if a lowering of the pH of the composition is sought. For the same purpose, suitable as acidic additives or acidifying agents are also suitable for other inorganic and organic non-surfactant acids which have no distinct complexing or hydrotropic properties, such as e.g. amidosulfonic acid, urea phosphate, boric acid, glycolic acid. In addition, in the cleaning agents according to the invention, there can be found dirt carriers which keep the dirt released from the taverns suspended in the raft and thereby prevent germination. For this purpose, water-soluble colloids are mostly organic in nature, e.g. the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carbonic or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also water-soluble polyamides containing acidic groups are suitable for this purpose. Further, soluble starch preparations and other than the above starch products, e.g. degraded starch, aldehyde starch and so on. Polyvinylpyrrolidone is also useful.

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As organic solvents especially water-soluble or water-emulsifiable alcohols, ether alcohols, e.g. ethanol, isopropyl alcohol, butanol, amyl alcohol, ethylene glycol, diethylene = glycol, methyl, ethyl or butyl glycol, but also terpene alcohols and terpenes such as e.g. pine oils and terpene oils can be added.

Suitable antimicrobials are e.g. benzoic acid, salicylic acid, sorbic acid, sodium fluoride and formaldehyde condensation products with lower amino alcohols, e.g. aminoethanol.

10

Also suitable as antimicrobial agents are halogenated phenol derivatives, such as e.g. alkylene bisphenols, hydroxybenzoic acid derivatives, especially anilides having 2 or 3 halogen atoms and / or trifluoro methyl groups in the benzoic acid residue and / or aniline residue and substituted o-phenoxyphenols such as e.g. compound 2-hydroxy-21,4,4'-trichlorodiphenyl ether.

Abrasive cleaning agents contain additional abrasive ingredients. Suitable abrasive agents are water-insoluble fine pre-painted minerals, such as quartz, feldspar, marble or fluospar, kaolin or pumice, which are different from the above defined alumina silicates and which act mechanically cleansing. Instead of mineral, mechanically cleansing constituents, finely ground organic substances such as e.g. wood flour or synthetic polymers, e.g. polyethylene and polypropylene powders or mixtures thereof with mineral scouring components. Mineral cleansing ingredients coated with an artificial resin film can also be used.

If one assumes a dry aluminum silicate powder, the liquid to paste-shaped cleaners according to the invention can be prepared in a manner known per se by mixing the ingredients in conventional mixers. It is convenient to first dissolve the water-soluble and water-dispersible components in the calculated amount of water or disperse them therein and introduce aluminum = the silicate powder. The total water content of the agent is then composed of the amount of water weighed into the starting material. and the amount of bound water still contained in the exterior dry aluminum = «ή T 4 4 *

DK 156175 B

10

In the preparation of the liquid to paste purifying media of the invention using terrain aluminum silicates, water which had previously been removed by drying the aluminum silicates must again be added. Therefore, it is convenient and advantageous to save this drying process and to use the non-grounded aluminum = silicates.

This preferred mode of preparation for the liquid to paste purification media makes it possible to process the finely divided crystalline aluminum silicates directly, i.e. without insulation and dice to the liquid for pasty preparations. In addition to the energy savings of avoiding the aluminum silicate drying process, it is a further advantage of this process that the aluminum = silicate particles thereby retain their particle size, while baking into stellar aggregates in an intermediate drying process and therefore require further milling and screening.

The crystalline aluminum silicates to be used in this process can be substantially processed in the following delivery states: ...

a) still liquid suspension of the aluminum silicate in the mother liquor in which it is after the crystallization process is completed, the mother liquor preferably containing no aluminum compounds dissolved; b) aluminum silicate from which the mother liquor has been partially separated; c) after partial or complete leaching of the mother liquor, still liquid suspension of aluminum silicate in water has emerged; d) aluminum silicate from which the wash water has been partially separated.

The delivery modes referred to in (b) and (d) include in particular cool 35 pastes, but also products that already look powdery but still contain adherent water.

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DK 156175 B

Partial or complete separation of the mother liquor and subsequent leaching of the aluminum silicates according to c) or d) is usually advantageous if either the mother liquor is to be returned to the production of aluminum silicates or if neutral to slightly alkaline is to be produced. reactive preparations.

