CH648590A5 - FREE-FLOWING, SPRAY-DRIED CUPBALLS. - Google Patents

Description

The invention relates to free-flowing, spray-dried hollow spheres which are suitable for the production of synthetic nonionic organic detergent compositions which are in particulate form and contain builders. The hollow spheres according to the invention and the compositions produced from them contain certain amounts of water-softening zeolite, bentonite and water-soluble builders for the detergent active ingredients within prescribed ranges. The product according to the invention leads to a lower deposition of zeolite compared to known products which contain comparable amounts of water-softening zeolite. The known products usually contain appreciable amounts of water-soluble silicate, but usually no bentonite.

In recent years, water-softening insoluble aluminosilicates such as hydrated zeolites have been used as builders in detergent compositions. Initially, there was interest in zeolites because of the need to make phosphate-free detergent compositions.

Trisodium nitrilotriacetate and other salts of nitrilotriacetic acid that have been proposed as potential replacements for the phosphates, particularly pentasodium tripolyphosphate, which has been used extensively in detergent compositions containing builders, have been feared by some agencies and have been accordingly in the United States from America products containing no nitrilotriacetate on the market for years. However, there has never been any serious doubt that phosphates are safe for humans, and recently the unfavorable assessment of the use of nitrilotriacetates in detergent compositions has been withdrawn by the United States authorities. Therefore, although certain phosphate-free detergents continue to be manufactured for areas located on lakes and rivers where phosphate is a necessary nutrient for algae growth and can thereby lead to some eutrophication of the water, detergents containing phosphate and / or nitrilotriacetate are again on the market .

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Although zeolites preferably contain zeolite A and in particular between their platelets, hydrated zeolite 4A has obviously not been recognized as builders in phosphate, nor has the explosive properties of the «hydrated» bentonite used for the combination of binding and free detergents free of nitrilotriacetates .

, they have now also become useful components of Also many known formulations contain noticeable amounts

improved detergents and the underlying 5 §s sodium sulfate, a filler that may be the

Hollow spheres have been shown to improve the phosphate (s) and / or nitrilotri- physical properties of the product particles in acetate. Normally, about 6 to 12% of water-based compositions according to the invention, but insoluble sodium silicate, are used in Crutcher mixtures, which therefore require a greater content of active substances, such as spray-dried hollow spheres or detergent components, including builders.

compositions are made. The silicate was used because of »The free-flowing ones according to the invention, as cleaning agents for its effect, the other components of the hollow and for the production of a particulate,

bind spheres so that stable hollow spheres receive synthetic nonionic organic

and it has been found that it can be spray dried to form a detergent composition

networked inner structure of the hollow spheres contributes. Austenete hollow spheres are characterized in that they also contain 5 to 60% by weight of water-softening zeolite, 2 on the basis of anticorrosive and inhibited chemical mixtures

Attack on the aluminum parts of the washing machine and other up to 4% by weight bentonite with sufficient moisture

Devices with which the detergent solution comes into contact to facilitate the dispersing of bentonite and which can. However, it has been found that in the earlier use, deposits of aluminosilicate on the washed laundry were found to be in proportions of e.g. B. 8 to 10% of the finished product inhibit and 5 to 6Q% water-soluble builders or

Combination of water-soluble silicate and zeolite containing 20 dne mixture of such builders.

Cruther mixture to form aggregates of these materials. The hollow spheres mentioned can contain up to 30% by weight.

This leads to the spray-dried hollow spheres, which in the water-soluble synthetic organic detergent and undesirably deposit on the washed material, contain up to 5% water-soluble silicate.

and affect the color of the laundry. According to the invention The zeolite has an essential interchangeability for bentonite and water calcium ions with certain amounts of zeolite and the bentonite has a marked swellability of soluble buildup with little or no water-soluble in water and contains a sufficient amount of moisture to silicate spray-dried hollow spheres with sufficient explosion the platelet-to-platelet bonds in it to mechanical strength for commercial use if the hollow spheres alone or in a mixture with ten, which at the same time less zeolite or zeolite-silicate aggre- other detergent components are added to water, deposit gate. Even if there is a large amount of silicate present, the water-soluble builder or the mixture of builder, the bentonite seems to the tendency of the Zeohths and the substance consists preferably of a polyphosphate, nitrilotri-silicate, larger particles than they normally in the zeolite acetate or carbonate, while no water-soluble silicate - are available to educate, to counteract. This avoids the undesirable deposition of zeolite or zeolite-silicate part. The hollow spheres according to the invention can be prevented or reduced by spraying on the washed fabrics. Drying of the formulation for the hollow spheres with an additionally the bentonite-containing composition - the crutch mixture containing anionic detergent tongues disintegrate much more easily in the wash water and are distributed in it, processed into detergent compositions or, in turn, probably due to the presence of the user by spraying on nonionic detergent in liquid tonits. A further advantage of the assemblage according to the invention is that of hollow-body compositions free of detergent active substances, which contain little or no water-soluble silicate, or on hollow spheres, which only contain a proportionate amount that the carbonate and / or bicarbonate contain an amount of anionic detergent or mixtures the formulations do not contain the presence of the gel formation of anionic detergent ingredients. Mixtures of such preventive materials require to prevent excessive compounding and mixed anionic nonionic thickening of the crutcher mixture. These additives detergent compositions are also useful and are usually not necessary if the main builders can result in superior washing properties. Detergent consists of a phosphate and if little or no carbonate and / or bicarbonate is present. In the case of phosphate, the free formulations contained in the hollow spheres according to the invention, which often comprise noticeable amounts of carbonate zeolites, comprise crystalline, amorphous and mixed crystalline

and / or bicarbonate, represents the omission of an amorphous zeolite that gives the calcium hardness ions in the wash water

Materials preventing gel formation counteract a decisive 50 satisfactorily quickly and sufficiently effectively.

This is an advantage, both in terms of processing and limping. These materials are preferably sufficiently visibly economical. react quickly with the calcium ions so that they alone or

It is known from the prior art for the production of detergents in conjunction with other softening agents, water softening compositions and softening detergents to soften the washing water before these ions are added to the detergents, that different detergent additives are used with other components of the synthetic organic compositions or several zeolites, Ben detergents can undergo adverse reactions. These tonite, silicate, phosphate, nitrilotriacetate, quaternary ammo-zeolites can be characterized as those that have high nium compounds (fabric softeners) and other exchangeability for the calcium ion, can normally be made to components, usually using from about 200 to 400 or more mg equivalents of calcium

use of synthetic organic detergent ingredients. In 60 carbonate hardness per g of aluminum silicate, preferably from 250 to extensive lists, which sometimes as "detergent - 350 mg equivalents per g. Also, they preferably have a first name, almost all materials have a softening rate of 0.02 to a residual hardness for any purpose in detergent and soft 0.05 mg CaC03 / l in one minute, preferably of 0.02 to 10 compositions are used, they contain 0.03 mg / l and less than 0.01 mg / l in 10 min, all of which, however, are not based on the clear teaching or reference to the invention-65 anhydrous zeolite.

corresponding formulations, especially not on formulations, although other ion-exchanging zeolites also contain genes which contain little or no soluble silicate. Those that can be important have normally for the

processing of bentonite, the finely divided synthetic zeolite

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builders the formula

(Na20) x. (Al203) y. (Si02) partly WW20,

where x = 1, y = 0.8-1.2, preferably about 1, z = 1.5-3.5, preferably 2-3 or about 2 and w = 0-9, preferably 2.5-6.

The zeolite should be a monovalent cation exchange zeolite, i. H. an aluminum silicate of a monovalent cation such as sodium, potassium, lithium (if possible) or another alkali metal, ammonium or hydrogen (sometimes). The monovalent cation of the zeolite used is preferably an alkali metal cation, in particular sodium or potassium and especially sodium.

Crystalline types of zeolite, which are at least partially useful as good ion exchangers, include, in particular, zeolites having the crystal structures A, X, Y, L, mordenite and erionite, of which types A, X and Y are preferred. Mixtures of these molecular sieve zeolites can also be useful, especially if zeolite A is present. These types of crystalline zeolites are known and are described in particular in “Zeolite Molecular Sieves” by Donald W. Breck, John Wiley & Sons, 1974. Typical commercially available zeolites with the aforementioned structures are listed in Table 9.6 on pages 747 to 749 of the above-mentioned book. Some of these and other suitable zeolites have been described as builders for detergent compositions in a number of patents published in recent years.

The zeolite contained in the hollow spheres according to the invention usually consists of a synthetic zeolite and is often through a network of substantially identical pores in the range from about 0.3 to 1.0 nm, often from about 0.4 nm (normal) characterized, this size was determined on the unit structure of the zeolite crystal. Type A or a similar structure, as described in particular on page 133 of the above-mentioned book, is preferred. Good results have been obtained with a 4A zeolite molecular sieve in which the monovalent cation of the zeolite is sodium and the pore size of the zeolite is approximately 0.4 nm. These zeolites are preferred. Zeolite molecular sieves of this type are described in US Pat. No. 2,882,243, where they are referred to as Zeolite A.

