CH633040A5 - Granular synthetic organic washing-agent composition of low density - Google Patents

Description

The invention relates to a granular, synthetic, organic detergent composition and to a process for the production of this granular, synthetic, organic detergent composition and relates to the inclusion in a mixer (crutcher mixture) of a small proportion of an organic hydrotropic salt ) before spray drying to an essentially inorganic granular base composition, to which nonionic surfactant is subsequently applied as a coating. It has been found that the presence of the hydrotropic compound in the mixer batch allows the base particles and also the particles of the finished detergent composition to be produced in a considerably lower density. The invention further encompasses a method for producing such base particles and the synthetic organic detergent compositions built up with ss builders, which can be obtained using these methods.

It has recently been found that granular 60 synthetic organic detergents and detergents built up with builders based on nonionic surfactants have numerous advantages over the previously granular detergents and cleaners for coarse and white products based on anion-active synthetic organic surfactants with builders - and have colored clothes. 65 However, there were still many problems in the production of the detergent compositions based on nonionic surfactants, if these were prepared using the methods previously customary for the production of such products

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Example by spray drying the final composition from a mixer batch. The dust formation of the nonionic surfactants during the spray drying process was particularly disruptive. This caused mist or smoke to emerge from the spray drying system and a loss of surfactant could not be avoided. In addition to being undesirable in terms of environmental pollution, this makes the process more expensive and the particulate detergent composition produced had large differences in active ingredient (nonionic surfactant) content depending on the conditions in the spray tower. Attempts have been made to remedy this by subsequently adding most or all of the nonionic surfactant, and commercial products have already been prepared in this way, cf. U.S. Patent 3,838,072, U.S. Patent 3,849,327, U.S. Patent 3,886,098 and U.S. Patent 3,971,726 and DT-OS 2514677.

It can be done by the subsequent addition of the nonionic surfactant, usually by spraying a melt of the surfactant onto the surface of moving particles of a base composition, which is generally essentially inorganic in nature, and from the auxiliaries in the detergent composition, or in any case Most parts of these auxiliaries exist, a usable product is obtained, but such a product generally has a higher bulk density than the previously prepared compositions based on anionic surfactants (including soaps) present in the mixer batch. In some cases, the higher density particles are unobjectionable and even desirable, but there are many cases in which it is important to manufacture products with low bulk density, for example those that are already used to the consumer, whose bulk densities generally are Range from 0.3 to 0.5 g / cm3. It has been found that when a mixer batch essentially consisting of inorganic constituents is spray-dried, the spherical particles obtained after the addition of the nonionic surfactant often have a higher than desired density and often with density values in the range from 0.55 to 0. 75 g / cm3 are present. When nonionic surfactant is subsequently sprayed or otherwise coated onto the particles of the base composition, the densities of these particles increase somewhat or sometimes remain the same. In order to create a commercially available washing and cleaning agent based on nonionic surfactant for rough, white and colored laundry with a normal density, it has therefore been attempted to increase the bulk density of the spray-dried spherical particles of the basic composition and to make granular from such basic particles To manufacture low-density detergents.

It was found that by using soap or other anionic surfactants in small amounts as components of an essentially inorganic mixer batch, the bulk density of the dried particles resulting from spray drying can be reduced. Such effects are described in US Pat. No. 3,971,726 and in the aforementioned DT-OS 2,514,677. However, the use of such detergent products, even if added in only small proportions, enhances foamability, and this is often undesirable for granular detergent compositions. In addition, if small quantities of anionic surfactants are also processed, as described in DT-OS 2 514 677, certain special process conditions in the spray tower have to be observed and in some cases only very specific compositions with the desired low bulk density can be produced.

The invention has for its object to avoid such undesirable properties of the products and the limitation to certain compositions and special working methods and to propose a method with which practically any compositions can be processed to end products with the desired low bulk density in a simple manner.

The synthetic organic detergent composition according to the invention with a low bulk density of 0.3 to 0.5 g / cm 3, consisting of particles of an essentially inorganic basic composition, a nonionic detergent being adsorbed on the surfaces of the particles, is characterized in that 10 to 50% by weight % of the basic composition from an inorganic builder are selected from the group consisting of alkali metal polyphosphates, alkali metal carbonates, alkali metal silicates, alkali metal borates, alkali metal bicarbonates and mixtures thereof, 0.2 to 5% by weight of the basic composition from a water-soluble, organic hydrotropic alkali metal salt of benzenesulfonic acid or of a lower alkyl-substituted benzenesulfonic acid or of mixtures thereof, and 3 to 16% by weight of the basic composition consist of water, and 4 to 17% by weight of the total product consist of a nonionic detergent which is the Condensation product kt is composed of a lower alkylene oxide and an organic compound which contains a hydrophobic chain with one or more active hydrogen atoms, the lower alkylene oxide content being sufficient to render the nonionic detergent water-soluble.

