NL8006872A - PROCESS FOR PREPARING A DETERGENT THAT MAY REDUCE THE CONTENT OF FREE, VARIABLE METAL IONS OF A WATER SOLUTION. - Google Patents

Description

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Process for preparing a detergent which can rapidly reduce the free, polyvalent metal ion content of an aqueous solution.

The invention relates to a process for the preparation of a detergent which can rapidly reduce the content of free polyvalent metal ions of an aqueous solution, wherein in the detergent agent a water-soluble organic surfactant and a water-insoluble , inorganic, synthetic, ion-exchanging aluminosilicate.

Rights are already claimed for such a method in the non-prepublished Dutch patent application 7403381 insofar as it is of older rank.

It has long been known that detergents are more effective in soft water than in water, which contains significant amounts of dissolved "hardness-causing" cations, for example, calcium, magnesium, etc. Hitherto, washing water has usually been softened before use. pass water through columns of zeolite or other cation exchange materials. The use of such zeolites or other cation exchange materials to pre-soften the water requires the use of a separate tank or device in which the water can be slowly percolated by the ion exchange material to remove the unwanted cations. Such pre-softening requires additional costs caused by the purchase of the softening device.

Another way of optimally washing fabrics in hard water involves the use of water-soluble reinforcing salts and / or chelating agents for sequestering the unwanted hardness-causing cations so that they cannot interact with the laundry and the detergent fabrics in the suds. With the use of such water-soluble builders, however, certain substances are introduced into the water, which may be undesirable if the sewage treatment is insufficient.

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As a result, it is sought to incorporate water-insoluble builders into detergents.

A number of methods have already been developed for simultaneously effecting a reinforcing and water-softening action during the washing cycle in the household washing, whereby no water-soluble detergent additives are required. In such a method, a phosphorylated cloth is used, which can be placed in the suds to sequester the hardness-causing ions and which can be removed after each wash; see 10 U.S. Patent 3,424,545.

The use of certain mineral clays to adsorb hardness-causing ions from washing soaps has also been described, see, for example, Rao, in Soap Vo. 3 ΦΦ 3 pp. 3-13 (1950); Schwarz, et al. "Surface Active Agents and Detergents", 15 Vol. 2, p. 297 et seq. (1966).

It has also been proposed to include zeolites, especially the naturally occurring aluminosilicate zeolites, in detergents; see U.S. Patent 2,213,641 and also U.S. Patent 2,264,103.

Various aluminosilicates have been mentioned as additives in and in addition to detergents; see, for example, U.S. Pat. Nos. 923,850 and 1,419,625 and British Pat. Nos. 339,355, 462,591, 461,103 and 522,097.

From the foregoing, it has been seen that many methods have hitherto been employed to remove hardness-causing cations from soaps during the wash cycle of a household wash. However, these processes have not had general success mainly because of the inability of the materials described in the art to rapidly and effectively reduce the free polyvalent metal ion content of wash soaps to an acceptable level of hardness. In order to actually be used in detergent compositions, an ion exchanger must have sufficient cation exchange capacity to effectively reduce the hardness of the suds without the need for excessive amounts of ion exchanger. In addition, the ion-exchanging agent must react quickly, that is to say, it must reduce the hardness caused by cations in a suds to an acceptable level within the limited time (approx. 10-12 min.) Required for the washing of a household wash. available. Optimally, effective ion exchange agents should be able to reduce the hardness caused by calcium to 1.5-3 ° DH within the first 5 1 to 3 minutes of the wash cycle. Finally, useful cation exchange enhancers are preferably water-insoluble inorganic substances which cause little or no ecological difficulties in the sewage system.

It has now been found that certain aluminosilicates exhibit both the strong ion exchange capability and the high exchange rate required for cation exchange builders in detergent compositions.

The invention is therefore characterized in that in a process as described in the preamble in the detergent composition, 5 to 95% by weight of ion-exchanging aluminosilicate of the formula Nag (A102) g. (SXO2), q. calcium ion exchange capacity of at least 200 mgeq / g and a calcium ion exchange rate of at least 0.129 / 3.8 l / min / g, 5 to 95% water-soluble organic anionic, nonionic, ampholytic and / or two-digionic detergent substance and, optionally, 5 to 50% by weight of water-soluble co-fortifying salt.