The zeolite molecular sieves with internal exchange capability and water softening properties can be made in a dewatered or calcined form containing about 0 or about 1.5 to 3% moisture, or in a hydrated or water-loaded form containing more bound water in an amount of about Contains 4% up to about 36% of the total weight of zeolite, depending on the type of zeolite used. The water-containing hydrated form of the zeolite molecular sieve, which is preferably about 15 to 70% hydrated, is preferred for the invention when a crystalline product is used. The production of such crystals is known. For example, in the manufacture of the aforementioned zeolite A, the hydrated zeolite crystals that form in the crystallization medium, such as water-containing amorphous sodium aluminum silicate gel, are used without high-temperature dehydration (calcination to a water content of 3% or less, which is normally used in the manufacture of such crystals for catalysts, for example Cracking catalysts is used). The crystalline zeolite is either fully or partially hydrated, can be recovered by filtering the crystals from the crystallization medium and can be air dried at ambient temperatures so that its water content is about 5 to 30%, preferably about 10.15 to 25%, such as 17 to 22 %, e.g. B. is 20%. However, the moisture content of the zeolite molecular sieve used can be much lower than previously stated. In this case, the zeolite is usually hydrated during the mixing process and other process steps.

The zeolite is preferably in a finely divided state, with outermost particle diameters up to 20 µm, e.g. B. 0.005 or 0.1 to 20 µm, in particular from 0.01 to 15 [im, z. B. 3 to 12 (in and especially with an average particle size of 0.01 to 8 (in, z. B. 3 to 7 [in the crystalline state, and from 0.01 to 0.1 [in, z. B. 0.01 to 0.05 (in the amorphous state. Although the outermost particle sizes are much smaller, the zeolite particles usually correspond to open mesh sizes from 0.149 to 0.037 mm, preferably from 0.105 to 0.044 mm. Zeolites with smaller particle sizes often develop in Dust and the larger particles cannot adhere sufficiently and satisfactorily to the carbonate, bicarbonate, phosphate and / or nitrilotriacetate particles, on which they together with the bentonite, for example in gel-like form or in the form of a film during spray drying the Crutcher mixture can be distributed to form hollow spheres.

The bentonite used is a colloidal clay (aluminum silicate) containing montmorillonite. Montmorillonite consists of a hydrated aluminum silicate, in which about% of the aluminum atoms can be replaced by magnesium atoms, and with which different amounts of hydrogen, sodium, potassium, calcium, magnesium and other metals can be loosely combined. The most suitable bentonite clay for the hollow spheres according to the invention is that known as sodium bentonite or Wyoming or Western bentonite, which normally consists of a light to off-white, imperceptible powder which forms a colloidal suspension with strong thixotropic properties in water. The swellability of the clay in water is usually 3 to 15 ml / g, preferably 7 to 15 ml / g, and its viscosity at 6% concentration in water is usually in the range of 3 to 3010 "3 Pa.s, preferably of 8 up to 3010 "3 Pa.s. Preferred swelling bentonites of this type are sold under the trademark Mineral Colloid as technical bentonites by the Benton Clay Company, a subsidiary of Georgia Kaolin Co. These materials, which are the same as those previously marketed under the Thixo-Jel trademark, are selectively mined and processed bentonite. The most useful is as Mineral Colloid No. 101 etc. according to Thixo-JelNr. 1,2,3 and 4 available. At 6% concentration in water, these materials have a pH in the range of 8 to 9.4, a maximum free moisture content of approximately 8% and a specific weight of approximately 2.6. About 85% of the pulverized quality passes through a sieve with a mesh size of 0.074 mm. Processed Wyoming bentonite is preferred as a component of the hollow spheres mentioned, although other bentonites can also be used, in particular if they form a smaller proportion of the bentonite used. Although it is desirable to limit the maximum free moisture content as mentioned, it is important to ensure that the bentonite used has sufficient free moisture that is believed to be most between adjacent platelets of the bentonite to facilitate rapid disintegration of the bentonite and adjacent materials in the particles when these particles or detergent compositions containing them are brought into contact with water such as wash water. It has been found that at least about 2%, preferably at least 3%, and especially about 4% or more water should be initially present in the bentonite before it is mixed with the other hollow bead components in the crutcher, and this should also be after be present for spray drying. In other words, overdrying to the point where the bentonite loses its “inner” moisture can significantly reduce the usefulness of the hollow spheres according to the invention

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reduce. If the moisture content in the bentonite is too low, the bentonite does not prevent the formation of silicate-zeolite agglomerates and does not promote the disintegration of the hollow spheres in the wash water. If the moisture content of the bentonite is satisfactory, it has an exchangeability for calcium oxide of 1 to 1.8% and for magnesium oxide an exchangeability of normally 0.04 to 0.41%. Typical chemical analysis values for these materials are: 64.8 to 73.0% Si02.1.4 to 1.8% A1203.1.6 to 2.7% MgO, 1.3 to 3.1% CaO, 2, 3 to 3.4% Fe203.0.8 to 2.8% Na20 and 0.4 to

7.0% K? 0.

The water-soluble builders or builder salts or mixtures thereof used can consist of one or more of the conventional materials that are proposed or used as builders for such purposes. They include inorganic and organic builders and their mixtures. The preferred inorganic builders include the various phosphates, preferably polyphosphates, e.g. B. tripolyphosphates and pyrophosphates, such as pentasodium tripolyphosphate and tetrasodium pyrophosphate. Tri-sodium nitrilotriacetate (NTA), which is preferably used as a monohydrate, and other nitrilotriacetates, such as disodium nitrilotriacetate, are preferred water-soluble builders. Sodium tripolyphosphate, sodium pyrophosphate and NTA can be used in hydrated forms, but even when anhydrous compounds are used, the bentonite appears and the zeolite to prevent caking during subsequent hydration. Of course, carbonates, such as sodium carbonate, are useful builders which can be used in the desired manner, alone or together with bicarbonates, such as sodium bicarbonate. If polyphosphates are used, it may be advantageous to use sodium pyrophosphate together with sodium tripolyphosphate in a ratio of 1:10 to 10: 1 and preferably 1: 5 to 5: 1, the total amount of these two builders being approximately the same as that for here the sodium tripolyphosphate is indicated. Other water-soluble builders that are believed to be effective include the various other inorganic and organic phosphates, borates, e.g. As borax, citrates, gluconates, ethylenediaminetetraacetic acid and iminodiacetates. The various builders are preferably in the form of their alkali metal salts, either as sodium or potassium salts or mixtures thereof, but the sodium salts are normally preferred. In some cases, e.g. B. If neutral or slightly acidic detergent compositions are to be prepared, acidic forms of builders, especially organic builders, may be preferred, but the salts are normally either neutral or basic. The silicates, preferably sodium silicate with a Na20: SiO2 ratio in the range from 1: 1.6 to 1: 3.0, preferably 1: 2 to 1: 2.8, e.g. B. 1: 2.35 or 1: 2.4 can also serve as builders, because of their strong binding properties and their characteristic feature to promote aggregates or agglomerates with zeolite particles, but they represent a special class of builders, and they are preferred not contained in the hollow spheres according to the invention. However, since they have anti-corrosive properties, which is particularly important when the detergent solution comes into contact with aluminum parts in washing machines or other devices, they are sometimes present in limited, small proportions. In these cases it can be advantageous to add the hydrated sodium silicate particles subsequently so that they do not react with the zeolite particles or form agglomerates during mixing in the crutcher and during spray drying. Although sodium sulfate and sodium chloride, as well as other filler salts, have no builder properties, they can sometimes be used as fillers in detergent compositions. They don't just increase the volume and that

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Weight of the product, which facilitates its dimension, but sometimes also improve the stability and physical properties of the hollow spheres for the detergent composition into which they are incorporated. Since the hollow spheres according to the invention are satisfactory even without any fillers, these substances are preferably omitted entirely or their proportion is reduced as far as possible, usually to a practical minimum.

The commonly used detersives are usually either non-ionic or anionic or both, but amphoteric or ampholytic detergents can also be used, especially together with nonionic and / or anionic detergents. Cationic detergent substances can serve as fabric softeners in the products according to the invention. However, they are not normally spray dried with anionic detergents as an undesirable mutual reaction can occur. The material classes mentioned are well known in the field of detergent active substances and have already been described repeatedly. Since they are not the preferred components of the hollow spheres according to the invention, a detailed explanation does not appear to be necessary.

Although various nonionic detergents with satisfactory physical properties can be used, including condensation products of ethylene oxide and propylene oxide with one another and with bases containing hydroxyl groups, such as nonylphenol and oxo-alcohols, the use of a condensation product of ethylene oxide and higher fatty alcohols as the nonionic detergent is preferred. In these products, the higher fatty alcohol contains 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms, and the nonionic detergent contains about 3 to 20 or 30 ethylene oxide groups per mole, preferably 6 to 12. In particular, the nonionic detergent consists of one in which the higher fatty alcohol contains about 12 to 13 or 15 carbon atoms and 6 to 7 or 11 moles of ethylene oxide. These detergent active ingredients are manufactured by Shell Chemical Company and are available under the trade names Neodol® 23-6.5 and 25.7. Their particularly advantageous properties, in addition to their good cleaning action with regard to oily stains on the materials to be washed, include a relatively low melting point, which is, however, noticeably above room temperature, so that they can be sprayed as a liquid onto the hollow spheres, which then solidify.