The base composition, which is sometimes also referred to as a carrier composition, generally consists essentially of inorganic materials, primarily one or more inorganic builders and preferably additionally one or more inorganic fillers. It can also contain other desired components of the finished detergent composition, with the exception of nonionic surfactants, provided that these are sufficiently heat-resistant and remain stable during a drying treatment, for example the usual spray drying. Preferably, detachment of detached dirt preventing agents, such as sodium carboxymethyl cellulose and all amounts of sodium silicate in excess of 15%, preferably 10%, based on the base composition, are added retrospectively, before, after or with the nonionic surfactant, advantageously in the form of solid individual particles. If desired, the flow-improving clays, for example the product sold under the trade name Satintone, can also be added retrospectively, but the use of such substances is normally not necessary for the production of a sufficiently free-flowing, non-tacky and non-baking product. Coloring agents, perfumes, optical brighteners, fungicides, herbicides and other adjuvants can also be added subsequently, and if they are sufficiently soluble, they can be dispersed or dissolved in the nonionic surfactant and thus applied, for example sprayed on, to the base particles.

The builder components of the compositions according to the invention are preferably water-soluble polyphosphates, carbonates, silicates, borates, bicarbonates and phosphates, usually in the form of the sodium or potassium salts, for example pentasodium

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tripolyphosphate, tetrapotassium pyrophosphate, sodium carbonate, potassium bicarbonate, sodium silicate (Naz0: Si02 = 1: 2.35), borax and disodium hydrogen phosphate, but it goes without saying that organic builder salts can also be used; they can at least partially replace the inorganic builders.

For this purpose it is also possible to use water-insoluble framework substances, such as, for example, sodium aluminosilicates, preferably crystalline or amorphous type A or X zeolites; numerous examples of this are described in US Pat. Nos. 2,882,243, BE-PS 813,581 and BE-PS 835,351, DT-OS 2412,837 and DT-OS 2,412,839 and in Austrian patent applications A 4484/73, A 4642 / 73, A 4666/73, A 4717/73, A4750 / 73, A4767 / 73, A4787 / 73, A4788 / 73, A 4816/73 and A 4888/73. Such insoluble builders are also described in Donald W. Breck's "Zeolite Molecular Sieves", published in 1974 by John Wiley & Sons, specifically compiled there in Table 9.6 on pages 747-749. Normally at least 50% of the builder substances used are present in the form of water-soluble inorganic builder salts, their proportion is preferably at least 80%, in particular at least 90% and particularly preferably 100%. While it is not absolutely necessary to incorporate a filler salt into the base particles or into the finished detergent composition, the presence of such substances often gives desirable results. Best proven as a filler, sodium sulfate, which is usually available alone as filler material, usually accounts for more than 50% and advantageously more than 90% of the filler content. The particle strength, stability and flowability can be influenced favorably and the cost factor can be reduced. However, other water-soluble and non-deliquescent inorganic salts that are thermally stable can be used, such as sodium chloride, which is sometimes present as an impurity in one of the product components, potassium sulfate, sodium bisulfate and potassium chloride.

The hydrotropic salt used is a water-soluble organic alkali metal salt of benzenesulfonic acid or a lower alkyl-substituted benzenesulfonic acid or a mixture thereof which has the ability to improve the water solubility of poorly soluble substances and thus to contribute to the formation of carrier material and end product particles with low density capable, especially when the mixer batches of a base composition are spray dried at elevated temperatures. As such compounds, preference is given to using the sodium and potassium salts, and especially the sodium salts. Although alkali benzene sulfonates, such as sodium benzene sulfonate, are useful hydrotropic compounds that can be used in the process according to the invention, it is more advantageous if one or more hydrogen atoms in the compound used on the benzene ring, for example by an alkyl group with 1 to 4 carbon atoms. Atoms, preferably with 1 to 2 carbon atoms and in particular with 1 carbon atom (methyl) are substituted. Examples include sodium toluenesulfonate, sodium xylene sulfonate, potassium toluenesulfonate and corresponding salts of kumol, mesitylene, ethylbenzene and pseudokumol. The sulfonates are usually mixtures of isomers in which the para and ortho configurations normally and preferably dominate. Examples include sodium p-methylbenzene sulfonate, sodium o, o-dimethylbenzene sulfonate and sodium o, p-dimethylbenzene sulfonate. Mixtures of various of the hydrotropic compounds can also be used, for example sodium toluenesulfonate and sodium xylene sulfonate or the corresponding potassium salts.