However, it is also possible to process the aluminum silicates in states (a) and (b), which is appropriate when preparing alkaline reacting compositions and the mother liquor content 10 of etching alkalis and / or alkali silicates can be utilized or if excess alkalinity in the delivery states a ) or b) can be neutralized by the addition of the above-described anionic surfactants and / or complexing or precipitating and / or hydrotropic compounds, at least partially in their acid form and optionally by additional acidic additives.

If the process is based on aluminum il icate suspensions in delivery states a) or c), it is advantageous to add the other components of the preparation, optionally, after prior dissolution or formation of a dough in enaliquot water to the aluminum = silicate suspensions. .

By contrast, using the moist aluminum silicates of b) and d}, it is convenient to dissolve the water-soluble and water-dispersible constituents of the composition in a calculated amount of water or disperse them therein and mix this solution or dispersion with the moist aluminum silicates of b) or d).

Examples.

30

First, the crystalline aluminum silicates to be used in the cleaners of the invention are described.

Synthesis of the Crystalline Aluminum Silicates 35 In a 20 L container was placed the aluminate solution and under vigorous stirring the silicate solution was added. The mixture was stirred for 12 hours

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10 minutes with an intensive agitator (eg agitator with dispersion = disk, 3000 rpm). The suspension of the precipitate thus formed was then transferred to a crystallization vessel and kept for some time at elevated temperature for crystallization. Below, the formation of large crystals was prevented by stirring (250 rpm) of the suspension. After suction of the liquor from the crystal crop and after washing with preferably deionized water until the running wash water had a pH of approx. 10, the filter residue was dried. In the to-10 phase, where further use of aluminum silicate suspensions and of damp aluminum silicates was made, this regulation was amended accordingly. Reference is made to the changes in the description of the special aluminum silicates. The drying of the aluminum silicates occurred in a drying cabinet at 100 ° C for 24 hours.

15

All percentages are weights.

Determination of the Calcium Bond Capacity of Aluminum Silicates 20 To 1 liter of an aqueous solution containing 0.594 g of CaCl 2 (= 300 mg Ca0 / l = 30 ° dH) adjusted to a pH of 10 with NaOH, add 1 g of aluminum silicate, with aluminum silicate = the amount is calculated on the anhydrous product obtained by drying at 800 ° C (= active substance (AS)). The suspension is then stirred vigorously for 15 minutes at a temperature of 22 ° C (- 2 ° C). After filtration of the aluminum silicate, the residual hardness x of the filtrate is determined. From this, the calcium binding capacity of the alminium silicate is calculated to (30-x) • 10 mg CaO / g AS.

If the calcium binding capacity is determined at higher temperatures, e.g. at 60 ° C, generally better values are found than at 22 ° C.

This circumstance marks the aluminum silicates above most soluble complexing agents which have hitherto been proposed for use in detergents and represent a particularly technical advance in their use.

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Aluminum Silicate Im Precipitation: 2,985 kg of aluminate solution of the composition: 17.7% Na 2 O, 15.8% Al 2 O 3, 66.5% H 2 0,150 kg etching sodium 9,420 kg water 10 2,445 kg of one of the commercially available water glass and light alkali = readable silicic acid freshly prepared, 25.8% solution of sodium = silicate of the composition 1 Na 2 O, 15 6 SiO 2

Crystallization: 6 hours at 90 ° C

Drying: 24 hours at 100 ° C

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

Crystallization degree: fully crystalline

Calcium binding capacity: 170 mg CaO / g AS.

25 Aluminum Silicate Ilm Precipitation: 2.115 kg of aluminate solution of the composition: 17.7% Na 2 O, 15.8% Al 2 O 5, 66.5% H 2 O 0.585 kg etching sodium 9.615 kg water 2.685 kg of a 25.8% solution of sodium silicate together -35 theorem 1 Na 2 O, 6 SiO 2 (presented as listed under Im)

Crystallization: 12 hours at 90 ° C

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Drying: 24 hours at 100 ° C

Composition: 0.8 Wa 2 O, 1 Al 2 O 2, 2.65 SiO 2, 5.2 H 2 O (= 23.2% H 2 O) Crystallization rate: fully crystalline

Calcium binding capacity: 145 mg CaO / g AS.