Various anionic detersives, usually in the form of the sodium salts, can be used, but the most advantageous are linear higher alkylbenzenesulfonates, higher alkyl sulfates and higher fatty alcohol polyethoxy lat sulfates. The higher alkylbenzenesulfonates are preferably present as the sodium salt and contain a linear alkyl group with 12 to 15, for. B. 13 carbon atoms. The alkyl sulfate is preferably a higher fatty alkyl sulfate having 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms, e.g. B. 12 and is also used in the form of the sodium salt. The higher alkyl ethoxamer sulfates similarly contain 10 or 12 to 18 carbon atoms, e.g. B. 12 in the higher alkyl group, which is preferably a fatty alkyl group, and its ethoxy content is normally 3 to 30 ethoxy groups per mole, preferably 3 or 5 to 20. Here too, the sodium salts are preferred. The alkyl groups are therefore preferably linear and represent fatty alkyl groups with 10 to 18 carbon atoms, the cation is preferably sodium and if a polyethoxy chain is present the sulfate group is at the end. Other useful anionic detersives include the higher olefin sulfonates and paraffin sulfonates, e.g. B. in the form of their sodium salts, the olefin or paraffin groups containing 10 to 18 carbon atoms. Specific at5

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games for preferred detergent ingredients are sodium tridecyl benzenesulfonate, sodium tallow alcohol polyethoxy (3 EtO) sulfate and hydrogenated talc alcohol sulfate in the form of the sodium salt. In addition to the preferred anionic detergent active substances mentioned, other substances from this known group may also be present, in particular in a smaller proportion with respect to those described above. Mixtures can also be used and in some cases these mixtures are superior to the individual detergent active ingredients. The various anionic detergent active ingredients are well known and are described by Schwartz, Perry and Berch in Suface Active Agents and Detergents, Volume II, 1958, Interscience Publishers, Inc.

Various auxiliaries may be present in the crutcher mixture from which the hollow spheres or the detergent compositions can be spray-dried, or these auxiliaries can be added subsequently, which is often due to the physical properties of the auxiliary, its resistance to high temperatures, its resistance to decomposition in water Crutch medium and its volatility is determined. The more important auxiliaries include a polyacrylate, which has been found to be useful for controlling the properties of the hollow spheres and their bulk density, has dispersing properties, counteracts deposition and renewed deposition in the hollow spheres according to the invention and contributes to keeping the crutch mixture fluid and homogeneous .

The polyacrylate contained in the preferred hollow spheres according to the invention has a low molecular weight, usually in the range from about 1000 to 5000, preferably from 1000 to 3000 and in particular from 1000 to 2000 or about 2000. The polyacrylate can be partially or completely neutralized, e.g. B. about half or a third are present as sodium polyacrylate. Although modified polyacrylates can be used in place of the sodium polyacrylate described, including some other alkali metal polyacrylates and hydroxylated polyacrylates, such replacement is preferably limited to a minor proportion, and preferably the polyacrylate consists of an unsubstituted sodium polyacrylate. These materials are available from Alco Chemical Corporation under the name Alcosperse®. The sodium polyacrylates are available as clear amber-colored liquids or powders, the solutions having a solids content of about 25 to 40%, e.g. B. 30% and the pH of these solutions or a 30% aqueous solution of the powder about 7.5 to 9.5, z. B, is about 9. These materials are completely soluble in water and have already been used as dispersants. They have been shown to have the ability to bind calcium ions and used them to prevent the deposition of insoluble calcium compounds from aqueous solutions. When spray drying, small amounts or percentages help to give the resulting hollow spheres higher porosity.

If the crutcher mixture preferably contains a carbonate and / or bicarbonate and silicate, the mixture may tend to form a gel or "freeze" in the crutcher, even if the amount of silicate is small, especially if the crutch mixture is longer due to processing delays than the normal 30 min or so is held in the crutcher. In such cases, in the presence of silicate in the mixture, it is preferred to use processing agents, which are accordingly also contained in the finished hollow spheres and in the detergent composition, in order to prevent premature solidification or gel formation. These agents are preferably citric acid and magnesium sulfate. Instead of citric acid, soluble citrates such as sodium citrate can be used. While anhydrous magnesium sulfate is preferred, various hydrates of magnesium sulfate, such as epsom salts,

be used. Magnesium citrate can also be used. Instead of the preferred gelation preventing system, other means and suitable systems can be used to keep the crutcher mixture fluid, such as sodium sesquicarbonate, which can be used in place of a portion of the sodium carbonate and sodium bicarbonate. While these processing aids are useful in many cases, it is a feature of the invention that they are not required for the manufacture of the preferred non-silicate hollow spheres.

Some auxiliaries such as fluorescent brighteners, pigments, e.g. Ultramarine blue, titanium dioxide and inorganic filler salts can be added to the crutcher, while others, such as perfumes, enzymes, bleaches, some coloring substances, bactericides, fungicides, fabric softeners and fluidity enhancers, are often sprayed or otherwise sprayed onto the hollow spheres or otherwise of the spray-dried detergent composition, together with and / or independently of a nonionic detergent, so that they are not affected by the elevated temperatures during spray drying and their presence in the spray-dried hollow spheres does not inhibit the absorption of the nonionic detergent when it is applied to the hollow spheres is sprayed on. Stable and normally solid auxiliaries can, however, be mixed into the starting mixture in the crutcher. It is envisaged that pigments and fluorescent whiteners, if used, will normally be contained in the crutcher mixture from which the hollow spheres are spray dried. The preferred dye is ultramarine blue, but other stable pigments and dyes can be used with or in its place.

Since the spray-dried hollow spheres according to the invention sometimes cannot have an attractive color, usually due to the use of naturally occurring minerals, the color tone of the dye can be adversely affected. It has been found that incorporating a small amount of titanium dioxide into the crutcher mixture helps maintain the desired hue of the dye. The presence of titanium dioxide does not appear to have an adverse effect on the appearance of laundry washed with detergent compositions based on hollow spheres containing titanium dioxide.

The preferred fluorescent brighteners include Tinopal 5BM, especially in an extra concentrated form. However, various other cotton brighteners, e.g. B. are sometimes used as CC / D AS brighteners, which are derived from the reaction product of cyanuric chloride and the disodium salt of diaminostilbene-disulfonic acid, including modifications with respect to the sutituites on the triazine ring and the aromatic rings. This class of brighteners is known in the field of detergents and is mostly used when there are no bleaches in the end product. Whenever bleaching agents such as sodium perborate or other oxidizing bleaching agents are present, brighteners resistant to these bleaching agents are usually incorporated into the crutch mixture. These include the benzidine sulfone disulfonic acids, naphthotriazolylstilbene sulfonic acids and benzimidazolyl derivatives. Polyamide brighteners that may also be present include aminocoumarin or diphenylpyrazoline derivatives, and polyester brighteners that may also be used include naphthotri-azolylstilbenes. These brighteners are normally used in the form of their soluble salts, but can also be added as acids. The cotton brighteners usually contain larger proportions of brightener systems.

Enzyme preparations that can normally be added to the hollow spheres afterwards because they are warm

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are usually selected from a variety of commercially available products, including Alcalase (manufacturer Novo Industri, A / S) and Maxatase, both of which are alkaline proteases (subtilisin). Maxazyme 375 is sometimes preferred. Although the alkaline proteases are most commonly used, amylotic enzymes such as a-amylase can also be used. The preparations mentioned usually contain active enzymes together with an inert powdery carrier such as sodium or calcium sulfate and the proportion of the active enzyme can vary widely, usually from 2 to 80% in the commercial product. In the present case, the amounts given relate to enzyme preparations and not to their active ingredient. The perfumes used, which are usually heat sensitive and may contain volatile components, including a solvent such as alcohol, are usually synthetic substances, sometimes mixed with natural components. They generally contain alcohols, aldehydes, terpenes, fixatives and other normal perfume components. In the present case, the flow promoters, such as specialty monons, which are sometimes added to detergent products because they often improve fluidity and reduce the stickiness of various compositions, are unnecessary, possibly due in part to the presence of bentonite and the absence or very limited amounts Silicate. However, if desired, they can be added to further improve the flowability. Although it has been found that the detergent compositions produced from the hollow spheres according to the invention do not require any anticorrosive additives which replace the omitted silicate, it is within the scope of the invention to use suitable materials of this type, and preferably those are used which are suitable under the conditions in Crutcher and spray tower are not affected. Such preferred anti-corrosive additives or antioxidants can be organic or inorganic, with the inorganic materials normally being preferred. They are selected in particular for their suitability for preventing the corrosion of aluminum particles in washing machines. If it is desired to continue to use a silicate for this purpose, or because of its interchangeability with water ions causing magnesium hardness, powdered silicate is usually preferred, such as water-containing sodium silicate, which is commercially available under the name Britesil® (manufacturer Philadelphia Quartz Co.) and has a Na20: Si02 ratio of 1: 2.4. This silicate is preferably added subsequently. However, other normally solid soluble silicates, preferably of alkali metals, can also be added subsequently to the hollow spheres according to the invention, preferably after the absorption of the nonionic detergent.