The nonionic surfactants used are preferably polyoxethylated higher fatty alcohols, such as, for example, the water-soluble condensation products of 3 to 15 moles, preferably 7 to 11 moles of ethylene oxide and fatty alcohols having 10 to 18 carbon atoms, preferably 12 to 15 carbon atoms. Such nonionic surfactants have such melting and softening properties that they can be sprayed in droplet form at a temperature below 45 ° C. An advantageous commercial product for this purpose, which is the condensation product of a mixture of 12 to 15 carbon atoms containing fatty alcohols with about 7 moles of ethylene oxide per mole of fatty alcohol, is the one manufactured by Shell Chemical Company and sold under the trade name Neodol 25-7 Product. Other commercially available nonionic components of this type which are also suitable for the purposes of the present invention are, for example: Neodol 45-11 (also manufactured by Shell Chemical Company); Alfonic 1618-65, which is an alkanol having an average of 10 to 11 moles of ethylene oxide per mole of alkoxylated 16 to 18 carbon atoms and manufactured by Continental Oil Company; and Plurafac B-26 manufactured by BASF-Wyandotte.

In addition to the preferred polyoxethylated higher fatty alcohols and similar alkanols, various other nonionic surfactants can be used, at least in part, for example up to 25 or 50%, as described in detail by McCutcheon's in "Detergents and Emulsifiers", born in 1973, and in " Surface Active Agents », Volume II, by Schwartz, Perry and Berch (Interscience Publishers, 1958). Nonionic surfactants of this type are usually pasty or waxy solvents at room temperature (20 ° C) and they either have sufficient water solubility to dissolve rapidly in water, especially in the presence of the hydrotropic compound, or they melt rapidly at the temperature which the wash water has, for example when its temperature is above 40 or 50 ° C, and distribute itself in it. It is advisable to use non-fluid surfactants usually only at room temperature, because otherwise there is a risk that they agglomerate the granular finished detergent into a sticky structure, so that it becomes poorly pourable and can become lumpy or solid when stored. Examples of nonionic surfactants which can be used according to the invention and which, at the concentrations in which detergent compositions according to the invention are used, for example 0.1 to 0.2% of detergent composition in the washing water, impart sufficient detergency are the polyalkenoxy derivatives which are customarily obtained by condensation of low alkylene oxide (containing 2 to 4 carbon atoms), for example ethylene oxide, propylene oxide (with sufficient ethylene oxide to make the product water-soluble), with a compound containing a hydrophobic, for example hydrocarbon, containing one or more active hydrogen atoms Chain has, such as higher alkylphenols, higher fatty acids, higher fatty mercaptans, higher fatty amines, higher fatty polyols and the above-mentioned higher fatty alcohols. In general, such compounds are oxalkylated with an average of about 3 to 30, preferably 3 to 15 and in particular 7 to 11 alkylene oxide units. Particularly useful are nonionic surfactants of the formula R0 (C2H40) nH, where R is a radical of a linear saturated primary alcohol (an alkyl) having 12 to 15 carbon atoms and n is an integer from 7 to 11. Examples of further nonionic surfactants that can be used for the purposes of the invention are those under the following trade names

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Products distributed: Igepale (GAF Co. Inc.), Pluronics (BASF-Wyandotte), Poly-Tergents (Olin Corp.) and Amidoxes (Stepan Chemical Co.).

In addition to the above-mentioned adjuvants, which are advantageously added subsequently to the spray-dried base particles, small amounts of anionic and amphoteric surfactants can be present in the base spherical particles or added to them subsequently. Such additives are not absolutely necessary for the production of the detergent particles according to the invention, and when they are used they are normally only present in small proportions, for example 0.5 to 2%. Examples of substances of this type are the alkali metal, preferably sodium alkylbenzenesulfonates with 12 to 15 carbon atoms in the alkyl group, which is preferably linear, higher fatty alcohol sulfates, higher alkyl sulfonates, higher olefin sulfonates and polyoxethylated higher fatty alcohol sulfates. The higher alkyl or alkene groups preferably contain 1 to 20 or 12 to 18 carbon atoms and are polyoxethylated up to a content of 3 to 30 or 3 to 15 alkylene oxides per mole. Instead of the specified synthetic anionic organic surfactants, it is possible to use the usual fatty acid soaps for all or part of them, usually sodium soaps of mixed fatty acids having 8 to 18 carbon atoms, for example the soaps obtained from tall oil and coconut oil, and mixtures of the anionic surfactants to use,

the total quantity must be within the previously specified percentage range. Instead of the anionic surfactants, amphoteric surfactants can also be used. These are usually higher fatty carboxylates, phosphates, sulfates or sulfonates which contain a cationic substituent, such as an amino group, which can be quaternized, for example, with lower alkyl groups, or whose chain on the amino group, for example can be extended by condensation with a lower alkylene oxide, for example ethylene oxide. Examples of commercially available water-soluble amphoteric organic surfactants are the commercial products Deriphat 151 and Miranol C2M. It may sometimes be desirable to use small amounts of cationic organic surfactants, for example as antistatic agents or plasticizers. Examples of such compounds are the products sold under the trade name Ethoduo-meens T / 12 and T / 13 (Armor Industriai Chemical Company), which are ethylene oxide condensates of N-tall oil trimethyldiamines and the trade names Ethylquad 18 / 12, 18/25 and 0/12 distributed products (Armor Industriai Chemical Co.), which are polyoxethylated quaternary ammonium chlorides. Various other synthetic surfactants and surfactants that can be used for the purposes of the present invention are described in the aforementioned publications by McCutcheon and Schwartz and co-workers.