The aluminum silicates Im and Ilm show the following interference lines in the X-ray diffraction diagram: the 10 d value recorded with Cu-Ka radiation in Â

Im Ilm 14.4 15 12.4 8.8 8.6 7.0 4.4 (+) 20 4- »3. (+) - 3.8 (+) 3.68 (+) 3.38 (+) 3.26 (+) 2.96 (+) 2.88 (+) 2.79 (+) 2.73 (+) 2.66 (+) 4n 2.60 30

It is quite possible that all of these interference lines do not appear in the X-ray diffraction diagram, especially if the aluminum silicates are not completely the structural types. Therefore, for the characterization of these types of most important d-values, they are denoted by an "(h-)". 3 5 15

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Aluminum silicate suspension S2: Precipitation: 8,450 kg of aluminate solution of the composition: 11.3% Na 2 O, 5 18.7% Al 2 O 3, 70.0% H 2 O 6,550 kg of a 34.9% solution of a sodium silicate of the composition: 1 Na 2 46 Si02 10 Further processing: Crystallization, use as suspension in the mother liquor

Na₂O excess: 0.55 kg = 3.7%

Aluminum silicate (calculated on active substance): 4,250 kg = 28.3% 15

Water content: 10.8 kg = 68%

Calcium binding capacity: 170 mg CaO / g AS

Composition of aluminum = the silicate (a sample was filtered, washed with water and dried to anhydrous): 0.9 Na 2 O, 1 Al 2 O 3, 1.9 SiO 2.

Aluminum silicate powder P2: 25

Starting material and precipitation: as for aluminum silicate suspension S2

Further processing: Crystallization, suction of the mother liquor, post-washing with 10 1 30 water and suction of the wash water.

Use as a moist product with 45% water

Aluminum silicate (calculated on active substance): 4,250 kg = 55% 35

16 DK 156175 B

Calcium binding capacity: 170 mg CaO / g AS

Composition of the aluminum silicate: as for the aluminum silicate suspension == Sion S2.

5

Aluminum Silicate RI: Precipitation: 7.63 kg of an aluminate solution of the composition: 13.2% Na 2 O, 8.0% A190, 78.8% Ho

10 d o <L

2.37 kg of a sodium silicate = solution with the composition: 8.0% Na 2 O, 26.9% SiO 2, 65.1% H 2 O

Mole ratio in starting material: 3.24 Wa 2 O, 1.0 Al 2 O 3, 1.78 SiO 2, 70.3 H 2 O

Crystallization: 6 hours at 90 ° C

Drying: 24 hours at 100 ° C

Composition of the 20 dried product: 0.99 Na 2 O, 1.00 ΑΙ 2, Ο 2, 1.83 SiO 2, 4.0 H 2 O (= 20.9% H 2 O)

Crystal shape: cubic with strongly rounded corners and edges

Average particle = 25 / diameter (for the range 0-30 μ): 5.4 μ

Maximum particle size = curvature distribution curve: below 3 μ 30 Calcium binding capacity: 172 mg CaO / g AS.

In the following, liquid to paste-shaped detergents according to the invention having a content of the aforementioned aluminum = silicates are described.

35

Example 1

This example gives the composition of a detergent whose preparation contains the water-soluble and water-dispersible components.

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mixed with water and to this mixture was added a dry aluminum silicate containing bound water.

Sodium dodecyl benzene sulfonate 12.0%

Sodium Coconut Alcohol (C 2 -C 3 g) Sulfate 14.0% Coconut Alcohol-12 EO 13.0%

Carboxymethyl cellulose sodium salt 1.0%

Sodium triphosphate 2.0%

Aluminum silicate Im (water content 21.6%) 8.0%

Water (weighed) 60.0%.

10

Example 2

This example gives the composition of a detergent which was prepared by mixing a moist washed aluminum silicate with an aqueous dispersion of the remaining ingredients.

Tallow alcohol polyglycol ether with 14 moles of ethylene oxide 15.0%

Carboxymethyl cellulose sodium salt 0.5% Sodium triphosphate 5.0%

Aluminum silicate P2 (water content 45%) 28.0%

Water (weighed) 51.5%.

Example 5 25

This example gives the composition of a liquid detergent which was prepared by adding a dried aluminum silicate of crystallites with rounded burrs and edges to an aqueous dispersion of the other ingredients.

30

Sodium dodecyl benzene sulfonate 4.0%

Coconut fatty acid monoethanolamide 3.0%

Aluminum silicate RI (water content 20.9%) 20.0%

Water (weighed) 73.0%.