If the product is to have textile-softening properties, plasticizers, preferably in dry powder form, can subsequently be added in a suitable manner to the hollow spheres. This class of substances is known and mostly these plasticizers are cationic compounds, especially quaternary ammonium compounds, such as quaternary ammonium halides. The quaternary ammonium chlorides and bromides with higher alkyl, alkylaryl and arylalkyl lower alkyl groups, such as distearyldimethylammonium chloride, are particularly preferred. Of the commercially available plasticizers, the one sold under the trade name Arosurf TA-100 (manufacturer Sherex Chemical Company, Inc.) is particularly preferred. These compounds also have antistatic and antibacterial activity, but

if desired, other antibacterial adjuvants can also be used, which are preferably added subsequently.

Of course, there is water in the crutcher, which acts as a medium for dispersing the various components

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serves for the hollow spheres, and there is also some water in the product, both in free form and in hydrate form. During the drying of the hollow spheres, their initial moisture content, which is approximately 25 to 60%, is usually reduced to approximately 5 to 15%, which is sufficient for the bentonite in the dried hollow spheres to contain at least 2% and preferably at least 4% moisture . Deionized water is preferably used so that the content of ions causing hardness is very low and metal ions which favor the decomposition of organic materials in the crutcher mixture, the hollow spheres and the detergent compositions produced therefrom are reduced to a minimum amount. However, city or tap water can also be used. Normally the hardness of the water is less than 150 ppm than CaCO3, preferably less than 100 ppm and in particular less than 50 ppm.

The proportions of the various components in the hollow spheres and the spray-dried detergent composition are adjusted so that the hollow spheres flow freely and in particular have sufficient absorption capacity for the nonionic detergent, which is generally applied to them in a liquid state, so that the detergent compositions also flow satisfactorily are. Of course, the detergent compositions are effective detergents, the builders supporting the cleaning action of the organic detergent substances in aqueous solutions. It is important that the products obtained do not lead to undesirable deposits of zeolite particles (or zeolite-silicate aggregates) on the washed materials. The zeolite particles and the bentonite particles, although insoluble, do not undesirably discolor the laundry or light colored laundry because their particle sizes are very small, but such discoloration can occur if zeolite aggregates are formed which are sufficiently large that they are held on the fabrics and easily perceived by the eye, especially when essential parts thereof are not removed from the washed laundry together with the drying air during automatic drying. It is also desirable that the hollow spheres and the detergent compositions made therefrom have an appropriate bulk density and attractive color.

It has been found that satisfactory hollow spheres which meet the aforementioned requirements contain 5 to 60% by weight of water-softening zeolite, 2 to 40% by weight of bentonite (with the desired moisture content) and 5 to 60% by weight of water-soluble builders or contain their mixtures. 0 to 30% by weight of water-soluble synthetic organic detergent and / or 0 to 5% by weight of water-soluble silicate can also be present, but are preferably often omitted. The spray-dried hollow spheres preferably contain 3 to 15% by weight of moisture, in particular 5 to 12% by weight and usually 7 to 10% by weight, including any water of hydration present. Such water of hydration can be contained in the zeolite, in the NTA, phosphate, carbonate, bicarbonate and magnesium sulfate,

if they are part of the formulation, in addition to that between the platelets of bentonite. The specified moisture content even includes strongly bound water of hydration, e.g. B. such that is retained by the zeolite even after distilling a toluene dispersion for several hours. In some cases, when the concentration of the zeolite in the product is high, so that up to about 12 to 15% moisture could be contained as water of hydration in the zeolite, the moisture content in the spray-dried hollow spheres can even be 20% and occasionally up to about 25% . In order to achieve good flowability of the product and to reduce the

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However, the upper limit of about 15% is preferred, regardless of whether or not these anionic detergents, especially when the final detergent composition contains them, and whether it is intended not to apply a noticeable amount of nonionic detergent ionic detergent to them or not. The stated percentage of zeolite includes the preferred formulations of the hollow spheres based on the water of hydration contained therein. It is also possible to make spray-dried hollow spheres containing 15 to 35 or 40% hydrated zeolite, 5 or 10 to 20% less than 3% moisture content, which is the only or main builder, provided the bentonite Bentonite and 20 to 50 or 60% NTA. If a phosphate, for the reasons given above, contains sufficient sodium tripolyphosphate, the main water-soluble water. Because of the strong attraction of moisture to builders, the same proportions of zeolite and the zeolite and the mode of action of the other hydrolyzable bentonite can be used, but usually more materials that may be present have usually been present with phosphate (than NTA). Preferably, however, it is found for those that a minimum of 3% moisture is required, on which nonionic detergent is applied, in order to spray a loss of the desired internal moisture or for comparable compositions of the bentonite, which prevents the Platelets to “Schmief based on carbonate or a mixture of bicarbonate and ren” seem to be easier to separate if one of these 15 carbonate (with the ratio carbonate: bicarbonate in the product containing bentonite being dispersed in water. If spray-dried hollow spheres in the area of about 1 to 3 anhydrous products, these tend to be self-contained), no water-soluble synthetic organic detergent - if sufficient moisture is retained in the bentonite and little or no water-soluble silicate is used, physical inconsistency will result in lighter powder formation if bicarbonate and Carbonate together in such n form and are subject to abrasion and decay. 20 stanchions are used, their amount usually makes up

The bulk density of the spray-dried hollow spheres together with 20 to 40% of the hollow spheres, and if carbonate can be in the range from 0.2 to 0.9 g / cm3. Bulk weights used alone, its amount is usually 10 to the lower part of this range are more easily obtained when the 30%.

spray-dry crutch mixture contains no silicate, and when an anionic detergent or other suitable - if little or no non-ionic detergent is absorbed into the crutch mixture by the 25 neter organic detergent. The higher bulk weights can be given, the proportions of which make up 3 or 5 to 30%, are preferably obtained when nonionic detergent in the manner 5 to 25% and in particular 10 to 25%, e.g. B. 10 or 15% porous beads is applied and some silicate in the product, the detergent preferably containing a bead. In sodium alkylbenzenesulfonate, the lighter products have a linear, 10 to 18 and in particular general bulk density in the range from 0.2 to 0.5 g / cm 3, often 30 alkyl groups containing 12 to 16 carbon atoms, from 0.3 to 0.4 g / cm3, while the bulk weights of the heavy sodium fatty alcohol sulfate, the alcohol of which contains 10 to 18 carbon particles in the range of 0.6 to 0.9 g / cm3 and usually in the atom, or a sodium fatty alcohol ethoxylate sulfate, range from 0.6 to 0, 8 g / cm3. The particle sizes of which the fatty alcohol contains 10 to 18 carbon atoms and the 3 beads usually correspond to a clear mesh size of up to 30 ethylene oxide groups per mole. Mixtures from 2.00 mm to 0.149 mm, i.e. H. they pass through a sieve with 35 of these detergent ingredients can be used. At the moment there is a mesh size of 2.00 mm and the most preferred washing active ingredient sodium tridecylbenzenesul with a mesh size of 0.149 mm remains on a sieve. Preferably phonate with a linear alkyl group.

they correspond to mesh sizes from 2.00 mm to “,.

0.25 mm. In preferred hollow spheres, the ratio is If preferred chemical active detergent from the

Bentonite to zeolite in the range 1: 4 to 1: 1, the ratio "spray-dried spheres is absorbed (sometimes water-soluble builders to zeolite in the range 1: 2 to 3: 1 and ^ m? Mer \ n, the ^ ner spray-dried particles the ratio bentonite water-soluble builders are absorbed in) their amount usually lies in the range

Range 1:10 to 1: 1. These areas preferably have the% ^ z ^^ evon 10 to 25%, z. B. at 15

following values: 1: 3 to 2: 3.2: 3 to 2: 1 or 1: 6 to 1: 2. In or 20%. In your cases the preferred is non-ionic

Expressed in percent, preferred hollow spheres contain 45 detergent active condensation product of 6 to 12 moles, preferably 10 to 40% of partially hydrated sodium zeolite, ethylene oxide and one mole of a higher fatty alcohol with 12

preferably 15 to 25% by weight of water of hydration contains up to 16 carbon atoms

and an exchangeability for calcium ions of 200 to 400 when e.g. em polyacrylate in the hollow spheres or

Containing milligram equivalents of calcium carbonate hardness per g of detergent to be made from water, it has free zeolite, 2 to 35% bentonite with a swellability of normally 0.5 to 1% and its molecular weight from 7 to 15 ml / g and a viscosity from 8 to 30 IO "3 Pa.s at hetia & preferably 1000 to 5000.

6% concentration in water, 10 to 50% water-soluble Since the presence of anionic detergent in the

Alkali metal builder salts or mixtures thereof, 0 to 25% spray-dried beads to form a hollow sphere.

water soluble synthetic anionic organic structure that has a desired amount of nonionic

Detergent and 0 to 3% water-soluble silicate, which, if 55 detergent is able to absorb, can inhibit it, it may be present to produce spray-dried detergents from an alkali metal silicate with an alkali and metal oxide: silicon dioxide ratio in the range of 1: 1.6 to mix them with beads, on the nonionic

1: 3, in particular from 1: 2 to 1: 2.8. More preferred formu- active detergent was sprayed on, so that the proportion of non-

Lulations of the hollow spheres contain 15 to 35% zeolite A, 5 ionic detergent active in the end product can be larger,

up to 20% processed Wyoming bentonite, 20 to 50% water-dissolving 60

Liche sodium builder salts or mixtures thereof, 0 to 20% den, e.g. l: 10 to 10: 1, l: 5 to 5: l and 1: 2 to 2: l of the water-soluble synthetic anionic organic components mentioned, depending on the desired properties of the

Active detergent and 0% sodium silicate. End product. The bulk density of the beads before

Although carbonate and bicarbonate builders for the mixtures should be approximately the same, preferably usable within the position of the hollow spheres according to the invention, 65 0.1 g / cm 3, as well as the particle sizes which one, in particular, normally thins onto the nonionic detergent Correspond to mesh sizes from 2.00 mm to 0.149 mm,

To be sprayed, polyphosphate and / or nitrilotrium are used to prevent trickling and separation in the final acetate builders often for the spray-dried hollow bead mixture.