For the preparation of the granular low density synthetic organic detergent compositions constructed according to the invention and the corresponding low density particulate base compositions, which are usually essentially inorganic material, provided that the normally solid constituents of the mixtures are used,

an aqueous solution dispersion is prepared, which is commonly referred to as a mixer approach (crutcher mixture) and which contains the various heat-resistant components of the end product, with the exception of the nonionic surfactant and other expedient materials to be added subsequently. The mixer batch should have as high a solids content as possible, for example about 50 to 80%, in order to save energy and to increase the throughput through the drying device. The rest, about 20 to 50%, is water. A higher proportion of water can be provided, but then the energy requirement increases, the throughput of the spray tower becomes lower, the resulting product can be sticky and have poorer flow properties, and it can happen that the granular base composition and finished detergent composition do not have the desired low density will. If the moisture content of the mixer batch is about 20 to 50%, the proportions of water-soluble inorganic builder salts are about 10 to 50%, the proportions of inorganic filler salts are about 5 to 50% and the content of water-soluble organic hydrotropic salts is about 0.2 until 5%. If inorganic filler salt is not present, the content of inorganic builder salt can make up the remaining amount of the composition in addition to the water content and the content of hydrotropic compound (as well as any other heat-stable adjuvants present). Preferred builder salts are sodium tripolyphosphate, which is normally introduced as pentasodium tripolyphosphate and usually makes up at least half of the builder salts in the crutcher. Sodium sulfate is used as the preferred filler salt, and this generally makes up at least half of the total filler salts present in the mixer batch. The water content in the mixer batch is preferably to be provided in such a way that the other constituents present are sufficiently dissolved or dispersed.

Various drying methods can be used, for example drum drying, plate drying, fluid bed drying, film drying and the like. Spray drying is preferred and the mixer batch is sprayed under elevated pressure, usually 3 to 50 kg / cm 2, preferably 20 to 40 kg / cm 2, through a spray nozzle into a spray tower through which drying air is passed so that the resulting drops of Mixer approach arise as round-grained, free-flowing particles with low density. Instead of the spray nozzles, equivalent atomizers or other devices can be used. The spray tower is preferably designed as a countercurrent system and is constructed at a tower height of usually 5 to 25 m, and the inlet temperature for the hot air, which is usually gaseous combustion products from oil or gas, is set to a temperature range from 200 to 400 ° C is set, while the air at the outlet is usually extracted at a temperature in the range of 50 to 90 ° C. Synchronous spray tower systems can also be used in which the inlet air and outlet air have approximately the same temperature. DT-OS 2514677 states that spherical particles with low density can be better manufactured if spray drying is used instead of countercurrent drying in cocurrent; in the process according to the invention, however, the desired products can be produced with low density using both types of spray tower. Preference is given to countercurrent drying because the drying process takes place with greater efficiency, since the heat gradient for the removal of moisture from the partially dried product near the tower outlet is greater.

The dimensions of the spray nozzle for producing droplets of the mixer batch in the desired dimensions are chosen so that the base particles are obtained in sizes in the range from 6 to 160 meshes (US standard sieve series). The product is preferably when it is from s

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removed from the spray tower, completely in the form of particles of this size range, but particles falling out of this size range, which may be present in a weight percentage of 2 to 10%, can either be sieved or crushed to the desired size range or this or a later mixer approach add again. For some uses, the product can be sieved with particles in the range of 6 to 160 meshes so that a narrower size range, for example between 8 and 100 meshes, is obtained. In order to obtain such a product by means of spray drying, so that further sieving or crushing can be dispensed with, the spray conditions can be changed accordingly.

After drying is complete and the particles are of the desired size, the nonionic surfactant is applied to the surface of these particles, preferably molten surfactant, which may be in the form of a concentrated aqueous solution but is preferably anhydrous, is applied to the surface at an angle sprayed tumbled tumbled base particles; the particles are moved forward from a higher filling point to the discharge exit end. Instead of an inclined drum, it is also possible to use fluid beds with different arrangements or other commercially available mixing devices, for example the Schugi mixer. The proportion of nonionic surfactant, preferably a polyoxethylated higher fatty alcohol, is advantageously 4 to 15% and the spherical particles onto which the surfactant is sprayed contain about 3 to 16%, preferably 5.6 to 13.3% and in particular 5.6 to 11.1% moisture, so that the final product has a water content of about 2.5 to 15%, advantageously 5 to 12% and preferably 5 to 10%. The moisture content of the base particles can also be set higher if moisture-free components are to be added subsequently.