For the sake of completeness, reference may be made to the prior art U.S. Pat. No. 3,755,180, Dutch patent application 7111852, as well as Ullmanns

Encyclopadie der Technische Chemie, vol. 8, p. 801-2 (1957) and Kirk-Othmer, Encyclopedia of Chemical Technology, vol. 18, p. 157 (1969), in which the ion-exchange properties of sodium aluminum silicates are discussed. This literature gives only 30 general facts about zeolites and does not in any way address the details of the present invention, namely the use of a very particular zeolite.

The detergent compositions herein may contain, in addition to ion exchange and organic detergent, various other ingredients commonly used in detergents.

For example, water-soluble 8006872-4 co-builders or auxiliary enhancers may be incorporated, in particular, in order to promote the elimination of the calcium-causing hardness and to sequester magnesium ions in water, in which dissolved magnesium salts cause considerable difficulties in connection with the hardness.

Furthermore, the present compositions may contain pH adjusting agents to maintain the pH of the suds within a certain range.

The sodium alumino silicate used according to the invention is generally known as zeolite B, also referred to as zeolite P.

An essential aspect of the present zeolite is that it is in the "sodium form". That is, it has surprisingly been found that, for example, the potassium and hydrogen forms of the present aluminosilicate exhibit neither the exchange rate nor the exchange power required for optimum use as an enhancer. After all, the present zeolite is further characterized by its calcium ion exchange capacity, which is at least 200 mgeq / g, calculated on an anhydrous basis and preferably between 300 and 352 mgeq / g, while the zeolite 20 is also characterized by its calcium ion exchange rate, which is at least 0.129 g / 3.8 l / min / g, where both exchange power and exchange rate are based on the hardness-causing calcium ions.

The ion exchange properties of the present aluminosilicates can be easily determined with a calcium ion electrode. This method determines the velocity • ++ m et and the capacity to absorb Ca from a solution m water, 8006872 ψ- - ♦ - 5 - 4.5 ° DH. The amount to use naturally depends on the original hardness of the water and the wishes of the user. Highly preferred detergent compositions of the invention contain 20 to 50 wt% reinforcing aluminosilicate and 5 to 50 wt% water-soluble organic detergent composition. In another highly preferred embodiment, the composition contains 10 to 50% by weight reinforcing aluminosilicate.

The detergent composition of the invention can use a variety of organic water-soluble anionic, nonionic, ampholytic and / or two-sided ionic detergents. A good list of groups and types of detergent compositions that can be included in the detergent compositions of the invention can be found in U.S. Pat. No. 3,664,961.

As mentioned above, the detergent compositions of the invention may contain, in addition to the ion-exchanging aluminosilicates, water-soluble auxiliary builders such as those already included in detergent compositions. Such auxiliary enhancers can be used to promote the sequestration of hardness-causing ions and are particularly suitable for use in combination with the reinforcing ion-exchange aluminosilicates in situations where magnesium onions contribute significantly to the hardness of the water. Such auxiliary builders can be used in concentrations of from about 5 to about 50% by weight, preferably from about 10 to about 35% by weight, of the detergent compositions to aid in their enhancing action.

The auxiliary builders to be used in the present case can be any of a variety of known inorganic and organic water-soluble builder salts.

Such auxiliary builders can be, for example, water-soluble phosphates, pyrophosphates, orthophosphates, polyphosphates, phosphonates, carbonates, polyhydroxysulfonates, silicates, polyacetates, carboxylates, polycarboxylates and succinates.

Good examples of inorganic reinforcing phosphates are sodium and potassium tripolyphosphates, pyrophosphate, phosphate and hexametaphosphate. Specifically, the polyphosphates include, for example, the 8006872-6 sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid, and the sodium and potassium salts of ethane-1,1,2- triphosphonic acid. Examples of these and other phosphorus-enhancing compounds are described in U.S. Pat. Nos. 3,159,581, 3,213,030. 3,422,021, 3,422,137, 3,400,176 and 3,400,148.