The proportions of auxiliaries and processing-promoting substances in the hollow spheres and in the spray-dried detergent are normally limited to 20%, preferably to 1 to 10% and in particular to 3 to 7%. The proportions of processing agents when magnesium sulfate and citric acid are used are normally 0.5 to 2% magnesium sulfate, preferably 1 to 1.5%, and 0.1 to 0.5% sodium citrate, preferably 0.1 to 0 , 3%. In the preferred use of coloring substances, pigments and fluorescent brighteners, their proportions normally make 0.05 to 0.6% coloring pigment, such as ultramarine blue, preferably 0.2 to 0.4%, and 0.1 to 4% fluorescent brightener, preferably 1 to 3% off. The proportion of titanium dioxide as the whitening pigment is normally 1 to 3%, preferably 1.5 to 2.5%. If e.g. Instead of a coloring pigment, one or more dyes are used, the amounts of which usually make up 1 to 50%, in particular 5 to 20%, of the amount of the coloring pigment.

The bulk density of the preferred spray-dried hollow spheres according to the invention, which may contain NTA or polyphosphate builders with or without synthetic organic detergent, or which may contain this detergent with any of the preferred water-soluble builder salts mentioned above, is in the range from 0.2 to 0.8 g / cm3, the aluminosilicate consists of hydrated zeolite A, the bentonite contains at least 3% moisture, based on the anhydrous bentonite, the water-soluble silicate, if it is present, sodium silicate with a Na20: Si02 ratio in the range of 1 : 2 to 1: 2.8 and the moisture content of the beads is 3 to 12%. If the beads e.g. Containing NTA or another sodium salt of nitrilotriacetic acid with or without synthetic organic detergent, the ratio bentonite: zeolite 1: 6 to 1: 2, the ratio NTA: zeolite 1: 2 to 2: 1 and the ratio bentonite: NTA 1: 6 up to 1: 2. The percentages of hydrated zeolite, bentonite, sodium nitrilotriacetate or silicate are generally in the range from 10 to 40%; 2 to 25%; 10 to 40% or 0 to 5%.

If the preferred NTA-containing beads also contain a synthetic anionic organic detergent together with zeolite A, bentonite and moisture and optionally soluble silicate, the amount of the synthetic anionic organic detergent preferably makes up 5 to 30%. It consists in particular of sodium alkylbenzene sulfonate with a linear alkyl group containing 10 to 18 carbon atoms, a sodium fatty alcohol sulfate whose alcohol contains 10 to 18 carbon atoms, or a sodium fatty alcohol ethoxylate sulfate whose fatty alcohol has 10 to 18 carbon atoms and which contains 3 to 30 ethylene oxide groups per mole , or from mixtures of 2 or more of these washing active ingredients. The water-soluble builder salt is preferably a sodium salt of nitrilotriacetic acid (NTA), the ratio bentonite: zeolite can be 1: 6 to 1: 1, the ratio NTA: zeolite 1: 3 to 3: 1, the ratio bentonite: NTA 1:10 to 1 : 1 and the ratio of synthetic anionic organic detergent: zeolite can be 1: 1 to 1: 4. The percentages of hydrated zeolite, bentonite, sodium nitrilotriacetate, synthetic anionic organic detergent and silicate are preferably 10 to 40%, 2 to 25%, 10 to 40%, 10 to 25% (preferred range) and 0 to 5%, respectively.

For preferred phosphate-containing beads, if pentasodium tripolyphosphate or tetrasodium pyrophosphate or a mixture thereof is used instead of NTA, the materials and ratios with or without synthetic detergent are the same as for the corresponding NTA-containing beads, but the percentages are usually 15 to 35 %, 5 to 20%, 15 to 40% and 0 to 5%, respectively. Similarly, for phosphate containing beads, using

648 590

anionic detergent, the materials and ratios are the same as for the corresponding NTA-containing beads, as are the percentages, with the exception that the percentage for the total polyphosphate is preferably 10 to 50%. The proportions of the various components in the base hollow spheres of the final detergent composition, if nonionic detergent, optionally together with other materials is subsequently applied, can easily be calculated from the values given for the hollow spheres by subtracting the proportion of the detergent and the other materials added subsequently. Conversely, the formulations of the end product can be used to calculate the proportions of the components contained in the hollow spheres and from these the proportions of the Crutcher mixture. If e.g. B. for the final detergent composition, only nonionic detergent was added, so that the end product contains 20% nonionic detergent, the various detergent product ranges for the components in the hollow spheres can be calculated if the first detergent product is 0.8 , d. H. (100-20) / 100 multiplied. Similarly, the multiplier is 0.92 to 0.75 when the proportion of nonionic detergent in formulations in which only this additive has been added to the hollow spheres is 8 to 25% of the detergent composition. The final percentage of nonionic detergent active in the product is primarily 8 to 30%, preferably 10 to 25% and especially 15 to 22%, e.g. B. about 20%. In some cases and for certain types of products, 8 to 13% may be preferred. Normally, the percentage of perfume in the end product is 0.1 to 1%, preferably 0.2 to 0.4%, the percentage of enzyme in particular 0.5 to 3%, preferably 1 to 2%, and, if water-containing sodium silicate, subsequently added, its amount is usually not less than 1%, and is preferably limited to about 5%, although up to 10% can be used in some cases. Wennz. B. a fabric softener is included in the final product, its amount normally makes up 3 to 12% and preferably 5 to 10%.

The hollow spheres of the invention and the detergent compositions can be spray dried from an aqueous crutcher mixture which normally contains from about 40 to about 70 to 75% and preferably from 50 to 65% solids, the remainder being water, preferably deionized water as previously indicated, but can also City water can be used. The Crutcher mixture is preferably produced by successive addition of the various components in such a way that the most miscible,

easily pumpable and non-settling slurry for spray drying is obtained. The order of addition of the materials can be varied depending on the circumstances, but the silicate solution, if used, should last, and if not last, at least after the addition of the gelation or "freezing" combination of additives or processing facilitating Agents such as citric acid and magnesium sulfate. It is usually preferred to add all or almost all of the water to the crutcher, preferably at about the processing temperature, after which the processing aids and other components, including pigment, fluorescent whitening agent and polyacrylate, may be used, if any used, and then the zeolite, water soluble builder, anionic detergent if used, bentonite and silicate if used. Usually, with these additions, each component is mixed thoroughly before the next component is added, but the type of addition can be varied depending on the circumstances, so that common additions are possible if feasible. Some-

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times the addition of a component can be sprayed in two or more. The zeolite, the bentonite and the poly

Proportions occur, and sometimes different composites, if any, also appear to premix the absorbents before adding them to speed up the mixing ability for liquid and the formation of solid beads. Usually, the blending will favor. The polyacrylate, if present, improves the speed and the mixing power with the addition of the materials 5 properties of the beads and also leads to a faster increase. E.g. can dry until after the addition of the last zeolite, which increases throughput through the tower or soluble builders slow mixing speeds.

applied, whereupon the mixing speed to a. After drying, the product can be brought to the desired medium and then to a high value, on the size of e.g. B. 2.00 to 0.25 mm or 0.149 mm, they are preferably sieved before, during and after the addition of the silicate and is then held for the spraying of the nonionic solution. Active detergent ready when it comes from a basic formulation

The temperature of the aqueous medium in the crutcher has been established, with the hollow beads in warm or usually at room temperature or elevated. Normal- room temperature can be cooled.

wise it is in the range from 20 to 80 ° G, preferably from 30 Usually the non-ionic detergent is up to 75 or 80 ° C and in particular from 40 to 70 ° C. B. 30 to 60 ° C, such as 50 ° C heated to mung the crutch medium can ensure the solution of water-soluble that it is liquid. When cooling to room salts in the mixture and thereby favoring the miscibility temperato, it solidifies in the desired manner and often forms an improvement, but heating in the crutcher can cause the product-wax-like solid. Even at room temperature, the non-ionization rate is slow and sometimes a settling ionic detergent is somewhat sticky, but this does not promote the mixture. An advantage of using FIG. 20 is that the final composition has little flow-promoting substances in the mixture, especially since the detergent active under or in the surface if soluble silicate is present, is that the hollow sphere penetrates. The non-ionic washing active

both at higher and lower temperatures, the substance in the form of a spray or droplets in known

Slurries are obtained which do not form a gel. The way in which the moved or circulated hollow spheres can be brought to temperatures above 80 ° C. and sometimes above 70 ° C. preferably consists of the condensate — usually avoided, since at these temperatures a product of ethylene oxide and higher fatty alcohols is formed how or several components of the Crutcher mixture, e.g. previously stated. However, other non-ionic ones can also be used

Can decompose sodium bicarbonate. In some cases, increased detergent ingredients are used. The enzyme preparation, which is also referred to as lower enzyme at lower crutcher temperatures, although it also contains carrier solids in the crutcher, probably because normally it contains 30 material, the water-containing silicate and other powdery gel-forming or settling components can be insoluble in additives the particles are dusted while

will. rend the perfume and other liquids to be added later

The mixing times in the crutcher to achieve good slurries at a suitable time before or after the addition can vary widely, from only 5 minutes in small powders that can be sprayed on.