The proportions of adjuvants are generally less than 15%, preferably less than 10% and in particular less than 5%, based on the total product, and the proportions of individual special adjuvants are in most cases less than 5%, preferably each below 2% and in particular less than 1%. The total adjuvant content can range from about 0 or 1 to 15%, preferably 1 to 5%, and the concentrations of the individual components can be 0 or 0.1 to 5%, preferably 0.2 to 1%. If a bleaching agent, such as sodium perborate, is usually to be incorporated as a tetrahydrate and activated into the washing and cleaning agent, larger percentages, such as, for example, 5 to 40%, preferably 10 to 30%, may be present. Accordingly, sodium perborate is not among the common adjuvants mentioned above in this regard. If it is also used, it should generally be added subsequently.

As has been found, the amount of builder salts or filler salts for particularly advantageous products can be in the range from 3: 1 to 1: 2, in particular 2: 1 to 1: 1.5. The base spherical particles have a bulk density in the range from 0.2 to 0.45 g / cm3 and the spherical particles in the end product have a bulk density in the range from 0.3 to 0.5 g / cm3. These bulk density values are preferably 0.2 to 0.35 or 0.3 to 0.45 g / cm 3.

Particularly advantageous detergent and cleaning agent compositions according to the invention consist of about 20 to 40% sodium tripolyphosphate, 3 to 15% sodium carbonate, 5 to 15% sodium silicate with a Na20: SiO2 ratio in the range from 1: 1.6 to 1: 3.0 up to 5% borax, 1 to 3%

Sodium toluenesulfonate or sodium xylene sulfonate, 20 to 50% sodium sulfate, 4 to 15% nonionic surfactant in the form of a condensation product of a higher fatty alcohol with polyethylene oxide and 5 to 12% water. In these products, as a condensation product of fatty alcohol and ethylene oxide, a substance is preferably present which has sufficient melting and softening properties that it can be sprayed in droplet form at a temperature below 45 ° C., and in the process according to the invention it is preferably melted and at a Temperature below 55 ° C is sprayed onto the surfaces of the spray-dried particles of the base material which are in motion and at a temperature below 45 ° C and above 10 ° C. The process according to the invention can be carried out particularly advantageously if the moisture content of the mixer batch is approximately 30 to 45% and the mixer batch has such a composition that a spray-dried finished washing and cleaning product is formed which, if there is 7 to 13% of it subsequently on the spray-dried spherical base particles applied nonionic surfactant in the form of a polyoxethylated higher fatty alcohol are present, 28 to 38% sodium tripolyphosphate, 3 to 8% sodium carbonate, 5 to 10% sodium silicate with a Na20: Si02 ratio of 1: 2 to 1: 2.4, 1.2 to 2% sodium toluenesulfonate (or sodium xylene sulfonate), 0.5 to 2% borax, 30 to 42% sodium sulfate and

Contains 5 to 10% moisture. In such a product, a non-ionic surfactant is advantageously a condensation product of a fatty alcohol containing 12 to 15 carbon atoms with about 7 moles of ethylene oxide per mole of fatty alcohol, which can be bought as a commercial product under the trade name Neodol 25-7. In this procedure, the mixer batch is generally sprayed at a temperature of 80 to 105 ° C into the spray drying tower, which is preferably operated in countercurrent and into which the air is introduced at an air inlet temperature in the range from 200 to 400 ° C, and the spray conditions become so adjusted that spray drops form, which form a particle mixture of particle sizes essentially in the range of

Dry 6 to 160 stitches (US standard sieve range). To obtain such particles, nozzles can be used whose nozzle outlet has a diameter of 0.2 to 0.8 mm. In the subsequent spraying process, the nonionic surfactant is preferably sprayed onto the surfaces of the particles of the base composition which are kept in motion in an inclined rotary drum. The rotary drum can be inclined at an angle of 5 to 15 ° and at a speed of rotation of about 5 to 50 rpm. rotate. When sprayed onto the circulated particles, the nonionic surfactant generally has a temperature of 35 to 50 ° C and the particles are kept at a temperature of 20 to 45 ° C.

The process for producing the spherical base or carrier particles has already been described in connection with the overall process for producing the particulate detergent and cleaning agent composition. However, if it is assumed that about 10% of nonionic surfactant is added to the base spherical particles subsequently, the preferred and particularly advantageous proportionate amounts of the different constituents of the spherical particles are somewhat different and are 22 to 44% sodium tripolyphosphate, 3.3 up to 16.7% sodium carbonate, 5.6 to 16.7% sodium silicate, 1.1 to 3.3% sodium toluenesulfonate or sodium xylene sulfonate, 0 to 5.6% borax, 22 to 56% sodium sulfate and 5.6 to 13.3 % Water, the corresponding particularly expedient ranges being the following: 31.1 to 42.2% or 3.3 to 8.9%

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or 5.6 to 11.1% or 1.3 to 2.2% or 0.5 to 2.2% or 33 to 47% or 5.6 to 11.1%.