35

Example 4

This example describes a cleaning paste which was prepared by stirring the other ingredients in an alkaline aluminum silicate =

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suspension, adding some of the other anionic surfactants in acid form to neutralize excess alkali. The concatenation of the finished preparation is indicated.

Sodium dodecyl benzene sulfonate 24.0% Sodium coconut alcohol (C C / C-) diglycol ether = sulfate 4.0%

Boiling salt 0.5%

Aluminum silicate suspension S2 (water content 68%) 18.0% Water (weighed) 53.5%.

Example 5

This example describes the composition of a liquid cleanser = 15 which was prepared by mixing the water-soluble or water-dispersible ingredients with the water and subsequent addition of a dry aluminum silicate.

Sodium dodecyl benzene sulfonate 1.0% Coconut fatty acid diethanolamide 3.0%

Potassium soap from cotton fatty acid 4.0%

Aluminum Silicate Odor (water content 23.2%) 10.0%

Water (weighed) 82.0%.

Example 6 This example describes the composition of a liquid detergent which was prepared by incorporating the other ingredients into the alkaline suspension of the aluminum silicate using a neutralization of excess anionic acid in the form of an acid surfactant and adjusting the final mixing at a pH of 9.5-10.5 by the addition of an acid.

Sodium dodecyl benzene sulfonate, 8.0% Sodium fatty alcohol diethylene glycol sulfate -2.0%

Potassium soybean oil fatty acid 2.0%

Butylglycol 5.0%

Pine oil (consisting essentially of a-terpineol) 1.5%

19 DK 156175 B

Aluminum silicate suspension S2 (water content 68%) 25.0%

Citric acid 1.0%

Water (weighed) 55.5%.

Example 7

This example describes the composition of a phosphate-free detergent which was prepared by stirring a damp aluminum silicate powder in a solution of the other ingredients.

10

Tallow alcohol polyglycol ether with 14 moles of ethylene oxide 15.0%

Tallow alcohol polyglycol ether with 5 moles of ethylene oxide 15.0% Sodium soap of C C / / C ^kok coconut fatty acid (iodine number 2) 5.0%

Sodium salt of nitrilotriacetic acid 1.5%

Cotton Clearing Agent 0.15%

Butyl diglycol 7.5% Propylene glycol 7.5%

Aluminum silicate P 2 (water content 45%) 25.0%

Water (weighed) 25.35%.

Example 8 25

This example gives the composition of a liquid scouring agent which was prepared by adding the abrasive components and a tart aluminum silicate containing bound water to a dispersion of the other ingredients.

Ethylene / cetyl alcohol polyglycol ether with 10 moles of ethylene oxide (iodine number of the alcohol 45) 2.0%

Oleic Acid Diethanolamide 2.0% Quartz Flour 45.0%

Aluminum silicate Im (water content 21.6%) 10.0%

Water (weighed) 41.0%.

Claims (3)

This example concerns a highly alkaline detergent, e.g. for grease-rubbed metal surfaces prepared by introducing the other components into an alkaline aluminum silicate suspension. 5 Oleyl / c ethyl alcohol polyglycol ether with 10 moles of ethylene oxide (iodine number of the alcohol 50) 3.0% Propylene glycol 5.0% 10 Butyl glycol 5.0% Monoethanolamine 8.0% Aluminum Silicate Suspension S 2 (water content 68%) 30.0% Water (weighed) 49.0%. Example 10 A composition suitable for cleaning metal surfaces of all kinds was prepared by entraining a damp aluminum silicate powder = 20 ver in a dispersion of the other constituents. Boiling point alcohol alcohol polyglycone with 12 moles of ethylene oxide 6.0% Polyvinyl alcohol (trade name Mowiol'S'4-98) 2.0% 25 Gasoline fraction boiling point 180-250 ° C 20.0% Aluminum silicate P 2 (water content 45%) 20.0% Water (weighed) 52.0%. Claims. Detergent according to claim 16 of Patent No. 151,231, characterized in that it contains 0.1-30% by weight of surfactant components, 1-50, preferably 5-35% by weight, aluminum silicate of formula 1 0.7- 1.1 Na2O, A1203, 1.3-3.3 SiO2 DK 156175 B with a calcium binding capacity of 50-200 mg CaO / g of active substance and 0.5-50% by weight of the usual constituents of liquid and paste-forming washing and detergents and at least 20% by weight of free water. 5 10 15 20 25 30 35