Crushers and slurries with a higher moisture content - 35 The spray-dried detergent, the spray-dried content, up to 4 hours in some cases. The required hollow spheres and the detergent additives made from them

Mixing time until all components of the crutcher mixture in the compositions contain little or no silicate from the substantially homogeneously mixed together in a medium. Cruther mixture, although some silicate is present in solid form, can be sluggishly as little as 10 minutes to 1 hour in some cases. This is preferred afterwards although 30 minutes is the preferred upper limit. Powdery silicate added below 40, if used, appears to take little time to react with the zeolite, including the initial blending times, so zeolite-silicate in the crutcher normally takes 15 minutes to 2 hours, e.g. B. 20 min to 1 h, agglomerates that tend to settle on washed articles, but the Crutcher mixture should be movable for at least 1 h, compared to deposits from products,

be, not form a gel or settle, preferably for 2 h and to which silicate had been added in the crutcher, in particular reduced for 4 h or longer after the preparation of the 45 has been completed. Although without existing bentonite silicate normal mixture. It is preferably movable for 10 to 30 hours until it is pumped out wisely because of its spray tower's properties which influence the properties of the hollow spheres, so that situations in which emission and its anti-corrosive effect are used, other production problems occur, taking into account the present formulations acceptable Can be hollow. and do not cause corrosion of aluminum counterparts.

The crutcher slurry, which stood the various salts and 50. In addition, the bentonite does not interfere with the other components, when dissolved or in particulate form, and even appears to be part of the product. It can be spray-dried in a conventional manner to hold the beads together, so that the tower that normally comes close to one another which she finds against breaking and powdering during transportation crutcher. The slurry will usually be resistant to and use. The bentonite improved bottom of the crutcher led to a positive displacement pump, which 55 essentially had the properties of the final assembly - they were high pressure through spray nozzles at the top of a tongue, which led to a stronger binding of calcium ions and to countercurrent or cocurrent conventional reduced deposit from zeolite to the washed

Spray tower in which the droplets of the slurry through tissues. If e.g. Low molecular weight polyacrylate - a hot dry gas, usually the combustion weight is present, the hollow spheres are more porous and absorbed by heating oil or natural gas, to the desired 60 beers better than the non-ionized liquid.

Hollow beads are dried. During the drying process, active detergent can be seen without the bulk density of the product being reduced to an undue extent, if any, of any bicarbonate present. If one converts the release of carbon dioxide into carbonate, that bentonite is a clay and serves as a binding agent, the polyacrylate contained in the spray-drying mixture, which should be expected to cause deposition and gelation problems, would have had the physical properties of the 65 die Reduced deposition, lack of gel formation and the easily formed hollow spheres improved, so that greater dispersion of the product are surprising. Important

Absorbability for liquids, like liquids, is that the preferred presence of the small proportion of nonionic detergent, which is subsequently applied to them, leads to an improved polyacrylate in the spray-dried beads.

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648 590

Spray drying of the base beads and the detergent compositions leads to an improved absorption of the liquid nonionic detergent by the base beads.

The following examples illustrate the invention. Unless otherwise stated, in the examples and in the description all temperatures mean 0 C and all parts are parts by weight. If weights and ratios are given for the zeolite, these refer to the normal hydrate, since it is assumed that the water of hydration of the zeolite does not leave the zeolite and does not become part of the aqueous medium in the crutch mixtures. Some of the water in the hollow spheres and in the detergent compositions is also present as water of hydration of the zeolite. Similarly, the moisture content associated with the bentonite is not considered free moisture. However, because of its lower percentage, this difference is often neglected for practical reasons.

Example 1 (comparative example)

A 100 part crutcher batch for the production of spray dried base beads, which are believed to be satisfactory for subsequent transfer to a detergent composition by adding synthetic nonionic organic detergent, is prepared in the following manner: 47 parts deionized water at a temperature of about 27 ° C and then one after the other and at the beginning with a low mixing speed, 1.4 parts of Tinopal 5BMExtraConc. (Ciba-Geigy), 0.13 parts ultramarine blue powder 0.07 parts sodium polyacrylate (Alcosperse 107D), 21.11 parts hydrated zeolite 4A (linden, 20% crystallization water), 6.25 parts mineral colloid No. 1 ( Bentonite), 15.75 parts of sodium bicarbonate (technical quality), 7.74 parts of sodium carbonate (natural anhydrous soda) and 0.91 part of titanium dioxide (anatase). During the mixing of the various components, the mixing speed is increased to a medium and finally to a high value, and after the addition of all the components, which takes about 15 minutes, mixing is continued for another hour (in some cases up to 4 hours) be mixed). During this time, part of the water present, e.g. B. about 2 to 6 parts of water are lost by evaporation and, if desired, replaced. During mixing, the crutcher slurry is constantly mobile, does not form a gel, does not settle or bake. Since bicarbonate is partially decomposed to carbonate during spray drying, the amounts of bicarbonate and carbonate in the crutcher formulation can be varied depending on the conditions in the spray drying tower.

About 5 minutes after all components of the crutcher mixture have been mixed in, the mixture from the crutcher is fed into a pump which, at a pressure of approximately 21 kg / cm 2, feeds it into the upper end of a counter-current spray drying tower with an initial temperature of approximately 430 ° C and a final temperature of about 105 ° C brings. The hollow spheres formed, which consist essentially of inorganic material, have a bulk density of approximately 0.6 to 0.7 g / cm 3, an initial adherence of less than 10%, particle sizes in a range which essentially has a mesh size of 2.00 mm up to 0.25 mm (they are screened out on this area) and a fine material content that passes through a screen with a mesh size of 0.297 mm of about 15%. The moisture content of the beads is 1 to 10% and is normally closer to 10%, e.g. B. at 8 to 10%. The spheres formed are free-flowing (flow rate 80%) non-sticky, satisfactorily porous and yet have a solid surface. They easily absorb substantial amounts of liquid nonionic detergent without becoming undesirably sticky.

Detergent products are made from the spray dried beads by spraying a normally waxy nonionic detergent active onto the moving surfaces of the beads. Neodol 23-6.5 is used, but 5 also Neodol 23-7 or Neodol 25-7 (and sometimes Neodol 45-11) can be used. The nonionic detergent is in the heated liquid state at a temperature of about 45 ° C). It is sprayed on in such an amount that the end product contains about 20% nonionic io detergent. Proteolytic enzyme (Alcalase 1.7T or Maxazyme 375) is applied in powder form in a concentration of approximately 1.5% of the product, and perfume is sprayed on in an amount such that its concentration is 0.25% of the product. The detergent compositions obtained have a bulk density of about 0.7 to 0.8 g / ml and contain about 32.45% zeolite (hydrated), 19.7% nonionic detergent, 18.5% sodium carbonate (part of which by Decomposition of sodium bicarbonate), 13.5% sodium bicarbonate, 1.3% free water, 1.4% enzyme, 20 1.6% fluorescent brightener, 0.25% perfume, 0.2% ultramarine blue, 9.6% Bentonite, 0.1% sodium polyacrylate and 1.4% titanium dioxide.

The detergent of the above formulation is an excellent heavy-duty detergent and is particularly suitable for washing household laundry in automatic washing machines. It is physically and aesthetically pleasing, since it does not dust and flows exceptionally freely, so that it can be filled into glass and plastic bottles with a narrow neck, from which it can be easily measured. The 30 bentonite-containing detergent compositions, as stated, have improved calcium ion binding capacity, but more importantly, they leave less zeolite residue on laundry that is washed with them in an automatic washing machine at the usual concentrations of such products and normal washing temperatures , especially when the laundry was dried on a line, as similar compositions with less bentonite and with sodium silicate in the spray dried beads. This difference is even more pronounced if the wash water is very hard, e.g. B. has a hardness of 200 ppm as calcium carbonate, the wash water is cold and a gentle cycle was applied.

The base hollow spheres and the detergent compositions made from them are acceptable standard 45 products over the other hollow spheres and detergent compositions of the following examples, with which they are advantageously comparable. The manufacturing processes are also essentially the same and are considered to be satisfactory.

50 Using the normal procedure, Crutcher mixes can be made quickly, sometimes in as little as 5 minutes, and pumped out of the crutcher just as quickly, sometimes in as little as 10 minutes. However, it is often important that the mixtures according to the invention can remain in the crutcher 55 for at least 1 hour without forming a gel or solidifying, since sometimes such periods of time occur in industrial production. The described crutcher mixture can be kept in the crutcher for up to 4 hours and often even longer, without forming a gel or solidifying at 6 °, which is at least partly attributed to the bentonite content and the absence of silicate. This effect of the bentonite is surprising since it has a thickening effect on the crutcher mixture, but although the mixture can be markedly thickened, it remains pumpable. The components of the crutcher mixture, such as fluorescent brightener and pigment, which are used in smaller amounts, as well as the enzyme and the perfume, can be omitted, although it is preferred that all of these materials are contained in the end product. The tempera

648 590 12

The crutch mixture can be modified, e.g. increased to 52 ° C compared to that of the control sample only about 75%, which becomes one, and the proportions of the various components can make a significant difference in the appearance of the washed products.

within the previously specified ranges by ± 10%, means products.