Neither can phosphorus-containing sequestrants be used as auxiliary enhancers in the present case.

Good examples of non-phosphorous inorganic detergent auxiliary builders are water-soluble inorganic carbonates, bicarbonates and silicates. In this connection, the alkali, for example sodium and potassium carbonates, bicarbonates and silicates are particularly suitable.

Water-soluble organic auxiliary enhancers 15 are also suitable. For example, the alkali metal, ammonium, and substituted ammonium polyacetates, carboxylates, polycarboxylates, and polyhydroxysulfonates are useful as auxiliary enhancers in the present compositions. Good examples of reinforcing polyacetates and polycarboxylates are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, nitrilotriacetic acid, hydroxydisuccinic acid, mellitic acid, benzene polycarboxylic acids and citric acid.

Highly preferred non-phosphorus auxiliary builders include sodium carbonate, sodium bicarbonate, sodium silicate, sodium citate, sodium oxydisuccinate, sodium mellietate, sodium nitrolotriacetate and sodium ethylenediamine tetraacetate and mixtures thereof.

Other highly preferred auxiliary enhancers are the reinforcing polycarboxylates disclosed in U.S. Pat. No. 3,308,067. Examples of such substances are the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids, for example maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid, methylene malonic acid, 1,1,2,2-ethane tetracarboxylic acid, dihydroxy- 35 tartaric acid and ketomalonic acid.

Still other preferred auxiliary enhancers are the water-soluble salts, especially the sodium and potassium salts of carboxymethyl malonic acid, carboxymethyl hydroxy succinic acid, cis cyclohexane hexacarboxylic acid, cis cyclopentane tetracarboxylic acid and phloroglucinol trisulfonic acid.

Good examples of highly preferred phosphorus-containing auxiliary builder salts are alkali pyrophosphates wherein the weight ratio of ion-exchanging agent to pyrophosphate is between about 1: 2 and 2: 1.

Still other preferred auxiliary enhancers, for example, sodium tripolyphosphate and alkali metal salts of nitrilotriacetic acid, yield similarly favorable results at a weight ratio of ion exchanger to auxiliary enhancer from about 1: 1 to about 1: 3. The ion exchange alumino silicates in combination with citrates used as auxiliary enhancers provide superior removal of free metal ions from the suds when the zeolites used have a 1: 1 mole ratio of AK 2 SiO 2. In the above-preferred, preferred proportions of auxiliary builder to alumino-silicate, the builder component may, of course, be formed by a builder mixture.

The detergent compositions herein which contain the builder ion exchange aluminosilicate and the water-soluble auxiliary builder are therefore so useful because the aluminosilicate preferably adsorbs calcium ions in the presence of the auxiliary builder. As a result, the calcium ions are mainly removed from the solution by the aluminosilicate, while the auxiliary builder remains free to sequester other polyvalent hardness-causing ions, for example, magnesium and iron ions.

The detergent compositions herein may contain a variety of additional additives commonly found in detergent and cleaning compositions. For example, the compositions may contain thickeners and soil suspending agents such as carboxymethyl cellulose, etc. Enzymes, especially the proteolytic and lipolytic enzymes commonly included in detergent compositions, may also be present. Various perfumes, optical brighteners, fillers, anti-lump agents, fabric softeners, etc., can be included in the present compositions to take advantage of the beneficial properties that such substances impart to detergents. Such additives are, of course, of use only insofar as they are compatible and stable in the presence of the enhancing ion-exchange aluminum silicates.

The present granular detergent compositions may well also contain a peroxygen bleaching component in an amount of from about 3 to about 40 weight percent, preferably from about 8 to about 33 weight percent. Examples of such peroxygen bleaches are perborates, persulphates, persilicates, perfosphates, percarbonates and more generally all inorganic and organic peroxygen bleaches known to be suitable for inclusion in the compositions concerned.