The numerous advantages of the method according to the invention and the resulting compositions have already been mentioned, which are to be briefly summarized here again. First and foremost, according to the invention, a detergent and cleaning agent for coarse, white and colored laundry composed of builders is produced based on nonionic surfactant, which is in particulate form, has a desired low density, has no stickiness, is not caked and is free-flowing. Products according to the invention can be manufactured by means of technically advantageous, economically working processes which allow suitable variations in the content of active constituents of the composition which give active detergency. The method according to the invention is environmentally friendly, no undesired vapors and no smoke are emitted from the drying devices, for example a spray tower. In addition, tower throughput is increased and energy consumption is reduced.

Despite the comparatively high proportions of nonionic surfactant in the final granular composition, the surfactant substance is quickly and easily sorbed by the spherical particles containing hydrotropic compounds, and comparatively short mixing times, for example 1 to 5 minutes, are sufficient. The presence of the hydrotropic compound in the product, which does not in any way affect the properties of the nonionic surfactant, improves the solubility of some of the comparatively insoluble soiling substances which are often present in soiled laundry, and also makes the solubility of heavy soluble adjuvants, which may be present in the detergent and cleaning agent, increased, thereby preventing undesirable deposition of such substances on the laundry. For example, it can be prevented that dyes present in the detergent and cleaning agent are deposited on pieces of fabric from the laundry. The main advantage of the present invention is that it is possible to produce particulate products with the desired low density. It is even possible with the process according to the invention, in which hydrotropic salts of the type described are also used, to produce products with a lower density than are available with soaps, mixtures of soaps and nonionic surfactants and anionic surfactants, used in equal amounts .

It has not yet been finally clarified theoretically as to what these special effects which can be achieved with the process according to the invention can be attributed to. One could theoretically imagine that the hydrotropic salts enable the preparation of a more homogeneous mixer approach and thereby avoid weak points or local crack-prone spots on the spray droplets or the solid particles during drying in the subsequent process. As a result, the spherical particles can swell to a larger dimension, and this dimension can be retained during drying, which leads to the production of a product with a lower density. But even if it is confirmed that this theory is correct, it is still surprising that the small proportions of hydrotrope salt used can be sufficiently effective to match the properties of a mixer batch containing such a high percentage of inorganic salts or To be able to significantly modify the basic spray drop.

If detergent compositions according to the invention are used in the same way as commercial granular detergents for coarse, white and colored laundry,

i.e. In usual concentrations, for example 0.1 to 0.2% used in cold, warm or hot wash water, the individual pieces of the wash items are cleaned very well. The granular detergent and cleaning agent can also be processed into a paste to treat very heavily soiled areas of the laundry. The presence of the hydrotropic substance supports the detachment of such stubborn stains so that they can be removed more easily during the washing process.

In the following examples, in which the present invention is explained in more detail, but is not limited, unless otherwise stated, all parts are to be understood as parts by weight and all temperature data as ° C. temperatures.

example 1

A mixer batch was prepared from 23.9% sodium tripolyphosphate, 3.6% sodium carbonate, 5.1% sodium silicate, 1.1% sodium toluenesulfonate, 0.7% borax, 25.6% sodium sulfate and 40% water. All ingredients except the sodium silicate and water were added as anhydrous powders. Sodium silicate was added as 10.2% of a 50% aqueous solution and the Na20: Si02 ratio was 1: 2.35. The aqueous composition was mixed for about 15 minutes in a conventional heated soap mixer (crutcher) (polyphosphate was added as the last component) and applied using a high-performance pump system (triplex) at a pressure of 25 kg / cm 2 at a temperature of 95 ° C. inflated a 20 m high spray tower and pressed through a large number of nozzles with a diameter of 0.5 mm. This resulted in a spray stream of spray droplets with a size of essentially 6 to 160 meshes (US standard sieve series), from which spherical particles of approximately the same size resulted. The drying air, which was introduced at the bottom of the spray tower, had a temperature of about 300 ° C and left the tower at a temperature of about 90 ° C. The spray droplets from the sprayed mixer batch which fell through the tower had an average residence time of approximately 1 minute. Depending on the special drying conditions, the residence times in Hesse vary between 30 seconds and 3 minutes. The spray-dried spherical particles, which consisted of more than 95% of particles of the desired size in the range from 6 to 160 meshes, were, after they had been somewhat pre-cooled, drawn off from the tower at a temperature of approximately 45 ° C. At this temperature, the spherical particles were introduced into an inclined rotating drum and at a temperature of about 40 ° C on the surface with a melt of Neodol 25-7 (mixture of 12 to 15 C-fatty alcohol, polyoxethylated with about 7 moles Ethylene oxide per mole) sprayed. The drum was inclined at an angle of about 7 ° and the residence time of the particles therein was about 3 to 5 minutes. The spray nozzles were so large that the spray droplets had a size of about 100 to 200 meshes (US standard sieve series) and the spray jet was aimed at the surfaces of the circulated particles. During the circulation, the product was cooled somewhat, and after removal from the circulation drum, cooling was carried out again to a temperature in the range from 20 to 30 ° C .; the product was then ready for packaging.