± 20% and ± 30% can be varied, but still workable The above-mentioned adhesion test, which determines the stickiness for detergents

Mixtures obtained that measure to the desired hollow products consist in that 10 g of the base beads gel and lead to detergent compositions. Also (or detergent composition in some cases)

Solids content in the Crutcher mixture can be brought evenly between two watch glasses, the benen range can be varied, z. B. to 45% and 65%, both having a diameter of 23 cm, the concave good mixing and spray drying is achieved. The side of both glasses is facing upwards, and there may be other orders in the addition of the top 10 glass weighing 500 g. After 5 min. Of application to the crutcher, but it is more normal - standing, the weight on the top glass is removed and it is wise to turn any silicate last or towards the bottom towards the bottom, whereupon you put this on this watch glass, and preferably the bentonite is also weighed into a late stuck product. The percentage adherence

Added the time of the procedure, in particular immediately the number of grams of product that is on the watch glass

before the silicate. Instead of zeolite 4A, zeolites X 15 can remain, multiplied by 10.

and Y are used, furthermore other types of zeolite A, and the flow index is the value determined in a flow test, although preferably the approximately 80% hydrated zeolite 4A is the volumetric velocity of the base beads

(Moisture content about 20%) of this example (and in some cases of the final product) and of standardized

however, different degrees of hydration of the Ottawa Sand zeolite (-20 +60, U.S. sieve series) are compared,

acceptable, and in some cases, nearly anhydrous 20 by measuring the times used to completely drain crystalline or amorphous zeolites. a 1.91 Mason vessel through an annular opening

Varying the amount of bentonite within the specified diameter of 2.2 cm in one on its closure

Area on z. B. 7%, 13% and 19% in the base hollow ball attached nozzle. The flow index in percent is the time

Chen still gives usable products, but are the ones that the sand needs divided by the time the test pro

Larger proportions of bentonite-containing products are required, times 100.

Zeolite deposits on laundry are usually more effective. In some cases it may be desirable to be within the range of Example 2

ranges specified in the description even higher percent hollow spheres as those of Example 1, but with NTA instead of using bentonite, whereby care is taken to ensure that part of the carbonate and bicarbonate are essentially

The other components of the base hollow spheres must be made in the same way as in Example 1. The fact that the beads are free-flowing and effective Reini formulation is only changed by being 5 parts of the detergent. The proportion of zeolite in the commercial products, 12 parts of sodium bicarbonate and 3 parts of the bentonite which is expediently used depends on a series of sodium carbonate in the crutcher through 20 parts of NTA as mono-

depends on factors, and is usually midway between hydrate of the trisodium salt replaced. The NTA is added during the desired reduction in zeolite residue and mixing after the sodium carbonate. The desired builder and other functional spheres obtained are not as strong as those of Example 1, but

The shafts of the other components of the detergent flow together satisfactorily. For this product it is sufficient

Settlement that could be incorporated instead of an increased amount of bentonite if it contains 12% non-ionic detergent instead of tet. 19.7% in the product of the example, with the final product

With the detergent composition of this example, 40 percentages of the other components are increased accordingly

that have less residue on washed laundry. The product obtained represents a satisfactory partial

The improvement achieved is shown by examining the detergent in the form of a chen.

The product described in comparison to a control product. According to a modification of this formulation, essentially the same formulation is found, which subsequently added 2.5% water-containing sodium silicate to contain no bentonite and about 8% sodium silicate. For achieving these 45 anti-corrosive properties and magnesium ion assessment, a Whirlpool Suds Saver model washer-to bind in the wash water. If the silicate uses approximately the same machine, with washing periods of 8 min with a particle size and density, it trickles during the mild wash cycle. The concentration of the detergent composition and the storage does not differ or differs from the composition is 0.06%, the washing water has a mixed other components. The product obtained fulfills the calcium-magnesium hardness of a total of 200 ppm as calcium requirements of a conventional heavy-duty detergent, but carbonate and the temperature of the water is 24 ° C. Small quantities of zeolite-silicate aggregate can be seen on the : 100% cotton; 100% polyester; 85% washed materials are found.

Acetate +15% nylon and 65% polyester + 35% cotton. According to another alternative formulation, 3%

The laundry was wet and, after drying on the line, sodium silicate with the Na20: SiOj ratio of about 1: 2.4 in (drying on the line usually results in 55 the final product by adding a more visible residue to the crutcher than drying in an automatic aqueous solution of this, along with 1.5% magnesium

dryer). In both cases, no residue was solidified and 0.4% citric acid to gel or adjust. Examination of the control detergent showed that it did not settle in the crutcher. The finished product provides moderate residue on all washed samples. a good full detergent, but store more zeolite silicate

The results of the practical back-60 aggregate described on washed, line-dried materials

Endurance tests were carried out by weighing the test media on a denim, as a comparable formulation in which the water

material deposited residue confirmed. In this test, sodium silicate containing was subsequently added. filtering the detergent composition according to the invention through a sample of the denim material, example 3

Detergent in solution-suspension in 0.12% concentration 65 The method of Example 2 is carried out with pentasodium tripoly-

repeated in water of 24 ° C and a hardness of 200 ppm (as CaC03) phosphate instead of NTA. The products obtained are located. The weight of the residue on the fabric is good detergent with a bulk density of about 0.8 g /

noted and compared. In this test, the residue was in cm3 (like that of Example 2), but the bulk weights can

13

648 590

by changing the conditions in the spray drying tower and the formulations to be in the range of 0.7 to 0.9 g / cm3, and in some cases the bulk densities can be reduced to 0.3 g / cm3. If the silicate is subsequently added, the bulk densities can be slightly higher, especially for those in the lower part of the range. The product is more free-flowing than that of Example 2, but has about the same detergency.

In the formulations above and those of the previous examples, an additional amount of bentonite can be added to the crutcher to obtain products containing 15% or more bentonite. These products are even better in terms of their binding effectiveness, dispersibility, and other desirable properties attributed to bentonite, and are good detergents (and base beads). Tripolyphosphate can also be replaced, either in whole or in part, e.g. B. half by tetrasodium pyrophosphate, similarly good products are obtained.

Example 4

A final detergent product is made essentially according to the procedure of Examples 1 and 2. It contains 30 parts zeolite, 30 parts NTA, 20 parts nonionic detergent, 10 parts bentonite, 5 parts sodium carbonate, 5 parts water and 1.3 parts enzyme. This product has a bulk density of 0.5 g / cm 3 and is a satisfactory detergent. To improve the flowability of the product, however, it is desirable to reduce the content of nonionic detergent to 15%, preferably 12%. In order to increase the bulk density to about 0.7 g / cm3, half of the bentonite can be replaced by sodium silicate (Na20: Si02 ratio 1: 2.4), which is the last component in the 47.5% aqueous solution Crutcher is added, and 1.5 parts of magnesium sulfate and 0.4 part of citric acid can be added accordingly as gelling agents at an earlier stage in the preparation of the crutcher mixture. The product obtained has a bulk density of about 0.7 g / cm 3 and can absorb about 20 parts of nonionic detergent without becoming sticky or having reduced fluidity. Although it deposits less zeolite-silicate agglomerates than formulations which conventionally contain larger amounts of silicate than crutcher additives, agglomerate can be found on laundry washed with the product and dried on a line.

Example 5

Instead of producing hollow spheres onto which a detergent is applied to form a detergent composition, a detergent composition can be obtained by directly spray drying a crutcher mixture containing a suitable synthetic organic detergent. Using essentially the same procedures as in Example 1, a crutcher mixture is prepared which is spray dried. The beads obtained contain 16 parts of linear tridecylbenzenesulfonate, 20 parts of zeolite, 12.5 parts of bentonite, 15 parts of NTA, 10 parts of sodium carbonate and conventional auxiliaries (dye, fluorescent brightener). The bulk density of the spray-dried product is in the range from 0.3 to 0.8, usually in the lower part of this range and is sometimes only 0.2 g / cm3. In the manufacturing process, the organic detergent is usually added after the water. It is usually dried to a moisture content of about 8 to 12%. The product obtained preferably contains about 3 parts of water-containing sodium silicate, which is added subsequently, together with the other normal auxiliaries, such as enzyme and perfume. It is a satisfactory heavy-duty detergent that does not deposit unwanted amounts of zeolite or zeolite-silicate aggregates on the washed fabrics. Due to the presence of the bentonite, the detergent appears to disperse very quickly when added to the wash water, and it is believed that at least part of this rapid dispersion in conjunction with the presence of the bentonite inhibits zeolite deposition.

10th

Example 6

The procedure of Example 5 is repeated, but the NTA is replaced by the same weight of calcined soda. The product is also a satisfactory heavy-duty detergent.