The detergent compositions of the invention can be prepared by any known method of preparing the commercial detergent compositions. For example, the compositions can be prepared by simply mixing the ion-exchanging aluminosilicate with the water-soluble organic detergent compound. The additional builder and optional ingredients can then simply be mixed as desired. However, an aqueous slurry of the builder ion exchange aluminosilicate containing the dissolved water-soluble organic detergent compound and optional and auxiliary components can be spray dried in a tower to obtain a granular composition. The granules of such spray-dried detergents contain the reinforcing ion exchange aluminosilicate, the organic detergent and the optional and auxiliary ingredients. Optionally, the present ion-exchange aluminosilicates can be used separately in washing soaps and rinsing baths to reduce the content of hardness-causing cations. Bee. such use, the user can simply add an effective amount, i.e., an amount sufficient to lower the hardness to about 1 to 2 grains per 3.78 l, to the water and then any 8006872 2- Add commercial detergent. When used in such a manner, the aluminosilicate is generally added in an amount of from about 0.005% to about 0.25% by weight of the wash or rinse water.

The present ion exchange alumino silicates can also be used in rinsing fabrics in combination with standard cationic fabric softeners. In such use, the aluminosilicates remove the hardness-causing cations, resulting in a softer feel of the softened fabrics. Good examples of cationic fabric softeners which can be used in combination with the ion exchange aluminosilicates are tallow trimethyl ammonium bromide, tallow trimethyl ammonium chloride, ditalk dimethyl ammonium bromide and di-tallow dimethyl ammonium chloride. Water-based fabric softeners containing the ion-exchange aluminosilicates contain about 5 to about 95 wt% alumino silicate and about 1 to about 35 wt% cationic fabric softener.

The detergent compositions herein are used as a water suds for cleaning surfaces, especially fabric surfaces, using any standard washing or cleaning method. Thus, the present compositions are particularly suitable for use in standard washing machines in concentrations from about 0.01 to about 0.50 wt%. Optimum results are obtained when the compositions are used in a suds in an amount of at least about 0.10% by weight. As with most commercially available detergents, the present dry compositions are usually added to ordinary washing soap in an amount of about 1.0 cup per 64 liters of water.

Although the present ion exchange alumino-silicates remove hardness-causing calcium ions over a wide pH range, it is preferred that detergents containing such materials have a pH of about 8.0 to about 11, preferably about 9, 5 to about 10.2.

As with other standard detergents, the present compositions in the basic pH range optimally remove dirt and triglycerides and stains. Although the present aluminosilicates from 8006872-10 provide themselves a basic solution, the detergent compositions containing the aluminosilicate and the organic detergent active may still contain from about 5 to about 25 weight percent pH adjuster. Such preparations can of course also contain the auxiliary enhancers 5 and optional components as described above. The pH adjuster used in such preparations is selected such that the pH of a mixture of the preparation with water containing 0.05% by weight of the preparation is from about 9.5 to about 10.2.

The pH adjusters which may be added can be any of a variety of water-soluble basic substances which are usually included in detergents. Good examples of such water-soluble substances are the sodium phosphates, sodium silicates, especially those with a weight ratio of silica: sodium oxide from about 1: 1 to about 1: 3.2, preferably from about 1: 1.7 to about 1: 2,3, sodium hydroxide, potassium hydroxide, triethanolamine, diethanolamine, ammonium hydroxide, etc. Preferred pH regulators are sodium hydroxide, triethanolamine and sodium silicate.

20

Example

A granular base detergent of the following composition is prepared by conventional spray drying: Ingredient Parts 25 TAE3S ^ 14.5

Sodium tallow alkyl sulfate 2.5

Solid silicates 13.0 (ratio: Na20 / Si02 = 2.0)

Sodium Sulphate 15.0 30 Side Ingredients, including sodium 5.0 toluene sulphonate, trisodium sulphosuccinate, moisture, etc.

(1) Sodium salt of ethoxylated tallow alkyl sulfate with an average of about 3 ethylene oxide units per molecule.