The product produced in this way was an excellent washing and cleaning agent for coarse, white and colored laundry, which was particularly suitable for use in cold and warm water and many detergents

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based on anionic detergent ingredients was superior. The bulk density of the product before packaging was 0.34 g / cm3; it had increased somewhat, from about 0.29 g / cm 3, during the addition of the nonionic surfactant. The moisture content to which the mixer batch was dried when the base grain particles were formed was 7.7%. The finished detergent composition gave the following analytical values: 33% sodium tripolyphosphate, 5% sodium carbonate, 7% sodium silicate, 1.5% sodium toluenesulfonate, 1% borax, 35.5% sodium sulfate, 10% non-ionic surfactant and 7% water.

In a comparison experiment in which the same composition was used, but with the difference that sodium toluenesulfonate was not contained in the mixer batch, spray-dried base spherical particles were obtained which had a density of more than 0.5 g / cm3, and the particles of the finished detergent composition had a density of 0.59 g / cm3. Such density values are unsatisfactorily high for a commercial product which is to be put on the market as a replacement for the spray-dried detergent compositions which have been customary to date.

In a modified embodiment of the process according to the invention, the mixer batch was dried by drum drying and plate drying, and the resulting products were reduced to a particle size of 6 to 160 meshes and smaller areas. With this procedure too, the desired reduction in the density of the product to density values in the range from 0.3 to 0.5 g / cm 3 was achieved, whereas higher density values outside this range resulted without the addition of hydrotropic salt. If desired, the bulk density can be reduced further by introducing air into the mixture in which the hydrotrope salt is present before drying. In this way, drum-dried and plate-dried products, as well as spray-dried products with a reduced bulk density and in particle size ranges from 8 to 140 and 8 to 100 meshes can be obtained, and the particles located outside these size ranges are separated off either crushed the desired area or fed back to the starting mixture to be treated.

In the event of further changes to the described procedure, in which spray drying was carried out, the quantitative proportions of the various components in the mixer batch could be modified individually by ± 10, ± 20 and ± 30%, the specified ranges being adhered to and the proportionate amounts of the others Components remained constant. Working conditions are also changing; so the temperature of the

Mixer approach to 85 ° C, 90 ° C and 100 ° C changed, the cross-sectional area of the spray nozzle could be increased or decreased by 10%, and the inlet temperature for the dry air Hess changed to 250 ° C and 350 ° C in various studies. Instead of the drum arranged inclined as indicated, the drum could be used with angles of inclination changed by up to 5 ° and 12 °, and in some cases the nonionic surfactant was applied by means of a Schugi device or passed into a fluid bed made of base particles. The temperature of the base spherical particles could be changed by ± 5 ° C, as could that of the nonionic surfactant sprayed on. In some cases, 0.6% perfume was added along with the nonionic surfactant (dissolved therein). In all of these experiments, useful products according to the invention were obtained which corresponded to the properties described above and were within the specified desired ranges.

Example 2

The procedure was as described in Example 1, but sodium xylene sulfonate was used instead of sodium toluenesulfonate. Essentially the same types of base composition and low density end product were obtained. If sodium benzene sulfonate was used instead, useful products could also be made, but their effectiveness was not quite as good as that of the products containing the methyl substituted benzenesulfonates. If the potassium salts, including potassium toluenesulfonate, were used as the hydro-troublesome constituent, then essentially the same types of detergent compositions are produced.

Equally good results were obtained when working as described above, with the difference that Neodol 45-11 or Alfonic 1618-65 were used instead of the Neodol 25-7. If tetrasodium pyrophosphate is used instead of pentatrium tripolyphosphate and if sodium tripolyphosphate is completely replaced by a mixture of two parts of sodium carbonate and one part of sodium silicate for the production of phosphate-free detergent compositions, products with the properties and specifications characteristic of the products according to the invention can also be produced. This also applies if sodium chloride is used instead of sodium sulfate or if the sodium sulfate is completely omitted and instead an increased amount of sodium tripolyphosphate and sodium carbonate is used, and if sodium silicate with a Na20: SiCh ratio of 1: 2.0 and 1: 2, 4 starts.