15 Example 7

The procedure of Example 5 is repeated, but with pentasodium tripolyphosphate instead of NAT. The product obtained is particularly free-flowing and is a good synthetic heavy-duty detergent. Although the silicate, if present, is preferably added subsequently as water-containing sodium silicate, up to 5 parts of silicate can be added to the crutcher, together with suitable amounts Magnesium sulfate and citric acid as described in the previous examples, whereupon useful detergent compositions are obtained, although some zeolite-silicate deposition occurs.

In addition to the conventional materials that can be added afterwards, softening amounts of a cationic material, e.g. B. 8% di-methyl-di-stearyl-ammonium chloride, an amphoteric detergent, e.g. 5% Miranol QM (1-carboxymethyl-l-carboxy-ethoxyethyl-2-coconut-imidazolinium betaine) or a bleach, e.g. B. 15% sodium perborate (preferably activated) 35 be given. Of course, the addition of these materials reduces the proportions of the other components in the final composition, changing the properties of the compositions somewhat, so that sometimes more product is required in the wash water to achieve the same cleaning effect.

In Examples 5 to 7, the linear tridecylbenzenesulfonate can be replaced by the same weight of sodium lauryl sulfate or sodium lauryl polyethoxy sulfate (3 to 10 EtO) or mixtures of these materials in equal parts. The 45 products obtained can also be used as detergents. Similarly, instead of the NTA, the carbonate, the carbonate and the bicarbonate, the polyphosphate, the sodium citrate and / or the sodium gluconate can be replaced, at least partially, e.g. B. a quarter or half, whereupon good detergents 50 are obtained.

Example 8

The products of Examples 1 and 7 (the main products described first) are mixed in equal proportions to obtain a final product with the properties of these two portions. Before the materials are mixed, they are both brought to approximately the same bulk density of approximately 0.5 g / cm 3 and to approximately the same particle sizes, corresponding to a clear mesh size of 2.00 mm to 0.25 mm, during transport and storage to prevent separation. The mixed product is particularly useful for removing dirt based on oil and clay, is free-flowing, stable and appealing. In some cases, one of the particulate starting materials can be colored or pigmented while leaving the other in its natural color to achieve special effects in appearance. In addition to the approximately identical particle sizes and bulk densities, approximately the same moisture content of e.g.

648 590

14

about 10%, so that the moisture does not migrate very much between the various hollow spheres.

In the material used in Example 7, the anionic detergent, sodium alkylbenzenesulfonate, can be replaced by a sodium a-olefin sulfonate (14 to 15 carbon atoms in the olefin) or a sodium paraffin sulfonate (12 to 15 carbon atoms in the paraffin). The mixtures obtained are also useful detergents.

Example 9 io

Essentially according to the procedure of Example 1, a crutcher mixture of 36.9 parts water, 1.2 parts fluorescent brightener (Tinopal 5BM, extra concentrated), 0.1 part Ultramarine Blue, 2.1 parts magnesium sulfate (heptahydrate), 0.3 Parts of sodium citrate, 22.4 parts of zeolite 4A powder (partially 15 hydrated to a moisture content of about 20%), 20.9 parts of trisodium nitriloacetate monohydrate, 7.4 parts of a 47.5% solution of sodium silicate (Na20: Si02 = 1 : 2.4), 3.7 parts of sodium bentonite (formerly sold as Thixo-Jel No. 2), 2.8 parts of natural anhydrous soda and 2.1 parts of 20 a mineral compound to increase the porosity of the hollow spheres and as a builder. The crutch mixture was spray dried in the same manner as previously described, with the loss of moisture in the drying stage being about 45.2%.

To 78.4 parts of the spray-dried hollow spheres with particle sizes corresponding to a clear mesh size of

2.00 mm to 0.149 mm (sieved), 20 parts of Neodol 23-6.5 were sprayed, the beads were mixed with 1.3 parts of high activity proteolytic enzyme, and then 0.3 parts of perfume were sprayed onto them. The end product has a zeolite content of 25%, an NTA content of 30%, a sodium bentonite content of 5%, and a water-soluble sodium silicate content of 5%. The moisture content was 5% and the content of detergent (polyethoxylated higher fatty alcohol) 20%. The bulk density was about 0.7 g / cm 3 and the pH of a 1% solution was about 10.

The detergent composition produced in this way is a satisfactory nonionic heavy-duty detergent, but deposits a little more zeolite-silicate aggregate on washed, line-dried fabric than a corresponding composition which was produced without water-soluble silicate solids. It is preferred in such corresponding compositions that about 0.1 to 0.5% low molecular weight sodium polyacrylate of the type described above is also present. Both products wash laundry well and are particularly effective for cold water washing, at least in part due to the bentonite content and the almost instant dispersion that is observed when the detergent is added to the washing water (this dispersion also reduces the time for a reaction between the soluble silicate and the zeolite to form undesirable aggregates).

M

Claims (14)

648 590 PATENT CLAIMS 1. Free-flowing, spray-dried hollow spheres which can be used as cleaning agents and for the production of a synthetic nonionic organic detergent composition present in particle form and containing builders, characterized in that they are 5 to 60% by weight water-softening zeolite, 2 to 40% by weight ben-tonite with a sufficient moisture content to facilitate the dispersion of the bentonite and to inhibit the deposition of aluminosilicate on the washed laundry and 5 to 60% by weight contain water-soluble builders or a mixture of such builders. Contains 2% by weight of moisture, the water-soluble builders consist of polyphosphate, pyrophosphate, orthophosphate, borate, nitrilotriacetate, citrate, gluconate, carbonate or bicarbonate or a mixture of two or more of these builders and that a water-soluble silicate is present which is an alkali metal (M) -silicate with an M20: Si02 weight ratio of 1: 1.6 to 1: 3. Hollow beads according to claim 1, characterized in that they contain up to 30% by weight of water-soluble synthetic organic detergent and up to 5% by weight of water-soluble silicate. 3. Hollow beads according to claim 1, characterized in that no water-soluble synthetic organic detergent is present and the water-soluble builders consist of poly-phosphate, pyrophosphate, orthosphosphate, borate, nitrilotriace-tat, gluconate, citrate or mixtures of two or more of these builders. 4. Hollow beads according to claim 1, characterized in that they have a bulk density of 0.2 to 0.9 g / cm3 and particle sizes in the range of 2.00 mm to 0.149 mm mesh size, the water-softening zeolite from a hydrated water-softening zeolite with 15 to 25% by weight of water of hydration and an exchangeability for calcium ions of 200 to 400 milligram equivalent calcium carbonate hardness per g of anhydrous zeolite, the bentonite is a swelling clay with a swellability in water of 3 to 15 ml / g and a viscosity of 3 to 3010 "3 Pa.s at 6 wt .-% concentration in water and at least on an anhydrous bentonite basis 5. Hollow beads according to claim 4, characterized in that the weight ratio bentonite to zeolite 1: 4 to 1: 1, the weight ratio of water-soluble builders to zeolite 1: 2 to 3: 1 and the weight ratio bentonite to water-soluble builders 1:10 to 1: 1 is. 6. Hollow beads according to claim 5, characterized in that they contain 10 to 40% by weight of hydrated sodium zeolite, 2 to 35% by weight of bentonite with a swellability in water of 7 to 15 ml / g and a viscosity of 8 to 3010 " 3 Pa.s at 6 wt .-% concentration in water, 10 to 50 wt .-% of the water-soluble builder salts as alkali metal salts or mixtures of these salts, 0 to 25 wt .-% water-soluble synthetic anionic organic detergents and 0 to 3 wt. -% contain water-soluble silicate. 7. Hollow beads according to claim 1, characterized in that they contain water-soluble, organic synthetic detergent and that the water-soluble builders consist of carbonate, bicarbonate, polyphosphate, nitrilotriacetate or a mixture of these builders and the bentonite on an anhydrous bentonite basis contains at least 3% by weight of moisture contains. 8. Hollow beads according to claim 1, characterized in that the bentonite contains at least 4 wt .-% moisture, the water-soluble builder comprises a nitrilotriacetate, such a composition of water-softening zeolite, bentonite and water-soluble builders, including nitrilotriacetate, the presence of water-soluble synthetic organic detergent and water-soluble silicate. 9. hollow spheres according to claim 8, characterized in that they contain 15 to 40 wt .-% hydrated zeolite A with 15 to 25 wt .-% water of hydration and an exchangeability for calcium ions of 200 to 400 milligram equivalent calcium carbonate hardness per g of anhydrous zeolite, 10 to Contain 20% by weight of Wyoming bentonite with a swellability of 7 to 15 ml / g and a viscosity of 3 to 3010'3 Pa.s at 6% by weight concentration in water and 20 to 60% by weight of nitrilotriacetate. 10. Hollow beads according to claim 1, characterized in that the bentonite contains at least 4 wt .-% moisture, the water-soluble builder comprises a polyphosphate and no water-soluble synthetic organic detergent and no water-soluble silicate is present. 11. Hollow beads according to claim 1, characterized in that they additionally contain 5 to 30% by weight of water-soluble synthetic organic detergent. 12. Hollow beads according to claim 1, characterized in that they additionally contain 3 to 30% by weight of water-soluble synthetic anionic organic detergent. 13. Hollow beads according to claim 1, characterized in that they contain no water-soluble synthetic organic detergent and no water-soluble silicate. 14. Hollow beads according to claim 3, characterized in that they contain 0.5 to 1 wt .-% polyacrylate with a molecular weight of 1000 to 5000.