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Thereafter, a mixture was prepared containing the above-mentioned base detergent as well as an enhancer tabulated below in the amounts indicated. The preparation thus obtained was used for cleaning polyester cloths soiled with a clay-containing dirt preparation. To this end, the cloths were washed for 10 minutes at 40 ° C in a solution containing 0.12% by weight of the abovementioned detergent. The hardness and calcium-magnesium ratio were varied as indicated. After washing, the patches were rinsed, taken out of the washing machine and dried. The cleaning effect was expressed as a sum of Hunter Whiteness readings for 0, 3, 6, 9, 12, 14 and 17 ° DH (Ca / Mg = 2/1), the Hunter Whiteness being zero if 0.06 used by weight of sodium sulfate in place of the builder mixture and is equal to 100 if 0.06% by weight of sodium tripolyphosphate is used as the builder. The amount of 0.06% by weight refers to the amount of these ingredients in the suds.

The reinforcing ingredient was a mixture of an aluminosilicate of the formula 20 Na6 (A102) 6 (SiO2)] 0.15 H2 O prepared as described above with an average particle diameter of 3 microns and an auxiliary enhancer in the form of sodium pyrophosphate, sodium tripolyphosphate, sodium nitrilotriacetate or sodium citrate.

The base detergent constituted 0.06 wt% of the suds with the remaining 0.06 wt% being a builder as indicated. The whiteness results were: 30 Aluminosilicate Sodium Pyrophosphate Hunter Hunter Whiteness 0.02 0.04 117 0.03 0.03 102 0.04 0.02 94 (1) in wt% wash.

Sodium citrate was evaluated as an auxiliary enhancer in place of sodium pyrophosphate using the above test conditions. In addition, the Ca / Mg hardness content was varied as indicated. The Hunter Whiteness readings were as follows: 5 Ca: Mg Aluminosilicate ^ Sodium Citrate ^ ^ Hunter Whiteness 1: 1 0.04 0.02 35 0.03 0.03 61 _M2_M4_51_ 2: 1 0.02 38 10 0.03 52 _M4_53_ 3: 1 0.04 0.02 37 0.03 0.03 54 0.02 0.04 50 15 (1) In wt% wash solution.

The sodium salt of nitrilo triacetate and sodium tripolyphosphate were also evaluated as auxiliary enhancers in place of the sodium pyrophosphate using the above test conditions. The Ca: Mg ratio was 2: 1. The Hunter Whiteness Readings read as follows:

Alumino- Sodium nitrile- Sodium tri-Hunter 25 silicate ^ triacetate ^ ^ polyphosphate ^ Whiteness 0.02 0.04 108 0.03 0.03 82 0.04_M2_64_ 0.02 0.04 95 30 0.03 0.03 91 0, 04 0.02 79 (1) In wt% wash solution.

The above test data strongly emphasizes the superior cleaning performance when using certain combinations of aluminosilicates and auxiliary builders in 8006872-13 washing.

Preparations which behave in much the same way are obtained by replacing the ethoxylated tallow alkyl sulfate with a substantially equivalent amount of sodium tallow 5 alkyl sulfate, sodium coconut alkyl sulfate or sodium decyl benzene sulfonate.

8006872

Claims (4)

1. A process for preparing a detergent composition which can rapidly reduce the free, polyvalent metal ion content of an aqueous solution, comprising in the detergent composition a water-soluble organic surfactant and a water-insoluble inorganic synthetic ion onion twisting aluminosilicate characterized in that 5 to 95% by weight of ion exchange and aluminosilicate 10 of the formula Nag (A102) g (SiO ^) -jq-15 H ^ O and with a calcium ion exchange capacity of at least 200 are included in the detergent mgeq / g and a calcium ion exchange rate of at least 0.129 g / 3.8 l / min / g as well as 5-95 wt% water-soluble organic anionic, nonionic, ampholytic and / or two-sided ionic surfactant 15 and optionally 5 up to 50% by weight of co-fortifying salt. 2. Process according to claim 1, characterized in that an ion exchange aluminosilicate with a particle diameter of 0.2 to 10 microns is used. 3. Process according to claim 2, characterized in that a cationic fabric softener is additionally included in the composition in an amount of 1 to 35% by weight. 4. Process according to claim 3, characterized in that talc trimethyl ammonium bromide, tallow trimethyl ammonium chloride, ditalk dimethyl ammonium bromide or ditalk dimethyl ammonium chloride are used as cationic fabric softener. 8006872