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Claims (9)

633040 2nd PATENT CLAIMS 1. Granular, synthetic organic detergent composition with a low bulk density of 0.3 to 0.5 g / cm 3, consisting of particles of an essentially inorganic basic composition, a nonionic detergent being adsorbed on the surfaces of the particles, characterized in that 10 to 50% by weight of the basic composition are composed of an inorganic builder, selected from the group consisting of alkali metal polyphosphates, alkali metal carbonates, alkali metal silicates, alkali metal borates, alkali metal bicarbonates and mixtures thereof, 0.2 to 5% by weight the base composition consists of a water-soluble organic hydrotropic alkali metal salt of benzenesulfonic acid or of a lower alkyl-substituted benzenesulfonic acid or mixtures thereof, and 3 to 16% by weight of the base composition consists of water, and 4 to 17% by weight of the total product consist of a nonionic detergent which is the condensation product of a lower alkylene oxide and an organic compound which contains a hydrophobic chain with one or more active hydrogen atoms, the lower alkylene oxide content being sufficient to render the nonionic detergent water-soluble. 2. Composition according to claim 1, characterized in that at least half of the builder is sodium tripolyphosphate, the hydrotrope is a water-soluble alkali metal salt of a lower alkyl-substituted benzenesulfonic acid, the nonionic detergent is a polyethoxylated higher fatty alcohol, which is the condensation product from a higher Is fatty alcohol having 10 to 18 carbon atoms and 3 to 30 moles of ethylene oxide per mole of higher fatty alcohol. 3. Composition according to claim 2, characterized in that 20 to 40 wt .-% of the basic composition sodium tripolyphosphate, 3 to 15 wt .-% of the basic composition sodium carbonate, 5 to 15 wt .-% of the basic composition sodium silicate with a Na20: Si02 weight . Ratio within the range of 1: 1.6 to 1: 3.1 to 3% by weight of the basic composition sodium toluenesulfonate or sodium xylene sulfonate, 0 to 5% by weight of the basic composition borax, 20 to 50% by weight of the basic composition Sodium sulfate, 5 to 12% by weight of the basic composition water, and 4 to 15% by weight of the total composition are a nonionic detergent made from a polyethoxylated alcohol. 4. The composition according to claim 3, characterized in that the nonionic detergent is one which melts and becomes soft enough to be sprayable in droplet form at a temperature of 45 ° C, and the particles of the composition essentially have a mesh number of 6 to 160 of the US Have standard sieve series. 5. Composition according to claim 4, characterized in that 28 to 38 wt .-% of the basic composition sodium tripolyphosphate, 3 to 8 wt .-% sodium carbonate, 5 to 10 wt .-% sodium silicate with a Na20: SiC> 2 wt .-% Ratio of 1: 2 to 1: 2,4,1,2 to 2% by weight sodium toluenesulfonate, 0 to 2% by weight borax, 30 to 42% by weight sodium sulfate, and 5 to 10% by weight water are. 6. The composition according to claim 5, characterized in that the nonionic detergent is a condensation product of a fatty alcohol having 12 to 15 carbon atoms and 7 moles of ethylene oxide per mole of such higher fatty alcohols. 7. A process for producing the granular, low-density organic detergent composition according to claim 1, characterized in that an essentially inorganic basic composition is obtained by mixing well together from 10 to 50% by weight of an inorganic builder, selected from the group consisting of alkali metal polyphosphates, Alkali metal carbonates, alkali metal silicates, alkali metal borates and alkali metal bicarbonates, and mixtures thereof, 0.2 to 5% by weight of a water-soluble, organic, hydrotropic alkali metal salt of benzenesulfonic acid or of lower alkyl-substituted-benzenesulfonic acid or of mixtures thereof, io and 20 to 50% by weight .-% water, forms, the mixture dries and on the particles of the dried granular basic composition of 4 to 17 wt .-%, based on the entire product, of a nonionic detergent which contains the condensation product of a lower alkylene oxide and an organic compound is which contains a hydrophobic chain with one or more active hydrogen atoms, the lower alkylene oxide content being sufficient to render the nonionic detergent water-soluble, and the detergent being adsorbed on the surfaces 20 of the particles. 8. The method according to claim 7, characterized in that the basic mixture contains 5 to 50 wt .-% of a water-soluble inorganic filler salt, of which at least half is sodium sulfate, and that the basic 25 mixture is spray dried into a granular form 9. The method according to claim 8, characterized in that at least half of the builder salt is sodium tripolyphosphate, the hydrotrope is a water-soluble alkali metal salt of a lower alkyl-substituted benzenesulfone. 30 acid, the nonionic detergent is a polyethoxylated higher fatty alcohol, which is the condensation product of a higher fatty alcohol having 10 to 18 carbon atoms and 3 to 30 moles of ethylene oxide per mole of higher fatty alcohol, and the spray drying is carried out in a countercurrent spray tower.